WO2009119641A1 - Process for producing monoatomic film - Google Patents

Process for producing monoatomic film Download PDF

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Publication number
WO2009119641A1
WO2009119641A1 PCT/JP2009/055905 JP2009055905W WO2009119641A1 WO 2009119641 A1 WO2009119641 A1 WO 2009119641A1 JP 2009055905 W JP2009055905 W JP 2009055905W WO 2009119641 A1 WO2009119641 A1 WO 2009119641A1
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film
monoatomic
single crystal
metal
substrate
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PCT/JP2009/055905
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French (fr)
Japanese (ja)
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忠平 大島
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学校法人早稲田大学
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Priority to JP2010505709A priority Critical patent/JP5553353B2/en
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0209—Pretreatment of the material to be coated by heating
    • 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
    • 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
    • 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]
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C23C16/342—Boron nitride
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements

Definitions

  • the present invention relates to a method for producing the thinnest monoatomic film such as a graphene film in the world, and more particularly, to a method for producing a high-quality monoatomic film having a large area as compared with the conventional method.
  • a graphene film in which carbon atoms have a honeycomb (honeycomb) structure is a strong film in which carbon-carbon bonds are bonded in a planar shape.
  • This graphene-laden material has been known for a long time as graphite (graphite, graphite), because of its chemical stability and heat resistance, nuclear reactor materials, nuclear fusion reactor first wall materials, electrodes, crucibles, It has been used for heaters.
  • Good quality crystals, such as lattice defects can be found in natural precipitates, but they are extremely difficult to obtain.
  • Examples of the artificial crystal include quiche graphite and highly oriented graphite which are slightly inferior in crystallinity. Since carbon does not melt at high temperatures under normal pressure and cannot be solidified by cooling from a liquid, it is generally difficult to obtain good crystals.
  • an h-BN monoatomic film in which carbon atoms are replaced with nitrogen and boron (boron) atoms is an electrically insulating film having a honeycomb structure, and is similar to a graphene film as shown in FIG. It is a film with strong chemical bonds spread in a plane. The difference from the graphene film is that the chemical bond between nitrogen and boron has an uneven charge distribution, and there is a band gap between the conduction band and the valence band, so that it becomes an electrically insulating film. Because of electrical polarization, the interaction with charges such as electrons is orders of magnitude greater than that of graphene films.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method of manufacturing a high-quality monoatomic film having a large area as compared with the prior art.
  • one side of the hexagon of the honeycomb structure is about 0.14 nm, and what can pass through this film has an ionic radius represented by H + ions larger than 0.14 nm. Limited to small cations. That is, these monoatomic films can hold all atoms larger than this.
  • the graphene film and the h-BN monoatomic film are substances having the highest transmittance for electrons and positrons accelerated to several eV to several hundred eV.
  • the graphene film is an electrically conductive substance having no charge bias (polarization) in chemical bonds, and thus is an ideal translucent electrode.
  • polarization charge bias
  • the present inventor regularly arranged atoms constituting the metal or metal compound on the surface of a substrate made of a chemically soluble metal or metal compound.
  • a single crystal surface of the metal or metal compound is formed, and a monoatomic film is formed on the single crystal surface by a chemical vapor deposition (CVD) method in which a raw material gas is brought into contact with the single crystal surface using the single crystal surface as a template.
  • the monoatomic film can be isolated by chemically dissolving the base from the base having the monoatomic film formed on the surface of the single crystal, and the thickness of the graphene film, the h-BN film, etc.
  • the inventors have found that a monoatomic film for one atom can be manufactured stably and with good reproducibility as a monoatomic film having a significantly larger area and higher quality than conventional monolayers.
  • the present invention provides the following method for producing a monoatomic film.
  • Claim 1 A single crystal surface of the metal or metal compound in which atoms constituting the metal or metal compound are regularly arranged is formed on the surface of a substrate made of a chemically soluble metal or metal compound.
  • a monoatomic film is formed on the single crystal surface by a chemical vapor deposition (CVD) method in which a source gas is brought into contact with the single crystal surface, and the substrate having the monoatomic film formed on the single crystal surface
  • CVD chemical vapor deposition
  • a source gas is brought into contact with the single crystal surface
  • the substrate having the monoatomic film formed on the single crystal surface A method for producing a monoatomic film, comprising isolating a monoatomic film by chemically dissolving a substrate.
  • Claim 2 2. The method according to claim 1, wherein the metal or metal compound is Fe, Ni, or Co.
  • Claim 3 The method according to claim 1, wherein the metal or metal compound is Ni, and the single crystal surface is a Ni (111) plane.
  • Claim 4 4. The manufacturing method according to claim 1, wherein the monoatomic film is a graphene film or an h-BN film.
  • Claim 5 The manufacturing method according to any one of claims 1 to 4, wherein a monoatomic film having an area of 1 ( ⁇ m) 2 or more is manufactured.
  • a monoatomic film having a thickness of 1 atom such as a graphene film and an h-BN film, can be stably manufactured with high reproducibility, and has a remarkably large area, In addition, a good quality monoatomic film can be manufactured.
  • a monoatomic film such as the graphene film and the h-BN (boron nitride) film shown in FIG. (1) forming a single-crystal surface of the metal or metal compound in which atoms constituting the metal or metal compound are regularly arranged on the surface of a substrate made of a chemically soluble metal or metal compound; (2) Using the single crystal surface as a template, a monoatomic film is formed on the single crystal surface by a chemical vapor deposition (CVD) method in which a source gas is brought into contact with the single crystal surface; (3) The substrate is produced by chemically dissolving the substrate from a substrate having a monoatomic film formed on the surface of the single crystal.
  • CVD chemical vapor deposition
  • a substrate made of a chemically soluble metal or metal compound is used as the substrate, and as the chemical dissolution, for example, dissolution with an acid can be applied.
  • the chemical dissolution for example, dissolution with an acid can be applied.
  • the metal compound carbides such as TiC and ZrC, and alloys of Fe, Co, and Ni are preferable.
  • the metal compound carbides such as TiC and ZrC, and alloys of Fe, Co, and Ni are preferable.
  • Fe, Co or Ni is preferably used.
  • hydrocarbon gas is suitably used when producing a graphene film
  • borazine (B 3 N 3 H 6 ) gas is suitably used when producing an h-BN film.
  • Fe, Co or Ni is particularly suitable in that a stronger action of dissociating and decomposing these gas molecules on the single crystal surface is required.
  • Ni is particularly preferable because the distance between the (111) planes approximates the interatomic distance of the graphene film or the h-BN film.
  • a single-crystal surface of a metal or metal compound in which atoms constituting the metal or metal compound are regularly arranged is formed on the surface of the substrate. Therefore, in the present invention, it is necessary that at least a portion of the substrate where the surface of the single crystal is formed is formed of a single crystal.
  • Such a single crystal surface can be formed by the following method, for example.
  • the crystal orientation of a single crystal part is determined by, for example, the Laue method, and a specific plane direction, for example, (110) plane, (111) plane for Fe, (001) plane, (111) plane for Co. , (111) plane, (100) plane for Ni, (111) plane, (100) plane for TiC, (111) plane, (100) plane for ZrC, etc. Cut out by etc.
  • these metal films and metal compound films grown epitaxially on the Si surface or the like can be used similarly.
  • the entire surface can be covered with a monoatomic film with an exposure amount of several hundreds of Langmuir, and with the (111) plane, the exposure amount of several to several tens of Langmuirs. Is particularly advantageous for the production of large area membranes.
  • Langmuir is a unit of exposure amount, which is given by the product of pressure and time.
  • the cut surface is polished with an abrasive such as alumina or diamond until an optical mirror surface is obtained.
  • ion bombardment treatment with argon ions or the like is performed to remove impurities on the surface, and further, ultra-vacuum (for example, under reduced pressure of 10 ⁇ 6 to 10 ⁇ 11 Pa) by a method such as electron beam heating, By heating to a temperature of 900 ° C. or more and about 90% of the melting point of the substrate (for example, about 1300 ° C. or less in the case of Ni), the impurities such as oxygen and carbon adsorbed on the surface are removed to remove atoms. Can form a clean single crystal surface of regularly arranged metal or metal compound.
  • a chemical vapor deposition (CVD) method (also called chemical vapor deposition method or chemical vapor deposition method) in which a source gas is brought into contact with the single crystal surface is formed on the single crystal surface.
  • a monoatomic film is formed.
