WO2012105777A2 - Procédé et appareil pour la fabrication de graphène - Google Patents

Procédé et appareil pour la fabrication de graphène Download PDF

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Publication number
WO2012105777A2
WO2012105777A2 PCT/KR2012/000690 KR2012000690W WO2012105777A2 WO 2012105777 A2 WO2012105777 A2 WO 2012105777A2 KR 2012000690 W KR2012000690 W KR 2012000690W WO 2012105777 A2 WO2012105777 A2 WO 2012105777A2
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WIPO (PCT)
Prior art keywords
catalyst metal
graphene
catalyst
catalyst metals
synthesizing apparatus
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/KR2012/000690
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English (en)
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WO2012105777A3 (fr
Inventor
Young-Il Song
Hyeong-Keun Kim
Byung-Hee Hong
Jong-Hyun Ahn
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Sungkyunkwan University
Hanwha Vision Co Ltd
Original Assignee
Samsung Techwin Co Ltd
Sungkyunkwan University
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Publication date
Priority claimed from KR1020110144978A external-priority patent/KR101912798B1/ko
Application filed by Samsung Techwin Co Ltd, Sungkyunkwan University filed Critical Samsung Techwin Co Ltd
Priority to US13/982,880 priority Critical patent/US9260309B2/en
Priority to CN201280016553.5A priority patent/CN103459316B/zh
Publication of WO2012105777A2 publication Critical patent/WO2012105777A2/fr
Publication of WO2012105777A3 publication Critical patent/WO2012105777A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B01J23/04—Alkali metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/464—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/186—Preparation by chemical vapour deposition [CVD]

Definitions

  • One or more embodiments of the present invention relate to methods and apparatuses for synthesizing graphene that may be used for manufacturing graphene.
  • carbon-based materials such as carbon nanotubes, diamond, graphite, and graphene, are being researched in various fields.
  • One or more embodiments of the present invention include a method and an apparatus for synthesizing a large quantity of fine-quality graphene.
  • a method of synthesizing graphene comprises loading catalyst metals into a chamber in the horizontal direction or the vertical direction; increasing sizes of grains of the catalyst metals by heating the catalyst metals; raising a temperature inside the chamber while providing a vapor carbon source in the catalyst metals; and forming graphene by cooling the catalyst metals.
  • a size of a grain of the catalyst metal may be greater than 100 ⁇ m.
  • the catalyst metal may contain one or more selected from the group consisting of nickel (Ni), cobalt (Co), iron (Fe), platinum (Pt), gold (Au), aluminum (Al), chrome (Cr), copper (Cu), magnesium (Mg), manganese (Mn), molybdenum (Mo), rhodium (Rh), silicon (Si), tantalum (Ta), titanium (Ti), and tungsten (W).
  • the step of raising the temperature inside the chamber while providing a vapor carbon source in the catalyst metals may comprise thermal chemical vapor deposition (T-CVD), rapid thermal chemical vapor deposition (RT-CVD), inductive coupled plasma chemical vapor deposition (ICP-CVD), or plasma enhanced chemical vapor deposition (PECVD).
  • T-CVD thermal chemical vapor deposition
  • RT-CVD rapid thermal chemical vapor deposition
  • ICP-CVD inductive coupled plasma chemical vapor deposition
  • PECVD plasma enhanced chemical vapor deposition
  • the catalyst metals may be loaded by at least a pair of roller units using a reel-to-reel method.
  • the catalyst metal may be loaded by fixing a surface or an edge of the catalyst metal to a frame.
  • graphene is synthesized by using the above-stated method.
  • Surface resistance of the graphene may be smaller than 35Ohm/sq.
  • a graphene synthesizing apparatus for manufacturing graphene, the graphene synthesizing apparatus comprises a frame comprising an accommodation space for accommodating catalyst metals extending in a vertical direction or a horizontal direction; and supporting units supporting the catalyst metals, wherein the catalyst metals are apart from each other.
  • the supporting units may be arranged apart from each other around the catalyst metal.
  • the supporting units may be coupled to at least one of edges of the catalyst metal.
  • the supporting units may support a surface of the catalyst metal.
  • a graphene synthesizing apparatus for manufacturing graphene, the graphene synthesizing apparatus comprises a frame comprising an accommodation space for accommodating catalyst metals extending in a vertical direction or a horizontal direction; and roller units supporting and transferring the catalyst metals, such that the catalyst metals are arranged apart from each other inside the accommodation space.
