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WO2016175195A1 - Graphène, élément électronique et son procédé de fabrication - Google Patents

Graphène, élément électronique et son procédé de fabrication Download PDF

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Publication number
WO2016175195A1
WO2016175195A1 PCT/JP2016/063014 JP2016063014W WO2016175195A1 WO 2016175195 A1 WO2016175195 A1 WO 2016175195A1 JP 2016063014 W JP2016063014 W JP 2016063014W WO 2016175195 A1 WO2016175195 A1 WO 2016175195A1
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graphene
substrate
metal
carbon
main surface
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Japanese (ja)
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藤田　淳一
勝久 村上
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University of Tsukuba NUC
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University of Tsukuba NUC
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D62/00—Semiconductor bodies, or regions thereof, of devices having potential barriers
    • H10D62/80—Semiconductor bodies, or regions thereof, of devices having potential barriers characterised by the materials
    • H10D62/81—Semiconductor bodies, or regions thereof, of devices having potential barriers characterised by the materials of structures exhibiting quantum-confinement effects, e.g. single quantum wells; of structures having periodic or quasi-periodic potential variation

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  • the present invention relates to a graphene production technique, and more particularly to a technique for producing large-area and high-quality single-layer graphene at low temperatures and a technique for applying such graphene to an electronic device.
  • Graphene has various specific properties due to its ideal two-dimensional structure, such as good conductivity and high electron / hole mobility.
  • inelastic electron conductivity, spin conductivity, mechanical strength, light absorption and emission, heat conduction, and other properties have attracted attention, and are expected to be industrially applied in various fields. It is.
  • the first discovery of graphene was by Novoselov et al. This graphene was obtained by peeling pyrolytic graphite crystals with a scotch tape and transferring them to a Si substrate. Although the size of the graphene crystal is about several microns, it is characterized in that a graphene film can be easily obtained with relatively high reproducibility (Non-Patent Documents 1 and 2).
  • the silicon carbide crystal is vacuum-heated at about 2000 ° C. to evaporate the Si element on the surface (silicon sublimation), thereby forming a graphene crystal layer on the silicon carbide surface (Non-Patent Documents 3 to 7). ).
  • a graphene film is formed by growing a hydrocarbon gas as a raw material on the surface of a metal crystal such as nickel or iron by a thermal CVD method (Non-Patent Documents 8 and 9).
  • Non-patent Document 10 Non-patent Document 10
  • Non-Patent Document 11 Single-layer graphene can be obtained even at a relatively low substrate temperature of about 600 ° C.
  • the Raman scattering spectrum of the obtained graphene is 1300 cm ⁇ . A very strong D peak due to defects appearing in the vicinity of 1 is observed.
  • the substrate temperature decreases, a large amount of fine graphene nuclei are generated, and as a result, when the synthesized graphene film is viewed microscopically, grain boundaries exist at high density, which significantly reduces electron mobility. I will let you.
  • Patent Document 1 a method for producing a graphene film that can produce large-area graphene without requiring high temperature.
  • an amorphous carbon film having a diameter of, for example, several millimeters to several centimeters and a thickness of several nanometers is first synthesized as a raw material for the target graphene film.
  • an organic film such as a collodion film or a Forvar film is formed as a raw material for the amorphous carbon film, and the organic film is scooped with a ceramic ring such as alumina, and the organic film is stretched on the ceramic ring.
  • the organic film is carbonized in an amorphous state by vacuum heat treatment to synthesize an amorphous carbon film.
  • a ceramic ring with an organic film is vacuum-heated at 500 ° C. for 30 minutes, the organic film is decomposed and denatured into carbon.
  • the amorphous carbon film thus obtained is transferred to the surface of liquid gallium and transferred, and heat treatment is performed in a vacuum. Due to the very strong surface tension of liquid gallium, the liquid level rises in a convex shape, and the amorphous carbon film is transferred onto the convex liquid surface of the liquid gallium.
  • the amorphous carbon film is heat-treated at 1000 ° C. in a vacuum for about 10 to 30 minutes, for example, so that graphene is formed at the contact interface between the liquid gallium and the amorphous carbon film.
  • Patent Document 1 The technique of Patent Document 1 is intended to synthesize graphene at a low temperature.