  • the formed single crystal surface is a clean surface in which atoms are regularly arranged. For example, when a graphene film is manufactured on this surface, a hydrocarbon gas is supplied at a partial pressure of 10 ⁇ 2 to 10 ⁇ 7 Pa.
  • the individual crystals constituting the surface of the single crystal.
  • the hydrocarbon gas is separated and adsorbed on the atoms and decomposes to release hydrogen molecules.
  • the remaining carbon maintains a certain crystal orientation relationship with the atomic arrangement on the surface of the underlying single crystal as a template, and the graphene film grows as a monoatomic layer.
  • the film thickness can be controlled with an accuracy of 1% or less by controlling the temperature and reaction time.
  • the hydrocarbon gas is not particularly limited, but may be present in a gas under the above-described reduced pressure.
  • chain saturated hydrocarbons such as methane, ethane, propane, butane, pentane, and hexane
  • cyclic saturated hydrocarbons such as cyclopentane and cyclohexane
  • chain unsaturated hydrocarbons such as ethylene, propylene, butylene and butadiene
  • aromatic hydrocarbons such as benzene, toluene and xylene.
  • borazine (B 3 N 3 H 6 ) gas is used at a partial pressure of 10 ⁇ 2 to 10 ⁇ 7 Pa, preferably at a temperature of 100 to 1000 ° C., more preferably 200
  • the borazine gas is separated and adsorbed on the atoms in the individual atoms constituting the single crystal surface, Releases hydrogen molecules.
  • the remaining boron and nitrogen maintain a certain crystal orientation relationship with the atomic arrangement on the surface of the underlying single crystal as a template, and the h-BN film grows as a monoatomic layer.
  • a gas of molecules preferably boron hydronitride
  • N nitrogen
  • B boron (B) atoms
  • the source gas when producing a graphene film or an h-BN film, the source gas may be used in the presence of an inert gas such as helium or argon.
  • the growth rate of the graphene film or h-BN film at this time depends on the reactivity with the surface of the single crystal, and when the surface of the metal or metal compound is exposed (that is, the atoms constituting it are exposed). On the other hand, if the surface is covered with a single atomic layer of carbon or boron and nitrogen, the adsorption probability of hydrocarbon gas and borazine is reduced by about two orders of magnitude. Under the same pressure, the single crystal surface is a monoatomic layer. Once covered, growth effectively stops.
  • a graphene film or an h-BN film can be formed as a monoatomic layer.
  • the monoatomic film is isolated by chemically dissolving the base from the base having the monoatomic film formed on the surface of the single crystal.
  • dissolution by an acid can be applied.
  • the graphene film and the h-BN film are materials that are not dissolved by an acid, it is preferable to use a substrate of the above-described material.
  • the monoatomic film can be isolated if at least the vicinity of the monoatomic film of the substrate is dissolved, the base is formed on a support that is not dissolved by the dissolving operation. Also good.
  • the vicinity of the monoatomic film of the substrate is dissolved, it is not always necessary to dissolve the entire substrate.
  • hydrochloric acid, nitric acid, sulfuric acid or the like can be used as an aqueous solution, an organic solvent solution, or the like, and the concentration, dissolution time, and the like may be appropriately selected.
  • a substrate 1 having a single crystal surface as a template is prepared (FIGS. 2A and 3A).
  • the single crystal surface is cleaned, for example, by ion bombardment or heat treatment in an ultra-high vacuum container. Further, the regular arrangement of atoms is confirmed by low-energy electron diffraction (LEED), and the surface impurities are hardly confirmed by Auger electron spectroscopy (AES) or X-ray photoelectron spectroscopy (XPS). It is confirmed that the number of atoms is 1/100 or less, preferably 1/1000 or less of the number of exposed atoms.
  • the monocrystal film 2 is formed by contacting a hydrocarbon gas or a borazine gas while heating the surface of the single crystal, which is a clean template, to 800 to 1000 ° C. under a reduced pressure of 10 ⁇ 2 to 10 ⁇ 9 Pa, for example.
  • a hydrocarbon gas or a borazine gas while heating the surface of the single crystal, which is a clean template, to 800 to 1000 ° C. under a reduced pressure of 10 ⁇ 2 to 10 ⁇ 9 Pa, for example.
  • AES or XPS when forming a graphene film on the surface, carbon and when forming an h-BN film, nitrogen and boron exist, and these elements increase even when gas is contacted. Make sure not to. In addition, it is confirmed that a regular atomic arrangement is made by LEED.
  • the holding unit 3 is deposited to a predetermined thickness (for example, 0.1 to 10 ⁇ m) (FIG. 3C).
  • a support member (not shown) is connected to the holding part in advance, and in the dissolution of the substrate described later, for example, suspended in the solution, By contacting with a chemical solution, the substrate is melted, and the monoatomic film can be obtained in a developed state, which is preferable.
  • the graphene film and the h-BN film are not dissolved (if the holding part is formed, this holding layer is not dissolved), and contacted with a chemical solution (such as an acid solution) that dissolves only the substrate as a template (for example, an acid solution)
  • a chemical solution such as an acid solution
  • the monoatomic film is isolated by dipping in a solution (FIGS. 2D and 3D).
  • the isolated monoatomic film can be recovered, for example, by scooping it up with a platinum or gold mesh.
  • the recovered monoatomic film can be further washed and dried as necessary, and divided into a predetermined size for use.
  • an unprecedented large-area monoatomic film having an area of 1 ( ⁇ m) 2 or more, particularly 100 ( ⁇ m) 2 or more, and a uniform lattice structure can be manufactured.
  • Example 1 From a single crystal Ni plate serving as a substrate, the crystal orientation was determined with an accuracy of ⁇ 0.3 degrees by the Laue method, and a Ni (111) single crystal surface having a diameter of 1 cm was cut out. This surface was polished with an alumina and diamond abrasive until it became an optical mirror surface, and inserted into an ultrahigh vacuum container of 2 ⁇ 10 ⁇ 8 Pa.
  • this surface is subjected to ion bombardment treatment with argon ions having an energy of 1 to 2 keV to remove impurities on the surface, and heated to 1000 ° C. by electron beam heating (1 keV, 30 mA), thereby allowing oxygen or carbon A clean surface free of impurities.
  • the cleanness of the surface was confirmed by the absence of impurities by Auger electron spectroscopy (AES) analysis and X-ray photoelectron spectroscopy (XPS) analysis.
  • AES Auger electron spectroscopy
  • XPS X-ray photoelectron spectroscopy
  • LEED low-energy electron diffraction
  • ethylene gas molecular gas
  • the ultra-high vacuum container While heating the substrate (single crystal surface) to 800 ° C., ethylene gas (molecular gas) is introduced into the ultra-high vacuum container until the internal pressure of the container reaches 5 ⁇ 10 ⁇ 4 Pa, and the ethylene molecules are simply The crystal surface was brought into contact with the crystal surface for 100 seconds, the ethylene gas was exhausted, and the ultrahigh vacuum of 2 ⁇ 10 ⁇ 8 Pa was returned. Then, it stood to cool and returned to normal pressure.
  • ethylene gas molecular gas
  • the low-energy electron diffraction (LEED) pattern and scanning tunneling microscope (STM) image of the film covering the single crystal surface of the substrate were evaluated.
  • the LEED pattern is shown in FIG. 4 (A)
  • the STM image is shown in FIG. 4 (B). From the LEED pattern, it was confirmed that the obtained film was a uniform 1 ⁇ 1 monoatomic film (graphene film) having a uniform planar crystal structure. A lattice image reflecting this uniform 1 ⁇ 1 structure was also observed from the STM image.
  • FIG. 5A shows a transmission electron microscope (TEM) image
  • FIG. 5B shows an electron beam diffraction pattern.
  • the target of the TEM image is a self-supporting graphene film that is on a 10 ⁇ m square mesh. The graphene film spread beyond the range of one hole in the mesh, and the size of this film was confirmed to be a large area with at least 50 to 100 ⁇ m on one side. It was also found that a large film could be 1 mm wide.
  • the obtained film has a film thickness of 1 atom, and the distance between the atoms is uniform, and that the film is a graphene film (self-holding film). It was found from the lattice constant (0.24 nm).
  • the obtained monoatomic film (graphene film) is an extremely large area and high quality monoatomic film compared to the conventional one.
  • Example 1 A film-like material was recovered in the same manner as in Example 1 except that a polycrystalline Ni plate was used as a substrate and a 1 cm diameter surface (not a single crystal surface) was cut out and used.
