WO2011105530A1 - 炭素膜積層体 - Google Patents
炭素膜積層体 Download PDFInfo
- Publication number
- WO2011105530A1 WO2011105530A1 PCT/JP2011/054243 JP2011054243W WO2011105530A1 WO 2011105530 A1 WO2011105530 A1 WO 2011105530A1 JP 2011054243 W JP2011054243 W JP 2011054243W WO 2011105530 A1 WO2011105530 A1 WO 2011105530A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- single crystal
- graphene
- copper
- substrate
- thin film
- Prior art date
Links
Images
Classifications
-
- 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
- C23C16/0281—Deposition of sub-layers, e.g. to promote the adhesion of the main coating of metallic sub-layers
-
- 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
-
- 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
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- 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
- C01B32/19—Preparation by exfoliation
-
- 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
- C01B32/50—Carbon dioxide
-
- 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
- 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
- C30B29/04—Diamond
-
- 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
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/20—Aluminium oxides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
Definitions
- the present invention relates to a large-area carbon film laminate for use in electronic devices, transparent conductive films, and the like.
- Graphene which is a planar single-layer carbon film with SP2-bonded carbon atoms, has high electrical conductivity and light transmittance, which can be said to be unique, and as a base material for ultra-high performance electronic devices and transparent conductive thin films. Use is expected. So far, graphene formation methods such as exfoliation from natural graphite, silicon desorption by high-temperature heat treatment of silicon carbide, and various metal surface formation methods have been developed.
- Non-Patent Documents 1 and 2 a method of forming single to several layers of graphene by chemical vapor deposition (CVD) on the copper foil surface has recently been developed (Non-Patent Documents 1 and 2).
- the graphene film formation method using copper foil as a base material is based on thermal CVD.
- methane gas which is a raw material gas, is thermally decomposed at about 1000 ° C. to form a single layer to several layers of graphene on the surface of the copper foil.
- methane gas which is a raw material gas
- the maximum crystal size of graphene obtained by a synthesis method using a copper foil as a base material is currently several tens of ⁇ m.
- graphene having a crystal size as large as possible is required, and increasing the crystal size is a problem.
- Xuesong Li Weiwei Cai, Jinho An, Seyoung Kim, Junghyo Nah, Dongxing Yang, Richard Piner, Aruna Velamakanni, Inhwa Jung, Emanuel Tutuc, Sanjay K. , Pp.1312-1314.
- Xuesong Li Yanwu Zhu, Weiwei Cai, Mark Borysiak, Boyang Han, David Chen, Richard D. Piner, Luigi Colombo, Rodney S. Ruoff, Nano Letters, Vol. 9, 363, 2009.
- the present invention has been made in view of the above circumstances, and solves the problem of small crystal size, which is a problem of graphene film formation by thermal CVD using a conventional copper foil as a substrate.
- An object of the present invention is to provide a carbon film laminate in which graphene having a large crystal size is formed.
- the present inventors have found a new method for obtaining a carbon film laminate in which graphene having a large crystal size is formed, whereby graphene is compared with the conventional method. It has been found that it can be formed in a remarkably large area and can solve the above-mentioned problems in the prior art.
- a carbon film laminate comprising a single crystal substrate, a copper (111) single crystal thin film formed by epitaxial growth on the substrate, and graphene deposited on the copper (111) single crystal thin film.
- the single crystal substrate is a sapphire (0001) single crystal substrate having a flat surface at an atomic level and a surface composed of atomic layer steps, or a diamond having a surface composed of a flat terrace surface and atomic layer steps at an atomic level.
- the crystal size is much larger than the conventional ( 10mm class) graphene can be created.
- This facilitates the creation of ultra-high performance electronic devices such as graphene transistors that have been developed using several tens of ⁇ m of graphene.
- integration of ultra-high performance devices is possible, and graphene devices with various functions can be created.
- Carbon film laminate comprising the sapphire (0001) single crystal substrate of the present invention, a copper (111) single crystal thin film formed by epitaxial growth on the substrate, and graphene deposited on the copper (111) single crystal thin film The schematic diagram which shows the laminated structure.
- region of 150 micrometers square, white observes I (2D) / I (G)> 2, black observes I (2D) / I (G) ⁇ 2 or D band Indicates the region that was created.
- Carbon film laminate 12 Sapphire (0001) single crystal substrate 14: Copper (111) single crystal thin film 16: Graphene
- Graphene is a planar single-layer carbon film composed of SP2 bonded carbon atoms.
- Graphene is described in detail in Non-Patent Document 1.
- the carbon film laminate in which graphene having a large crystal size according to the present invention is formed is mainly based on employing specific manufacturing conditions.
- the carbon film stack in which graphene with a large crystal size is formed uses a copper (111) single crystal thin film formed by epitaxial growth on a sapphire (0001) single crystal substrate with good flatness as a base material for graphene synthesis. .
- graphene was formed by thermal CVD using a copper foil base material by the methods disclosed in Non-Patent Document 1 and Non-Patent Document 2. Since the copper foil is polycrystalline, its surface is divided into regions having different plane orientations. Then, it was measured how the graphene formed by Raman spectroscopy was distributed on the copper foil surface. Further, the crystallographic plane orientation distribution on the copper foil surface was measured by backscattered electron diffraction (EBPS). From these measurements, it was found that graphene was deposited in the copper (111) plane and copper (100) plane regions, preferably in the copper (111) plane region on the copper foil surface.
