WO2012173145A1 - Procédé de fabrication d'une matière à base de graphène, matière à base de graphène et structure de fil à base de graphène - Google Patents

Procédé de fabrication d'une matière à base de graphène, matière à base de graphène et structure de fil à base de graphène Download PDF

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Publication number
WO2012173145A1
WO2012173145A1 PCT/JP2012/065131 JP2012065131W WO2012173145A1 WO 2012173145 A1 WO2012173145 A1 WO 2012173145A1 JP 2012065131 W JP2012065131 W JP 2012065131W WO 2012173145 A1 WO2012173145 A1 WO 2012173145A1
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graphene
layer
metal layer
catalyst metal
shape
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PCT/JP2012/065131
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English (en)
Japanese (ja)
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重弥 成塚
隆浩 丸山
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学校法人 名城大学
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Priority claimed from JP2011131743A external-priority patent/JP5783526B2/ja
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Publication of WO2012173145A1 publication Critical patent/WO2012173145A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C01B32/186—Preparation by chemical vapour deposition [CVD]

Definitions

  • the present invention relates to a graphene material manufacturing method, a graphene material, and a graphene wiring structure.
  • Graphene is a two-dimensional material in which six-membered rings of carbon atoms are connected in a single layer to form a planar shape. This graphene is said to have an electron mobility of 100 times or more that of silicon.
  • a transistor using graphene as a channel material has been proposed (see Patent Document 1).
  • Patent Document 1 a catalyst film pattern separated by an insulating separation film is formed on an insulating substrate, a graphene sheet is grown on the catalyst film pattern, and then a drain electrode and a source electrode are formed on both sides of the graphene sheet.
  • a gate electrode is formed on the graphene sheet by breaking the gate insulating film.
  • the catalyst film pattern is separated by the insulating film, but the graphene sheet extends in the lateral direction at the end of the catalyst film pattern, so that the graphene sheet extends from the catalyst film pattern on both sides of the insulating separation film. It is explained that the above connected structure is obtained.
  • the present invention has been made to solve such problems, and an object thereof is to easily produce a graphene material having a desired shape. It is another object of the present invention to easily produce a graphene material having a desired shape having electrode terminals that are difficult to peel off. It is another object of the present invention to provide a flexible graphene wiring structure that can flow a relatively large current.
  • the method for producing the graphene material of the present invention is as follows: (A-1) forming a catalyst metal layer having a predetermined shape having a function of promoting graphenization and a mask material for masking side surfaces of the catalyst metal layer on the substrate body; (B-1) supplying a carbon source to the surface of the catalytic metal layer to grow graphene; (C-1) extracting the graphene having the predetermined shape from the catalyst metal layer as a graphene material; Is included.
  • the shape of the graphene material inherits the shape of the catalytic metal layer as it is, if the catalytic metal layer is patterned into a desired shape, the graphene material of the desired shape can be obtained. Can do. Further, since the mask material is formed on the side surface of the catalyst metal layer, it is possible to suppress the growth of the graphene material on the side surface of the catalyst metal layer. Thereby, graphene closer to the desired shape can be produced, and the graphene material can be easily peeled off from the catalyst metal layer.
  • the graphene material refers to a material having one or more layers of graphene in which six-membered rings of carbon atoms are connected in a single layer.
  • the function of promoting grapheneization refers to a function of promoting the formation of graphene by contacting with a carbon source and combining the carbon components contained in the carbon source with each other.
  • the catalyst metal layer having a shape that can be drawn with one stroke may be formed. In this way, even when the area of the substrate is small, the length of the obtained graphene material can be increased. In this case, graphene having the same shape as that of the metal layer is obtained, but a linear graphene material is obtained by grasping and extending both ends thereof. Such a linear graphene material can be used for electrical wiring and the like.
  • the shape that can be drawn with one stroke may be, for example, a zigzag shape, a spiral shape, or a spiral shape. Specifically, when the substrate body is flat, the catalyst metal layer may be formed in a zigzag shape or a spiral shape, and when the substrate body is cylindrical, the catalyst metal layer may be formed in a spiral shape.
  • the substrate body is not particularly limited.
  • a c-plane sapphire substrate, an a-plane sapphire substrate, a Si substrate having a SiO 2 layer formed thereon, a SiC substrate, a ZnO substrate examples thereof include a GaN substrate (including a template substrate), a refractory metal substrate such as W, and a metal substrate having a grapheneization promoting catalytic ability.
  • a single crystal substrate is preferable because the crystal orientation of the catalytic metal layer is easily aligned.
  • the orientation of the catalytic metal layer may be aligned even if it is not a single crystal substrate.
  • the substrate body is basically required not to deteriorate in the step (b-1) of growing graphene.
  • a Si substrate having a SiO 2 layer formed on the surface is used as the substrate body, in order to suppress the reaction between Si and the catalytic metal layer, Ti, Pt, An intermediate layer such as SiO 2 is preferably provided.
  • the thickness of the intermediate layer is not particularly limited, but may be about 1 nm to 10 nm, for example.
  • examples of the material for the catalyst metal layer include Cu, Ni, Co, Ru, Fe, Pt, Au, and the like.
  • these metals those having a triangular lattice (a structure in which metal atoms are arranged at the apexes of the triangle) on the surface are preferable.
  • the FCC (111) plane, the BCC (110) plane, and the HCP (0001) plane are triangular lattices.
  • the thickness of the catalyst metal layer is not particularly limited, but may be about 1 to 500 nm, for example. However, if the film thickness is too thin, there is a possibility that the catalyst metal may be formed into particles, so that the thickness is preferably set so as not to form particles.
  • the material of the catalytic metal layer is preferably one that can dissolve carbon.
  • the carbon released from the catalyst metal layer becomes graphene in the step (b-1) described later, so that the graphene can be easily thickened.
  • the catalyst metal layer is preferably thick (for example, 200 nm or more).
  • a catalytic metal layer capable of solid-dissolving carbon Co capable of solid-dissolving carbon up to 4.1 at%, Ni capable of solid-dissolving carbon up to 2.7 at%, and carbon up to 0.7 at%. Examples thereof include Fe that can be dissolved in 095 at%.
  • Co and Ni that do not form a stable oxide with carbon are preferable.
  • the metal may be held at a high temperature in a vacuum or in an inert gas, and a carbon raw material (methane, acetylene, alcohol, etc.) may be supplied to the surface. .
  • step (a-1) in order to form a catalyst metal layer having a predetermined shape, patterning may be performed by, for example, a well-known photolithography method.
  • a catalytic metal full-surface coating layer (crystal layer) is first formed on the entire surface of the substrate, and then a resist pattern is formed so that a predetermined shape of the catalytic metal layer remains, and then wet etching or dry etching may be performed.
  • an etching solution may be appropriately selected according to the metal species of the catalyst metal layer.
  • dry etching a gas to be used may be selected as appropriate according to the metal species of the catalyst metal layer.
  • the catalyst metal In order to form a catalyst metal layer having a predetermined shape, the catalyst metal may be deposited or sputtered using a shadow mask that covers a portion other than the predetermined shape.
  • the material of the mask material is not particularly limited.
  • Refractory metals such as Ta and Mo. Since graphene hardly grows on the surface of such a mask material, a graphene sheet having a desired shape that is closer to the shape of the catalyst metal layer can be obtained.
  • the method for forming the mask material is not particularly limited, for example, the mask material may be deposited or sputtered.
  • step (a-1) the catalyst metal layer having the predetermined shape is formed on the substrate body, and then a mask layer is formed on the substrate body so that the catalyst metal layer is embedded, and the mask After forming a resist pattern so as to cover a portion of the layer other than the portion facing the catalyst metal layer, the mask layer is etched to mask the side surfaces of the catalyst metal layer with the mask material. Good.