  • the collected film was dried and the electron diffraction pattern was evaluated, and a ring-shaped diffraction image was observed. Since the surface used in this case has a large number of small single crystal planes with different atomic arrangement directions, graphene with different arrangement directions grows on this surface to obtain a monoatomic film having a uniform planar crystal structure. I could not.

Abstract

In a surface of a substrate comprising a chemically dissoluble metal or metal compound, a surface of a single crystal of the metal or metal compound is formed in which atoms constituting the metal or metal compound have been regularly arranged. This surface of the single crystal is used as a template, and a monoatomic film is formed on the single-crystal surface by the chemical vapor deposition (CVD) method in which a raw-material gas is brought into contact with the single-crystal surface. After the monoatomic film has been formed on the single-crystal surface of the substrate, this substrate is chemically dissolved away, whereby the monoatomic film is isolated. According to this process, a monoatomic film having a thickness corresponding to one atom, such as a graphene film or h-BN film, can be stably produced with satisfactory reproducibility. A monoatomic film having a far larger area than conventional ones and having satisfactory quality can be produced.

Description

単原子膜の製造方法Monoatomic film manufacturing method
　本発明は、世の中で最も薄い、グラフェン膜等の単原子膜の製造方法に関連し、特に、従来に比較して飛躍的に大面積の良質な単原子膜を製造する方法に関する。 The present invention relates to a method for producing the thinnest monoatomic film such as a graphene film in the world, and more particularly, to a method for producing a high-quality monoatomic film having a large area as compared with the conventional method.
　厚さが１原子分である究極的に薄い単原子膜の実現は、その特性から多くの応用分野で研究が進展し、その製造方法も提案されているが、従来の方法では、大きさが、１辺が数ｎｍから数百ｎｍ程度で、実用になる大きさの膜が製造できず、その結晶の質も劣っていた。 The realization of an extremely thin monoatomic film with a thickness of one atom has been studied in many fields of application due to its properties, and its manufacturing method has been proposed. Since one side is about several nm to several hundred nm, a film having a practical size could not be manufactured, and the quality of the crystal was inferior.
　図１（Ａ）に示されるように炭素原子がハニカム（蜂の巣）構造をもったグラフェン膜は、炭素間結合が平面状に結合した強固な膜である。このグラフェンが平行に積み重なった物質が、石墨（グラファイト、黒鉛）として古くから知られており、その化学的安定性や耐熱性から原子炉材料、核融合炉の第一壁材、電極、坩堝、ヒーター等に利用されてきた。格子欠陥などにおいて良質の結晶は天然析出物に見出すことがあるが、入手は極端に困難である。人工結晶としては、結晶性はやや劣ったキッシュグラファイト、高配向性グラファイト等がある。炭素は、常圧の状態では高温でも融けず、液体から冷却して固化することができないため、一般には良い結晶を得ることは困難であった。 As shown in FIG. 1A, a graphene film in which carbon atoms have a honeycomb (honeycomb) structure is a strong film in which carbon-carbon bonds are bonded in a planar shape. This graphene-laden material has been known for a long time as graphite (graphite, graphite), because of its chemical stability and heat resistance, nuclear reactor materials, nuclear fusion reactor first wall materials, electrodes, crucibles, It has been used for heaters. Good quality crystals, such as lattice defects, can be found in natural precipitates, but they are extremely difficult to obtain. Examples of the artificial crystal include quiche graphite and highly oriented graphite which are slightly inferior in crystallinity. Since carbon does not melt at high temperatures under normal pressure and cannot be solidified by cooling from a liquid, it is generally difficult to obtain good crystals.
　最近の研究では、グラフェン膜の端の構造によって、半導体から金属へ電子構造を制御できることが報告され、単原子膜グラフェン膜のデバイス素子、センサー素子への応用でも良質のグラフェン膜の製造が切望されていた。しかしながら、従来のグラフェン膜の製造方法は、既知手段の熱分解高配向グラファイトと呼ばれる一部結晶化した物質からへき開によって剥ぎ取ったグラフェン膜をのみを使用していた。この結晶は、欠陥を多く含みまた小さな微小結晶（数から数百ｎｍの大きさ）であった。 Recent research has reported that the electronic structure can be controlled from the semiconductor to the metal by the structure of the edge of the graphene film, and the production of high-quality graphene films is eagerly desired for application to device elements and sensor elements of monoatomic graphene films. It was. However, the conventional method for producing a graphene film uses only a graphene film peeled off by cleavage from a partially crystallized material called pyrolytic highly oriented graphite, which is a known means. This crystal contained many defects and was a small microcrystal (a size of several to several hundred nm).
　同様に、炭素原子を、窒素とホウ素（ボロン）原子に置き換えたｈ－ＢＮ単原子膜は、ハニカム構造の電気的絶縁膜であり、図１（Ｂ）に示されるようにグラフェン膜と同様に平面状に広がった強固な化学結合をもつ膜である。グラフェン膜との違いは窒素とホウ素との化学結合に電荷分布の偏りがあり、伝導バンドと価電子バンド間にバンドギャップがあるため電気的絶縁膜となる。電気的分極のため、電子等の電荷との相互作用はグラフェン膜よりも桁違いに大きい。 Similarly, an h-BN monoatomic film in which carbon atoms are replaced with nitrogen and boron (boron) atoms is an electrically insulating film having a honeycomb structure, and is similar to a graphene film as shown in FIG. It is a film with strong chemical bonds spread in a plane. The difference from the graphene film is that the chemical bond between nitrogen and boron has an uneven charge distribution, and there is a band gap between the conduction band and the valence band, so that it becomes an electrically insulating film. Because of electrical polarization, the interaction with charges such as electrons is orders of magnitude greater than that of graphene films.
　本発明は、上記事情に鑑みなされたものであり、従来に比較して飛躍的に大面積の良質な単原子膜を製造する方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method of manufacturing a high-quality monoatomic film having a large area as compared with the prior art.
　グラフェン膜及びｈ－ＢＮ単原子膜ともに、蜂の巣構造の６角形の１辺は約０．１４ｎｍであり、この膜を通過できるものは、Ｈ+イオンを代表とするイオン半径が０．１４ｎｍよりも小さい陽イオンに限られる。即ち、これらの単原子膜は、これより大きい全ての原子を保持することができる。 In both the graphene film and the h-BN monoatomic film, one side of the hexagon of the honeycomb structure is about 0.14 nm, and what can pass through this film has an ionic radius represented by H + ions larger than 0.14 nm. Limited to small cations. That is, these monoatomic films can hold all atoms larger than this.
　一方、グラフェン膜及びｈ－ＢＮ単原子膜は、数ｅＶ～数百ｅＶに加速された電子や陽電子にとっては、透過率の最も高い物質である。特に、グラフェン膜は、化学結合に電荷の偏り（分極）がない電導性物質であるため、理想的な半透明な電極となる。電子顕微鏡では従来の静電場や静磁場を利用した電子レンズでは凸レンズのみが実現しており、凹レンズを作ることが困難なため、球面収差により空間分解能が限られてきた。電子線照射に対する耐性をもつ数十μｍから数ｍｍサイズの大きさの丈夫な膜が実現すれば、極めて単純で、しかも透過率の高い性能をもつ凹レンズが実現し、電子顕微鏡の空間分解能が著しく向上する。 On the other hand, the graphene film and the h-BN monoatomic film are substances having the highest transmittance for electrons and positrons accelerated to several eV to several hundred eV. In particular, the graphene film is an electrically conductive substance having no charge bias (polarization) in chemical bonds, and thus is an ideal translucent electrode. In an electron microscope, only a convex lens is realized in a conventional electron lens using an electrostatic field or a static magnetic field, and it is difficult to make a concave lens. Therefore, spatial resolution has been limited by spherical aberration. If a strong film with a size of several tens of μm to several mm with resistance to electron beam irradiation is realized, a concave lens with extremely simple and high transmittance performance can be realized, and the spatial resolution of the electron microscope is remarkable. improves.
