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WO2014189271A1 - Graphene en monocouche moncristalline a grande surface et procede de fabrication associe - Google Patents

Graphene en monocouche moncristalline a grande surface et procede de fabrication associe Download PDF

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WO2014189271A1
WO2014189271A1 PCT/KR2014/004517 KR2014004517W WO2014189271A1 WO 2014189271 A1 WO2014189271 A1 WO 2014189271A1 KR 2014004517 W KR2014004517 W KR 2014004517W WO 2014189271 A1 WO2014189271 A1 WO 2014189271A1
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graphene
single crystal
crystal
substrate
catalyst layer
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Korean (ko)
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박호범
김한수
윤희욱
박선미
이민용
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Industry University Cooperation Foundation IUCF HYU
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Industry University Cooperation Foundation IUCF HYU
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Priority claimed from KR1020140057218A external-priority patent/KR101701237B1/ko
Application filed by Industry University Cooperation Foundation IUCF HYU filed Critical Industry University Cooperation Foundation IUCF HYU
Priority to CN201480029328.4A priority Critical patent/CN105229196A/zh
Priority to US14/892,658 priority patent/US20160108546A1/en
Publication of WO2014189271A1 publication Critical patent/WO2014189271A1/fr
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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
    • C23C16/44—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 method of coating
    • C23C16/54—Apparatus specially adapted for continuous coating
    • C23C16/545—Apparatus specially adapted for continuous coating for coating elongated substrates
    • 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
    • C01B32/188—Preparation by epitaxial growth
    • 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
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/02—Single layer graphene

Definitions

  • the present invention relates to a large area single crystal single film graphene and a method for manufacturing the same, and more particularly, to a large area single crystal single crystal having a graphene layer formed on a single crystal metal catalyst layer oriented only on a (111) crystal plane without a substrate or without a substrate.
  • the present invention relates to a film graphene and a method for producing a single-crystal single film graphene having a large area oriented only to the (111) crystal plane through heat treatment and chemical vapor deposition of a metal precursor.
  • Graphene is a two-dimensional structure of one atom thick in which carbon atoms are each connected by sp 2 bonds, and benzene-shaped hexagonal carbon rings form a honeycomb crystal structure.
  • Such graphene is very transparent and exhibits high transmittance with respect to visible light, and has excellent mechanical properties and excellent conductivity, and thus has been spotlighted as a transparent electrode material, a semiconductor device, a separator, or various sensor materials.
  • a single crystal transition metal catalyst layer is formed on a single crystal substrate such as sapphire or magnesium oxide by thermal evaporation, electron beam evaporation or sputtering, and the graphene is deposited on the catalyst layer by CVD.
  • a single crystal substrate such as sapphire or magnesium oxide
  • CVD chemical vapor deposition
  • a graphitization catalyst such as a commercially available copper foil may be pre-heated at 500 to 3,000 ° C. for 10 minutes to 24 hours, and chemically polished to prepare a single layer graphene.
  • a graphitization catalyst such as a commercially available copper foil may be pre-heated at 500 to 3,000 ° C. for 10 minutes to 24 hours, and chemically polished to prepare a single layer graphene.
  • Patent Document 1 Korean Patent Publication No. 10-2013-0020351
  • Patent Document 2 Korean Registered Patent No. 10-1132706
  • Patent Document 3 Korean Patent Publication No. 10-2013-0014182
  • Non-Patent Document 1 Zheng Yan et al., ACS Nano 2012, 6 (10), 9110-9117
  • the present invention has been made in view of the above problems, and an object of the present invention is to form a single crystal metal catalyst layer oriented only on the (111) crystal plane on or without a substrate, and a large area in which a graphene layer is formed on the catalyst layer. It is to provide a method for producing a single-crystal single film graphene of a large area of the single crystal graphene oriented only to the (111) crystal surface through the heat treatment and chemical vapor deposition of the metal catalyst layer.