  • a catalytic metal full-surface coating layer covering the entire surface of the substrate body is formed, and then a resist pattern having the same shape as the predetermined shape is formed on the entire surface coating layer.
  • Etching the entire surface covering layer forms the catalyst metal layer having the predetermined shape on the substrate body, and then leaving the resist pattern on the catalyst metal layer, the substrate body and the substrate
  • a mask layer that is thicker than the catalyst metal layer and thinner than the sum of the thickness of the catalyst metal layer and the resist pattern is formed on the resist pattern, and then the resist pattern and the mask layer on the resist pattern are formed.
  • the side surface of the catalyst metal layer may be masked by the mask material.
  • the catalyst metal has a function of promoting grapheneization.
  • examples of the carbon source include hydrocarbons and alcohols having 1 to 6 carbon atoms.
  • examples of the method for growing graphene include alcohol CVD, thermal CVD, plasma CVD, and gas source MBE.
  • the growth temperature is set to 400 to 850 ° C.
  • a saturated vapor of alcohol such as methanol or ethanol is supplied as a carbon source.
  • the alcohol saturated vapor may be generated by flowing a carrier gas through a bubbler.
  • Argon, hydrogen, nitrogen or the like can be used as the carrier gas.
  • the pressure may be atmospheric pressure or under reduced pressure.
  • Thermal CVD sets the growth temperature to 800-1000 ° C. and supplies methane, ethylene, acetylene, benzene, etc. as the carbon source.
  • the carbon source is supplied with argon or hydrogen as a carrier gas, and the partial pressure of the carbon source is, for example, about 0.002-5 Pa.
  • the growth time may be 1-20 minutes, for example, and the pressure may be under pressure (for example, 1 kPa) or under reduced pressure. Hot filaments are often used to decompose the carbon source.
  • the growth temperature is 950 ° C.
  • the pressure is 1-1. 1 Pa
  • the carbon source is methane
  • the methane flow rate is 5 sccm
  • the carrier gas is hydrogen
  • the hydrogen flow rate is 20 sccm
  • the plasma power is about 100 W.
  • the gas source MBE uses, for example, ethanol as a carbon source, a flow rate of nitrogen or hydrogen gas saturated with ethanol at 0.3-2 sccm, and a W filament heated to 2000 ° C. for decomposition of the carbon source in a vacuum. .
  • the substrate temperature is about 400-600 ° C.
  • the catalyst metal layer in the step (c-1), the catalyst metal layer may be dissolved and the graphene having the predetermined shape may be taken out as the graphene material. In this way, the graphene material can be easily taken out.
  • step (c-1) for example, an acidic solution is used to dissolve the catalyst metal layer.
  • which acidic solution is used depends on the metal species of the catalyst metal layer. For example, dilute nitric acid is used when the material of the catalytic metal layer is Ni.
  • dilute nitric acid is used when the material of the catalytic metal layer is Ni.
  • the graphene material is turned off from the etched portion and mechanically peeled off. Also good.
  • the mask material in the step (c-1), may also be dissolved to take out the graphene having the predetermined shape as the graphene material. In this way, the graphene material can be taken out more easily.
  • the mask material is SiO 2 or Ti, hydrofluoric acid is used.
  • the graphene material of the present invention is a self-supporting graphene material having a shape that can be drawn with a single stroke (for example, a zigzag shape or a spiral shape). Such a graphene material can be easily obtained by the above-described method for producing a graphene material. Note that “self-supporting” means independent without having a support such as a tape.
  • (A-1) forming a catalytic metal full-surface coating layer that covers the entire surface of the substrate body, and then forming a mask material having a negative shape and a predetermined shape on the surface of the entire surface coating layer; (B-2) supplying a carbon source to the surface of the entire covering layer on which the mask material is formed to grow graphene on a portion where the mask material is not formed; (C-3) extracting the graphene having the predetermined shape from the entire surface coating layer as a graphene material; May be included.
  • the graphene is grown after forming a mask material on the surface of the catalyst metal full-surface coating layer without going through the step of patterning the entire surface coating layer to form a catalyst metal layer.
  • the graphene raw material of a desired shape can be obtained by a simpler process.
  • the shape having a negative relationship with the predetermined shape refers to the shape of the portion (remaining part) other than the predetermined shape.
  • the various aspects demonstrated with the manufacturing method of the graphene raw material mentioned above are employable.
  • the method for producing the graphene material of the present invention is as follows: (A-2) forming a catalyst metal layer having a predetermined shape on the substrate body having a function of promoting grapheneization; (B-2) supplying graphene to the surface of the catalytic metal layer to grow graphene; (C-2) extracting the graphene as a graphene material from the catalyst metal layer; Including Before or after taking out the graphene as a graphene material in the step (c-2), a Ti layer as a base and a protective layer mainly composed of a metal selected from the group consisting of Mo, Ni, Ta and W are formed. An electrode terminal having a laminated structure is formed.
  • the shape of the graphene material inherits the shape of the catalytic metal layer as it is, if the catalytic metal layer is patterned into a desired shape, the graphene material of the desired shape can be obtained. Can do.
  • the electrode terminal uses Ti having good reactivity with carbon as a layer in contact with graphene, the electrode terminal is an excellent ohmic electrode.
  • Mo, Ni, Ta, or W which does not easily react with Ti, is used for the protective layer formed immediately above the Ti layer, the phenomenon that Ti diffuses into the protective layer and peels from the graphene hardly occurs.
  • the protective layer may be made of a metal selected from the group described above (however, it includes an inevitable impurity component).
  • the graphene material refers to a material having one or more layers of graphene in which six-membered rings of carbon atoms are connected in a single layer.
  • the function of promoting grapheneization refers to a function of promoting the formation of graphene by contacting with a carbon source and combining the carbon components contained in the carbon source with each other.
  • the thickness of the Ti layer may be 1 nm-100 nm, and the thickness of the protective layer may be 5 nm-100 nm.
  • the catalyst metal layer having a shape that can be drawn with one stroke may be formed. In this way, even when the area of the substrate is small, the length of the obtained graphene material can be increased. In this case, graphene having the same shape as that of the metal layer is obtained, but a linear graphene material is obtained by grasping and extending both ends thereof. Such a linear graphene material can be used for electrical wiring and the like.
  • the shape that can be drawn with one stroke may be, for example, a zigzag shape, a spiral shape, or a spiral shape. Specifically, when the substrate body is flat, the catalyst metal layer may be formed in a zigzag shape or a spiral shape, and when the substrate body is cylindrical, the catalyst metal layer may be formed in a spiral shape.
  • the substrate body is not particularly limited.
  • a c-plane sapphire substrate, an a-plane sapphire substrate, a Si substrate having a SiO 2 layer formed on the surface, a SiC substrate, a ZnO substrate examples thereof include a GaN substrate (including a template substrate), a refractory metal substrate such as W, and a metal substrate having a grapheneization promoting catalytic ability.
  • a single crystal substrate is preferable because the crystal orientation of the catalytic metal layer is easily aligned.
  • the orientation of the catalytic metal layer may be aligned even if it is not a single crystal substrate.
  • the substrate main body basically needs to be not deteriorated in the step (b-2) of growing graphene.
  • a Si substrate having a SiO 2 layer formed on the surface is used as the substrate body, in order to suppress the reaction between Si and the catalytic metal layer, Ti, Pt, An intermediate layer such as SiO 2 is preferably provided.
  • the thickness of the intermediate layer is not particularly limited, but may be about 1 nm to 10 nm, for example.
  • examples of the material for the catalyst metal layer include Cu, Ni, Co, Ru, Fe, Pt, Au, and the like.
  • these metals those having a triangular lattice (a structure in which metal atoms are arranged at the apexes of the triangle) on the surface are preferable.