　また、最近の生物・医学関連の要請から数ナノメーター寸法の有機分子や生体関連の単原子を電子顕微鏡で観察する要請が増してきたが、これらの分子を支え保持する実用的な膜が全く存在していない。現状は、薄く延ばした金箔をイオン衝撃で更に薄く削って、偶然発生したナノメーター寸法の穴を利用しているが、その穴の大きさは１０ｎｍ程度であって、有機分子や生体関連分子を乗せて保持することが困難であり、より確実に分子を保持する膜を必要としている。グラフェン膜は電子の透過率が高く、この用途に適合する物質であることから、高面積かつ良質のグラフェン膜を安定的に製造することのインパクトは大きい。 In addition, due to recent biological and medical-related requirements, there has been an increasing demand for observing organic molecules with a size of several nanometers and biologically relevant single atoms with an electron microscope, but there are no practical membranes that support and hold these molecules. Does not exist. At present, the thinly stretched gold foil is further thinned by ion bombardment, and a nanometer-sized hole that is accidentally generated is used. The hole is about 10 nm in size, and organic molecules and biological molecules are removed. It is difficult to hold it on the surface, and a film that holds the molecule more securely is required. Since the graphene film has a high electron transmittance and is a material suitable for this application, the impact of stably producing a high-quality and high-quality graphene film is great.
　本発明者は、上記目的を達成するため鋭意検討を重ねた結果、化学的に溶解可能な金属又は金属化合物からなる基体の表面に、この金属又は金属化合物を構成する原子が規則的に配列した上記金属又は金属化合物の単結晶表面を形成し、この単結晶表面をテンプレートとして、単結晶表面に原料ガスを接触させる化学気相堆積（ＣＶＤ）法により単結晶表面上に単原子膜を形成し、この単結晶表面上に単原子膜が形成された基体から該基体を化学的に溶解させることにより、単原子膜を単離することができ、グラフェン膜、ｈ－ＢＮ膜等の厚さが１原子分の単原子膜を、従来に比較して飛躍的に大面積、かつ良質な単原子膜として、再現性よく安定的に製造することができることを見出し、本発明をなすに至った。 As a result of intensive studies to achieve the above object, the present inventor regularly arranged atoms constituting the metal or metal compound on the surface of a substrate made of a chemically soluble metal or metal compound. A single crystal surface of the metal or metal compound is formed, and a monoatomic film is formed on the single crystal surface by a chemical vapor deposition (CVD) method in which a raw material gas is brought into contact with the single crystal surface using the single crystal surface as a template. The monoatomic film can be isolated by chemically dissolving the base from the base having the monoatomic film formed on the surface of the single crystal, and the thickness of the graphene film, the h-BN film, etc. The inventors have found that a monoatomic film for one atom can be manufactured stably and with good reproducibility as a monoatomic film having a significantly larger area and higher quality than conventional monolayers.
　従って、本発明は、下記の単原子膜の製造方法を提供する。
請求項１：
　化学的に溶解可能な金属又は金属化合物からなる基体の表面に、上記金属又は金属化合物を構成する原子が規則的に配列した上記金属又は金属化合物の単結晶表面を形成し、該単結晶表面をテンプレートとして、上記単結晶表面に原料ガスを接触させる化学気相堆積（ＣＶＤ）法により単結晶表面上に単原子膜を形成し、この単結晶表面上に単原子膜が形成された基体から該基体を化学的に溶解させることにより、単原子膜を単離することを特徴とする単原子膜の製造方法。
請求項２：
　上記金属又は金属化合物がＦｅ、Ｎｉ又はＣｏであることを特徴とする請求項１記載の製造方法。
請求項３：
　上記金属又は金属化合物がＮｉであり、単結晶表面がＮｉ（１１１）面であることを特徴とする請求項１記載の製造方法。
請求項４：
　単原子膜がグラフェン膜又はｈ－ＢＮ膜であることを特徴とする請求項１乃至３のいずれか１項記載の製造方法。
請求項５：
　面積が１（μｍ）2以上の単原子膜を製造することを特徴とする請求項１乃至４のいずれか１項記載の製造方法。 Accordingly, the present invention provides the following method for producing a monoatomic film.
Claim 1:
A single crystal surface of the metal or metal compound in which atoms constituting the metal or metal compound are regularly arranged is formed on the surface of a substrate made of a chemically soluble metal or metal compound. As a template, a monoatomic film is formed on the single crystal surface by a chemical vapor deposition (CVD) method in which a source gas is brought into contact with the single crystal surface, and the substrate having the monoatomic film formed on the single crystal surface A method for producing a monoatomic film, comprising isolating a monoatomic film by chemically dissolving a substrate.
Claim 2:
2. The method according to claim 1, wherein the metal or metal compound is Fe, Ni, or Co.
Claim 3:
The method according to claim 1, wherein the metal or metal compound is Ni, and the single crystal surface is a Ni (111) plane.
Claim 4:
4. The manufacturing method according to claim 1, wherein the monoatomic film is a graphene film or an h-BN film.
Claim 5:
The manufacturing method according to any one of claims 1 to 4, wherein a monoatomic film having an area of 1 (µm) 2 or more is manufactured.
　本発明によれば、グラフェン膜、ｈ－ＢＮ膜等の厚さが１原子分の単原子膜を、再現性よく安定的に製造することができ、従来に比較して飛躍的に大面積、かつ良質な単原子膜を製造することができる。 According to the present invention, a monoatomic film having a thickness of 1 atom, such as a graphene film and an h-BN film, can be stably manufactured with high reproducibility, and has a remarkably large area, In addition, a good quality monoatomic film can be manufactured.
（Ａ）グラフェン膜及び（Ｂ）ｈ－ＢＮ膜の構造を示す図である。It is a figure which shows the structure of (A) graphene film and (B) h-BN film. 単原子膜の製造工程の一例を示す説明図である。It is explanatory drawing which shows an example of the manufacturing process of a monoatomic film. 単原子膜の製造工程の他の例を示す説明図である。It is explanatory drawing which shows the other example of the manufacturing process of a monoatomic film. 実施例１で得られた基体の単結晶表面を覆ったグラフェン膜の（Ａ）低速電子線回折（ＬＥＥＤ）パターン及び（Ｂ）走査型トンネル顕微鏡（ＳＴＭ）像である。It is (A) low-energy electron diffraction (LEED) pattern and (B) scanning tunneling microscope (STM) image of the graphene film which covered the single crystal surface of the base | substrate obtained in Example 1. FIG. 実施例１で製造されたグラフェン膜（自己保持膜）の（Ａ）透過型電子顕微鏡（ＴＥＭ）像（Ｂ）電子線回折パターンである。It is an (A) transmission electron microscope (TEM) image (B) electron diffraction pattern of the graphene film (self-holding film) manufactured in Example 1.
　以下、本発明につき更に詳しく説明する。
　本発明においては、図１に示されるグラフェン膜、ｈ－ＢＮ（窒化ホウ素）膜などの単原子膜を、
（１）化学的に溶解可能な金属又は金属化合物からなる基体の表面に、上記金属又は金属化合物を構成する原子が規則的に配列した上記金属又は金属化合物の単結晶表面を形成し、
（２）該単結晶表面をテンプレートとして、上記単結晶表面に原料ガスを接触させる化学気相堆積（ＣＶＤ）法により単結晶表面上に単原子膜を形成し、
（３）この単結晶表面上に単原子膜が形成された基体から該基体を化学的に溶解させる
ことにより製造する。 Hereinafter, the present invention will be described in more detail.
In the present invention, a monoatomic film such as the graphene film and the h-BN (boron nitride) film shown in FIG.
(1) forming a single-crystal surface of the metal or metal compound in which atoms constituting the metal or metal compound are regularly arranged on the surface of a substrate made of a chemically soluble metal or metal compound;
(2) Using the single crystal surface as a template, a monoatomic film is formed on the single crystal surface by a chemical vapor deposition (CVD) method in which a source gas is brought into contact with the single crystal surface;
(3) The substrate is produced by chemically dissolving the substrate from a substrate having a monoatomic film formed on the surface of the single crystal.
　まず、基体として化学的に溶解可能な金属又は金属化合物からなるものを用いるが、化学的な溶解としては、例えば、酸による溶解が適用できる。このようなものとしては、例えば、グラフェン膜やｈ－ＢＮ膜を製造する場合、金属としては、Ｆｅ、Ｃｏ、Ｎｉなどが好ましい。一方、金属化合物としては、ＴｉＣ、ＺｒＣ等の炭化物、Ｆｅ、Ｃｏ、Ｎｉの合金が好ましい。なかでも、グラフェン膜を構成する元素（炭素）やｈ－ＢＮ膜を構成する元素（ホウ素及び窒素）との親和性や、単結晶表面上でのこれら元素の原子の濡れ性等の点から、Ｆｅ、Ｃｏ又はＮｉを用いることが好ましい。 First, a substrate made of a chemically soluble metal or metal compound is used as the substrate, and as the chemical dissolution, for example, dissolution with an acid can be applied. For example, when a graphene film or an h-BN film is manufactured, Fe, Co, Ni, or the like is preferable as the metal. On the other hand, as the metal compound, carbides such as TiC and ZrC, and alloys of Fe, Co, and Ni are preferable. Among these, from the viewpoint of the affinity with the elements (carbon) constituting the graphene film and the elements (boron and nitrogen) constituting the h-BN film, the wettability of atoms of these elements on the single crystal surface, etc. Fe, Co or Ni is preferably used.