  • the inventors of the present invention “from the study of the reaction process between gallium and carbon, graphitization reaction at the interface between liquid gallium and amorphous carbon. Is induced at a relatively low temperature of about 1000 ° C., and a large area of graphene can be formed. Therefore, the low temperature is not sufficient.
  • the present invention has been made in view of such problems of the conventional method, and its purpose is to produce large-area and high-quality graphene at a low temperature that could not be achieved by the conventional method. It is to provide technology to do.
  • the graphene production method made in view of the above-described problems includes a first step of forming a carbon six-membered ring production nucleus on the main surface of the substrate, and 2 around the production nucleus.
  • a second step of dimensionally forming a carbon six-membered ring to form a graphene film is provided, and the formation of the carbon six-membered ring in the second step is performed at a temperature of 300 ° C. or lower.
  • a gas containing a hydrocarbon is supplied in a state where a metal droplet having a melting point of 400 ° C. or lower is in contact with the main surface of the substrate, and the main surface of the substrate and the The production nuclei are formed on the contact surface with the metal.
  • the metal having a melting point of 400 ° C. or lower is at least one selected from the group consisting of gallium, indium, and gallium-indium alloy.
  • the formation nuclei in the first step are formed by previously forming amorphous carbon nuclei arranged on the main surface of the substrate by a photolithography method, and a liquid is formed on the main surface of the substrate.
  • the heat treatment is performed with gallium in contact.
  • the product nucleus formed in the first step is a carbon six-membered ring formed by a peeling method.
  • the hydrocarbon is formed in a state in which a metal having a catalytic action for graphene synthesis and having a melting point of 400 ° C. or lower is in contact with the main surface region of the substrate on which the generation nuclei are formed.
  • a gas to be contained is supplied, and the carbon six-membered ring is formed from the contact interface between the main surface of the substrate and the metal to form a graphene film.
  • a metal having a melting point lower than the formation temperature of the carbon six-membered ring is selected as the catalytic metal, and the metal droplet is in contact with the main surface region of the substrate.
  • a six-membered carbon ring is formed.
  • the metal having a melting point of 400 ° C. or lower is at least one selected from the group consisting of gallium, indium, and gallium-indium alloy.
  • the gas containing the hydrocarbon is supplied in the form of plasma.
  • the graphene production method includes a first step of forming a carbon 6-membered ring formation nucleus on the main surface of the substrate, and a graphene synthesis on the main surface of the substrate on which the generation nucleus is formed.
  • a metal having a melting point of 400 ° C. or less is brought into contact with the metal, and a gas containing hydrocarbon is supplied in a state where the metal is maintained at a temperature exceeding the melting point.
  • a second step of growing graphene on the contact interface includes a first step of forming a carbon 6-membered ring formation nucleus on the main surface of the substrate, and a graphene synthesis on the main surface of the substrate on which the generation nucleus is formed.
  • the metal having a melting point of 400 ° C. or lower is at least one selected from the group consisting of gallium, indium, and gallium-indium alloy.
  • the first step is performed by supplying a gas containing hydrocarbon in a state where the substrate is held at a temperature of 1000 ° C. or higher.
  • the gas containing the hydrocarbon in a state where a metal having a catalytic action for graphene synthesis and having a melting point of less than 1000 ° C. is in contact with the main surface of the substrate.
  • a metal having a catalytic action for graphene synthesis and having a melting point of less than 1000 ° C. is in contact with the main surface of the substrate.
  • the metal having a melting point of less than 1000 ° C. is at least one selected from the group of gallium, indium, antimony and alloys thereof.
  • the first step is performed by transferring graphite or graphene to the main surface of the substrate by a peeling method.
  • the first step is performed by patterning graphite or graphene on the main surface of the substrate by a photolithographic method.
  • the second step is performed by increasing the decomposition efficiency of the hydrocarbon gas by a plasma assist method.
  • the second step is performed at a temperature of 300 ° C. or lower, selecting gallium as the metal having a melting point of 400 ° C. or lower.
  • a third step of separating the graphene from the substrate is provided.
  • the substrate is a sapphire whose principal surface is a (0001) plane (C plane) having an absolute value of an off angle within 30 °.
  • a metal having a catalytic action for synthesizing graphene and having a melting point of 400 ° C. or lower is brought into contact with a resist pattern formed on the main surface of the substrate, and the metal exceeds the melting point.