  • the FCC (111) plane, the BCC (110) plane, and the HCP (0001) plane are triangular lattices.
  • the thickness of the catalyst metal layer is not particularly limited, but may be about 1 to 500 nm, for example. However, if the film thickness is too thin, there is a possibility that the catalyst metal may be formed into particles, so that the thickness is preferably set so as not to form particles.
  • step (a-2) in order to form a catalyst metal layer having a predetermined shape, patterning may be performed by, for example, a well-known photolithography method.
  • a catalytic metal layer may be formed on the entire surface of the substrate, and then a resist pattern may be formed so as to leave a catalyst metal layer having a predetermined shape, followed by wet etching or dry etching.
  • wet etching an etching solution may be appropriately selected according to the metal species of the catalyst metal layer.
  • dry etching a gas to be used may be selected as appropriate according to the metal species of the catalyst metal layer.
  • the catalyst metal In order to form a catalyst metal layer having a predetermined shape, the catalyst metal may be deposited or sputtered using a shadow mask that covers a portion other than the predetermined shape.
  • examples of the carbon source include hydrocarbons and alcohols having 1 to 6 carbon atoms.
  • examples of the method for growing graphene include alcohol CVD, thermal CVD, plasma CVD, gas source MBE, and the like, as in step (b-1).
  • step (c-2) for example, an acidic solution is used to dissolve the catalyst metal layer.
  • which acidic solution is used depends on the metal species of the catalyst metal layer. For example, dilute nitric acid is used when the material of the catalytic metal layer is Ni.
  • dilute nitric acid is used when the material of the catalytic metal layer is Ni.
  • the graphene material is turned off from the etched portion and mechanically peeled off. Also good.
  • the electrode terminal has a structure in which a Ti layer, a protective layer, and a surface layer made of Au or Sn are laminated in this order as the electrode terminal. Things may be formed.
  • the electrode terminal since the electrode terminal has a surface layer made of Au or Sn, bonding can be performed easily and reliably.
  • each layer constituting the electrode terminal may be formed by, for example, an electron beam evaporation method. In this case, it is preferable to deposit in vacuum at a temperature of room temperature to 200 ° C. Alternatively, it may be formed by electrolytic plating.
  • heat treatment may be performed in an inert gas or in a vacuum at about 500 ° C. in order to improve electrode characteristics.
  • heat treatment may be performed in an inert gas or in vacuum in order to evaporate and desorb impurities.
  • the graphene material of the present invention is a self-supporting graphene material having a shape that can be drawn with a single stroke (for example, zigzag shape or spiral shape), and includes a Ti layer and Mo, Ni, Ta, and W that form a base on both ends.
  • the electrode terminal has a structure in which a protective layer mainly composed of a selected metal is laminated in this order.
  • Such a graphene material can be easily obtained by the above-described method for producing a graphene material.
  • self-supporting means independent without having a support such as a tape.
  • graphene layer refers to a layer having one or a plurality of (for example, 2 to 10) graphene sheets in which six-membered rings of carbon atoms are connected in a single layer.
  • a catalyst metal layer having a function of promoting grapheneization may be interposed between the insulating resin layer and the graphene layer.
  • a catalytic metal layer is formed on an insulating resin layer and graphene is grown by supplying a carbon source to the catalytic metal layer, the gap between the insulating resin layer and the graphene layer is increased.
  • a catalyst metal layer is interposed, but such a catalyst metal layer has good conductivity and may be left as it is.
  • a catalytic metal layer is interposed between the insulating resin layer and the graphene layer.
  • the “function to promote graphenization” refers to a function that promotes the formation of graphene by contacting the carbon source and combining the carbon components contained in the carbon source with each other.
  • each graphene layer may be formed by stacking an odd number of graphene sheets, or may be formed by stacking an even number of graphene sheets. Since graphene layers with odd-numbered graphene sheets have similar electrical characteristics, if each graphene layer is a stack of odd-numbered graphene sheets, graphene layers with the odd-numbered graphene sheets stacked The electrical properties of the layer are emphasized. In addition, since the graphene layers with an even number of graphene sheets are similar in electrical characteristics, if each graphene layer is an even number of graphene sheets, the even number of graphene sheets are stacked. The electrical properties of the graphene layer are emphasized.
  • the method for producing a graphene wiring structure of the present invention may include, for example, a process of repeating a work of providing an insulating resin layer on the graphene layer after providing the graphene layer on the insulating resin layer.
  • a separately prepared graphene layer may be disposed on the insulating resin layer.
  • a catalyst metal layer having a function of promoting graphene formation is formed on a substrate in a shape that can be drawn with one stroke, and a carbon source is supplied to the surface of the catalyst metal layer.
  • the graphene may be grown, and the graphene may be taken out as a graphene material from the catalyst metal layer.
  • the graphene wiring structure of the present invention may be manufactured by pulling both ends of the plurality of graphene materials taken out in this way into a substantially straight shape and then solidifying with an insulating resin while maintaining the state.
  • a method in which a catalytic metal layer having a function of promoting graphene formation is interposed between an insulating resin layer and a graphene layer is obtained by, for example, placing a catalytic metal layer on the insulating resin layer.
  • a graphene layer is formed by growing a graphene by supplying a carbon source to the surface of the catalyst metal layer and forming the graphene layer so that the shape can be written (for example, linear, zigzag, spiral)
  • a step of repeating an operation of providing an insulating resin layer on the graphene layer while leaving the layer may be included.
  • a manufacturing method in which a catalytic metal layer having a function of promoting graphene formation is not interposed between the insulating resin layer and the graphene layer is, for example, a shape in which the catalytic metal layer can be drawn with a single stroke on the insulating resin layer.
  • the graphene layer was formed by growing a graphene by supplying a carbon source to the surface of the catalyst metal layer, and the catalyst metal layer was melted and removed in a state where one end of the graphene layer was sandwiched between sandwiching members Further, it may include a step of repeating the operation of providing an insulating resin layer on the graphene layer.
  • the shape when the wiring is routed in advance is determined, if the insulating resin layer and catalytic metal layer are formed in the same shape, the completed graphene wiring structure can be used as it is without bending. Can do.
  • patterning may be performed by, for example, a well-known photolithography method.
  • a catalytic metal layer may be formed on the entire surface of the substrate, and then a resist pattern may be formed so as to leave a catalyst metal layer having a predetermined shape, followed by wet etching or dry etching.
  • wet etching an etching solution may be appropriately selected according to the metal species of the catalyst metal layer.
  • dry etching a gas to be used may be selected as appropriate according to the metal species of the catalyst metal layer.
  • the catalyst metal may be deposited or sputtered using a shadow mask that covers a portion other than the predetermined shape.
  • examples of the carbon source include hydrocarbons having 1 to 6 carbon atoms and alcohols.
  • examples of the method for growing graphene include alcohol CVD, thermal CVD, plasma CVD, gas source MBE and the like, as in the above-described step (b-1).
  • the growth temperature may be set appropriately below the heat resistance temperature of the insulating resin layer.
  • a temperature slightly lower than the heat resistance temperature may be used.
  • FIG. It is explanatory drawing (perspective view) showing the procedure which manufactures the graphene raw material 10.
  • FIG. It is explanatory drawing (sectional drawing) showing the manufacturing process of the board
  • FIG. It is a top view of the board
  • FIG. It is a top view of the board
  • FIG. 3 is a cross-sectional view showing a structure of an electrode terminal 218.
  • FIG. It is explanatory drawing of the state which pulled the graphene material 210, (a) is explanatory drawing when pulled loosely, (b) is explanatory drawing when it pulls strongly.
  • It is a top view of the board
  • FIG. 3 is a perspective view of a graphene wiring structure 310.