- EBPS backscattered electron diffraction
- a single-crystal copper thin film having a crystallographic (111) surface (hereinafter referred to as “copper (111) single-crystal thin film”) for the formation of graphene with a large crystal size. Prepared. Through experiments of single crystal growth of copper on various substrates, the inventors have found that a copper (111) single crystal thin film is epitaxially grown on a single crystal substrate by film formation by magnetron sputtering.
- a copper (111) single crystal thin film formed by epitaxial growth on a sapphire (0001) single crystal substrate and a graphene deposited on the copper (111) single crystal thin film A carbon film laminate comprising:
- a copper (111) single crystal thin film is preferable for film formation of graphene having a large crystal size. Since graphene is a two-dimensional crystal of one carbon atom layer, the crystal size is considered to be greatly influenced by the flatness of the copper (111) single crystal thin film surface. Therefore, in the present invention, a sapphire (0001) single crystal substrate having a flat surface at the atomic level and a surface composed of atomic layer steps is used as a substrate for epitaxial growth of a copper (111) single crystal thin film.
- FIG. 1 is an atomic force microscope image (2 ⁇ m square region) of the surface of the sapphire (0001) single crystal substrate.
- a sapphire (0001) single crystal substrate having a flat terrace surface at the atomic level and a surface composed of atomic layer steps is used as a substrate for epitaxial growth of a copper (111) single crystal thin film.
- substrate is a single crystal substrate having a flat surface at an atomic level and a surface composed of atomic layer steps.
- FIG. 2-1 is a schematic diagram showing a cross section of a crystal surface having irregularities that are not normally flat.
- FIGS. 2-2 and 2-3 are a schematic view showing a cross section of a flat crystal surface composed of a flat terrace surface and atomic layer steps at the atomic level and a schematic view seen from above, respectively.
- the broken line (---) indicates the actual inclination of the surface
- the one-dot broken line (-----) indicates the crystal orientation of the crystallographic surface.
- the terrace has a width determined by the angle ⁇ formed by the crystallographic surface crystal orientation (-----) and the actual surface inclination (---).
- ⁇ formed by the crystallographic surface crystal orientation (-----) and the actual surface inclination (---).
- a carbon film stack including graphene deposited on a single crystal thin film was formed, and graphene with a large crystal size was obtained. Details of the examples will be described below, but the present invention is not limited to these examples.
- FIG. 3 is a schematic view showing a carbon film laminate according to the present invention.
- the carbon film laminate 10 includes a sapphire (0001) single crystal substrate 12, a copper (111) single crystal thin film 14 formed by epitaxial growth on the substrate 12, and a graphene deposited on the copper (111) single crystal thin film. 16.
- a DC magnetron sputtering method was used for epitaxial growth of a copper (111) single crystal thin film on a sapphire (0001) single crystal substrate.
- a sapphire (0001) single crystal substrate was placed on a substrate stage that was placed in a sputtering apparatus and capable of heating the substrate.
- the detailed specifications of the sapphire (0001) single crystal substrate are as follows. Manufacturer / Seller: Shinkosha Co., Ltd.
- the film forming substrate was heated to 100 ° C. and held. Thereafter, a film was formed at a gas pressure of 1.3 ⁇ 10 ⁇ 1 Pa and a power of 100 W to form a copper (111) single crystal thin film having a thickness of 1 ⁇ m on the sapphire (0001) single crystal substrate.
- Detailed film forming conditions are as follows.
- Vapor deposition material Copper (Purity 99.99% or more) Pre-exhaust: 2.0 ⁇ 10 ⁇ 4 Pa Discharge gas: Argon (purity 99.999%) Discharge power: 100W (constant power mode) Discharge current: 370 to 380 mA Discharge voltage: 338-340V Discharge gas pressure: 1.3 ⁇ 10 ⁇ 1 Pa Discharge time: 28 minutes 6 seconds Setting film thickness: 1000 nm Substrate temperature: approx. 100 ° C. (measured substrate holder measured during film formation: 106-113 ° C.)
- the X-ray diffractometer used was Rigaku Co., Ltd.
- X-ray diffractometer RINT2100-XRD-DSCII and the goniometer was a Rigaku Ultima III horizontal goniometer.
- a multipurpose sample stand for thin film standard is attached to this goniometer.
- X-ray diffraction measurement was performed with the copper thin film having a thickness of 1 ⁇ m prepared by the above-described method attached to the sapphire (0001) single crystal substrate.
- a copper (Cu) K ⁇ 1 line was used as the X-ray.
- the applied voltage and current of the X-ray tube were 40 kV and 40 mA.
- a scintillation counter was used as the X-ray detector.
- the sample surface is irradiated with X-rays at an angle ⁇
- the X-ray detector is placed at a position twice the angle ⁇ (2 ⁇ ) from the direction of the irradiated X-rays, and the 2 ⁇ angle is set to 40 ° to 100 °.
- This measurement method is generally called 2 ⁇ - ⁇ measurement, and detects X-ray reflection by a crystal plane parallel to the sample surface.
- the computer program used for the measurement is RINT2000 / PC software Windows (registered trademark) version manufactured by Rigaku Corporation.
- Fig. 4 shows the measured X-ray diffraction spectrum.