  • the metal having a melting point of 400 ° C. or lower is at least one selected from the group of gallium, indium, and alloys thereof.
  • the graphene according to the present invention is composed of a plurality of domains composed of an assembly of carbon six-membered rings, and each of the plurality of domains has a nucleus for forming the carbon six-membered ring in the domain, and the density thereof is 1 ⁇ 10 6 cm -2 or less
  • the orientation of the carbon six-membered ring in the domain is substantially the same in the range of at least 10 ⁇ 7 cm 2 of the graphene film, and the continuous film has an area of 1 ⁇ 10 ⁇ 7 cm 2 or more.
  • a substantially monolayer film is preferably used.
  • the intensity of the peak of the D band peak and 1300 cm -1 near the G band of 1590 cm -1 vicinity found in the Raman scattering spectrum obtained from graphene ratio (G / D ratio I G / I D ) Is 3 or more.
  • the electronic device according to the present invention is an electronic device provided with the above graphene.
  • it has a channel region made of the graphene.
  • a six-membered carbon nucleus is formed in advance on the substrate, and a two-dimensional carbon six-membered ring is formed around this nucleus. This provides a low-temperature synthesis technique for large-area and high-quality single-layer graphene.
  • FIG. 1 is a diagram for explaining an example of a technique for synthesizing (manufacturing) graphene according to the present invention, in which FIG. 1 (a) is a diagram showing a configuration example of a reaction system, and FIG. 1 (b) is a process temperature sequence; It is a figure which shows the example of. SEM image (FIG. 2 (a)) of the formed nuclei formed after the first step (1050 ° C. for 5 minutes), SEM image of graphene grown after the second step (6 minutes at 400 ° C.) (FIG. 2 ( b)), SEM image of graphene grown after the second step (7 minutes at 400 ° C.) (FIG.
  • FIG. 5 is an example of an optical micrograph (FIG. 5A) of an FET experimentally produced by the present inventors using the graphene of the present invention, and its CV curve (FIG. 5B).
  • 2 is an SEM image of graphene obtained at a synthesis temperature of 200 ° C. It is a Raman scattering spectrum from graphene obtained at a synthesis temperature of 200 ° C. It is a Raman scattering spectrum from graphene obtained at a synthesis temperature of 100 ° C.
  • the metal acting as a catalyst is described as gallium.
  • the present invention does not exclude a metal having a catalytic action similar to that of gallium.
  • examples of such a metal include indium and antimony. Can be illustrated.
  • an alloy of gallium, indium, and antimony may be used as one having such a catalytic action.
  • FIG. 1 is a diagram for explaining an example of a method for synthesizing (manufacturing) graphene according to the present invention.
  • FIG. 1 (a) is a diagram showing a configuration example of a reaction system
  • FIG. FIG. 4 is a diagram showing an example of a process temperature sequence.
  • a metal having a catalytic action for synthesizing graphene and having a melting point of 1000 on the main surface of the substrate 10 inside the quartz tube 100 capable of high-frequency heating As a first step, a metal having a catalytic action for synthesizing graphene and having a melting point of 1000 on the main surface of the substrate 10 inside the quartz tube 100 capable of high-frequency heating.
  • a gas containing hydrocarbon is supplied in a state in which the metal 20 having a temperature lower than 0 ° C. is in contact, and a carbon six-membered ring production nucleus is formed on the main surface of the substrate 10 by a CVD method.
  • the generation nuclei of the carbon six-membered ring are, for example, hexagonal graphite or multilayer graphene, and the carbon that is the source of such generation nuclei is supplied to the contact interface between the substrate 10 and the metal 20 and enters the interface region. Generation nuclei will be formed.
  • the reason why the melting point of the metal 20 is less than 1000 ° C. is that the metal 20 needs to be in a liquid state in order to exert a catalytic action for the synthesis of graphene, and the formation nucleus of the carbon six-membered ring is efficiently This is because a temperature of 1000 ° C. or higher is required to form the film.
  • the generated nuclei are formed by the CVD method. Formation is performed.
  • examples of the metal having a melting point of less than 1000 ° C. include gallium (melting point 29.78 ° C.), indium (melting point 156.61 ° C.), antimony (melting point 630.74 ° C.), and the like. At least one of these metals is selected. Further, instead of these metals, an alloy of gallium, indium and antimony may be used. That is, at least one selected from the group of gallium, indium, antimony, and alloys thereof may be selected as the above-mentioned “metal having a melting point lower than 1000 ° C.”.