  • FIG. FIG. 13 is a cross-sectional view taken along line AA in FIG. 12. 6 is a manufacturing process diagram of the graphene wiring structure 310.
  • FIG. 3 is a perspective view of a graphene wiring structure 360.
  • FIG. It is BB sectional drawing of FIG. It is a manufacturing process diagram of the graphene material 410. It is a top view of the board
  • FIG. 1 is an explanatory diagram (perspective view) illustrating a procedure for manufacturing the graphene material 10
  • FIG. 2 is an explanatory diagram (sectional view) illustrating a manufacturing process of the graphene forming substrate 11.
  • a substrate body 12 made of rectangular c-plane sapphire is prepared (see FIG. 2A), and Ni is formed on the entire surface of the substrate body 12 to form a whole surface coating layer (crystal layer) 14 (FIG. 1 (a) and FIG. 2 (b)).
  • a resist pattern 13 is formed by lithography so that the entire surface coating layer 14 can be patterned in a single stroke, here a zigzag pattern (see FIG. 2C), and the entire surface coating layer 14 is formed into a zigzag type catalyst.
  • the metal layer 16 is used (see FIG. 2D).
  • the resist pattern 13 is removed to expose the catalyst metal layer 16 (see FIG.
  • Ti is formed so that the catalyst metal layer is embedded, and this is used as a mask layer 17 (FIG. 2). (See (f)), the surface of the mask layer 17 is polished to expose the catalytic metal layer 16 (see FIGS. 1B and 2G). In this manner, the graphene forming substrate 11 in which the Ti mask material 19 is formed on the side surface of the catalytic metal layer 16 is manufactured.
  • C atoms are supplied to Ni of the catalyst metal layer 16 by a mixed gas of acetylene and argon at a temperature of 600 ° C. and a pressure of 1 kPa. Then, the Ni surface is rearranged in the (111) plane. On the Ni (111) plane, a triangular lattice having Ni atoms as vertices is formed. The supplied C atoms are arranged right above the center of gravity of each triangle composed of Ni atoms, so that a hexagon having the C atom as a vertex is formed. The graphene grows by going (see FIG. 1C). Since graphene is formed on the catalyst metal layer 16 and is not easily formed on the mask material 19, it has the same shape as the catalyst metal layer 16, that is, a zigzag shape.
  • the graphene material 10 obtained in this manner is a zigzag self-supporting material, but can be formed into a wire by gripping and stretching the electrodes 18 and 20 at both ends (see FIG. 1 (f)). .
  • Such a wire is thin and can be used as an electrical wiring capable of flowing a large current.
  • a transistor structure can be fabricated in the middle of the electrical wiring thus fabricated to control the current flow.
  • the shape of the graphene material 10 inherits the shape of the catalyst metal layer 16 as it is, so that the catalyst metal layer 16 only needs to be patterned into a desired shape.
  • the graphene material 10 having the desired shape can be obtained.
  • the mask material 19 is formed on the side surface of the catalytic metal layer 16, it is possible to suppress the growth of graphene on the side surface of the catalytic metal layer 16.
  • the graphene material 10 closer to the desired shape can be produced.
  • the graphene material 10 can be easily peeled off from the catalyst metal layer 16.
  • the catalyst metal layer 16 has a zigzag shape that can be drawn with a single stroke, the length of the obtained graphene material 10 can be increased even when the area of the substrate body 12 is small.
  • the substrate body may be linear or cylindrical. By using a substrate having such a shape, a longer wiring structure can be easily manufactured.
  • graphene is grown using the graphene forming substrate 11 shown in FIGS. 1 and 2, but the graphene forming substrate 31 shown in FIG. 3 and the graphene forming substrate 41 shown in FIG. It may be produced and graphene may be grown using this.
  • the mask materials 39 and 49 are formed so as to be higher than the catalyst metal layer 16, it is possible to suppress the growth of graphene in the lateral direction, and the shape closer to the desired shape.
  • a graphene sheet is obtained.
  • the mask material be formed higher than the catalyst metal layer because graphene easily grows in the lateral direction.
  • FIG. 3 is an explanatory diagram (cross-sectional view) showing a manufacturing process of the graphene forming substrate 31.
  • FIGS. 3A to 3F are the same as FIGS. 2A to 2F, description thereof is omitted here.
  • a resist pattern 35 is formed so as to cover a portion of the mask layer 17 other than the portion facing the catalytic metal layer 16 (see FIG. 3G).
  • the mask layer 17 where the resist pattern 35 is not formed is removed by etching (see FIG. 3H), and the resist pattern 35 is further removed (see FIG. 3I).
  • the graphene forming substrate 31 in which the Ti mask material 39 is formed on the side surface of the catalytic metal layer 16 is obtained.
  • a substrate from which the pattern 35 is not removed may be used as it is as a substrate for forming graphene.
  • FIG. 4 is an explanatory diagram (cross-sectional view) showing a manufacturing process of the graphene forming substrate 41.
  • the substrate body 12 is prepared (see FIG. 4A), and Ni is formed on the entire surface of the substrate body 12 to form the entire coating layer 14 (see FIG. 4B).
  • a resist pattern 13 having the same zigzag shape as the graphene sheet 10 is formed (see FIG. 4C), and a portion of the entire covering layer 14 where the resist pattern 13 is not formed is removed by etching.
  • a zigzag catalyst metal layer 16 is formed (see FIG. 4D).
  • Ti is formed to be thinner than this, and this is used as a mask layer 47 (see FIG. 4E).
  • the mask layer 47 formed on the resist pattern 13 is also removed (see FIG. 4F).
  • the graphene forming substrate 41 in which the Ti mask material 49 is formed on the side surface of the catalytic metal layer 16 is obtained.
  • FIG. 5 is an explanatory diagram (perspective view) showing a procedure for manufacturing the graphene material 110.
  • a substrate main body 112 made of c-plane sapphire on a quadrilateral is prepared, and Ni is formed on the entire surface of the substrate main body 112 to form the entire surface covering layer 114 (see FIG. 5A).
  • a mask material 119 having a shape that can be drawn with a single stroke, here a zigzag shape, and a negative shape is formed on the surface of the entire covering layer 114 (see FIG. 5B).
  • the graphene forming substrate 111 is manufactured.
  • C atoms are supplied to Ni of the entire surface coating layer 114 by a mixed gas of acetylene and argon at a temperature of 600 ° C. and a pressure of 1 kPa.
  • graphene grows (see FIG. 5C). Since graphene is formed on the entire surface covering layer 114 and is not easily formed on the mask material 119, the graphene has the same shape as the entire surface covering layer 114 on which the mask material 119 is formed, that is, a zigzag shape.
  • square electrodes 118 and 120 are attached to both ends of the zigzag graphene (see FIG. 5D).
  • the graphene material 110 is a zigzag self-supporting material, but can be formed into a wire by grasping and stretching the electrodes 118 and 120 at both ends (see FIG. 5 (f)). . According to this manufacturing method, it is not necessary to perform patterning of the catalytic metal layer, so that a graphene sheet having a desired shape can be obtained more easily.
  • the zigzag-shaped catalyst metal layer 16 is formed on the substrate body 12, but the spiral-shaped catalyst metal layer 56 may be formed on the substrate body 52 as shown in FIG. 6 (plan view). Good. Also in this case, after growing graphene on the catalytic metal layer 56 in the same manner as in the above-described embodiment, if electrodes are attached to both ends of the graphene and then the catalytic metal layer 56 is melted, the graphene becomes a spiral graphene material. It can be taken out. Moreover, if both ends of the spiral graphene material are grasped and stretched, a wire can be obtained.
  • a graphene material having a shape other than the zigzag shape and the spiral shape can be taken out in the same manner as in the above-described embodiment as long as it is a one-stroke drawing shape.