- the X-ray used is a copper (Cu) K ⁇ 1 line. It can be seen that there is a clear peak at 2 ⁇ of 43.4 °. This peak is due to the (111) reflection of copper. There is also a weak peak at 25.4 at 95.4 °, which is due to the (222) reflection of copper. If this copper thin film has (200) and (220) plane components parallel to the surface, peaks are observed at 2 ⁇ of 50.6 ° and 74.3 °, respectively. It was not observed at all. From the above, it was clarified that this copper thin film was composed of crystals with a (111) plane parallel to the surface and was a (111) single crystal. Thus, it was confirmed that the copper (111) single crystal thin film was epitaxially grown on the sapphire (0001) single crystal substrate.
- graphene is formed by thermal CVD on the surface of a copper (111) single crystal thin film formed by epitaxial growth on a sapphire (0001) single crystal substrate.
- a sapphire (0001) single crystal substrate as shown in FIG. 3, a copper (111) single crystal thin film formed by epitaxial growth on the substrate, and graphene deposited on the copper (111) single crystal thin film are provided.
- a carbon film laminate was obtained.
- an infrared gold image furnace capable of performing rapid heating and cooling of a sample and precise temperature control was used (hereinafter referred to as a heating furnace).
- the heating furnace used was ULVAC-RIKO MINI-LAMP-ANNEALER “MILA3000-PN”.
- the film formation was performed according to the following procedure.
- a copper (111) single crystal thin film (hereinafter referred to as “base material”) prepared by epitaxial growth on a sapphire (0001) single crystal substrate was placed on the quartz sample stage of the heating furnace together with the sapphire substrate.
- the heating furnace was closed and preliminary vacuum evacuation was performed to 3 ⁇ 10 ⁇ 4 Pa or less.
- Hydrogen gas was flowed at 2 SCCM, and the pressure in the heating furnace was maintained at 5.3 Pa.
- Heating was started in this state, and the temperature of the substrate was raised from room temperature to 1000 ° C. over 5 minutes.
- the time required for the termination procedure was 10 seconds or less.
- the heated substrate was cooled while the inside of the heating furnace was evacuated and kept at a pressure of 1 ⁇ 10 ⁇ 3 Pa or less.
- the time required for cooling to 300 ° C. after the heating was completed was about 6 minutes, and the time required for cooling to 100 ° C. was about 19 minutes.
- the vacuum exhaust was stopped, and then air was introduced into the heating furnace to take out the film-formed substrate.
- a carbon film laminate comprising the sapphire (0001) single crystal substrate of the present invention, a copper (111) single crystal thin film formed by epitaxial growth on the substrate, and graphene deposited on the copper (111) single crystal thin film.
- Raman spectroscopy was performed to evaluate the quality of graphene.
- FIG. 5 shows the measured Raman scattering spectrum of graphene.
- the measuring device is an XploRA type machine manufactured by HORIBA, Ltd.
- the excitation laser wavelength is 632 nm
- the laser beam spot size is 1 micron in diameter
- the spectroscope grating is 600
- the measurement time is 5 seconds. Is accumulated.
- the measurement was performed with the graphene attached to the copper (111) single crystal thin film on the sapphire (0001) single crystal substrate.
- FIG. 5 Raman shift over a smooth background and around 2670cm -1, respectively distinct peaks in 1590 cm -1 was observed.
- the peak around 1590 cm ⁇ 1 is due to a normal six-membered ring of carbon and is called the G band.
- the peak near 2670 cm ⁇ 1 is due to the overtone of the G band and is generally called the 2D band.
- the gentle background is due to the fluorescence of the copper thin film of the substrate.
- a peak may be observed in the vicinity of 1358 cm ⁇ 1 , which is due to a defect of a normal six-membered ring of carbon and is called a D band.
- FIG. 5 shows no peak of the D band, and thus graphene prepared by the method of the present invention is a film having good crystallinity with few defects.
- the number of graphene layers constituting the film can be identified by the intensity ratio between the 2D band and the G band of the Raman spectrum of graphene (see Non-Patent Document 1 above).
- Non-Patent Document 1 when the ratio of the intensity I (2D) of the 2D band to the intensity I (G) of the G band is I (2D) / I (G) ⁇ 2, the film is 1 It is supposed to be composed of one or two layers of graphene.
- the 2D band and G band peaks in FIG. 5 were fitted by subtracting the respective backgrounds, and the peak area was calculated to obtain the intensity ratio.
- I (2D) / I (G) 3.27. It was. Therefore, it was found that the region where the Raman measurement was performed (the region having a diameter of 1 micron which is the spot size of the laser beam for measurement) is graphene.
- the 150 ⁇ m square area is filled with a 150 ⁇ m square area in steps of 1 ⁇ m, which is the size of the laser beam spot. Measurements were made.
- FIG. 7 shows the results of this measurement.
- I (2D) / I (G) ⁇ 2 and in the black region, I (2D) / I (G) ⁇ 2 or D band was observed.
- I (2D) / I (G) ⁇ 2 in almost the entire measurement region of 150 ⁇ m square (18840 points out of all 22801 measurement points), and graphene is formed in almost the entire region of 150 ⁇ m square. I understood. Therefore, it was found that the carbon film laminate of the present invention has a graphene region of 150 ⁇ m square or more.
- FIG. 8 shows the result of this measurement.
- I (2D) / I (G) ⁇ 2 and in the black area, I (2D) / I (G) ⁇ 2 or D band was observed.
- I (2D) / I (G) ⁇ 2 in almost all measurement areas of 10 mm square (2131 points out of all 2601 measurement points), and graphene is formed on almost the entire 10 mm square. all right.