  • a metal having a catalytic action of rafen synthesis and having a melting point of less than 1000 ° C. is contacted with the main surface of the substrate.
  • a gas containing hydrocarbons is supplied.
  • carbon 6-membered ring nuclei may be formed on the main surface of the substrate as follows.
  • a hydrocarbon-containing gas is supplied with a metal droplet having a melting point of 400 ° C. or less in contact with the main surface of the substrate, and a carbon six-membered ring is formed on the contact surface between the main surface of the substrate and the metal. Nuclei can also be formed.
  • examples of the metal having a melting point of 400 ° C. or lower include at least one selected from the group of gallium, indium, and gallium-indium alloy.
  • amorphous carbon nuclei arranged in advance on the main surface of the substrate are formed by photolithography, and heat treatment is performed with liquid gallium in contact with the main surface of the substrate, so that the main surface of the substrate and the metal It is also possible to form a carbon 6-membered ring production nucleus on the contact surface with the.
  • a carbon six-membered ring may be formed on the main surface of the substrate by a peeling method, and this may be used as a production nucleus.
  • a carbon six-membered ring is formed two-dimensionally around the generation nuclei to form a graphene film.
  • a metal 25 having a catalytic action for synthesizing graphene and having a melting point of 400 ° C. or lower is brought into contact with the main surface of the substrate 10 after formation of the formation nucleus.
  • graphene is grown by supplying a gas containing hydrocarbon as in the first step.
  • a gas containing hydrocarbon in a state where a metal having a catalytic action for graphene synthesis and a metal having a melting point of 400 ° C. or lower is in contact with the main surface region of the substrate on which the formation nucleus is formed. And a carbon six-membered ring is formed from the contact interface between the main surface of the substrate and the metal to form a graphene film.
  • a metal having a melting point lower than the formation temperature of the carbon six-membered ring is selected as the metal having catalytic action, and the carbon six-membered ring is formed in a state where the metal droplet is in contact with the main surface region of the substrate.
  • the metal having a melting point of 400 ° C. or lower is at least one selected from the group consisting of gallium, indium, and gallium-indium alloy.
  • the gas containing hydrocarbons may be supplied in plasma form.
  • the carbon atoms constituting the graphene are supplied to the contact interface between the substrate 10 and the metal 25, and the graphene is CVD-grown around the generation nucleus in the interface region.
  • the reason for setting the melting point of the metal 25 to 400 ° C. or lower is that the metal 25 needs to be in a liquid state in order to exhibit the catalytic action of the graphene synthesis, and the purpose of the present invention is to lower the graphene synthesis temperature.
  • it is intended to synthesize graphene at a low temperature of about 400 ° C. assuming hybridization with an existing silicon device.
  • the graphene according to the present invention can be manufactured even if the processing temperature in the second step is set to a temperature exceeding 400 ° C.
  • the metal having a melting point of 400 ° C. or lower can be exemplified by gallium (melting point 29.78 ° C.) or indium (melting point 156.61 ° C.), and may be an alloy thereof.
  • the first aspect of the method for producing graphene of the present invention includes a first step of forming a carbon-membered ring production nucleus on the main surface of the substrate, and a two-dimensional carbon around the production nucleus.
  • a second step of forming a six-membered ring to form a graphene film is provided, and the formation of the carbon six-membered ring in the second step is performed at a temperature of 300 ° C. or lower.
  • a gas containing a hydrocarbon is supplied in a state where a metal droplet having a melting point of 400 ° C. or less is in contact with the main surface of the substrate, and the main surface of the substrate
  • the nuclei are formed on the contact surface between the metal and the metal.
  • the second aspect of the graphene production method of the present invention includes a first step of forming a carbon 6-membered ring formation nucleus on the main surface of the substrate, and a graphene on the main surface of the substrate on which the generation nucleus is formed.
  • a metal having a catalytic action of synthesis a metal having a melting point of 400 ° C. or less is brought into contact, and a gas containing hydrocarbon is supplied in a state where the metal is maintained at a temperature exceeding the melting point; And a second step of growing graphene on the contact interface.