  • the roller units may comprise a pair of rollers that are arranged in parallel to each other and arranged around the accommodation space.
  • a plurality of pairs of rollers may be arranged, and each pair of rollers may be arranged apart from each other in a direction perpendicular to an surface of the catalyst metal.
  • the pair of rollers may comprise a first roller unit providing the catalyst metal layer; and a second roller unit supporting and transferring the catalyst metal supplied by the first roller unit in a direction .
  • a large quantity of high-quality graphene may be synthesized simply by increasing sizes of grains of catalyst metals.
  • FIG. 1 is a perspective view of a catalyst metal loading device of a graphene synthesizing apparatus according to an embodiment of the present invention
  • FIGS. 2A and 2B are schematic perspective views showing a combination of a supporting unit and a catalyst metal in the catalyst metal loading device of FIG. 1;
  • FIG. 3 is a schematic front view of a graphene synthesizing apparatus including the catalyst metal loading device of FIG. 1;
  • FIG. 4 is a schematic perspective view of a catalyst metal loading device according to another embodiment of the present invention.
  • FIG. 5 is a schematic perspective view of a catalyst metal loading device according to another embodiment of the present invention.
  • FIG. 6 is a schematic front view of a graphene synthesizing apparatus including the catalyst metal loading device of FIG. 5;
  • FIG. 7 is a schematic perspective view of a catalyst metal loading device according to another embodiment of the present invention.
  • FIG. 8 is a schematic front view of a graphene synthesizing apparatus including the catalyst metal loading device of FIG. 7;
  • FIG. 9 is a schematic perspective view of a catalyst metal loading device according to an embodiment of the present invention.
  • FIG. 10 is a schematic flowchart of a method of synthesizing graphene according to another embodiment of the present invention.
  • FIGS. 11A and 11B are magnified views of an area X of a catalyst metal to illustrate changing of sizes of grains of the catalyst metal;
  • FIG. 12 is a diagram showing that grains adjacent to each other merge with each other while the catalyst metal is being heated
  • FIG. 13 is a graph showing surface resistance characteristics of graphene synthesized using a method of synthesizing graphene according to an embodiment of the present invention.
  • catalyst metal refers to a catalyst metal used for forming graphene and may be provided as a single metal layer containing a metal only or in combination with other member(s).
  • the catalyst metal may be provided as being arranged on a surface of a substrate such as a silicon wafer containing silicon oxide (SiO 2 ).
  • FIG. 1 is a perspective view of a catalyst metal loading device of a graphene synthesizing apparatus according to an embodiment of the present invention.
  • FIGS. 2A and 2B are schematic perspective views showing a combination of a supporting unit and a catalyst metal in the catalyst metal loading device of FIG. 1.
  • the catalyst metal loading device 10 of the graphene synthesizing apparatus includes a frame 100, supporting units 200 which support a catalyst metal 300 loaded to the frame 100.
  • the frame 100 has a substantially hexahedral shape and six surfaces of the frame 100 may be opened.
  • An accommodation space for accommodating the catalyst metal 300 having a horizontally extending surface is arranged inside the frame 100, and the catalyst metals 300 may be arranged to be a predetermined distance apart from each other in the vertical direction (the direction D3). In this case, the plurality of catalyst metal 300 may be arranged to be parallel to each other.
  • the catalyst metal 300 has a plate-like shape and a predetermined area and may contain one or more selected from a group consisting of nickel (Ni), cobalt (Co), iron (Fe), platinum (Pt), gold (Au), aluminum (Al), chrome (Cr), copper (Cu), magnesium (Mg), manganese (Mn), molybdenum (Mo), rhodium (Rh), silicon (Si), tantalum (Ta), titanium (Ti), and tungsten (W).
  • the supporting unit 200 fixes position of the catalyst metal 300 arranged inside the frame 100.
  • a plurality of the supporting units 200 may be arranged apart from each other around the catalyst metal 300 and may support four corners of the catalyst metal 300.
  • the supporting units 200 may be arranged around the catalyst metal 300 and fix the catalyst metal 300 by supporting four corners of the catalyst metal 300.
  • the supporting unit 200 may include a groove 210 to which the catalyst metal 300 may be inserted.
  • the supporting unit 200 and the catalyst metal 300 may be coupled to each other via the groove 210.
  • the groove 210 may be formed to have a depth identical to the thickness of the catalyst metal 300, such that the catalyst metal 300 may be inserted into the groove 210.