- the sapphire (0001) single crystal substrate of the present invention As described above, the sapphire (0001) single crystal substrate of the present invention, the copper (111) single crystal thin film formed by epitaxial growth on the substrate, and the graphene deposited on the copper (111) single crystal thin film are provided. Compared with the conventional thermal CVD synthesis of graphene using a copper foil, it became possible to obtain graphene with a significantly larger crystal size by the carbon film laminate. In the carbon film laminate of the present invention, graphene deposited on the surface of the copper (111) single crystal thin film can be separated from the copper (111) single crystal thin film to obtain graphene having a large crystal size. it can.
Abstract
Description
この銅箔を基材とする手法では銅の表面の特性を利用し、従来のニッケルなど他の金属を用いる手法と比較して、グラフェンを制御性よく合成することが可能である。一方、銅箔を基材として用いた合成手法で得られるグラフェンの結晶サイズは今のところ数十μmが最大である。グラフェンを高性能電子デバイスなどの材料として利用するためには、できるだけ大きな結晶サイズのグラフェンが求められており、結晶サイズの拡大が課題となっている。
[1]単結晶基板と、該基板上にエピタキシャル成長させて形成された銅(111)単結晶薄膜と、該銅(111)単結晶薄膜上に堆積されたグラフェンとを備える炭素膜積層体。
[2]前記単結晶基板は、サファイア(0001)単結晶基板又はダイヤモンド(111)単結晶基板であることを特徴とする上記[1]の炭素膜積層体。
[3]前記単結晶基板は、原子レベルで平坦なテラス面と原子層ステップからなる表面を有するサファイア(0001)単結晶基板又は原子レベルで平坦なテラス面と原子層ステップからなる表面を有するダイヤモンド(111)単結晶基板であることを特徴とする上記[1]の炭素膜積層体。
[4]前記グラフェンは、減圧下で水素ガス及びメタンガスを用いて熱CVD法により形成したものであることを特徴とする上記[1]~[3]のいずれかの炭素膜積層体。
[5]単結晶基板にエピタキシャル成長させて形成された銅(111)単結晶薄膜上に堆積されたものであることを特徴とするグラフェン。
[6]減圧下で水素ガス及びメタンガスを用いて熱CVD法により形成されたものであることを特徴とする上記[5]のグラフェン。
[7]前記銅(111)単結晶薄膜から剥離して得られる上記[5]又は[6]に記載のグラフェン。
12:サファイア(0001)単結晶基板
14:銅(111)単結晶薄膜
16:グラフェン
以上の結果から、結晶サイズの大きなグラフェンを作成するためには、銅(111)面の領域をもつ銅表面を成膜の基材として使用する。したがって、大面積のグラフェンの成膜には、結晶学的な(111)面をもつ単結晶の銅を用いることが好ましい。
きわめて良好な表面平坦性が出現すると、図2-2、図2-3に示すように、原子レベルで平坦なテラスと原子層の高さの段差、すなわち原子層ステップが周期的に表れる。テラスは結晶学的な表面の結晶方位(-・-・-)と実際の表面の傾斜(---)とのなす角度θによって決まる幅をもつ。このような表面を原子間力顕微鏡で観察すると図1のような縞模様のコントラストを得る。
以下に実施例の詳細について述べるが、本発明はこの実施例に限定されるものではない。
サファイア(0001)単結晶基板の詳細なスペックは以下のとおりである。
製造・販売元:株式会社信光社(http://www.shinkosha.com/index.html)
品名:サファイアSTEP基板
材質:Al2O3(サファイア)
面方位:(0001)
大きさ:10mm×10mm×厚さ0.5mm
研磨:片面
面方位公差:0.3°以下
平行度:幅10mmの基材の端と端で0.020mm以下
平坦度:光学的な測定限界以下
表面形状:原子レベルで平坦なテラス面と原子層ステップ(図1参照)
蒸着材料:銅(純度99.99%以上)
予備排気:2.0×10-4Pa
放電気体:アルゴン(純度99.999%)
放電電力:100W(定電力モード)
放電電流:370~380mA
放電電圧:338~340V
放電気体圧力:1.3×10-1Pa
放電時間:28分6秒
設定膜厚:1000nm
基板温度:約100℃(成膜時基板ホルダー実測値で106~113℃)
熱CVDに必要な加熱装置には、試料の急速加熱冷却と温度の精密制御を行うことが可能な、赤外線ゴールドイメージ炉を用いた(以下、加熱炉という)。使用した加熱炉はアルバック理工株式会社製MINI-LAMP-ANNEALER「MILA3000-P-N」であった。
成膜は以下の手順で行った。
(1)サファイア(0001)単結晶基板にエピタキシャル成長させて作成した銅(111)単結晶薄膜(以下、「基材」と呼ぶ)をサファイア基板ごと加熱炉の石英製サンプルステージに乗せた。
(2)加熱炉を閉め、3×10-4Pa以下まで予備真空排気した。
(3)水素ガスを2SCCM流し、加熱炉内の圧力を5.3Paに保った。
(4)この状態で加熱を開始し、基材の温度を室温から1000℃まで5分間かけて上昇させた。
(5)基材の温度が1000℃に達したと同時に、温度を1000℃に保ちながら、水素ガス2SCCMに加えてメタンガス35SCCM流し、圧力を5.3Paから66.5Paに上昇させた。圧力を上昇するのに1分20秒ほど時間を要した。
(6)温度1000℃、水素ガス2SCCM、メタンガス35SCCM、圧力66.5Paを維持し、グラフェンの成膜を行った。成膜時間は20分間であった。
(7)上記状態を20分間保って成膜を行った後、成膜を終了した。終了の手順は、メタンガスを止める→水素ガスを止める→真空排気をスタート→加熱ストップ、で行った。終了手順に要した時間は10秒以下であった。
(8)加熱炉内を真空排気して1×10-3Pa以下の圧力に保ちながら、成膜済みの基材を冷却した。加熱を終了してから300℃まで冷却するのに要した時間はおよそ6分、100℃まで冷却するのに要した時間はおよそ19分であった。
(9)成膜済みの基材が100℃以下に冷却されたのを確認し、真空排気を停止、その後加熱炉に空気を導入して成膜済みの基材を取り出した。
図5の2DバンドとGバンドのピークをそれぞれのバックグラウンドを差し引いてフィッティングし、ピークの面積を算出して強度比を求めたところ、I(2D)/I(G)=3.27であった。したがって、このラマン測定を行った領域(測定用レーザービームのスポットサイズである直径1ミクロンの領域)はグラフェンであることがわかった。
また、本発明の炭素膜積層体において、銅(111)単結晶薄膜の表面に堆積されたグラフェンを、該銅(111)単結晶薄膜から剥離することにより、結晶サイズの大きなグラフェンを得ることができる。
Claims (7)
- 単結晶基板と、該基板上にエピタキシャル成長させて形成された銅(111)単結晶薄膜と、該銅(111)単結晶薄膜上に形成されたグラフェンとを備える炭素膜積層体。