  • the CVD conditions are appropriately optimized including the selection of the hydrocarbon gas species as the carbon source.
  • 5% methane (CH 4 ) gas is used as the source gas in the quartz tube 100 with 1 sccm and a purity of 6N.
  • Argon (Ar) gas is supplied at 250 sccm, and the pressure during the CVD reaction is maintained at approximately 0.5 atm. Under this condition, the partial pressure of methane is approximately 10 Pa.
  • a sapphire whose principal surface is a (0001) plane (C plane) having an absolute value of an off angle within 30 ° can be used.
  • the off-angle may be appropriately selected in consideration of the density (and terrace width) of steps that become kinks when forming nuclei.
  • the absolute value of the off angle is preferably within 30 °.
  • the inventors mainly used a C-plane sapphire substrate having an absolute off angle of 0.2 °.
  • Liquid gallium as the metal 20 (25) acting as a catalyst has low wettability with the main surface of the sapphire substrate 10. Therefore, the liquid gallium is close to the state of being “dropped on the substrate”, and the contact interface with the main surface of the substrate also maintains the “surface” property. As a result, the contact angle is in contact with the main surface of the substrate in a state where the contact angle greatly rises beyond 90 °.
  • the methane gas decomposes into hydrogen (H or H 2 ) and carbon (C) on the surface of the liquid gallium even at a very low temperature of about 100 ° C., for example.
  • hydrogen H or H 2
  • C carbon
  • gallium and carbon are totally non-solid solution, gallium atoms and carbon atoms can be bonded, so that some of the carbon atoms generated by the decomposition of methane gas are on the surface of liquid gallium. Bond with an atom.
  • the supply of carbon atoms to the contact interface with the main surface of the substrate is from the surface of the liquid gallium (including the contact interface with the main surface of the substrate). Will be made only. That is, in the method of the present invention, the supply of carbon atoms to the main surface of the substrate is substantially limited to a two-dimensional one, and the supply of three-dimensional carbon atoms is suppressed. Very advantageous for synthesis.
  • the temperature is raised to 1050 ° C. in an Ar atmosphere, methane gas is supplied, and the first step (1st step) is performed. Formation of product nuclei in the first step starts immediately after the supply of methane gas, and product nuclei with sufficient density are formed in a short time of about 5 minutes.
  • the temperature was 1050 ° C. for 5 minutes. After the reaction, formation nuclei having a hexagonal spiral structure were obtained at a density of the order of 10 5 cm ⁇ 2 .
  • the substrate 10 is rapidly cooled in the quartz tube 100, the temperature is raised again to 400 ° C., and the methane gas is supplied. Then, the second step (2nd step) is performed, and a carbon six-membered ring is grown around the graphene formation nucleus formed in the first step.
  • graphene grows even at a temperature lower than 400 ° C. (for example, 100 ° C.).
  • a temperature lower than 400 ° C. for example, 100 ° C.
  • gallium is selected as a metal having a melting point of 400 ° C. or lower
  • a high-quality monolayer is formed even at a temperature of 300 ° C. or lower.
  • Graphene can be obtained in the second area.
  • the rate at which carbon atoms diffuse on the surface of liquid gallium decreases and, as a result, the supply rate to the product nuclei decreases, so the reaction time for obtaining single-layer graphene of a given area Becomes longer. That is, the reaction time of the second step is appropriately set according to the reaction temperature and the film area of the graphene that is finally desired.
  • a technique for increasing the decomposition efficiency of hydrocarbon gas by the plasma assist method is effective for the problem that the growth rate is lowered because the graphene growth temperature is lowered. If the plasma assist method is applied, a desired growth rate can be secured even when the growth temperature is lowered.
  • FIG. 2 shows an SEM image (FIG. 2 (a)) of nuclei formed after the first step (1050 ° C. for 5 minutes) and an SEM image of graphene grown after the second step (6 minutes at 400 ° C.).
  • FIG. 2B SEM image (FIG. 2C) of graphene grown after the second step (7 minutes at 400 ° C.), sapphire substrate, production nucleus, graphene, and ⁇ from the graphene edge Raman scattering spectrum (FIG. 2 (d)), AFM image (FIG. 2 (e)) showing that the production nucleus shown in FIG. 2 (a) has a hexagonal spiral structure, and the second It is an AFM image (FIG.2 (f)) which shows the surface state of the graphene obtained after the process.