  • the present invention for achieving the above object is a single crystal metal catalyst layer oriented only on the (111) crystal plane on or without a substrate; And a graphene layer formed on the single crystal metal catalyst layer.
  • the substrate is characterized in that the single crystal substrate or non-monocrystalline substrate.
  • the substrate may be a silicon substrate, a metal oxide substrate, or a ceramic substrate.
  • the substrate is silicon (Si), silicon dioxide (SiO 2 ), silicon nitride (Si 3 N 4 ), zinc oxide (ZnO), zirconium dioxide (ZrO 2 ), nickel oxide (NiO), hafnium oxide (HfO 2 ), oxidizing agent Cobalt (CoO), cupric oxide (CuO), ferric oxide (FeO), magnesium oxide (MgO), alpha-aluminum oxide (a-Al 2 O 3 ), aluminum oxide (Al 2 O 3 ), strontium titanate (SrTiO 3 ), lanthanum aluminate (LaAlO 3 ), titanium dioxide (TiO 2 ), tantalum dioxide (TaO 2 ), niobium dioxide (NbO 2 ), and boron nitride (BN) It is done.
  • the single crystal metal catalyst layer is copper (Cu), nickel (Ni), cobalt (Co), iron (Fe), ruthenium (Ru), platinum (Pt), palladium (Pd), gold (Au), silver (Ag), Aluminum (Al), Chromium (Cr), Magnesium (Mg), Manganese (Mn), Molybdenum (Mo), Rhodium (Rh), Silicon (Si), Tantalum (Ta), Titanium (Ti), Tungsten (W) ), Uranium (U), vanadium (V), iridium (Ir), and zirconium (Zr) is characterized in any one selected from the group consisting of.
  • the single crystal metal catalyst layer is characterized in that the shape of the foil, plate, block or tube.
  • the present invention comprises the steps of: i) preparing a polycrystalline metal precursor having a variety of crystal plane orientation without the crystal plane is biased in either direction;
  • the metal precursor of step i) is copper (Cu), nickel (Ni), cobalt (Co), iron (Fe), ruthenium (Ru), platinum (Pt), palladium (Pd), gold (Au), silver ( Ag), aluminum (Al), chromium (Cr), magnesium (Mg), manganese (Mn), molybdenum (Mo), rhodium (Rh), silicon (Si), tantalum (Ta), titanium (Ti), It is characterized in that any one selected from the group consisting of tungsten (W), uranium (U), vanadium (V), iridium (Ir), and zirconium (Zr).
  • the metal precursor of step i) is characterized in that the shape of the foil, plate, block or tubular.
  • the metal precursor of step i) is characterized in that the commercialized copper foil.
  • the commercialized copper foil is characterized in that the thickness ranges from 5 ⁇ m to 18 ⁇ m.
  • Heat treatment of step ii) is characterized in that performed for 1 to 5 hours at 900 ⁇ 1,200 °C, 1 torr ⁇ 760 torr in a hydrogen or mixed gas atmosphere of hydrogen and argon.
  • the hydrogen, or a mixed gas atmosphere of hydrogen and argon is characterized in that the injection of hydrogen 10 ⁇ 100 sccm, or hydrogen 10 ⁇ 100 sccm / argon 10 ⁇ 100 sccm.
  • step ii) Chemical vapor deposition of step ii) is carried out for 10 minutes to 3 hours at 900 ⁇ 1,200 °C, 0.1 torr ⁇ 760 torr in a mixed gas atmosphere of hydrogen and carbon-containing gas.
  • the mixed gas atmosphere of the hydrogen and carbon-containing gas is characterized in that the injection of hydrogen 1 ⁇ 100 sccm / carbon-containing gas 10 ⁇ 100 sccm.
  • the carbon-containing gas is characterized in that any one selected from the group consisting of hydrocarbon gas, gaseous hydrocarbon compound, gaseous alcohol having 1 to 6 carbon atoms, carbon monoxide, and mixtures thereof.