- 前記単結晶基板は、サファイア(0001)単結晶基板又はダイヤモンド(111)単結晶基板であることを特徴とする請求項1に記載の炭素膜積層体。
- 前記単結晶基板は、原子レベルで平坦なテラス面と原子層ステップからなる表面を有するサファイア(0001)単結晶基板又は原子レベルで平坦なテラス面と原子層ステップからなる表面を有するダイヤモンド(111)単結晶基板であることを特徴とする請求項1に記載の炭素膜積層体。
- 前記グラフェンは、減圧下で水素ガス及びメタンガスを用いて熱CVD法により形成したものであることを特徴とする請求項1~3のいずれか1項に記載の炭素膜積層体。
- 単結晶基板にエピタキシャル成長させて形成された銅(111)単結晶薄膜上に堆積されたものであることを特徴とするグラフェン。
- 減圧下で水素ガス及びメタンガスを用いて熱CVD法により形成されたものであることを特徴とする請求項5に記載のグラフェン。
- 前記銅(111)単結晶薄膜から剥離して得られる請求項5又は6に記載のグラフェン。
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201180020414.5A CN102859032B (zh) | 2010-02-26 | 2011-02-25 | 碳膜叠层体 |
US13/580,468 US9074278B2 (en) | 2010-02-26 | 2011-02-25 | Carbon film laminate |
JP2012501871A JP5569825B2 (ja) | 2010-02-26 | 2011-02-25 | 炭素膜積層体 |
EP11747486.6A EP2540862B1 (en) | 2010-02-26 | 2011-02-25 | Carbon film laminate |
KR1020127025248A KR101472948B1 (ko) | 2010-02-26 | 2011-02-25 | 탄소막 적층체 |
ES11747486.6T ES2615730T3 (es) | 2010-02-26 | 2011-02-25 | Laminado de película de carbono |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010-041419 | 2010-02-26 | ||
JP2010041419 | 2010-02-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011105530A1 true WO2011105530A1 (ja) | 2011-09-01 |
Family
ID=44506928
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/054243 WO2011105530A1 (ja) | 2010-02-26 | 2011-02-25 | 炭素膜積層体 |
Country Status (7)
Country | Link |
---|---|
US (1) | US9074278B2 (ja) |
EP (1) | EP2540862B1 (ja) |
JP (1) | JP5569825B2 (ja) |
KR (1) | KR101472948B1 (ja) |
CN (1) | CN102859032B (ja) |
ES (1) | ES2615730T3 (ja) |
WO (1) | WO2011105530A1 (ja) |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013107789A (ja) * | 2011-11-21 | 2013-06-06 | Jx Nippon Mining & Metals Corp | グラフェン製造用銅箔及びグラフェンの製造方法 |
JP2013107036A (ja) * | 2011-11-21 | 2013-06-06 | Jx Nippon Mining & Metals Corp | グラフェン製造用銅箔及びグラフェンの製造方法 |
JP2014037336A (ja) * | 2012-08-16 | 2014-02-27 | Jx Nippon Mining & Metals Corp | グラフェン製造用圧延銅箔、及びグラフェンの製造方法 |
US8778782B2 (en) | 2010-11-29 | 2014-07-15 | IHP GmbH—Innovations for High Performance Microelectronics | Fabrication of graphene electronic devices using step surface contour |
WO2014128834A1 (ja) * | 2013-02-19 | 2014-08-28 | Jx日鉱日石金属株式会社 | グラフェン製造用銅箔及びグラフェンの製造方法 |
WO2014128833A1 (ja) * | 2013-02-19 | 2014-08-28 | Jx日鉱日石金属株式会社 | グラフェン製造用銅箔及びグラフェンの製造方法 |
JPWO2012165548A1 (ja) * | 2011-06-02 | 2015-02-23 | Jx日鉱日石金属株式会社 | グラフェン製造用銅箔、及びグラフェンの製造方法 |
US20150079342A1 (en) * | 2013-01-14 | 2015-03-19 | California Institute Of Technology | Method and system for graphene formation |
CN104603052A (zh) * | 2012-08-30 | 2015-05-06 | Lg电子株式会社 | 制造石墨烯的方法、所述石墨烯及制造所述石墨烯的设备 |
JP2015515082A (ja) * | 2012-02-13 | 2015-05-21 | タイコ・エレクトロニクス・コーポレイションTyco Electronics Corporation | 電気導体の製造方法 |
CN104975344A (zh) * | 2015-07-09 | 2015-10-14 | 中国科学院上海微***与信息技术研究所 | 基于氧化亚铜薄膜衬底低成核密度石墨烯单晶的制备方法 |
WO2015190739A1 (ko) * | 2014-06-09 | 2015-12-17 | 한양대학교 산학협력단 | 수소 원자 또는 수소 이온을 함유하는 단결정 금속막 및 그 제조방법 |
US9399581B2 (en) | 2012-03-30 | 2016-07-26 | Isis Innovation Limited | Process for producing two-dimensional nanomaterials |
WO2017034018A1 (ja) * | 2015-08-26 | 2017-03-02 | 並木精密宝石株式会社 | グラフェン膜、複合体、それらの製造方法、及び単結晶サファイア基板 |
KR101767242B1 (ko) * | 2014-06-09 | 2017-08-10 | 한양대학교 산학협력단 | 수소 원자 또는 수소 이온을 함유하는 단결정 금속막 및 그 제조방법 |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103924207B (zh) * | 2013-01-10 | 2017-04-19 | 中国科学院上海微***与信息技术研究所 | 一种增强泡沫铜在较高温度下抗氧化能力的方法 |