  • any shape other than the one-stroke shape for example, a polygon such as a triangle or a quadrangle, a circle, an ellipse, or a star shape may be employed.
  • a graphene material having an arbitrary shape can be taken out.
  • graphene is grown by thermal CVD.
  • graphene may be grown by a method other than thermal CVD, for example, alcohol CVD, plasma CVD, gas source MBE, or the like.
  • Ni is used as the material of the catalyst metal layer 16, but any material may be used as long as it has a function of promoting the growth of graphene.
  • any material may be used as long as it has a function of promoting the growth of graphene.
  • Ni for example, Cu, Co, Ru, Fe, Pt, Au and the like can be mentioned.
  • the graphene material 10 when removing the graphene material 10 from the catalyst metal layer 16, all of the catalyst metal layer 16 is dissolved. For example, only the vicinity of the end portion of the catalyst metal layer 16 on which the electrodes 18 and 20 are produced is etched with an acidic solution. Then, the graphene material 10 may be taken out by mechanically peeling off the graphene from the etched portion. Since graphene is a laminate of planar structures in which hexagonal carbon is secondarily bonded, about one or two layers of graphene remain on the catalyst metal layer 16, but the rest peel off cleanly. Note that the graphene remaining on the catalyst metal layer 16 can also serve as a seed for graphene growth when the catalyst metal layer 16 is reused. In the above-described embodiment, the mask material 19 is melted, but may be physically cut.
  • the substrate body 12 is plate-shaped
  • the substrate body may be cylindrical.
  • the substrate body may be hollow (the interior is empty) or solid (the interior is clogged).
  • the catalyst metal layer When growing graphene on a cylindrical and hollow substrate body, the catalyst metal layer may be patterned on either the outer surface or the inner surface of the substrate body, and the graphene may be grown on the surface of the catalyst metal layer, Alternatively, the catalyst metal layer may be patterned on both the outer surface and the inner surface of the substrate body, and graphene may be grown on the surfaces of both catalyst metal layers.
  • a technique according to ordinary photolithography may be applied while rotating the substrate body, or mechanical lithography using nanoimprint technology. The pattern may be transferred, or may be mechanically patterned using a fine marking needle.
  • vapor deposition may be employed, or a liquid raw material containing the metal is sprayed, or a substrate is immersed in the liquid, followed by heat treatment to form a catalyst metal thin film. May be adopted.
  • a carbon source is supplied to the surface of the catalytic metal layer.
  • the substrate body is cylindrical and hollow, the substrate body is regarded as a vacuum chamber and carbon is contained therein. Since graphene can be grown by flowing the source gas as a source, there is no need to prepare a vacuum chamber, and there are many excellent effects such as greatly simplifying the equipment configuration and eventually improving productivity and reducing production costs. Can be expected.
  • the magnitude of a magnetic field generated from a coil is determined by the product of the number of turns of the coil and the current flowing as indicated by electromagnetics.
  • a graphene sheet is used, a thin wire shape is easier to produce than when a normal copper wire is used, and a larger current can be passed, so the coil according to the present invention has a smaller shape and a larger magnetic field. Can be generated. That is, a large conductance can be shown.
  • the coil can be wound 400 times with a length of 1 cm. it can.
  • a very simple manufacturing method that is, without winding the coil. Since the current that can be passed through the graphene sheet is also larger than that of a normal copper wire, the magnetic force generated from the coil can be increased.
  • this coil can be used not only as an inductance but also as a transformer by coupling and combining two coils with an iron core or the like, or as an electromagnet used for a motor or the like.
  • the coil shape is not limited to a cylindrical shape, but can be assembled into equipment as it is grown if the substrate shape is changed to an elliptical cylindrical shape, a rectangular cylindrical shape, etc. according to the iron core shape of a motor or the like. .
  • the coil formed on the outside and inside of the cylindrical substrate is equipped with an iron core for use.
  • a transformer can be configured by dividing a graphene sheet coil containing an iron core into parts and using them as independent windings.
  • this structure can be applied to devices such as motors and transformers by winding in a coil shape. As described above, a structure in which a metal conductor is fused with a graphene sheet can also be easily produced according to the present invention.
  • FIG. 7 is an explanatory diagram (perspective view) showing a procedure for manufacturing the graphene material 210.
  • a substrate body 212 made of rectangular c-plane sapphire is prepared, and Ni is formed on the entire surface of the substrate body 212 to form a crystal layer 214 (see FIG. 7A).
  • the crystal layer 214 is patterned into a shape that can be drawn with a single stroke by a lithography method, here, in a zigzag shape, and the crystal layer 214 is used as a catalyst metal layer 216 (see FIG. 7B).
  • C atoms are supplied to Ni of the catalyst metal layer 216 by a mixed gas of acetylene and argon at a temperature of 600 ° C. and a pressure of 1 kPa. Then, the Ni surface is rearranged in the (111) plane. On the Ni (111) plane, a triangular lattice having Ni atoms as vertices is formed. The supplied C atoms are arranged right above the center of gravity of each triangle composed of Ni atoms, so that a hexagon having the C atom as a vertex is formed. Graphene grows by going (see FIG. 7C).
  • graphene Since graphene is formed on the catalyst metal layer 216, it has the same shape as the catalyst metal layer 216, that is, a zigzag shape. Note that if the graphene grows too much, the groove that extends in the lateral direction and closes the groove that forms the zigzag is blocked.
  • the electrode terminal 218 is made of an underlying Ti layer 218a, a protective layer 218b mainly composed of a metal selected from the group consisting of Mo, Ni, Ta, and W, and Au or Sn.
  • the surface layer 218c is laminated in this order.
  • the electrode terminals 220 are laminated so as to have a three-layer structure.
  • Each layer may be formed by an electron beam evaporation method. In this case, it is preferable to deposit in vacuum at a temperature of room temperature to 200 ° C. Alternatively, it may be formed by electrolytic plating.
  • heat treatment may be performed in an inert gas or in a vacuum at about 500 ° C. in order to improve electrode characteristics.
  • heat treatment may be performed in an inert gas or in vacuum in order to evaporate and desorb impurities.
  • the electrode terminals 218 and 220 are appropriately protected with a protective film, and the catalytic metal layer 216 is dissolved with an acidic solution.
  • the catalyst metal layer 216 is Ni, dilute nitric acid is used.
  • the protective film of the electrode terminals 218 and 220 is removed (see FIG. 7E).
  • the protective film for the electrode terminals 218 and 220 include photoresist and wax. Further, when a photoresist is used as the protective film, it is removed with acetone and a stripping solution, and when a wax is used, it is removed with an organic solvent.
  • the graphene material 210 obtained in this way is a zigzag self-supporting material, but can be made into a wire by gripping and stretching the electrode terminals 218 and 220 at both ends (see FIG. 7 (f)). ).
  • Such a wire is thin and can be used as an electrical wiring capable of flowing a large current.
  • a transistor structure can be fabricated in the middle of the electrical wiring thus fabricated to control the current flow.
  • the wire shown in FIG. 9A is obtained.
  • Such a structure is telescopic, and for example, when both ends are greatly separated from the shape shown in FIG. 9A, the shape becomes elongated as shown in FIG. 9B.
  • a cylinder having an inner diameter smaller than the width wa in FIG. 9A and larger than the width wb in FIG. 9B is prepared. After inserting the wire in the state shown in FIG. When unwound, the wire is fixed in the cylinder by the restoring force. If this cylinder is formed of an insulator, this cylinder becomes a covering material and can be used as an electric cable. At this time, the space in the cylinder may be filled with an insulating resin.
  • the shape of the graphene material 210 inherits the shape of the catalyst metal layer 216 as it is, and therefore, as long as the catalyst metal layer 216 is patterned into a desired shape.