  • the hydrocarbon gas is characterized in that any one selected from the group consisting of methane, ethane, propane, butane, ethylene, propylene, butylene, acetylene, butadiene, and mixtures thereof.
  • the gaseous hydrocarbon compound is characterized in that any one selected from the group consisting of pentane, hexane, cyclohexane, benzene, toluene, xylene, and mixtures thereof.
  • step iii characterized in that it further comprises an artificial cooling step.
  • the cooling step is characterized in that it is carried out slowly at a cooling rate of 10 ⁇ 50 °C / min.
  • the cooling step is characterized in that it is carried out while injecting hydrogen at 10 ⁇ 1,000 sccm.
  • the present invention provides a transparent electrode including the large area single crystal graphene graphene.
  • the present invention provides a display device including the large area single crystal single layer graphene.
  • the present invention provides a semiconductor device including the large area single crystal single film graphene.
  • the present invention provides a separation membrane comprising the large area single crystal graphene graphene.
  • the present invention provides a fuel cell comprising the large area single crystal single film graphene.
  • the present invention provides a solar cell including the large area single crystal single film graphene.
  • the present invention provides a sensor comprising the large area single crystal single film graphene.
  • Example 2 is a scanning electron microscope (SEM) image of a commercialized copper foil according to Example 1 of the present invention.
  • Example 3 is an X-ray diffraction (XRD) pattern of a commercialized copper foil according to Example 1 of the present invention.
  • SEM 4 is a scanning electron microscope (SEM) image when graphene is formed on a commercialized copper foil catalyst layer according to Example 1 of the present invention.
  • Example 5 is an X-ray diffraction (XRD) pattern when graphene is formed on a commercialized copper foil catalyst layer according to Example 1 of the present invention.
  • XRD X-ray diffraction
  • Example 6 is an electron backscattering diffraction (EBSD) pattern of a copper catalyst layer formed according to Example 1 of the present invention.
  • EBSD electron backscattering diffraction
  • Example 8 is a Raman map of the graphene layer formed according to Example 1 of the present invention.
  • SEM 9 is a scanning electron microscope (SEM) image when graphene is formed on a commercially available copper foil catalyst layer according to Comparative Example 1 of the present invention.
  • SEM 10 is a scanning electron microscope (SEM) image when graphene is formed on a copper foil catalyst layer commercialized according to Comparative Example 2 of the present invention.
  • EBSD electron backscattering diffraction
  • XRD 12 is an X-ray diffraction (XRD) pattern when graphene is formed on a copper foil catalyst layer commercialized according to Comparative Example 2 of the present invention.
  • FIG. 13 is a scanning electron microscope (SEM) image of graphene formed on a copper foil catalyst layer commercialized according to Comparative Example 3 of the present invention.
  • SEM scanning electron microscope
  • FIG. 14 is a graph showing sheet resistance values of single crystal single layer graphene prepared from Example 1 of the present invention and sheet resistance values of polycrystalline single layer graphene published in the related art.
  • FIG. 15 is a graph showing values of carrier mobility of single crystal single layer graphene prepared from Example 1 of the present invention and values of current carrier mobility of polycrystalline single layer graphene published in the related art. .
  • FIG. 16 is a graph showing values of the transmittance of single crystal single layer graphene prepared from Example 1 of the present invention and values of the polycrystalline single layer graphene published in the related art.
  • the metal catalyst layer when a metal catalyst layer is formed on an amorphous substrate such as a silicon oxide film (SiO 2 ), the metal catalyst layer has a polycrystalline structure and is formed on a metal foil or sheet such as copper, nickel, or cobalt without a substrate. Even when the graphene is formed directly on the metal foil or the sheet itself is polycrystalline by the conventional chemical vapor deposition method, the formed graphene also has domains and domain boundaries, resulting in poor quality and difficult to realize large area graphene. .