WO2014189271A1 (ko) * | 2013-05-21 | 2014-11-27 | 한양대학교 산학협력단 | 대면적의 단결정 단일막 그래핀 및 그 제조방법 |
WO2015126139A1 (en) * | 2014-02-19 | 2015-08-27 | Samsung Electronics Co., Ltd. | Wiring structure and electronic device employing the same |
KR101541517B1 (ko) * | 2014-03-26 | 2015-08-03 | 부산대학교 산학협력단 | 단결정 구리를 이용한 나노 망사 다층 구조의 투명전극 및 그 제조방법 |
CN103943601A (zh) * | 2014-05-09 | 2014-07-23 | 浙江大学 | 一种具有铜-石墨烯复相的互连线及其制备方法 |
CN104045079A (zh) * | 2014-06-25 | 2014-09-17 | 无锡格菲电子薄膜科技有限公司 | 在蓝宝石与外延金属界面外延生长石墨烯的方法 |
KR101629697B1 (ko) | 2014-10-14 | 2016-06-13 | 한국화학연구원 | 그래핀 적층 구조체의 제조방법 및 이로 제조된 그래핀 적층 구조체 |
CN104576862B (zh) * | 2014-12-24 | 2017-08-25 | 江苏巨晶新材料科技有限公司 | 一种基于铜衬底的氮化物led垂直芯片及其制备方法 |
KR101704723B1 (ko) | 2015-04-06 | 2017-02-09 | 연세대학교 산학협력단 | 탄소 박막 소자 및 이의 제조 방법 |
GB201514542D0 (en) | 2015-08-14 | 2015-09-30 | Thomas Simon C S | A method of producing graphene |
CN106584976A (zh) * | 2016-08-10 | 2017-04-26 | 上海交通大学 | 一种高导电石墨烯/铜基层状复合材料及其制备方法 |
FR3062398B1 (fr) | 2017-02-02 | 2021-07-30 | Soitec Silicon On Insulator | Procede de fabrication d'un substrat pour la croissance d'un film bidimensionnel de structure cristalline hexagonale |
WO2020053102A1 (en) | 2018-09-10 | 2020-03-19 | Centre National De La Recherche Scientifique | Process for preparing single-crystal thin films |
KR102170111B1 (ko) * | 2018-12-18 | 2020-10-26 | 한양대학교 산학협력단 | 다결정 금속 필름의 비정상입자성장에 의한 단결정 금속 필름 및 그 제조방법 |
CN109811306A (zh) * | 2019-02-27 | 2019-05-28 | 台州学院 | 一种与基体表面具有垂直取向关系的碳涂层材料 |
KR102443562B1 (ko) * | 2020-11-11 | 2022-09-16 | 광주과학기술원 | 그래핀올 화합물 및 그래핀올 합성 방법 |
CN114604860B (zh) * | 2022-03-15 | 2023-10-03 | 北京石墨烯技术研究院有限公司 | 石墨烯薄膜生长基底及其制备方法和应用 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009143799A (ja) * | 2007-12-17 | 2009-07-02 | Samsung Electronics Co Ltd | 単結晶グラフェンシートおよびその製造方法 |
WO2011025045A1 (ja) * | 2009-08-31 | 2011-03-03 | 独立行政法人科学技術振興機構 | グラフェン薄膜とその製造方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7311889B2 (en) * | 2002-06-19 | 2007-12-25 | Fujitsu Limited | Carbon nanotubes, process for their production, and catalyst for production of carbon nanotubes |
US8557213B2 (en) | 2005-11-25 | 2013-10-15 | National Institute For Materials Science | Carbon nanotubes, substrate and electron emission device with such carbon nanotubes and carbon nanotube synthesizing substrate as well as methods of and apparatus for making them |
KR101019029B1 (ko) * | 2007-08-14 | 2011-03-04 | 한국과학기술연구원 | 그라핀 하이브리드 물질 및 그 제조 방법 |
US7781061B2 (en) * | 2007-12-31 | 2010-08-24 | Alcatel-Lucent Usa Inc. | Devices with graphene layers |
CN101285175B (zh) | 2008-05-29 | 2010-07-21 | 中国科学院化学研究所 | 化学气相沉积法制备石墨烯的方法 |
KR101490111B1 (ko) | 2008-05-29 | 2015-02-06 | 삼성전자주식회사 | 에피택셜 그래핀을 포함하는 적층구조물, 상기적층구조물의 형성방법 및 상기 적층구조물을 포함하는전자 소자 |
FR2937343B1 (fr) * | 2008-10-17 | 2011-09-02 | Ecole Polytech | Procede de croissance controlee de film de graphene |
US20100255984A1 (en) * | 2009-04-03 | 2010-10-07 | Brookhaven Science Associates, Llc | Monolayer and/or Few-Layer Graphene On Metal or Metal-Coated Substrates |
AU2010307229B2 (en) * | 2009-09-18 | 2016-02-25 | President And Fellows Of Harvard College | Bare single-layer graphene membrane having a nanopore enabling high-sensitivity molecular detection and analysis |
-
2011
- 2011-02-25 JP JP2012501871A patent/JP5569825B2/ja active Active
- 2011-02-25 EP EP11747486.6A patent/EP2540862B1/en not_active Not-in-force
- 2011-02-25 KR KR1020127025248A patent/KR101472948B1/ko active IP Right Grant