  • the supporting unit 200' may be a clip such that bulldog clip.
  • the catalyst metal 300 may be inserted into a gap 210' formed by pressing a grip 220' of the clip-like supporting unit 200'.
  • the supporting units 200 may has a hole, such that the supporting units 200' may be coupled to the catalyst metal 300 and fixed to the frame 100 at the same time.
  • the present invention is not limited thereto. As long as the catalyst metal 300 may be fixed to the frame 100, any of various shapes and types of supporting units may be employed.
  • FIG. 3 is a schematic front view of a graphene synthesizing apparatus including the catalyst metal loading device of FIG. 1.
  • the graphene synthesizing apparatus may include a chamber 30 and a catalyst metal loading device 10 arranged inside the chamber 30.
  • the frame 100 accommodating the catalyst metals 300 that are arranged in parallel to each other by the supporting units 200 may be accommodated inside the chamber 30.
  • Graphene may be synthesized inside the chamber 30 via chemical vapor deposition (CVD) using the catalyst metal 300 .
  • CVDs may include thermal chemical vapor deposition (T-CVD), rapid thermal chemical vapor deposition (RT-CVD), inductive coupled plasma chemical vapor deposition (ICP-CVD), and plasma enhanced chemical vapor deposition (PECVD).
  • RT-CVD rapid thermal chemical vapor deposition
  • ICP-CVD inductive coupled plasma chemical vapor deposition
  • PECVD plasma enhanced chemical vapor deposition
  • atomic layer deposition (ALD) or rapid thermal anneal (RTA) may be employed.
  • FIG. 4 is a schematic perspective view of a catalyst metal loading device according to another embodiment of the present invention.
  • a graphene synthesizing apparatus according to the present embodiment also includes a chamber (not shown) and the catalyst metal loading device 10 arranged inside the chamber.
  • the catalyst metal loading device 10 shown in FIG. 4 may be arranged inside the chamber as shown in FIG. 3.
  • the catalyst metal loading device 10 includes the frame 100 and a supporting unit 400 which supports a catalyst metal loaded onto the frame 100. Furthermore, the frame 100 includes spaces for accommodating a plurality of plate-like catalyst metals.
  • the catalyst metal loading device 10 shown in FIG. 4 is similar to the catalyst metal loading device 10 described above with reference to FIGS. 1 through 3.
  • the supporting unit 400 is arranged on a surface of a catalyst metal, that is, the bottom surface. As the supporting unit 400 is arranged on the bottom surface of a catalyst metal and supports the catalyst metal overall, the catalyst metal is loaded in the horizontal direction. Furthermore, the supporting unit 400 maintains a distance between a plurality of catalyst metals.
  • the supporting unit 400 may be fixed to the frame 100.
  • FIG. 5 is a schematic perspective view of a catalyst metal loading device according to another embodiment of the present invention.
  • the catalyst metal loading device 10 includes the frame 100 and a supporting unit 500 which supports a catalyst metal loaded to the frame 100. Furthermore, the frame 100 includes spaces for accommodating a plurality of plate-like catalyst metals.
  • the catalyst metal loading device 10 shown in FIG. 5 is similar to the catalyst metal loading device 10 described above with reference to FIGS. 1 through 3.
  • the catalyst metals 300 have surfaces extending in the vertical direction and are arranged apart from each other in the horizontal direction (the direction D1), and a position of the supporting unit 500 differs from those in the previous embodiments. Descriptions below will focus on the differences therebetween.
  • the supporting unit 500 may be coupled to an edge of the catalyst metal 300 to fix the position of the catalyst metal 300.
  • the supporting unit 500 is coupled to the upper edge of the catalyst metal 300, such that the catalyst metal 300 is loaded in the vertical direction.
  • the supporting unit 500 may include grooves into which the catalyst metals 300 may be inserted or may be a clip. A plurality of the supporting units 500 may be arranged apart from each other.
  • the present invention is not limited thereto.
  • a plurality of the supporting units 500 may be arranged, and the plurality of supporting units 500 may be arranged apart from each other and are coupled to two opposite upper corners of the catalyst metal 300 to fix the position of the catalyst metal 300.
  • FIG. 6 is a schematic front view of a graphene synthesizing apparatus including the catalyst metal loading device of FIG. 5.
  • the graphene synthesizing apparatus may include a chamber 60 and the catalyst metal loading device 10 arranged inside the chamber 60.