  • the graphene layer formed by the chemical vapor deposition method on the copper 100 single crystal grown directly on the conventional single crystal 100 sapphire substrate has two (0, 30 degree) directions
  • the graphene layer formed by the chemical vapor deposition method on the copper (111) single crystal grown directly on the conventional single crystal (111) magnesium oxide substrate produces a single surface without grain boundary, that is, a single crystal single film. can do.
  • an expensive single crystal (111) magnesium oxide or sapphire substrate was necessary.
  • a special heat treatment of a polycrystalline metal foil having various crystal surface orientations without any bias in any direction and simultaneously performed without expensive substrates for single crystal growth having a copper (111) crystal surface unlike conventional By forming an in-situ chemical vapor deposition, a single crystal metal foil layer oriented only to the (111) crystal plane and a graphene layer formed on the single crystal metal foil layer could realize a large area of single crystal single film graphene. .
  • the present invention provides a single crystal metal catalyst layer oriented only on the (111) crystal plane on or without a substrate; And a graphene layer formed on the single crystal metal catalyst layer.
  • the single crystal metal catalyst layer can be formed without an expensive single crystal substrate such as magnesium oxide or sapphire, but, of course, the conventional single crystal substrate can be used to form the single crystal metal catalyst layer.
  • the conventional single crystal substrate can be used to form the single crystal metal catalyst layer.
  • Non single-crystalline substrates may also be used.
  • the substrate may be a silicon substrate, a metal oxide substrate, or a ceramic substrate, and examples thereof include silicon (Si), silicon dioxide (SiO 2 ), and silicon nitride (Si 3 N 4).
  • BN boron nitride
  • the single crystal metal catalyst layer oriented only to the (111) crystal plane of the present invention includes copper (Cu), nickel (Ni), cobalt (Co), iron (Fe), ruthenium (Ru), platinum (Pt), and palladium (Pd).
  • the catalyst layer is more preferred, but is not limited thereto.
  • the single crystal metal catalyst layer oriented only to the (111) crystal plane of the present invention may be formed regardless of its shape, and may be in any form including a foil, a flat plate, a block, or a tubular shape, but a foil shape is preferable. Do.
  • a graphene layer is formed on the single crystal metal catalyst layer oriented only to the (111) crystal plane to obtain a large area single crystal graphene graphene according to the present invention.
  • a large area single crystal graphene graphene is prepared by the following manufacturing method. It can be manufactured.
  • step ii) thermally treating the metal precursor of step i) and simultaneously forming a single crystal metal catalyst layer oriented only to the (111) crystal plane through chemical vapor deposition;
  • Examples of the polycrystalline metal precursors having various crystal plane orientations include copper (Cu), nickel (Ni), cobalt (Co), iron (Fe), ruthenium (Ru), platinum (Pt), palladium (Pd), and gold (Au).
  • It may be of any type, including flat, block, or tubular, but is preferably in the form of a foil for the formation of a homogeneous single crystal metal catalyst layer by heat treatment, and particularly preferably a commercially available copper foil, which is readily available and inexpensive. Can be used.
  • the crystal plane of the polycrystalline metal precursor has various crystal plane orientations without being biased in one direction, and in fact, the (100) crystal plane has a predominantly dominant orientation ( 111) Since the polycrystalline metal precursors having a predominant orientation in a crystal plane direction other than the crystal plane do not have various crystal plane orientations, the crystal plane direction does not change even by heat treatment or cannot have a single crystal structure oriented only in the (111) crystal plane. do.
  • the thickness is another important variable as an important factor capable of forming a single crystal metal catalyst layer oriented only on the (111) crystal plane.
  • the metal precursor is in the form of a foil, since it affects the solid solubility of carbon in the process of graphene formation by recrystallization and chemical vapor deposition after heat treatment according to the thickness, according to the present invention It is preferable that the thickness of a metal precursor is 5 micrometers-18 micrometers.
  • the thickness of the metal precursor is less than 5 ⁇ m, it is too thin to perform a smooth heat treatment and chemical vapor deposition process, so recrystallization cannot be expected, and when it exceeds 18 ⁇ m, only the (111) crystal plane is oriented even if heat treatment is performed under the same conditions.