- 2011-02-25 US US13/580,468 patent/US9074278B2/en active Active
- 2011-02-25 WO PCT/JP2011/054243 patent/WO2011105530A1/ja active Application Filing
- 2011-02-25 CN CN201180020414.5A patent/CN102859032B/zh not_active Expired - Fee Related
- 2011-02-25 ES ES11747486.6T patent/ES2615730T3/es active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009143799A (ja) * | 2007-12-17 | 2009-07-02 | Samsung Electronics Co Ltd | 単結晶グラフェンシートおよびその製造方法 |
WO2011025045A1 (ja) * | 2009-08-31 | 2011-03-03 | 独立行政法人科学技術振興機構 | グラフェン薄膜とその製造方法 |
Non-Patent Citations (5)
Title |
---|
ARIEL ISMACH ET AL.: "Direct Chemical Vapor Deposition of Graphene on Dielectric Surfaces", NANO LETTERS, vol. 10, no. 5, 12 May 2010 (2010-05-12), pages 1542 - 1548, XP055070383 * |
LI GAO ET AL.: "Epitaxial Graphene on Cu(111)", NANO LETTERS, vol. 10, no. 9, 2 August 2010 (2010-08-02), pages 3512 - 3516, XP002695342 * |
See also references of EP2540862A4 |
XUESONG LI; WEIWEI CAI; JINHO AN; SEYOUNG KIM; JUNGHYO NAH; DONGXING YANG; RICHARD PINER; ARUNA VELAMAKANNI; INHWA JUNG; EMANUELTU, SCIENCE, vol. 324, 2009, pages 1312 - 1314 |
XUESONG LI; YANWU ZHU; WEIWEI CAI; MARK BORYSIAK; BOYANG HAN; DAVID CHEN; RICHARD D. PINER; LUIGI COLOMBO; RODNEY S. RUOFF, NANO LETTERS, vol. 9, 2009, pages 4359 - 4363 |
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8778782B2 (en) | 2010-11-29 | 2014-07-15 | IHP GmbH—Innovations for High Performance Microelectronics | Fabrication of graphene electronic devices using step surface contour |
JPWO2012165548A1 (ja) * | 2011-06-02 | 2015-02-23 | Jx日鉱日石金属株式会社 | グラフェン製造用銅箔、及びグラフェンの製造方法 |
JP2013107036A (ja) * | 2011-11-21 | 2013-06-06 | Jx Nippon Mining & Metals Corp | グラフェン製造用銅箔及びグラフェンの製造方法 |
JP2013107789A (ja) * | 2011-11-21 | 2013-06-06 | Jx Nippon Mining & Metals Corp | グラフェン製造用銅箔及びグラフェンの製造方法 |
JP2015515082A (ja) * | 2012-02-13 | 2015-05-21 | タイコ・エレクトロニクス・コーポレイションTyco Electronics Corporation | 電気導体の製造方法 |
US9399581B2 (en) | 2012-03-30 | 2016-07-26 | Isis Innovation Limited | Process for producing two-dimensional nanomaterials |
JP2014037336A (ja) * | 2012-08-16 | 2014-02-27 | Jx Nippon Mining & Metals Corp | グラフェン製造用圧延銅箔、及びグラフェンの製造方法 |
US20150368109A1 (en) * | 2012-08-30 | 2015-12-24 | Lg Electronics Inc. | Method for manufacturing graphene, said graphene, and apparatus for manufacturing same |
CN104603052A (zh) * | 2012-08-30 | 2015-05-06 | Lg电子株式会社 | 制造石墨烯的方法、所述石墨烯及制造所述石墨烯的设备 |
CN104603052B (zh) * | 2012-08-30 | 2016-09-21 | Lg电子株式会社 | 制造石墨烯的方法、所述石墨烯及制造所述石墨烯的设备 |
US9764956B2 (en) * | 2012-08-30 | 2017-09-19 | Lg Electronics Inc. | Method for manufacturing graphene, said graphene, and apparatus for manufacturing same |
US20150079342A1 (en) * | 2013-01-14 | 2015-03-19 | California Institute Of Technology | Method and system for graphene formation |
US10041168B2 (en) * | 2013-01-14 | 2018-08-07 | California Institute Of Technology | Graphene structure |
US10837102B2 (en) | 2013-01-14 | 2020-11-17 | California Institute Of Technology | Method and system for graphene formation |
WO2014128833A1 (ja) * | 2013-02-19 | 2014-08-28 | Jx日鉱日石金属株式会社 | グラフェン製造用銅箔及びグラフェンの製造方法 |
WO2014128834A1 (ja) * | 2013-02-19 | 2014-08-28 | Jx日鉱日石金属株式会社 | グラフェン製造用銅箔及びグラフェンの製造方法 |
WO2015190739A1 (ko) * | 2014-06-09 | 2015-12-17 | 한양대학교 산학협력단 | 수소 원자 또는 수소 이온을 함유하는 단결정 금속막 및 그 제조방법 |
KR101767242B1 (ko) * | 2014-06-09 | 2017-08-10 | 한양대학교 산학협력단 | 수소 원자 또는 수소 이온을 함유하는 단결정 금속막 및 그 제조방법 |
CN104975344A (zh) * | 2015-07-09 | 2015-10-14 | 中国科学院上海微***与信息技术研究所 | 基于氧化亚铜薄膜衬底低成核密度石墨烯单晶的制备方法 |