  • the catalyst metal 300 is loaded to the frame in the vertical direction by the supporting unit 500, and the frame 100 to which the plurality of catalyst metals 300 are loaded in parallel to each other may be accommodated inside the chamber 60.
  • Graphene may be fabricated via CVD inside the chamber 60.
  • FIG. 7 is a schematic perspective view of a catalyst metal loading device according to another embodiment of the present invention.
  • the graphene synthesizing apparatus includes the frame 100 and a roller unit 700 which supports and transfers the catalyst metals 300 loaded to the frame 100.
  • the frame 100 has a substantially hexahedral shape and six surfaces of the frame 100 may be opened.
  • An accommodation space for accommodating the catalyst metal 300 having a horizontally extending surface is arranged inside the frame 100, and the plurality of catalyst metals 300 may be arranged to be a predetermined distance apart from each other in the vertical direction (the direction D3). In this case, the plurality of catalyst metal 300 may be arranged to be parallel to each other.
  • the catalyst metal 300 has a plate-like shape and a predetermined area and may contain one or more selected from a group consisting of nickel (Ni), cobalt (Co), iron (Fe), platinum (Pt), gold (Au), aluminum (Al), chrome (Cr), copper (Cu), magnesium (Mg), manganese (Mn), molybdenum (Mo), rhodium (Rh), silicon (Si), tantalum (Ta), titanium (Ti), and tungsten (W).
  • the roller unit 700 supports and transfers the catalyst metal 300 arranged inside the frame 100.
  • the roller unit 700 includes a pair of roller units 710 and 720.
  • the pair of roller units 710 and 720 are arranged in parallel to each other, such that the catalyst metals 300 may be located therebetween.
  • the first roller unit 710 and the second roller unit 720 may be arranged on outer surfaces of the frame 100 at a same height.
  • the first roller unit 710 is wound with the catalyst metal 300 and rotates in a direction (for example, clockwise or counterclockwise), and the second roller unit 720 rotates in the same direction as the first roller unit 710, and thus the catalyst metal 300 may be transferred in the direction D1.
  • a plurality of pairs of rollers 710 and 720 are arranged apart from each other in the direction D3.
  • the catalyst metals 300 loaded in the horizontal direction may be arranged apart from each other in the vertical direction according to the arrangement of the plurality of pairs of rollers 710 and 720.
  • FIG. 8 is a schematic front view of a graphene synthesizing apparatus including the catalyst metal loading device of FIG. 7.
  • the graphene synthesizing apparatus may include a chamber 80 and the catalyst metal loading device 10 arranged inside the chamber 80.
  • the catalyst metals 300 are loaded to the frame 100 in the horizontal direction by the roller units 710 and 720, and the frame 100 to which the plurality of catalyst metal 300 are loaded in parallel to each other may be accommodated inside the chamber 80.
  • the first roller unit 710 which is wound with the catalyst metal 300, may be arranged outside the chamber 80 and may provide the catalyst metal 300 into the chamber 80.
  • the catalyst metals 300 transferred in the direction D1 by rotating of the first roller unit 710 and the second roller unit 720 may be used for formation/synthesis of graphene inside the chamber 80.
  • FIG. 9 is a schematic perspective view of a catalyst metal loading device according to an embodiment of the present invention.
  • the catalyst metal loading device 10 includes the frame 100 and a roller unit 900 which supports and transfers the catalyst metal 300, where the frame 100 includes a space for accommodating the plurality of catalyst metals 300, like the catalyst metal loading device described above with reference to FIG. 7.
  • the catalyst metals 300 have surfaces extending in the vertical direction and are arranged apart from each other in the horizontal direction.
  • the position of the roller unit 900 is different from that of the roller unit 700. Descriptions below will focus on the differences therebetween.
  • the roller unit 900 includes a pair of roller units 910 and 920.
  • the pair of roller units 910 and 920 are arranged in parallel to each other, such that the accommodation space is located therebetween.
  • the first roller unit 910 and the second roller unit 920 extend in the vertical direction.
  • the first roller unit 910 and the second roller unit 920 are arranged on outer surfaces of the frame 100.
  • the first roller unit 910 is wound with the catalyst metal 300 and rotates in a direction (clockwise or counterclockwise), and the second roller unit 920 rotates in the same direction as the first roller unit 910 and transfers the catalyst metal 300 in the direction D1.
  • a plurality of pairs of roller units 910 and 920 are arranged apart from each other in the horizontal direction (the direction D2), so that the catalyst metals 300 may be loaded to be apart from each other and in parallel to each other.