  • a single crystal metal catalyst layer can never be obtained, only a metal catalyst layer having various crystal plane directions as a metal precursor or having a crystalline structure in which the (100) crystal plane is dominant is obtained, and also formed by chemical vapor deposition carried out simultaneously with the heat treatment. In the graphene layer, a large number of grain boundaries exist, such that a single layer is not obtained.
  • step ii) the crystal plane prepared in step i) is crystallized by heat treatment and chemical vapor deposition at the same time without crystallization in either direction and crystallized by chemical vapor deposition.
  • a single crystal metal catalyst layer is formed.
  • step ii) is performed in a hydrogen atmosphere to prevent oxidation of the metal catalyst layer, or in a mixed gas atmosphere of hydrogen and argon for 1 to 5 hours at 900 ⁇ 1,200 °C, 1 torr ⁇ 760 torr,
  • hydrogen, or a mixed gas atmosphere of hydrogen and argon is preferably heat treatment while injecting hydrogen 10 ⁇ 100 sccm, or hydrogen 10 ⁇ 100 sccm / argon 10 ⁇ 100 sccm.
  • the heat treatment process is a variable temperature, pressure, time and hydrogen, or the rate of injection of hydrogen and argon gas, especially the pressure conditions are very important, out of the above range, single crystal metal oriented only to the (111) crystal plane A catalyst layer is not formed, and thus a high quality graphene thin film is difficult to obtain. Therefore, in the present invention, by controlling the process parameters for the heat treatment of step ii) within the above range to crystallize the metal precursor to form a single crystal metal catalyst layer oriented only to the (111) crystal plane, and then in step iii) high quality single crystal A single layer graphene layer can be formed.
  • the present invention is fundamentally different from the technical idea of forming a single crystalline metal thin film on a substrate using a conventional single crystal substrate, or forming a polycrystalline metal catalyst layer by heat treating a metal precursor even when the substrate is not used.
  • the present invention is heat-treated and chemical vapor phase of the metal precursor having any size as it is, regardless of the size of the metal precursor Since it is possible to produce single crystal single film graphene having a large area (arbitrary area) by evaporation, commercialization by mass production can be realized.
  • step ii) is carried out for 10 minutes to 3 hours at 900 ⁇ 1,200 °C, 0.1 torr ⁇ 760 torr in a mixed gas atmosphere of hydrogen and carbon containing gas, wherein the hydrogen and carbon containing gas
  • the mixed gas atmosphere is preferably injected at 1-100 sccm of hydrogen / 10-100 sccm of carbon-containing gas.
  • the carbon-containing gas may be any one selected from the group consisting of a hydrocarbon gas, a gaseous hydrocarbon compound, a gaseous alcohol having 1 to 6 carbon atoms, carbon monoxide, and a mixture thereof, and in particular, a hydrocarbon gas may be preferably used.
  • hydrocarbon gas any one selected from the group consisting of methane, ethane, propane, butane, ethylene, propylene, butylene, acetylene, butadiene, and mixtures thereof, and using methane gas that is easy to handle is used. More preferred.
  • the gaseous hydrocarbon compound may be any one selected from the group consisting of pentane, hexane, cyclohexane, benzene, toluene, xylene, and mixtures thereof, but is not limited thereto.
  • step ii) when the process of step ii) is finished, it is possible to obtain a single crystal single layer graphene having a large area as a target in step iii), but may further include an artificial cooling step after the step iii), if necessary.
  • the cooling step is preferably carried out slowly at a cooling rate of 10 ⁇ 50 °C / min.
  • the rapid cooling over the range of the cooling rate is necessary to pay attention because the graphene is uniformly grown and can be cracked in the process of uniformly arranged.
  • the cooling step may be cooled while injecting hydrogen at 10 ⁇ 1,000 sccm.
  • a transparent electrode a display device, a semiconductor device, a separator, a fuel cell, a solar cell or various sensors including the large-area single crystal single film graphene produced in the present invention.