  • the black contrast portion appearing in the SEM image shown in FIG. 2A is a production nucleus formed in the first step.
  • Each of the generated nuclei has a substantially hexagonal outline with a diameter of about 2 to 3 ⁇ m, and has a weak contrast region around it. Such generated nuclei are formed at intervals of several ⁇ m.
  • graphene grows around the individual nuclei and combines with the graphene grown from the adjacent nuclei to form a single film. You can see how it becomes. Then, as shown in FIG. 2C, it can be confirmed that graphene covers most of the substrate surface 7 minutes after the start of the second step.
  • the four ⁇ -Raman scattering spectra shown in FIG. 2D are measured points (sapphire substrate portions) indicated by rhombus marks in FIG. 2A, and square marks (graphene end portions) in FIG. 2B. , Obtained from the measurement points indicated by the triangular mark (graphene part) and the round mark (generated nucleus part).
  • the 2D / G ratio of two layers of graphene is about 1, and the 2D / G ratio of four layers of graphene is about 0.5. Therefore, if the 2D / G ratio is 2 or more, it may be determined that the layer is almost complete.
  • the present inventors judge the height of “single layer property” by this 2D / G ratio, and evaluate a graphene having a 2D / G ratio of 1 or more as graphene having a high single layer property.
  • the product nuclei formed in the first step may already be graphene with extremely high monolayer properties. High nature. And since the 2D / G ratio of the Raman scattering spectrum from the graphene grown in the second configuration also maintains a value close to 2, the above-mentioned graphene having a very single layer property is used as a production nucleus, and a single layer is formed around this. It is thought that graphene with extremely high properties is growing.
  • the intensity of the D band due to the defect structure is very low, and the G / D ratio exceeds 10. Accordingly, it is considered that graphene having high crystallinity has already been formed at the stage of formation nuclei, and that graphene is growing around the formation nuclei having high crystallinity while maintaining the crystallinity.
  • the area of the graphene obtained depends on the area of the formation region of the product nucleus on the substrate, a large-area high-quality single-layer graphene can be obtained by widening the area.
  • nuclei have a hexagonal spiral structure as shown in the AFM image shown in FIG.
  • a carbon six-membered ring grows two-dimensionally around this product nucleus and merges with the carbon six-membered ring grown around the adjacent product nucleus to form a graphene film.
  • the white linear contrast observed in the AFM image shown in FIG. 2 (f) is a trace that the carbon six-membered rings that have grown from adjacent product nuclei merged into one graphene film.
  • this nuclei can be a single-layer graphene or a multilayer graphene. It can also be a production nucleus.
  • FIG. 3 shows 2D / G ratio Raman mapping (FIGS. 3 (a) to (c)) and G / D ratio corresponding to each sample whose SEM images are shown in FIGS. 2 (a) to 2 (c). It is a Raman mapping (FIGS. 3D to 3F).
  • 3A to 3C are regions that show a 2D / G ratio of 1.5 or more.
  • 3 (d) to 3 (f) is a region showing a G / D ratio of 1.5 or more.
  • graphene grows two-dimensionally around the production nucleus and eventually becomes a single graphene film.
  • the graphene thus obtained is composed of a plurality of domains composed of a set of carbon six-membered rings, and each of the plurality of domains has a carbon six-membered ring nucleus in the domain.
  • the orientation of the carbon six-membered ring in the domain is substantially the same over the entire surface of the graphene film, and is substantially the same in a range of at least 10 ⁇ 7 cm 2 .
  • substantially the same means that the deviation of the orientation of the carbon six-membered ring in the region of interest is 15 ° or less.
  • the density of the production nuclei of the carbon six-membered ring is preferably 1 ⁇ 10 6 pieces / cm 2 or less. If the density of the nuclei is too high, it will be difficult to make the orientation of the carbon six-membered ring in the domain substantially the same over the entire surface of the graphene film.
  • the area of one continuous graphene film depends on the area of the formation nucleus formation region on the substrate and is, for example, 1 ⁇ 10 ⁇ 7 cm 2 or more (generally corresponding to 3 ⁇ m ⁇ 3 ⁇ m). In particular, it may be a single layer continuous film.