  • the first roller unit 910 is arranged outside a chamber (not shown) and provides the catalyst metal 300 into the chamber for the formation of graphene.
  • the catalyst metal loading device 10 may be arranged in the chamber 80 to constitute a graphene synthesizing apparatus.
  • FIG. 10 is a schematic flowchart of a method of synthesizing graphene according to another embodiment of the present invention.
  • a catalyst metal is loaded.
  • the catalyst metal may be loaded to the catalyst metal loading device described above with reference to FIGS. 1 and 4 in the horizontal direction.
  • the catalyst metal may be loaded to the catalyst metal loading device described above with reference to FIG. 5.
  • the catalyst metal may be loaded when the catalyst metal is coupled to a supporting unit.
  • the catalyst metal may be loaded to the catalyst metal loading device described above with reference to FIG. 7 in the horizontal direction.
  • the catalyst metal may be loaded to the catalyst metal loading device described above with reference to FIG. 9 in the vertical direction.
  • the catalyst metal may be loaded by a pair of roller units using a reel-to-reel method. By using the reel-to-reel method, the catalyst metal may be continuously provided into a chamber.
  • the catalyst metal may contain one or more selected from a group consisting of nickel (Ni), cobalt (Co), iron (Fe), platinum (Pt), gold (Au), aluminum (Al), chrome (Cr), copper (Cu), magnesium (Mg), manganese (Mn), molybdenum (Mo), rhodium (Rh), silicon (Si), tantalum (Ta), titanium (Ti), and tungsten (W).
  • a pre-processing operation may be performed before the catalyst metal is loaded to the catalyst metal loading device.
  • surfaces of the catalyst metal may be cleaned by using an acidic/alkalic solution.
  • the catalyst metal is heated to increase sizes of grains of the catalyst metal.
  • the catalyst metal may be heated to a temperature about 900°C or higher, and, as the catalyst metal is heated, sizes of grains of the catalyst metal may be about 100 ⁇ m or larger.
  • size of grain refers to a value measured by a line method.
  • the line method is a method for determining size of grains by counting a number of grains passing through an arbitrary straight line in an electron back scattered diffraction (EBSD) map or a fine tissue image and then dividing the length of the arbitrary straight line by the counted number of grains.
  • EBSD electron back scattered diffraction
  • FIGS. 11A and 11B are magnified views of an area X of a catalyst metal to illustrate changing of sizes of grains of the catalyst metal
  • FIG. 12 is a diagram showing that grains adjacent to each other merge with each other while the catalyst metal is being heated.
  • a plurality of grains are densely arranged within a catalyst metal.
  • a state of the catalyst metal changes to the state shown in FIG. 11B.
  • grains adjacent to each other merge with each other as shown in section A of FIG. 12, and thus sizes of grains increase.
  • FIG. 11A showing the state of the catalyst metal before being heated
  • FIG. 11B showing the state of the catalyst metal after being heated
  • a gaseous carbon source is injected to the catalyst metal and the temperature inside the chamber is raised.
  • the operation S1030 may be performed via CVD.
  • CVD thermal chemical vapor deposition
  • RT-CVD rapid thermal chemical vapor deposition
  • ICP-CVD inductive coupled plasma chemical vapor deposition
  • PECVD plasma enhanced chemical vapor deposition
  • the gaseous carbon source may be one or more selected from a group of consisting of carbon monoxide, ethane, ethylene, ethanol, acetylene, propane, propylene, butane, butadiene, pentane, cyclopentadiene, hexane, cyclohexane, benzene, and toluene.
  • methane (CH 4 ) gas which is a gaseous carbon source, is separated to carbon atoms and hydrogen atoms, and the separated carbon atoms are absorbed by surfaces of the catalyst metal. The separated carbon atoms are diffused into grains of the catalyst metal.
  • graphene is formed by cooling the catalyst metal.
  • the carbon atoms absorbed by surfaces of the catalyst metal in operation S1030 are synthesized to the surfaces of the catalyst metal, that is to say, graphene is synthesized.
  • the catalyst metal may be cooled within a relatively short period of time.
  • the catalyst metal may be cooled inside the chamber or may be cooled outside the chamber after the catalyst metal is carried out of the chamber after operation S1030.
  • a carrier member (not shown) may be stacked on graphene, and the catalyst metal may be removed via etching.
  • the carrier member may be polydimethylsiloxane (PDMS), for example.
  • Graphene from which the catalyst metal is removed is transferred by the carrier member and may be transferred to a target substrate (not shown).