  • a copper foil (HOHSEN, 99.9%, Japan) having a thickness of 18 ⁇ m and a length of 10 cm x 10 cm was placed in a chamber, and heat-treated while injecting hydrogen at 100 sccm for 2 hours at 1,005 ° C and 500 torr.
  • the copper catalyst layer was formed, and at the same time, a graphene layer was formed on the copper catalyst layer by performing a chemical vapor deposition (CVD) process while injecting hydrogen / methane at a ratio of 5 sccm / 20 sccm for 60 minutes at 1,005 ° C. and 0.5 torr.
  • CVD chemical vapor deposition
  • Table 1 shows the heat treatment and CVD process parameters according to Examples 1-3 and Comparative Examples 1-3.
  • Example 2 18 1,005 500 50 sccm2 hours 1,005 0.5 5/20 sccm60 minutes
  • Example 3 18 1,005 500 100 sccm2 hours 1,020 500 5/20 sccm30 minutes Comparative Example 1 18 None None None 1,005 0.5 5/20 sccm60 minutes Comparative Example 2 18 1,005 0.5 20 sccm2 hours 1,005 0.5 5/20 sccm60 minutes Comparative Example 3 75 1,005 500 100 sccm2 hours 1,005 0.5 5/20 sccm60 minutes
  • FIG. 2 shows a scanning electron microscope (SEM) image of a commercially available copper foil as a metal precursor according to Example 1 of the present invention. As shown in FIG. 2, it can be seen that grains and grain boundaries exist. And Figure 3 is to measure the X-ray diffraction pattern to determine the crystallinity of the commercialized copper foil, it was confirmed that the polycrystalline (polycrystalline) having a variety of crystal plane orientation.
  • SEM scanning electron microscope
  • FIG. 4 is a scanning electron microscope (SEM) image when graphene is formed after heat treatment and chemical vapor deposition (CVD) of the commercialized copper foil according to Example 1 of the present invention, and the copper catalyst layer has a grain boundary. From the X-ray diffraction pattern of FIG. 5, it was confirmed that a single crystal catalyst layer oriented only to the (111) crystal plane was formed due to recrystallization by heat treatment and chemical vapor deposition.
  • Example 6 shows electron backscatter diffraction (EBSD) characteristics in order to further analyze the crystal plane orientation of the copper catalyst layer formed according to Example 1 of the present invention, and has no grain boundaries and defects in the entire area. It was confirmed that the single crystal catalyst layer oriented only on the (111) plane was formed.
  • EBSD electron backscatter diffraction
  • Figure 7 shows the Raman spectrum of the graphene layer formed in accordance with Example 1 of the present invention, the G peak, which is a characteristic peak of graphene is found around 1580 cm -1 , in particular around 2700 cm -1 A strong and sharp 2D peak was found at, indicating that the graphene layer was formed as a monolayer.
  • the D peak intensity near 1340 cm ⁇ 1 found in conventional graphene was measured so weakly that it was unknown, and it was found that the graphene formed according to Example 1 of the present invention had almost no defects, and the G peak intensity The relative ratio of the D peak intensity to about was also measured about 0.22 to confirm that the crystallinity is very high.
  • Example 2 which differs only in the hydrogen injection rate as a heat treatment atmosphere
  • Example 3 which changed the CVD process conditions
  • Example 1 the heat treatment of the copper foil commercialized according to Comparative Example 2 of the present invention under relatively low pressure was carried out in Example 1 and Even though the CVD process is performed under the same conditions, it can be seen that the copper grains and grain boundaries are still present in the copper catalyst layer. Also, from the X-ray diffraction pattern of FIG. It was confirmed that it did not change even after performing.
  • FIG. 14 is a graph showing the measurement of sheet resistance of single crystal single-layer graphene prepared from Example 1 of the present invention using a 4-point probe according to ASTM D257.