WO2017034018A1 (ja) * | 2015-08-26 | 2017-03-02 | 並木精密宝石株式会社 | グラフェン膜、複合体、それらの製造方法、及び単結晶サファイア基板 |
Also Published As
Publication number | Publication date |
---|---|
US20130052121A1 (en) | 2013-02-28 |
JP5569825B2 (ja) | 2014-08-13 |
JPWO2011105530A1 (ja) | 2013-06-20 |
EP2540862A1 (en) | 2013-01-02 |
EP2540862A4 (en) | 2015-12-09 |
ES2615730T3 (es) | 2017-06-08 |
CN102859032A (zh) | 2013-01-02 |
EP2540862B1 (en) | 2016-11-23 |
US9074278B2 (en) | 2015-07-07 |
KR101472948B1 (ko) | 2014-12-15 |
CN102859032B (zh) | 2015-01-14 |
KR20130001253A (ko) | 2013-01-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5569825B2 (ja) | 炭素膜積層体 | |
US9187824B2 (en) | Rapid synthesis of graphene and formation of graphene structures | |
Son et al. | Direct growth of graphene pad on exfoliated hexagonal boron nitride surface | |
Kang et al. | Monolayer graphene growth on sputtered thin film platinum | |
TWI828633B (zh) | 藉由電漿增強化學氣相沉積生長石墨烯奈米帶之方法 | |
Mohapatra et al. | Strictly monolayer large continuous MoS2 films on diverse substrates and their luminescence properties | |
US20120082614A1 (en) | Aa stacked graphene-diamond hybrid material by high temperature treatment of diamond and the fabrication method thereof | |
EP2851457B1 (en) | Method for manufacturing a single crystal diamond | |
Thanh Trung et al. | Direct growth of graphitic carbon on Si (111) | |
JP2011178617A (ja) | グラフェン膜の形成方法 | |
Verguts et al. | Growth of millimeter-sized graphene single crystals on Al2O3 (0001)/Pt (111) template wafers using chemical vapor deposition | |
Sun et al. | The effect of the surface energy and structure of the SiC substrate on epitaxial graphene growth | |
TWI736556B (zh) | 在鈷薄膜上磊晶成長無缺陷、晶圓級單層石墨烯 | |
WO2013003083A1 (en) | Method of growing graphene nanocrystalline layers | |
Mohanty et al. | Analyses of orientational superlattice domains in epitaxial ZnTe thin films grown on graphene and mica | |
Du et al. | Thickness-controlled direct growth of nanographene and nanographite film on non-catalytic substrates | |
Cheng et al. | Large-area epitaxial growth of MoSe2 via an incandescent molybdenum source | |
Kertész et al. | Polarized light microscopy of chemical-vapor-deposition-grown graphene on copper | |
JP2013237575A (ja) | グラフェン膜の形成方法 | |
Mannan et al. | Synthesis of Hexagonal boron carbonitride without nitrogen void defects | |
Kargin et al. | PLD grown SiC thin films on Al2O3: morphology and structure | |
Pant | Raman and Photoluminescence Studies of In-plane Anisotropic Layered Materials | |
Zhu et al. | Effective diamond deposition on Ti: sapphire with a Cr interlayer via microwave plasma chemical vapor deposition | |
Jugdersuren et al. | Hydrogenated silicene grown by plasma enhanced chemical-vapor deposition | |
Rodríguez-Villanueva et al. | Graphene Growth Directly on SiO2/Si by Hot Filament Chemical Vapor Deposition. Nanomaterials 2022, 12, 109 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180020414.5 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11747486 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012501871 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20127025248 Country of ref document: KR Kind code of ref document: A |
|
REEP | Request for entry into the european phase |
Ref document number: 2011747486 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011747486 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13580468 Country of ref document: US |