  • the target substrate may be polyethyleneterephthalate (PET), for example.
  • defects may frequently occur, e.g., crystallinity and directivity of graphene may change at boundaries between grains or bonds between carbon atoms constituting graphene may be cut. Crystallinity and directivity of graphene affect movement of electrons. Therefore, if crystallinity and directivity of graphene change, flow of electrons is interfered with, and thus surface resistance of the graphene increases. Flow of electrons is also interfered with by defects occurring around boundaries between grains, and thus surface resistance of the graphene increases.
  • high-quality graphene may be synthesized by increasing sizes of grains of the catalyst metal.
  • grains are densely arranged within the predetermined portion X before a catalyst metal is heated.
  • a number of grains within the same portion X decreases.
  • FIG. 13 is a graph showing surface resistance characteristics of graphene synthesized using a method of synthesizing graphene according to an embodiment of the present invention.
  • An embodiment A is an embodiment in which catalyst metal is loaded in the vertical direction, whereas an embodiment B is an embodiment in which catalyst metal is loaded in the horizontal direction.
  • the case in which the catalyst metal is loaded in the vertical direction features superior surface resistance characteristics.
  • the reason for this is that, when the catalyst metal is loaded in the vertical direction, grains of the catalyst metal are not only heated in the operation S1020, but are also affected by gravity. In other words, when sizes of grains of the catalyst metal increase as grains adjacent to each other merge with each other, gravity works on the grains, and thus sizes of grains further increase. As a result, an environment for synthesizing high-quality graphene may be provided.
  • a large quantity of high-quality graphene may be synthesized simply by increasing sizes of grains of catalyst metals.

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Abstract

L'invention porte sur un procédé et un appareil pour la synthèse de graphène. Le procédé comprend le chargement de métaux catalyseurs dans une chambre dans la direction horizontale ou la direction verticale ; l'augmentation des tailles de grains des métaux catalyseurs par chauffage des métaux catalyseurs ; l'élévation de la température à l'intérieur de la chambre avec apport simultané d'une source de carbone sous forme vapeur aux métaux catalyseurs ; et la formation de graphène par refroidissement des métaux catalyseurs.
PCT/KR2012/000690 2011-01-31 2012-01-30 Procédé et appareil pour la fabrication de graphène Ceased WO2012105777A2 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103121670A (zh) * 2013-02-19 2013-05-29 西安交通大学 远程等离子体增强原子层沉积低温生长石墨烯的方法
US20150368109A1 (en) * 2012-08-30 2015-12-24 Lg Electronics Inc. Method for manufacturing graphene, said graphene, and apparatus for manufacturing same
CN112938945A (zh) * 2021-01-29 2021-06-11 北京石墨烯技术研究院有限公司 Cvd制石墨烯装置及石墨烯薄膜的制备方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004060800A1 (fr) * 2002-12-27 2004-07-22 Bussan Nanotech Research Institute Inc. Procede et appareil de production d'un nanotube de carbone a paroi unique
KR20090026568A (ko) * 2007-09-10 2009-03-13 삼성전자주식회사 그라펜 시트 및 그의 제조방법
KR100923304B1 (ko) * 2007-10-29 2009-10-23 삼성전자주식회사 그라펜 시트 및 그의 제조방법
KR101344493B1 (ko) * 2007-12-17 2013-12-24 삼성전자주식회사 단결정 그라펜 시트 및 그의 제조방법

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150368109A1 (en) * 2012-08-30 2015-12-24 Lg Electronics Inc. Method for manufacturing graphene, said graphene, and apparatus for manufacturing same
US9764956B2 (en) * 2012-08-30 2017-09-19 Lg Electronics Inc. Method for manufacturing graphene, said graphene, and apparatus for manufacturing same
CN103121670A (zh) * 2013-02-19 2013-05-29 西安交通大学 远程等离子体增强原子层沉积低温生长石墨烯的方法
CN103121670B (zh) * 2013-02-19 2015-04-29 西安交通大学 远程等离子体增强原子层沉积低温生长石墨烯的方法
CN112938945A (zh) * 2021-01-29 2021-06-11 北京石墨烯技术研究院有限公司 Cvd制石墨烯装置及石墨烯薄膜的制备方法
CN112938945B (zh) * 2021-01-29 2023-03-07 北京石墨烯技术研究院有限公司 Cvd制石墨烯装置及石墨烯薄膜的制备方法

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