　また、本発明においては、後述するとおり、グラフェン膜を製造する場合には炭化水素ガス、ｈ－ＢＮ膜を製造する場合にはボラジン（Ｂ3Ｎ3Ｈ6）ガスが好適に用いられるが、これらからグラフェン膜又はｈ－ＢＮ膜を生成するには、単結晶表面上でこれらのガス分子を解離分解させるより強い作用が必要である点においてもＦｅ、Ｃｏ又はＮｉは特に好適である。更に、Ｎｉは、その（１１１）面の面間隔が、グラフェン膜やｈ－ＢＮ膜の原子間距離に近似していることから特に好適である。 Further, in the present invention, as will be described later, hydrocarbon gas is suitably used when producing a graphene film, and borazine (B 3 N 3 H 6 ) gas is suitably used when producing an h-BN film. In order to produce a graphene film or an h-BN film from these, Fe, Co or Ni is particularly suitable in that a stronger action of dissociating and decomposing these gas molecules on the single crystal surface is required. Further, Ni is particularly preferable because the distance between the (111) planes approximates the interatomic distance of the graphene film or the h-BN film.
　基体の表面には、上記金属又は金属化合物を構成する原子が規則的に配列した金属又は金属化合物の単結晶表面が形成される。そのため、本発明においては、基体の少なくとも単結晶表面が形成される部分は、単結晶で形成されているものであることが必要である。 A single-crystal surface of a metal or metal compound in which atoms constituting the metal or metal compound are regularly arranged is formed on the surface of the substrate. Therefore, in the present invention, it is necessary that at least a portion of the substrate where the surface of the single crystal is formed is formed of a single crystal.
　このような単結晶表面は、例えば、以下のような方法で形成することができる。まず、単結晶部分を例えば、ラウエ法によって結晶方位を決め、特定の面方向、例えば、Ｆｅであれば（１１０）面、（１１１）面、Ｃｏであれば（００１）面、（１１１）面、Ｎｉであれば（１１１）面、（１００）面、ＴｉＣであれば（１１１）面、（１００）面、ＺｒＣであれば（１１１）面、（１００）面などを放電加工機やダイヤモンドカッター等によって切り出す。また、Ｓｉ表面等にエピタキシャルに成長したこれらの金属膜及び金属化合物膜も同様に用いることができる。 Such a single crystal surface can be formed by the following method, for example. First, the crystal orientation of a single crystal part is determined by, for example, the Laue method, and a specific plane direction, for example, (110) plane, (111) plane for Fe, (001) plane, (111) plane for Co. , (111) plane, (100) plane for Ni, (111) plane, (100) plane for TiC, (111) plane, (100) plane for ZrC, etc. Cut out by etc. Also, these metal films and metal compound films grown epitaxially on the Si surface or the like can be used similarly.
　例えば、（１００）面では、数百ラングミューアの露出量で、更に（１１１）面では、数～数十ラングミューアの露出量で、表面全体を単原子膜で覆うことができ、これらの面が、大面積の膜製造に特に有利である。ここで、ラングミューアは露出量の単位で、圧力と時間の積で与えられる量であり、１ラングミューアは、１トール＝１３３．３２パスカルの原料ガス（ベンゼン）分圧に固体表面を１マイクロ秒露出した量である。 For example, with the (100) plane, the entire surface can be covered with a monoatomic film with an exposure amount of several hundreds of Langmuir, and with the (111) plane, the exposure amount of several to several tens of Langmuirs. Is particularly advantageous for the production of large area membranes. Here, Langmuir is a unit of exposure amount, which is given by the product of pressure and time. One Langmuir is 1 micron of solid surface with a partial pressure of 1 Torr = 133.32 Pascal of source gas (benzene). The amount of exposure.
　次に、切り出した表面を、アルミナ、ダイヤモンドなどの研磨剤で、光学的鏡面になるまで研磨する。次に、アルゴンイオンなどによるイオン衝撃処理を施して、表面の不純物を除去し、更に、電子ビーム加熱等の方法で、超真空下（例えば、１０-6～１０-11Ｐａの減圧下）、９００℃以上、基体の融点の９割程度の温度（例えば、Ｎｉの場合は１３００℃程度以下）に加熱することにより、表面に吸着している酸素や炭素等の不純物を除去することによって、原子が規則的に配列した金属又は金属化合物の清浄な単結晶表面を形成することができる。 Next, the cut surface is polished with an abrasive such as alumina or diamond until an optical mirror surface is obtained. Next, ion bombardment treatment with argon ions or the like is performed to remove impurities on the surface, and further, ultra-vacuum (for example, under reduced pressure of 10 −6 to 10 −11 Pa) by a method such as electron beam heating, By heating to a temperature of 900 ° C. or more and about 90% of the melting point of the substrate (for example, about 1300 ° C. or less in the case of Ni), the impurities such as oxygen and carbon adsorbed on the surface are removed to remove atoms. Can form a clean single crystal surface of regularly arranged metal or metal compound.
　次に、形成した単結晶表面をテンプレートとして、単結晶表面に原料ガスを接触させる化学気相堆積（ＣＶＤ）法（化学気相析出法、化学気相蒸着法とも呼ばれる）により単結晶表面上に単原子膜を形成する。形成された単結晶表面は、原子が規則的に配列した清浄な表面であり、この表面に、例えば、グラフェン膜を製造する場合、炭化水素ガスを、１０-2～１０-7Ｐａの分圧で、好ましくは３００～１０００℃の温度、より好ましくは８００～１０００℃の温度で、例えば０．１～１００００秒間、特に１～１００秒間、接触、吸着させると、単結晶表面を構成する個々の原子において、炭化水素ガスは、原子に乖離吸着して分解し、水素分子を放出する。そして、残った炭素はテンプレートである下地単結晶表面の原子配列と一定の結晶方位関係を保持してグラフェン膜が単原子層として成長する。この方法で、温度と反応時間の制御によって、膜厚を誤差１％以下の精度で制御できる。 Next, using the formed single crystal surface as a template, a chemical vapor deposition (CVD) method (also called chemical vapor deposition method or chemical vapor deposition method) in which a source gas is brought into contact with the single crystal surface is formed on the single crystal surface. A monoatomic film is formed. The formed single crystal surface is a clean surface in which atoms are regularly arranged. For example, when a graphene film is manufactured on this surface, a hydrocarbon gas is supplied at a partial pressure of 10 −2 to 10 −7 Pa. And preferably at a temperature of 300 to 1000 ° C., more preferably at a temperature of 800 to 1000 ° C., for example, for 0.1 to 10,000 seconds, particularly 1 to 100 seconds, the individual crystals constituting the surface of the single crystal. In the atoms, the hydrocarbon gas is separated and adsorbed on the atoms and decomposes to release hydrogen molecules. The remaining carbon maintains a certain crystal orientation relationship with the atomic arrangement on the surface of the underlying single crystal as a template, and the graphene film grows as a monoatomic layer. By this method, the film thickness can be controlled with an accuracy of 1% or less by controlling the temperature and reaction time.
　炭化水素ガスとしては、特に限定されるものではないが、上述した減圧下で、気体で存在し得るものであり、例えば、メタン、エタン、プロパン、ブタン、ペンタン、ヘキサン等の鎖状飽和炭化水素、シクロペンタン、シクロヘキサン等の環状飽和炭化水素、エチレン、プロピレン、ブチレン、ブタジエン等の鎖状不飽和炭化水素、ベンゼン、トルエン、キシレン等の芳香族炭化水素等が挙げられる。 The hydrocarbon gas is not particularly limited, but may be present in a gas under the above-described reduced pressure. For example, chain saturated hydrocarbons such as methane, ethane, propane, butane, pentane, and hexane And cyclic saturated hydrocarbons such as cyclopentane and cyclohexane, chain unsaturated hydrocarbons such as ethylene, propylene, butylene and butadiene, and aromatic hydrocarbons such as benzene, toluene and xylene.