  • FIG. 4 is a TEM image obtained from graphene after completion of the second step. This graphene is grown by setting the CVD reaction temperature in the second step to 500 ° C., but a similar TEM image can be obtained from graphene grown at a temperature of 400 ° C. or lower.
  • FIGS. 4 (a) is a dark field image
  • FIG. 4 (b) is a bright field image
  • FIGS. 4 (c) and 4 (d) are high magnification images.
  • the difference in the orientation of the carbon six-membered ring in the film was less than 5%. That is, it can be confirmed that the single-layer graphene obtained by the present invention is composed of an assembly of carbon six-membered rings whose orientations are substantially aligned in the same direction over the entire surface of the film.
  • the generated nuclei in the first step are not required to be formed by the CVD method as described above, and may be performed, for example, by transferring graphite or graphene to the main surface of the substrate by a peeling method.
  • the first step may be performed by patterning graphite or graphene on the main surface of the substrate by a photolithographic method.
  • a step of separating graphene from the substrate may be provided following the second step.
  • Graphene has a unique conical band structure with a smooth side surface in which the conduction band and the valence band are in contact at one point (Dirac point). Since it has such a specific band structure, electrons in graphene are in a kind of free state, and the mobility of carriers shows a very large value. Taking advantage of this characteristic, carrier density (conductivity) can be continuously controlled by providing graphene in the gate region and changing the voltage applied to the graphene.
  • graphene is applied to electronic devices, its good conductivity, high electron / hole mobility, inelastic electron conductivity and spin conductivity, mechanical strength, light absorption and emission, heat conduction, etc. High performance electronic devices can be realized due to superior characteristics.
  • an electronic element for example, a field effect transistor having a channel region made of such graphene can be exemplified.
  • the electronic device is, for example, a metal having a catalytic action for graphene synthesis and having a melting point of 400 ° C. or lower (for example, at least one of gallium and indium, or gallium- Indium alloy) is brought into contact, a gas containing hydrocarbon is supplied in a state where the metal is maintained at a temperature exceeding the melting point, graphene is grown at the contact interface with the metal on the substrate main surface, and the resist pattern is graphene It can be manufactured by a process including a step of forming a circuit by forming a circuit.
  • FIG. 5 is an example of an optical micrograph (FIG. 5 (a)) of an FET experimentally produced by the present inventors using the graphene described above, and its CV curve (FIG. 5 (b)).
  • the hole mobility is estimated at about 600 cm 2 / V s .
  • a sapphire substrate (1 cm ⁇ 1 cm) having an off angle of 0.2 ° was used as the substrate.
  • a cleaning process by oxygen plasma ashing is performed, gallium metal is placed on the main surface of the sapphire substrate, and as shown in FIG. Inserted into.
  • RF heating was performed while flowing Ar gas as a carrier gas to raise the substrate temperature to 850 ° C., and this temperature was maintained to melt gallium.
  • RF heating is performed while flowing Ar gas as a carrier gas to raise the substrate temperature to 200 ° C.
  • Ar gas is flowed at 200 sccm and CH 4 gas at a flow rate (0.5 atm), and the substrate temperature is 200 ° C. Hold at 10 ° C. for 10 minutes. Thereafter, the supply of CH 4 gas was stopped and cooled to room temperature in an Ar gas atmosphere.
  • FIG. 6 is an SEM image of graphene thus obtained.
  • the obtained graphene is composed of a plurality of domains composed of a set of carbon six-membered rings, and each of the plurality of domains has a generation nucleus of the carbon six-membered ring in the domain. Are connected neatly to form a single film.
  • a sapphire substrate (1 cm ⁇ 1 cm) having an off angle of 0.2 ° was used as the substrate.
  • a cleaning process by oxygen plasma ashing is performed, gallium metal is placed on the main surface of the sapphire substrate, and as shown in FIG. Inserted into.
  • RF heating was performed while flowing Ar gas as a carrier gas to raise the substrate temperature to 850 ° C., and this temperature was maintained to melt gallium.
  • RF heating is performed while flowing Ar gas as a carrier gas to raise the substrate temperature to 200 ° C.
  • Ar gas is flowed at 200 sccm and CH 4 gas at a flow rate (0.5 atm), and the substrate temperature is 200 ° C. Hold at 20 ° C. for 20 minutes. Thereafter, the supply of CH 4 gas was stopped and cooled to room temperature in an Ar gas atmosphere.