  • ASTM D257 [ACS NANO, VOL 5, 6916 (2011)] is shown with the sheet resistance value of the polycrystalline single-layer graphene, the single crystal single-layer graphene prepared from Example 1 of the present invention has a sheet resistance value compared to the conventional polycrystalline single-layer graphene
  • the improvement effect is about 80%. This is because the electron mean free path is improved by decreasing the defect density such as grain boundary in the single crystal single film. Therefore, the single crystal single layer graphene manufactured in the present invention is expected to be applicable to a flexible OLED or a solar cell device as a display device of low power and high efficiency beyond the touch screen level.
  • Figure 15 is measured according to the conventional Hall effect measurement (carrier mobility) of the single crystal single-film graphene prepared from Example 1 of the present invention known Appl. Phys. Lett., 102, 163102 (2013) is shown with the current carrier mobility value of the polycrystalline single-layer graphene published in the present invention, the monocrystalline single-layer graphene prepared from Example 1 of the present invention is a conventional polycrystalline single-layer graphene
  • the improvement effect is about 300%. This is because the scattering rate of the charge carrier is improved by reducing the defect density such as grain boundary in the single crystal single film. Therefore, the single crystal single layer graphene manufactured in the present invention may be applied to low power rapid next generation semiconductor logic devices or next generation 10 nm or less ultra fine channel materials.
  • FIG. 16 shows the transmittances of the single crystal single layer graphene prepared from Example 1 of the present invention and the polycrystalline single layer graphene published in the publication [Nature Nanotechnology, Vol 5, August (2010)].
  • the monocrystalline single film graphene prepared from Example 1 of the present invention has an increase in the transmittance value of about 0.8% compared to the conventional polycrystalline single film graphene, which is the highest value ever published. This result is interpreted to be due to the improvement of scattering and refraction upon transmission of light by decreasing defect density such as grain boundary in the single crystal single film according to the present invention.
  • the transmittance is improved as the thickness decreases and the resistance is increased as the thickness increases, so that the transmittance and resistance have a trade-off relationship with respect to the thickness. It can be seen that the effect is shown.
  • the single crystal single film graphene prepared from the embodiment of the present invention has a grain and grain boundary through heat treatment and chemical vapor deposition of the metal precursor without an expensive substrate, compared to the single layer graphene prepared by the comparative example or the conventional method. It is possible to obtain high quality single crystal single layer graphene which does not exist, and in particular, since the metal precursor is heat-treated and chemical vapor deposition as it is, irrespective of the size and shape of the metal precursor, the large area of the metal precursor intact is as large as it is. Has a surprising effect of producing single crystal single layer graphene.
  • the large-area single crystal graphene graphene prepared according to the present invention is expected to be applicable to transparent electrodes, display devices, semiconductor devices, separators, fuel cells, solar cells or various sensors.

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Abstract

La présente invention concerne : du graphène en monocouche monocristalline à grande surface dans lequel une couche de graphène est formée sur une couche de catalyseur métallique monocristallin orientée uniquement dans le plan cristallin (111), sur un substrat ou sans un substrat ; et un procédé de fabrication de graphène en monocouche monocristalline à grande surface orienté uniquement dans le plan cristallin (111), à l'aide d'un traitement thermique d'un précurseur de métallique et d'un dépôt chimique en phase vapeur. Selon la présente invention, une couche de catalyseur métallique monocristallin orientée uniquement dans le plan cristallin (111) peut être formée, sur un substrat ou même sans un substrat, selon divers modes de feuille, de plaque plate, de bloc ou de tube, et par fabrication de graphène en monocouche monocristalline à grande surface dans lequel une couche de graphène est formée sur la couche de catalyseur, il est possible de commercialiser des couches minces de graphène à grande surface à l'aide de la fabrication de masse, et il est possible d'utiliser l'invention en tant que matériau d'électrode transparente et matériau pour des éléments d'affichage, des éléments semi-conducteurs, des films de séparation, des piles à combustible, des cellules solaires ou divers types de capteurs.