　一方、ｈ－ＢＮ膜を製造する場合は、ボラジン（Ｂ3Ｎ3Ｈ6）ガスを、１０-2～１０-7Ｐａの分圧で、好ましくは１００～１０００℃の温度、より好ましくは２００～１０００℃の温度で、例えば０．１～１００００秒間、特に１～１００秒間、接触、吸着させると、単結晶表面を構成する個々の原子において、ボラジンガスは、原子に乖離吸着して分解し、水素分子を放出する。そして、残ったホウ素及び窒素はテンプレートである下地単結晶表面の原子配列と一定の結晶方位関係を保持してｈ－ＢＮ膜が単原子層として成長する。なお、ボラジン以外にも、ボロン（Ｂ）原子の数と同じ数の窒素（Ｎ）を含む分子（好ましくは水素化窒化ホウ素）のガスを原料ガスとして用いることもできる。 On the other hand, when producing an h-BN film, borazine (B 3 N 3 H 6 ) gas is used at a partial pressure of 10 −2 to 10 −7 Pa, preferably at a temperature of 100 to 1000 ° C., more preferably 200 When contacted and adsorbed at a temperature of ˜1000 ° C., for example, for 0.1 to 10,000 seconds, particularly 1 to 100 seconds, the borazine gas is separated and adsorbed on the atoms in the individual atoms constituting the single crystal surface, Releases hydrogen molecules. The remaining boron and nitrogen maintain a certain crystal orientation relationship with the atomic arrangement on the surface of the underlying single crystal as a template, and the h-BN film grows as a monoatomic layer. In addition to borazine, a gas of molecules (preferably boron hydronitride) containing the same number of nitrogen (N) as the number of boron (B) atoms can be used as a source gas.
　なお、グラフェン膜を製造する場合、ｈ－ＢＮ膜を製造する場合のいずれにおいても、原料ガスは、ヘリウム、アルゴン等の不活性ガスとの共存下で用いてもよい。 Note that, when producing a graphene film or an h-BN film, the source gas may be used in the presence of an inert gas such as helium or argon.
　このときのグラフェン膜やｈ－ＢＮ膜の成長速度は、単結晶表面との反応性に依存し、金属又は金属化合物の表面が露出している場合（即ち、それを構成する原子が露出している場合）に対し、表面が炭素、又はホウ素及び窒素で１原子層覆われると、炭化水素ガスやボラジンの吸着確率は約２桁下がり、同じ圧力下においては、単結晶表面が単原子層で覆われると、事実上成長は停止する。従って、Ｘ線光電子分光法（ＸＰＳ）やオージェ電子分光法（ＡＥＳ）のような表面元素分析法で観測し、炭素ピーク強度が変化しなくなったところで反応を止めると、グラフェン膜又はｈ－ＢＮ膜を単原子層として形成することができる。 The growth rate of the graphene film or h-BN film at this time depends on the reactivity with the surface of the single crystal, and when the surface of the metal or metal compound is exposed (that is, the atoms constituting it are exposed). On the other hand, if the surface is covered with a single atomic layer of carbon or boron and nitrogen, the adsorption probability of hydrocarbon gas and borazine is reduced by about two orders of magnitude. Under the same pressure, the single crystal surface is a monoatomic layer. Once covered, growth effectively stops. Therefore, when the reaction is stopped when the carbon peak intensity no longer changes when observed by surface elemental analysis such as X-ray photoelectron spectroscopy (XPS) or Auger electron spectroscopy (AES), a graphene film or an h-BN film Can be formed as a monoatomic layer.
　次に、この単結晶表面上に単原子膜が形成された基体から該基体を化学的に溶解させることにより単原子膜を単離する。この場合、上述したとおり、例えば、基体として酸により溶解される金属又は金属化合物を用いれば、酸による溶解を適用することができる。グラフェン膜やｈ－ＢＮ膜は、酸により溶解しない材料であることから、上述した材質の基体を用いることが好適である。なお、この溶解は、少なくとも基体の単原子膜近傍が溶解されれば、単原子膜の単離が可能であることから、基体は、その溶解操作によっては溶解されない支持体上に形成されていてもよい。また、基体の単原子膜近傍が溶解されれば、かならずしも基体全体を溶解させる必要はない。 Next, the monoatomic film is isolated by chemically dissolving the base from the base having the monoatomic film formed on the surface of the single crystal. In this case, as described above, for example, if a metal or a metal compound that is dissolved by an acid is used as the substrate, dissolution by an acid can be applied. Since the graphene film and the h-BN film are materials that are not dissolved by an acid, it is preferable to use a substrate of the above-described material. In this dissolution, since the monoatomic film can be isolated if at least the vicinity of the monoatomic film of the substrate is dissolved, the base is formed on a support that is not dissolved by the dissolving operation. Also good. Moreover, if the vicinity of the monoatomic film of the substrate is dissolved, it is not always necessary to dissolve the entire substrate.
　溶解に用いる酸としては、塩酸、硝酸、硫酸などを、水溶液、有機溶媒溶液等として用いることが可能であり、その濃度、溶解時間等は、適宜選定すればよい。 As the acid used for dissolution, hydrochloric acid, nitric acid, sulfuric acid or the like can be used as an aqueous solution, an organic solvent solution, or the like, and the concentration, dissolution time, and the like may be appropriately selected.
　次に、図２，３を参照して、本発明の単原子膜の製造方法を、更に説明する。
　まず、テンプレートとなる単結晶表面を形成した基体１を準備する（図２（Ａ），図３（Ａ））。単結晶表面は、超高真空容器内で、例えばイオン衝撃や加熱処理によって清浄にする。更に、低速電子線回折法（ＬＥＥＤ）で原子の規則的配列を確認し、オージェ電子分光法（ＡＥＳ）やＸ線光電子分光法（ＸＰＳ）によって、表面の不純物がほとんど確認されない状態、例えば、不純物原子数が露出原子数の１／１００以下、好ましくは１／１０００以下であることを確認する。 Next, with reference to FIGS. 2 and 3, the method for producing a monoatomic film of the present invention will be further described.
First, a substrate 1 having a single crystal surface as a template is prepared (FIGS. 2A and 3A). The single crystal surface is cleaned, for example, by ion bombardment or heat treatment in an ultra-high vacuum container. Further, the regular arrangement of atoms is confirmed by low-energy electron diffraction (LEED), and the surface impurities are hardly confirmed by Auger electron spectroscopy (AES) or X-ray photoelectron spectroscopy (XPS). It is confirmed that the number of atoms is 1/100 or less, preferably 1/1000 or less of the number of exposed atoms.
　次に、清浄なテンプレートである単結晶表面を、例えば１０-2～１０-9Ｐａの減圧下、８００～１０００℃に加熱しつつ、炭化水素ガス又はボラジンガスを接触させて単原子膜２を形成する（図２（Ｂ），図３（Ｂ））。ＡＥＳやＸＰＳによって、表面に、グラフェン膜の形成の場合は、炭素、ｈ－ＢＮ膜の形成の場合は、窒素とボロンが存在し、これ以上、ガスを接触させても、これらの元素が増加しないことを確認する。また、ＬＥＥＤによって規則的な原子配列ができていることを確認する。 Next, the monocrystal film 2 is formed by contacting a hydrocarbon gas or a borazine gas while heating the surface of the single crystal, which is a clean template, to 800 to 1000 ° C. under a reduced pressure of 10 −2 to 10 −9 Pa, for example. (FIG. 2B, FIG. 3B). By AES or XPS, when forming a graphene film on the surface, carbon and when forming an h-BN film, nitrogen and boron exist, and these elements increase even when gas is contacted. Make sure not to. In addition, it is confirmed that a regular atomic arrangement is made by LEED.
　次に、必要に応じて、単原子層のグラフェン膜又はｈ－ＢＮ膜で覆われた面の外周縁部に、単離後の単原子膜を保持するための例えば、白金、金などからなる保持部３を、所定厚さ（例えば０．１～１０μｍ）に蒸着する（図３（Ｃ））。図３（Ｃ）に示されるように保持部を形成した場合、この保持部に予め支持部材（図示せず）を接続し、後述する基体の溶解において、例えば溶液中に懸垂しておけば、化学溶液と接触させることにより基体が溶け落ち、単原子膜を展開した状態で得ることができ好適である。 Next, it is made of, for example, platinum, gold or the like for holding the isolated monoatomic film on the outer peripheral edge of the surface covered with the monoatomic graphene film or h-BN film, if necessary. The holding unit 3 is deposited to a predetermined thickness (for example, 0.1 to 10 μm) (FIG. 3C). When the holding part is formed as shown in FIG. 3C, a support member (not shown) is connected to the holding part in advance, and in the dissolution of the substrate described later, for example, suspended in the solution, By contacting with a chemical solution, the substrate is melted, and the monoatomic film can be obtained in a developed state, which is preferable.