  • the graphene material 210 having the desired shape can be obtained.
  • the catalytic metal layer 216 has a zigzag shape that can be drawn with a single stroke, the length of the obtained graphene material 210 can be increased even when the area of the substrate body 212 is small.
  • the electrode terminals 218 and 220 are excellent ohmic electrodes because Ti having good reactivity with carbon is used for the base layer in contact with the graphene.
  • the substrate body may be linear or cylindrical. By using a substrate having such a shape, a longer wiring structure can be easily manufactured.
  • the zigzag-shaped catalyst metal layer 216 is formed on the substrate body 212.
  • the spiral catalyst metal layer 226 is formed on the substrate body 212. May be.
  • electrodes are attached to both ends of the graphene, and then the catalyst metal layer 226 is melted, so that the graphene becomes a spiral graphene material. It can be taken out.
  • both ends of the spiral graphene material are grasped and stretched, a wire can be obtained.
  • a graphene material having a shape other than the zigzag shape and the spiral shape can be taken out in the same manner as in the above-described embodiment as long as it is a one-stroke drawing shape.
  • any shape other than the one-stroke shape for example, a polygon such as a triangle or a quadrangle, a circle, an ellipse, or a star shape may be employed.
  • a graphene material having an arbitrary shape can be taken out.
  • graphene is grown by thermal CVD.
  • graphene may be grown by a method other than thermal CVD, for example, alcohol CVD, plasma CVD, gas source MBE, or the like.
  • Ni is adopted as the material of the catalyst metal layer 216, but any material may be adopted as long as it has a function of promoting the growth of graphene.
  • any material may be adopted as long as it has a function of promoting the growth of graphene.
  • Ni for example, Cu, Co, Ru, Fe, Pt, Au and the like can be mentioned.
  • the catalyst metal layer 216 when the graphene material 210 is taken out from the catalyst metal layer 216, the catalyst metal layer 216 is completely dissolved. For example, only the vicinity of the end of the catalyst metal layer 216 from which the electrode terminals 218 and 220 are manufactured is an acidic solution.
  • the graphene material 210 may be taken out by etching away and mechanically peeling off the graphene from the etched portion. Since graphene is formed by stacking a planar structure in which hexagonal carbon is secondarily bonded, about one or two layers of graphene remain on the catalyst metal layer 216, but the rest peels cleanly. Note that the graphene remaining on the catalyst metal layer 16 can also serve as a seed for graphene growth when the catalyst metal layer 216 is reused.
  • the substrate body 212 is plate-shaped
  • the substrate body may be cylindrical.
  • patterning of the catalytic metal layer is performed in a spiral manner as if a ribbon is wound around the substrate body, and graphene is grown on the surface of the catalytic metal layer, thereby producing very long and smooth linear graphene.
  • the material can be easily obtained.
  • FIG. FIG. 11A shows a state in which a spiral catalyst metal layer 236 is provided on a cylindrical substrate body 232
  • FIG. 11B shows a graphene material 250 grown by growing graphene on the surface of the catalyst metal layer 236. The formed state is shown.
  • the substrate main body 232 is illustrated as being solid (the inside is clogged), but may be hollow (the inside is hollow).
  • the helical graphene material 250 taken out from the catalyst metal layer 236 also becomes longer when both ends are pulled, and at the same time the coil diameter becomes smaller.
  • a cylinder having an inner diameter smaller than the coil diameter when the force is loosened is prepared larger than the coil diameter when both ends are pulled, and after inserting the graphene material 250 with both ends pulled into this cylinder, the both ends are gripped. Is released, the graphene material 250 is fixed in the cylinder by the restoring force. If this cylinder is formed of an insulator, this cylinder becomes a covering material and can be used as an electric cable. At this time, the space in the cylinder may be filled with an insulating resin.
  • a spiral catalytic metal layer may be patterned on either the outer surface or the inner surface of the substrate body, and the graphene may be grown on the surface of the catalyst metal layer.
  • a helical catalyst metal layer may be patterned on both the outer surface and the inner surface of the substrate body, and graphene may be grown on the surfaces of both catalyst metal layers.
  • a technique according to ordinary photolithography may be applied while rotating the substrate body, or mechanical lithography using nanoimprint technology.
  • the pattern may be transferred, or may be mechanically patterned using a fine marking needle.
  • vapor deposition may be employed, or a liquid raw material containing the metal is sprayed, or a substrate is immersed in the liquid, followed by heat treatment to form a catalyst metal thin film. May be adopted.
  • a carbon source is supplied to the surface of the catalytic metal layer.
  • the substrate body When the substrate body is cylindrical and hollow, the substrate body is regarded as a vacuum chamber and carbon is contained therein. Since graphene can be grown by flowing the source gas as a source, there is no need to prepare a vacuum chamber, and there are many excellent effects such as greatly simplifying the equipment configuration and eventually improving productivity and reducing production costs. Can be expected.
  • the magnitude of a magnetic field generated from a coil is determined by the product of the number of turns of the coil and the current flowing as indicated by electromagnetics.
  • a graphene sheet is used, a thin wire shape is easier to produce than when a normal copper wire is used, and a larger current can be passed, so the coil according to the present invention has a smaller shape and a larger magnetic field. Can be generated. That is, a large conductance can be shown.
  • the coil can be wound 400 times with a length of 1 cm. it can.
  • a very simple manufacturing method that is, without performing a coil winding operation. Since the current that can be passed through the graphene sheet is also larger than that of a normal copper wire, the magnetic force generated from the coil can be increased.
  • this coil can be used not only as an inductance but also as a transformer by coupling and combining two coils with an iron core or the like, or as an electromagnet used for a motor or the like.
  • the coil shape is not limited to a cylindrical shape, but can be assembled into equipment as it is grown if the substrate shape is changed to an elliptical cylindrical shape, a rectangular cylindrical shape, etc. according to the iron core shape of a motor or the like. .
  • the coil formed on the outside and inside of the cylindrical substrate body is equipped with an iron core for use.
  • a transformer can be configured by dividing a graphene sheet coil containing an iron core into parts and using them as independent windings.
  • this structure can be applied to devices such as motors and transformers by winding in a coil shape. As described above, a structure in which a metal conductor is fused with a graphene sheet can also be easily produced according to the present invention.
  • FIG. 12 is a perspective view of the graphene wiring structure 310
  • FIG. 13 is a cross-sectional view taken along the line AA of FIG.
  • insulating resin layers 312, 322, 332, and 342 and graphene layers 316, 326, and 336 are repeatedly stacked. Insulating resin layers 312 and 322 exist above and below the graphene layer 316, insulating resin layers 322 and 332 exist above and below the graphene layer 326, and insulating resin layers 332 and 342 exist above and below the graphene layer 336. .
  • a catalytic metal layer 314 is interposed between the insulating resin layer 312 and the graphene layer 316
  • a catalytic metal layer 324 is interposed between the insulating resin layer 322 and the graphene layer 326
  • a catalytic metal layer 334 is interposed between the layers 336.
  • the catalytic metal layers 314, 324, and 334 have a function of promoting grapheneization.
  • Each of the graphene layers 316, 326, and 336 is formed by laminating an odd number (three in this case) of graphene sheets.
  • FIG. 14 is a manufacturing process diagram of the graphene wiring structure 310.
  • an insulating resin layer 312 made of heat-resistant polyimide (for example, Kapton H type manufactured by DuPont) is prepared (see FIG. 14A). At this time, a substrate on which the insulating resin layer 312 is formed may be prepared.
  • a catalytic metal layer 314 is vapor-deposited on the insulating resin layer 312 and patterned by a well-known photolithography method if necessary, and then heat treatment is performed to crystallize the catalytic metal layer 314 (FIG. 14). (See (b)).