  • a sapphire substrate (1 cm ⁇ 1 cm) having an off angle of 0.2 ° was used as the substrate.
  • a cleaning process by oxygen plasma ashing is performed, gallium metal is placed on the main surface of the sapphire substrate, and as shown in FIG. Inserted into.
  • RF heating was performed while flowing Ar gas as a carrier gas to raise the substrate temperature to 850 ° C., and this temperature was maintained to melt gallium.
  • RF heating is performed while flowing Ar gas as a carrier gas to raise the substrate temperature to 100 ° C.
  • Ar gas is flowed at 200 sccm and CH 4 gas at a flow rate (0.5 atm), and the substrate temperature is set to 100 ° C. Hold at 60 ° C. for 60 minutes. Thereafter, the supply of CH 4 gas was stopped and cooled to room temperature in an Ar gas atmosphere.

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Thin Film Transistor (AREA)

Abstract

Selon la présente invention, dans une première étape, un produit noyau pour un cycle à six chaînons de carbone est formé sur la surface principale d'un substrat, et ensuite, dans une deuxième étape, un métal tel que le gallium ayant un point de fusion de 400 °C ou moins et ayant une activité catalytique pour la synthèse de graphène est mis en contact avec la surface principale du substrat sur laquelle le produit noyau est formé, un gaz contenant un hydrocarbure est fourni à ce dernier dans un état dans lequel le métal est maintenu à une température supérieure au point de fusion, et un graphène est amené à croître au niveau de l'interface de contact de la surface principale de substrat avec le métal. La matière de départ gazeuse dans la présente invention se décompose en hydrogène et en carbone à la surface du métal liquide même à une température extrêmement basse d'environ 100 °C, et se lie avec les atomes de gallium ou d'autres atomes sur la surface du métal liquide. Les atomes de carbone diffusent aisément à travers la surface du métal liquide dans un état dans lequel ils sont dirigés vers les atomes de gallium ou d'autres atomes, et le carbone est rapidement alimenté à l'interface de contact avec la surface principale du substrat.
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WO2017034018A1 (fr) * 2015-08-26 2017-03-02 並木精密宝石株式会社 Film de graphène, corps composite, son procédé de production, et substrat en saphir monocristallin
JP2018188329A (ja) * 2017-05-02 2018-11-29 学校法人 名城大学 構造体
KR102369636B1 (ko) 2017-08-22 2022-03-03 테르마 코퍼레이션 그래핀 나노리본, 그래핀 나노 플레이틀렛 및 이들의 혼합물 그리고 합성 방법
KR20200044072A (ko) * 2017-08-22 2020-04-28 테르마 코퍼레이션 그래핀 나노리본, 그래핀 나노 플레이틀렛 및 이들의 혼합물 그리고 합성 방법
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WO2019070872A1 (fr) * 2017-10-03 2019-04-11 Northwestern University Barrières interfaciales en graphène conducteur pour dispositifs électroniques à base de métal liquide
JP2022521587A (ja) * 2019-02-20 2022-04-11 ピーピージー・インダストリーズ・オハイオ・インコーポレイテッド グラフェン炭素ナノ粒子及び分散剤樹脂を含有する分散液
JP7447135B2 (ja) 2019-02-20 2024-03-11 ピーピージー・インダストリーズ・オハイオ・インコーポレイテッド グラフェン炭素ナノ粒子及び分散剤樹脂を含有する分散液
CN112730558A (zh) * 2020-12-24 2021-04-30 宁波材料所杭州湾研究院 一种基于金刚石/石墨烯异质结的耐超声电极及其制备方法
CN112730558B (zh) * 2020-12-24 2023-10-31 宁波材料所杭州湾研究院 一种基于金刚石/石墨烯异质结的耐超声电极及其制备方法
JP2023086331A (ja) * 2021-12-10 2023-06-22 日本碍子株式会社 ガス反応方法およびガス反応装置
JP7719708B2 (ja) 2021-12-10 2025-08-06 日本碍子株式会社 ガス反応方法およびガス反応装置
US12371326B2 (en) 2021-12-22 2025-07-29 Nabors Energy Transition Solutions Llc Sulfur doped carbon-based nanomaterial and methods of forming the same

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