　そして、グラフェン膜やｈ－ＢＮ膜を溶解せず（保持部を形成した場合は、この保持層も溶解せず）、テンプレートとした基体のみを溶解する化学溶液（酸溶液など）と接触（例えば溶液に浸漬）させて単原子膜を単離する（図２（Ｄ），図３（Ｄ））。単離した単原子膜は、例えば、白金や金のメッシュですくい上げることで回収することができる。回収した単原子膜は、必要に応じて更に洗浄、乾燥し、所定の大きさに分割して使用することができる。 Then, the graphene film and the h-BN film are not dissolved (if the holding part is formed, this holding layer is not dissolved), and contacted with a chemical solution (such as an acid solution) that dissolves only the substrate as a template (for example, an acid solution) The monoatomic film is isolated by dipping in a solution (FIGS. 2D and 3D). The isolated monoatomic film can be recovered, for example, by scooping it up with a platinum or gold mesh. The recovered monoatomic film can be further washed and dried as necessary, and divided into a predetermined size for use.
　本発明によれば、面積が１（μｍ）2以上、特に１００（μｍ）2以上の従来にない大面積、かつ格子構造が均一な単原子膜を製造することができ、電子顕微鏡用のレンズや、生物・医学関連分野における生体分子等の保持膜としての用途において用いることができる、良質な単原子膜を安定的に製造することができる。 According to the present invention, an unprecedented large-area monoatomic film having an area of 1 (μm) 2 or more, particularly 100 (μm) 2 or more, and a uniform lattice structure can be manufactured. In addition, it is possible to stably produce a high-quality monoatomic film that can be used in applications as a holding film for biomolecules and the like in the fields related to biology and medicine.
　以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記実施例に限定されるものではない。 Hereinafter, although an example and a comparative example are shown and the present invention is explained concretely, the present invention is not limited to the following example.
　　［実施例１］
　基体となる単結晶Ｎｉ板から、ラウエ法によって、結晶方位を±０．３度の精度で決めて、直径１ｃｍのＮｉ（１１１）単結晶表面を切り出した。この表面を、アルミナ、ダイヤモンド研磨剤で、光学的鏡面になるまで研磨し、２×１０-8Ｐａの超高真空容器に挿入した。 [Example 1]
From a single crystal Ni plate serving as a substrate, the crystal orientation was determined with an accuracy of ± 0.3 degrees by the Laue method, and a Ni (111) single crystal surface having a diameter of 1 cm was cut out. This surface was polished with an alumina and diamond abrasive until it became an optical mirror surface, and inserted into an ultrahigh vacuum container of 2 × 10 −8 Pa.
　次に、この表面に対して１～２ｋｅＶのエネルギーのアルゴンイオンでイオン衝撃処理を施して表面の不純物を除去し、電子ビーム加熱（１ｋｅＶ、３０ｍＡ）で１０００℃に加熱することにより、酸素や炭素の不純物のない清浄面にした。この表面が清浄であることは、オージェ電子分光（ＡＥＳ）分析とＸ線光電子分光（ＸＰＳ）分析によって、不純物がなくなったことにより確認された。また、この表面が、原子配列が整列した（１１１）面構造であることは低速電子線回折（ＬＥＥＤ）によって確認された。 Next, this surface is subjected to ion bombardment treatment with argon ions having an energy of 1 to 2 keV to remove impurities on the surface, and heated to 1000 ° C. by electron beam heating (1 keV, 30 mA), thereby allowing oxygen or carbon A clean surface free of impurities. The cleanness of the surface was confirmed by the absence of impurities by Auger electron spectroscopy (AES) analysis and X-ray photoelectron spectroscopy (XPS) analysis. Moreover, it was confirmed by low-energy electron diffraction (LEED) that this surface has a (111) plane structure in which atomic arrangements are aligned.
　次に、基体（単結晶表面）を８００℃に加熱しつつ、超高真空容器内にエチレンガス（分子気体）を容器内圧力が５×１０-4Ｐａになるまで導入し、エチレン分子を単結晶表面に１００秒間接触させてエチレンガスを排気し、２×１０-8Ｐａの超高真空に戻した。その後、放冷し、常圧に戻した。 Next, while heating the substrate (single crystal surface) to 800 ° C., ethylene gas (molecular gas) is introduced into the ultra-high vacuum container until the internal pressure of the container reaches 5 × 10 −4 Pa, and the ethylene molecules are simply The crystal surface was brought into contact with the crystal surface for 100 seconds, the ethylene gas was exhausted, and the ultrahigh vacuum of 2 × 10 −8 Pa was returned. Then, it stood to cool and returned to normal pressure.
　基体の単結晶表面を覆った膜の低速電子線回折（ＬＥＥＤ）パターン及び走査型トンネル顕微鏡（ＳＴＭ）像を評価した。ＬＥＥＤパターンを図４（Ａ）に、ＳＴＭ像を図４（Ｂ）に各々示す。ＬＥＥＤパターンから、得られた膜が、一様な平面結晶構造を有する均一な１×１構造の単原子膜（グラフェン膜）であることが確認された。また、ＳＴＭ像からも、この均一な１×１構造を反映した格子像が観測された。 The low-energy electron diffraction (LEED) pattern and scanning tunneling microscope (STM) image of the film covering the single crystal surface of the substrate were evaluated. The LEED pattern is shown in FIG. 4 (A), and the STM image is shown in FIG. 4 (B). From the LEED pattern, it was confirmed that the obtained film was a uniform 1 × 1 monoatomic film (graphene film) having a uniform planar crystal structure. A lattice image reflecting this uniform 1 × 1 structure was also observed from the STM image.
　次に、回収した基体（単結晶Ｎｉ板）を、１２ｍｏｌ／Ｌの塩酸水溶液（濃塩酸）中に投入し、基体を完全に溶解させたところ、膜状物が浮いてきたので、これを金メッシュですくい取って回収した。 Next, when the recovered substrate (single crystal Ni plate) was put into a 12 mol / L hydrochloric acid aqueous solution (concentrated hydrochloric acid) and the substrate was completely dissolved, a film-like substance floated. It was scooped with a mesh and collected.
　回収した膜状物を乾燥し、透過型電子顕微鏡（ＴＥＭ）とその電子線回折を観察した。図５（Ａ）に透過型電子顕微鏡（ＴＥＭ）像、図５（Ｂ）に電子線回折パターンを各々示す。ＴＥＭ像の対象は一辺が１０μｍ角のメッシュ上にのっている自己保持グラフェン膜である。グラフェン膜は、メッシュの１つの穴の範囲を越えて広がっており、この膜の大きさは１辺が少なくとも５０～１００μｍの大面積であることが確認された。また、大きな膜では１ｍｍの幅にもなることも分かった。更に、電子線回折像から、得られた膜は膜の厚さが１原子であり、原子間の間隔も揃った膜であること、また、グラフェン膜（自己保持膜）であることが、その格子定数（０．２４ｎｍ）から判明した。 The collected film-like material was dried, and a transmission electron microscope (TEM) and its electron beam diffraction were observed. FIG. 5A shows a transmission electron microscope (TEM) image, and FIG. 5B shows an electron beam diffraction pattern. The target of the TEM image is a self-supporting graphene film that is on a 10 μm square mesh. The graphene film spread beyond the range of one hole in the mesh, and the size of this film was confirmed to be a large area with at least 50 to 100 μm on one side. It was also found that a large film could be 1 mm wide. Further, from the electron diffraction pattern, the obtained film has a film thickness of 1 atom, and the distance between the atoms is uniform, and that the film is a graphene film (self-holding film). It was found from the lattice constant (0.24 nm).
　以上の結果から、得られた単原子膜（グラフェン膜）が、従来に比較して極めて大面積、かつ良質な単原子膜であることがわかる。 From the above results, it can be seen that the obtained monoatomic film (graphene film) is an extremely large area and high quality monoatomic film compared to the conventional one.
　　［比較例１］
　基体として多結晶Ｎｉ板を用い、直径１ｃｍの表面（単結晶表面ではない）を切り出して用いた以外は、実施例１と同様の方法で膜状物を回収した。 [Comparative Example 1]
A film-like material was recovered in the same manner as in Example 1 except that a polycrystalline Ni plate was used as a substrate and a 1 cm diameter surface (not a single crystal surface) was cut out and used.