  • the catalyst metal layer 314 may be crystallized while being deposited by a pulse sputtering deposition (PSD) technique.
  • PSD pulse sputtering deposition
  • the material of the catalyst metal layer 314 include Cu, Ni, Co, Ru, Fe, Pt, and Au.
  • these metals those having a triangular lattice (a structure in which metal atoms are arranged at the apexes of the triangle) on the surface are preferable.
  • the FCC (111) plane, the BCC (110) plane, and the HCP (0001) plane are triangular lattices.
  • the thickness of the catalyst metal layer 314 is not particularly limited, but may be about 1 to 500 nm, for example. However, if the film thickness is too thin, there is a possibility that the catalyst metal may be formed into particles, so that the thickness is preferably set so as not to form particles.
  • Ni is used as the catalyst metal layer 314 and is patterned so as to be a rectangular thin plate. When Ni is crystallized, the Ni surface is rearranged in the (111) plane. A triangular lattice with Ni atoms as vertices is formed on the Ni (111) plane.
  • An insulating resin layer 312 provided with a crystallized catalyst metal layer 314 is placed in a reaction vessel (not shown), and a graphene is grown by supplying a carbon raw material on the catalyst metal layer 314 so that the graphene layer 316 is formed. It forms (refer FIG.14 (c)).
  • the graphene layer 316 may be formed by the above-described alcohol CVD, thermal CVD, plasma CVD, gas source MBE, or the like without exceeding the heat resistance temperature of the insulating resin layer 312. Grow. In the graphene growth process, C atoms are arranged immediately above the center of gravity of each triangle composed of Ni atoms.
  • the number of graphene sheets in the graphene layer 316 is controlled by monitoring the Raman shift position of the graphene layer 316 with a Raman spectrum measurement device attached to the reaction vessel. Specifically, it is known that the Raman shift positions in the case of one, two, five, and ten graphene sheets are different (Fig. 2 of PhysicalPhysReview Letters, Vol.97, p187401 (2006)). reference). For this reason, the number of graphene sheets is determined in advance, the Raman shift position corresponding to the number of sheets is confirmed in advance, and graphene is grown until the Raman shift position is reached.
  • An insulating resin layer 322 made of heat-resistant polyimide is formed on the graphene layer 316 (see FIG. 14D), and then the above-described step (2) is performed again to pattern and crystallize.
  • the catalyst metal layer 324 is formed on the insulating resin layer 322 (see FIG. 14E), and the graphene layer 326 is formed on the catalyst metal layer 324 by performing the above-described step (3) ( (Refer FIG.14 (f)).
  • the insulating resin layer 322 for example, after applying a thermosetting polyimide resin, the resin is cured by heat treatment, or a heat-resistant polyimide film is attached.
  • step (4) described above is repeated a predetermined number of times according to the number of graphene layers (here, three) of the target graphene wiring structure 310 (see FIG. 14G).
  • the insulating resin layer 332, the catalytic metal layer 334, and the graphene layer 336 are stacked in this order on the graphene layer 326.
  • thermosetting polyimide resin is applied to the graphene layer 336 and cured by heat treatment to form the insulating resin layer 342, thereby obtaining the target graphene wiring structure 310 (see FIG. 14H).
  • substrate is removed.
  • both ends of the insulating resin layers 312, 322, 332, and 342 of the graphene wiring structure 310 are removed to expose the graphene layers 316, 326, 336 and the catalytic metal layers 314, 324, 334, and the exposed portions. Is covered with metal.
  • metal portions 312 a, 322 a, 332 a, and 342 a are formed at one end, which are one end of the graphene layers 316, 326, 336 and one end of the catalytic metal layers 314, 324, 334.
  • metal portions 312b, 322b, 332b, and 342b are formed at the other end, which are integrated with the other ends of the graphene layers 316, 326, and 336 and the other ends of the catalytic metal layers 314, 324, and 334. It becomes an electrode.
  • the graphene wiring structure 310 having electrodes formed at both ends in this manner is used for bus bars such as fuel cells and lithium secondary batteries and automobile harnesses.
  • the graphene wiring structure 310 of the present embodiment described in detail above since the graphene layers 316, 326, and 336 are multi-stage (three stages), for example, a larger current flows than in the case of only the graphene layer 316. Can do.
  • the presence of the insulating resin layers 312, 322, 332, and 342 ensures flexibility, and the graphene layers 316, 326, and 336 are protected.
  • a catalytic metal layer 314 is interposed between the insulating resin layer 312 and the graphene layer 316
  • a catalytic metal layer 324 is interposed between the insulating resin layer 322 and the graphene layer 326, and the insulating resin layer 332 and the graphene layer
  • the catalyst metal layer 334 is interposed between the layer 336 and the catalyst metal layers 314, 324, and 334 have good conductivity, it is advantageous when a large current flows.
  • each of the graphene layers 316, 326, and 336 is formed by stacking an odd number of graphene sheets (here, three sheets), but the graphene layers formed by stacking an odd number of graphene sheets have similar electrical characteristics. Therefore, the electrical characteristics of the graphene layer in which the odd number of graphene sheets are stacked are emphasized.
  • FIG. 16 is a perspective view of the graphene wiring structure 360
  • FIG. 17 is a cross-sectional view taken along the line BB of FIG.
  • insulating resin layers 362, 372, 382, 392 and graphene layers 366, 376, 386 are repeatedly stacked.
  • the insulating resin layers 362 and 372 exist above and below the graphene layer 366
  • the insulating resin layers 372 and 382 exist above and below the graphene layer 376
  • the insulating resin layers 382 and 392 exist above and below the graphene layer 386, respectively.
  • Each of the graphene layers 366, 376, and 386 is formed by laminating an odd number (three in this case) of graphene sheets.
  • FIG. 18 is a manufacturing process diagram of the graphene material 410 used as the graphene layers 366, 376, and 386.
  • a substrate body 412 made of rectangular c-plane sapphire is prepared, and Ni is deposited on the entire surface of the substrate body 412 to form a crystal layer 414 (see FIG. 18A).
  • the crystal layer 414 is patterned by a lithography method into a shape that can be written with a single stroke, here a zigzag shape, and the crystal layer 414 is used as a catalyst metal layer 416 (see FIG. 18B).
  • C atoms are supplied to Ni of the catalyst metal layer 416 by a mixed gas of acetylene and argon at a temperature of 600 ° C. and a pressure of 1 kPa. Then, the Ni surface is rearranged in the (111) plane. On the Ni (111) plane, a triangular lattice having Ni atoms as vertices is formed. The supplied C atoms are arranged immediately above the center of gravity of each triangle composed of Ni atoms, so that a hexagon having the C atom as a vertex is formed. As a result, graphene grows to become a graphene material 410 (see FIG. 18C).
  • the graphene material 410 Since the graphene material 410 is formed on the catalyst metal layer 416, the graphene material 410 has the same shape as the catalyst metal layer 416, that is, a zigzag shape.
  • the graphene material 410 is formed of three graphene sheets by controlling the number of sheets as in the third embodiment. Note that if the graphene grows too much, the groove that extends in the lateral direction and closes the groove that forms the zigzag is blocked.
  • the catalyst metal layer 416 is dissolved with an acidic solution.
  • the catalyst metal layer 416 is Ni, dilute nitric acid is used.
  • the graphene material 410 is taken out (see FIG. 18D).
  • the obtained graphene material 410 has a zigzag shape, that is, a shape including linear portions 410a and bent portions 410b alternately. Note that when the graphene material 410 is taken out, instead of melting the catalyst metal layer 416, the graphene material 410 may be mechanically peeled off.