PCT/KR2014/004517 2013-05-21 2014-05-21 Graphene en monocouche moncristalline a grande surface et procede de fabrication associe Ceased WO2014189271A1 (fr)

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US14/892,658 US20160108546A1 (en) 2013-05-21 2014-05-21 Large-area single-crystal monolayer graphene film and method for producing the same

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WO2017041401A1 (fr) * 2015-09-07 2017-03-16 Peking University Croissance rapide de graphène monocristallin de grande taille assistée par un substrat d'oxyde adjacent
EP3444375A1 (fr) * 2017-08-14 2019-02-20 INL - International Iberian Nanotechnology Laboratory Procédé de formation d'une couche de graphène
US20190390366A1 (en) * 2017-02-02 2019-12-26 Soitec Process for manufacturing a two-dimensional film of hexagonal crystalline structure
CN114481101A (zh) * 2021-12-15 2022-05-13 中南大学 一种调控金属镀层晶面取向的方法获得的金属材料和应用
CN114525581A (zh) * 2022-02-11 2022-05-24 中国科学院上海微系统与信息技术研究所 一种双层30度扭角石墨烯单晶晶圆的制备方法
CN115418714A (zh) * 2022-07-18 2022-12-02 华南师范大学 一种在金属衬底上制备单晶二维材料的通用方法

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EP2540862A1 (fr) * 2010-02-26 2013-01-02 National Institute of Advanced Industrial Science And Technology Stratifié de film de carbone
KR20130000964A (ko) * 2011-06-24 2013-01-03 삼성전자주식회사 그래핀 제조방법
KR20130020351A (ko) * 2011-08-19 2013-02-27 한국전기연구원 그래핀 박막의 형성방법 및 그 방법에 의해 제조된 그래핀

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US20120196074A1 (en) * 2009-08-31 2012-08-02 Kyushu University Graphene sheet and method for producing the same
EP2540862A1 (fr) * 2010-02-26 2013-01-02 National Institute of Advanced Industrial Science And Technology Stratifié de film de carbone
KR20130000964A (ko) * 2011-06-24 2013-01-03 삼성전자주식회사 그래핀 제조방법
KR20130020351A (ko) * 2011-08-19 2013-02-27 한국전기연구원 그래핀 박막의 형성방법 및 그 방법에 의해 제조된 그래핀

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017041401A1 (fr) * 2015-09-07 2017-03-16 Peking University Croissance rapide de graphène monocristallin de grande taille assistée par un substrat d'oxyde adjacent
US20190390366A1 (en) * 2017-02-02 2019-12-26 Soitec Process for manufacturing a two-dimensional film of hexagonal crystalline structure
US11913134B2 (en) * 2017-02-02 2024-02-27 Soitec Process for manufacturing a two-dimensional film of hexagonal crystalline structure using epitaxial growth on a transferred thin metal film
EP3444375A1 (fr) * 2017-08-14 2019-02-20 INL - International Iberian Nanotechnology Laboratory Procédé de formation d'une couche de graphène
CN114481101A (zh) * 2021-12-15 2022-05-13 中南大学 一种调控金属镀层晶面取向的方法获得的金属材料和应用
CN114481101B (zh) * 2021-12-15 2023-09-29 中南大学 一种调控金属镀层晶面取向的方法获得的金属材料和应用
CN114525581A (zh) * 2022-02-11 2022-05-24 中国科学院上海微系统与信息技术研究所 一种双层30度扭角石墨烯单晶晶圆的制备方法
CN114525581B (zh) * 2022-02-11 2023-10-20 中国科学院上海微系统与信息技术研究所 一种双层30度扭角石墨烯单晶晶圆的制备方法
CN115418714A (zh) * 2022-07-18 2022-12-02 华南师范大学 一种在金属衬底上制备单晶二维材料的通用方法
CN115418714B (zh) * 2022-07-18 2024-02-13 华南师范大学 一种在金属衬底上制备单晶二维材料的通用方法

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