　回収した膜状物を乾燥し、電子線回折パターンを評価したところ、リング状の回折像が観察された。この場合に用いた表面には、原子配列方向の異なる微小単結晶面が多数あるため、この表面には配列方向が異なるグラフェンが成長し、一様な平面結晶構造を有する単原子膜を得ることができなかった。 The collected film was dried and the electron diffraction pattern was evaluated, and a ring-shaped diffraction image was observed. Since the surface used in this case has a large number of small single crystal planes with different atomic arrangement directions, graphene with different arrangement directions grows on this surface to obtain a monoatomic film having a uniform planar crystal structure. I could not.

Claims (5)

  1. 　化学的に溶解可能な金属又は金属化合物からなる基体の表面に、上記金属又は金属化合物を構成する原子が規則的に配列した上記金属又は金属化合物の単結晶表面を形成し、該単結晶表面をテンプレートとして、上記単結晶表面に原料ガスを接触させる化学気相堆積（ＣＶＤ）法により単結晶表面上に単原子膜を形成し、この単結晶表面上に単原子膜が形成された基体から該基体を化学的に溶解させることにより、単原子膜を単離することを特徴とする単原子膜の製造方法。 A single crystal surface of the metal or metal compound in which atoms constituting the metal or metal compound are regularly arranged is formed on the surface of a substrate made of a chemically soluble metal or metal compound. As a template, a monoatomic film is formed on the surface of the single crystal by a chemical vapor deposition (CVD) method in which a source gas is brought into contact with the surface of the single crystal, and the substrate having the monoatomic film formed on the surface of the single crystal is used for the template. A method for producing a monoatomic film, comprising isolating a monoatomic film by chemically dissolving a substrate.
  2. 　上記金属又は金属化合物がＦｅ、Ｎｉ又はＣｏであることを特徴とする請求項１記載の製造方法。 The method according to claim 1, wherein the metal or metal compound is Fe, Ni or Co.
  3. 　上記金属又は金属化合物がＮｉであり、単結晶表面がＮｉ（１１１）面であることを特徴とする請求項１記載の製造方法。 The method according to claim 1, wherein the metal or metal compound is Ni and the single crystal surface is a Ni (111) plane.
  4. 　単原子膜がグラフェン膜又はｈ－ＢＮ膜であることを特徴とする請求項１乃至３のいずれか１項記載の製造方法。 The manufacturing method according to any one of claims 1 to 3, wherein the monoatomic film is a graphene film or an h-BN film.
  5. 　面積が１（μｍ）2以上の単原子膜を製造することを特徴とする請求項１乃至４のいずれか１項記載の製造方法。 The manufacturing method according to any one of claims 1 to 4, wherein a monoatomic film having an area of 1 (µm) 2 or more is manufactured.
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Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011162877A (en) * 2010-02-08 2011-08-25 Sungkyunkwan Univ Foundation For Corporate Collaboration Graphene roll-to-roll coating apparatus and graphene roll-to-roll coating method using the same
JP2011168448A (en) * 2010-02-19 2011-09-01 Fuji Electric Co Ltd Method for manufacturing graphene film
JP2011168473A (en) * 2010-01-21 2011-09-01 Hitachi Ltd Substrate having graphene film grown thereon and electro-optical integrated circuit device using the same
CN102184942A (en) * 2010-01-04 2011-09-14 宋健民 Device having graphene and hexagonal boron nitride and associated device
US20110269299A1 (en) * 2010-04-30 2011-11-03 The Regents Of The University Of California Direct chemical vapor deposition of graphene on dielectric surfaces
JP2012001431A (en) * 2010-06-21 2012-01-05 Samsung Electronics Co Ltd Graphene substituted with boron and nitrogen, method for producing the same, and transistor provided with the same
WO2012036608A1 (en) 2010-09-16 2012-03-22 Rositza Yakimova Process for growth of graphene
WO2012086641A1 (en) * 2010-12-21 2012-06-28 学校法人 名城大学 Method for producing graphene material and graphene material
JP2012246211A (en) * 2011-05-27 2012-12-13 Qinghua Univ Method for producing graphene/carbon nanotube composite structure
JP2012246210A (en) * 2011-05-27 2012-12-13 Qinghua Univ Method for producing graphene/carbon nanotube composite structure
JP2012246212A (en) * 2011-05-27 2012-12-13 Qinghua Univ Method for producing graphene conductive film
JP2013008680A (en) * 2010-11-24 2013-01-10 Fuji Electric Co Ltd Conductive thin film and transparent conductive film containing graphene
KR20130014182A (en) * 2011-07-29 2013-02-07 삼성전자주식회사 Process for preparing graphene sheet
CN103101906A (en) * 2011-11-15 2013-05-15 海洋王照明科技股份有限公司 Graphene, and preparation method and application thereof
CN103101907A (en) * 2011-11-15 2013-05-15 海洋王照明科技股份有限公司 Graphene, and preparation method and application thereof
KR20130097746A (en) * 2010-08-11 2013-09-03 더 트러스티스 오브 더 유니버시티 오브 펜실바니아 Large-scale graphene sheet: articles, compositions, methods and devices incorporating same
CN103774113A (en) * 2014-02-24 2014-05-07 中国科学院上海微***与信息技术研究所 Method for preparing hexagonal boron nitride film
JP2014516911A (en) * 2011-06-14 2014-07-17 アプライド グラフェン マテリアルズ ユーケー リミテッド Method for producing graphene
JP2014522321A (en) * 2011-03-22 2014-09-04 ユニバーシティ・オブ・マンチェスター Structures and methods for graphene
JP2014172788A (en) * 2013-03-08 2014-09-22 Waseda Univ Method for producing graphene
JP2015091756A (en) * 2008-11-19 2015-05-14 カナトゥ オイ Crystal surface structure and production method thereof
US9321254B2 (en) 2010-12-08 2016-04-26 3M Innovative Properties Company Article and method of making and using the same
CN106082400A (en) * 2016-06-02 2016-11-09 安徽普氏生态环境工程有限公司 A kind of preparation method of the novel bora Graphene electrodes for sewage disposal
US9515143B2 (en) 2013-03-18 2016-12-06 Samsung Electronics Co., Ltd. Heterogeneous layered structure, method of preparing the heterogeneous layered structure, and electronic device including the heterogeneous layered structure
JP2018050052A (en) * 2013-05-09 2018-03-29 サンエディソン・セミコンダクター・リミテッドＳｕｎＥｄｉｓｏｎ Ｓｅｍｉｃｏｎｄｕｃｔｏｒ Ｌｉｍｉｔｅｄ Direct and sequential formation of boron nitride and graphene on substrates
WO2018128193A1 (en) 2017-01-06 2018-07-12 国立研究開発法人科学技術振興機構 Hexagonal boron nitride thin film and method for manufacturing same
JP2020514835A (en) * 2017-03-24 2020-05-21 ソウル大学校産学協力団Ｓｅｏｕｌ Ｎａｔｉｏｎａｌ Ｕｎｉｖｅｒｓｉｔｙ Ｒ＆Ｄｂ Ｆｏｕｎｄａｔｉｏｎ Functional contact lens and manufacturing method thereof
CN112756602A (en) * 2020-12-23 2021-05-07 苏州大学张家港工业技术研究院 Independent monoatomic thick metal film and preparation method and application thereof

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
GEIM, A. K. ET AL.: "The rise of graphene", NATURE MAT., vol. 6, no. 3, March 2007 (2007-03-01), pages 183 - 191 *
MEYER, J. C. ET AL.: "The structure of suspended graphene sheets", NATURE, vol. 446, no. 7131, 1 March 2007 (2007-03-01), pages 60 - 63 *
OBRAZTSOV, A. N. ET AL.: "Chemical vapor deopsition of thin graphite films of nanometer thickness", CARBON, vol. 45, no. 10, September 2007 (2007-09-01), pages 2017 - 2021 *
RISA URATANI ET AL.: "Graphite Usumaku o Mochiita Teisoku Denshi Kaisetsu Kenbikyo-yo Shiryo Shijimaku no Kaihatsu", EXTENDED ABSTRACTS; THE JAPAN SOCIETY OF APPLIED PHYSICS, vol. 68, 4 September 2007 (2007-09-04), pages 598 *
SONAMI, P. R. ET AL.: "Planer nano-graphenes from camphor by CVD", CHEM. PHYS. LETT., vol. 430, 19 October 2006 (2006-10-19), pages 56 - 59 *

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