  • the graphene material 410 thus obtained is a zigzag self-supporting material, but can be formed into a wire material by grasping and stretching both ends (see FIG. 18 (e)). However, it does not actually extend straight, but has a shape in which a plurality of linear portions 410a are connected by bent portions 410b as shown in parentheses. Three such graphene materials 410 are prepared, both ends are gripped and stretched to have a shape close to a straight line, and are arranged with a gap in the vertical direction, and in that state, are solidified with an insulating resin. In this way, even if the gripping of both ends of the graphene material 410 is released, the graphene material 410 maintains a shape close to a straight line.
  • insulating resin layers 362, 372, 382, and 392 are shown, but as can be seen from this manufacturing method, the insulating resin layers 362, 372, 382, and 392 are insulated resin at a time. It is formed integrally by solidifying.
  • the graphene wiring structure 360 is previously solidified with an insulating resin so that both ends of the graphene layers 366, 376, and 386 are exposed. Therefore, if the exposed portion is covered with metal, electrodes are formed at both ends of the graphene wiring structure 360 as in the third embodiment.
  • the graphene wiring structure 360 in which the electrodes are thus formed at both ends is used, for example, for a bus bar such as a fuel cell or a lithium secondary battery, and a harness for an automobile.
  • the graphene layers 366, 376, and 386 are multi-stage (three stages), for example, a larger current flows than in the case of the graphene layer 366 alone. Can do.
  • the presence of the insulating resin layers 362, 372, 382, and 392 ensures flexibility, and the graphene layers 366, 376, and 386 are protected.
  • Each of the graphene layers 366, 376, and 386 is formed by stacking an odd number of graphene sheets (here, three sheets), but the graphene layers formed by stacking an odd number of graphene sheets have similar electrical characteristics. Therefore, the electrical characteristics of the graphene layer in which the odd number of graphene sheets are stacked are emphasized.
  • both ends of the insulating resin layers 312, 322, 332, and 342 of the graphene wiring structure 310 are removed, and the graphene layers 316, 326, 336, and Although the catalyst metal layers 314, 324, and 334 were exposed and the exposed portions were covered with metal, the insulating resin layer 12 having metal portions 312a and 312b instead of the insulating resin layer 312 in the manufacturing process diagram shown in FIG. May be used.
  • the other insulating resin layers 322, 332, and 342 have the same configuration.
  • a graphene wiring structure 310 having electrodes at both ends shown in FIG. 15 is obtained.
  • each graphene layer is composed of the same odd number of graphene sheets, but different odd numbers of graphene sheets may be used.
  • the graphene layer 316 of the third embodiment may be one
  • the graphene layer 326 may be three
  • the graphene layer 336 may be five.
  • all the graphene layers may be composed of the same even number of graphene sheets, or different even numbers of graphene sheets.
  • the zigzag-shaped catalyst metal layer 416 is formed on the substrate body 412, but a spiral-shaped catalyst metal layer 426 is formed on the substrate body 412 as shown in FIG. 19 (plan view). May be.
  • the graphene can be taken out as a spiral graphene material by melting the catalyst metal layer 426 or peeling the graphene. It can be made into a wire by gripping and stretching both ends of the spiral graphene material.
  • the graphene material having the shape can be taken out in the same manner as in the above-described fourth embodiment as long as it is a one-stroke drawing shape.
  • any shape other than the one-stroke shape for example, a polygon such as a triangle or a quadrangle, a circle, an ellipse, or a star shape may be employed.
  • a graphene material having an arbitrary shape can be taken out.
  • the substrate body 412 is plate-shaped
  • the substrate body may be cylindrical.
  • the substrate body may be hollow (the interior is empty) or solid (the interior is clogged).
  • the catalyst metal layer When growing graphene on a cylindrical and hollow substrate body, the catalyst metal layer may be patterned on either the outer surface or the inner surface of the substrate body, and the graphene may be grown on the surface of the catalyst metal layer, Alternatively, the catalyst metal layer may be patterned on both the outer surface and the inner surface of the substrate body, and graphene may be grown on the surfaces of both catalyst metal layers.
  • a technique according to ordinary photolithography may be applied while rotating the substrate body, or mechanical lithography using nanoimprint technology. The pattern may be transferred, or may be mechanically patterned using a fine marking needle.
  • vapor deposition may be employed, or a liquid raw material containing the metal is sprayed, or a substrate is immersed in the liquid, followed by heat treatment to form a catalyst metal thin film. May be adopted.
  • a carbon source is supplied to the surface of the catalytic metal layer.
  • the substrate body is cylindrical and hollow, the substrate body is regarded as a vacuum chamber and carbon is contained therein. Since graphene can be grown by flowing the source gas as a source, there is no need to prepare a vacuum chamber, and there are many excellent effects such as greatly simplifying the equipment configuration and eventually improving productivity and reducing production costs. Can be expected.
  • FIG. 14H has been described as an example of the graphene wiring structure of the present invention.
  • the outermost graphene layer 336 is not covered with an insulating resin. What is exposed can also be said to be an example of the graphene wiring structure of the present invention.
  • an insulating resin layer and a graphene layer are repeatedly stacked except for the catalytic metal layer 334 and the graphene layer 336, and an insulating resin layer exists above and below each graphene layer.
  • the structure of FIG. 14G includes the graphene wiring structure of the present invention.
  • Those having the structure shown in FIG. 14G may be used as bus bars for fuel cells, lithium secondary batteries, and the like.
  • the graphene material and the graphene wiring structure of the present invention can be used for fine electrical wiring and the like, for example, a bus bar for a lithium secondary battery, an automobile harness, and the like.

Abstract

Un corps principal de substrat (12) est préparé tout d'abord et une couche de nickel cristalline (14) est formée sur la totalité d'une surface du corps principal de substrat (12). Successivement, la couche cristalline (14) est soumise à une formation de motifs en zigzag par lithographie pour former une couche métallique de catalyseur (16). De plus, du titane est déposé comme matière de masque (17) sur les parois latérales de la couche métallique de catalyseur (16). Ultérieurement, les atomes de carbone sont introduits dans la couche métallique de catalyseur (16) par alimentation d'un mélange de gaz d'acétylène et d'argon. Comme résultat, la surface de nickel subit un réarrangement dans le plan (111) et les atomes de carbone introduits forment un réseau hexagonal pour faire croître du graphène. Etant donné que le graphène est formé sur la couche métallique de catalyseur (16), le graphène vient à avoir la même forme que la couche métallique de catalyseur (16), à savoir, une forme en zigzag. Ensuite, des électrodes carrées (18, 20) sont attachées aux deux extrémités du graphène en zigzag. Ensuite, la couche métallique de catalyseur (16) est dissoute au moyen d'une solution acide et le graphène est retiré comme matière à base de graphène (10).
PCT/JP2012/065131 2011-06-14 2012-06-13 Procédé de fabrication d'une matière à base de graphène, matière à base de graphène et structure de fil à base de graphène WO2012173145A1 (fr)

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JP2011-131743 2011-06-14
JP2011131743A JP5783526B2 (ja) 2010-12-21 2011-06-14 グラフェン素材の製造方法及びグラフェン素材
JP2011-149418 2011-07-05
JP2011149418A JP5783529B2 (ja) 2010-12-21 2011-07-05 グラフェン素材の製造方法
JP2011163193A JP5783530B2 (ja) 2010-12-21 2011-07-26 グラフェン配線構造
JP2011-163193 2011-07-26

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CN112573511A (zh) * 2020-12-03 2021-03-30 铜仁学院 一种石墨烯的简单制备方法
CN113363480A (zh) * 2021-04-01 2021-09-07 万向一二三股份公司 一种包含条状石墨烯导电剂的正极片及锂离子电池
CN113363480B (zh) * 2021-04-01 2022-09-06 万向一二三股份公司 一种包含条状石墨烯导电剂的正极片及锂离子电池

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