WO2012036537A2 - Appareil et procédé pour fabriquer du graphène en utilisant une lampe flash ou un faisceau laser et graphène fabriqué par ceux-ci - Google Patents

Appareil et procédé pour fabriquer du graphène en utilisant une lampe flash ou un faisceau laser et graphène fabriqué par ceux-ci Download PDF

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WO2012036537A2
WO2012036537A2 PCT/KR2011/006917 KR2011006917W WO2012036537A2 WO 2012036537 A2 WO2012036537 A2 WO 2012036537A2 KR 2011006917 W KR2011006917 W KR 2011006917W WO 2012036537 A2 WO2012036537 A2 WO 2012036537A2
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graphene
substrate
layer
flash lamp
manufacturing
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PCT/KR2011/006917
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English (en)
Korean (ko)
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WO2012036537A3 (fr
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이건재
최인성
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한국과학기술원
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Priority claimed from KR1020100091640A external-priority patent/KR101198482B1/ko
Priority claimed from KR1020110006115A external-priority patent/KR101172625B1/ko
Priority claimed from KR1020110062484A external-priority patent/KR101260606B1/ko
Application filed by 한국과학기술원 filed Critical 한국과학기술원
Publication of WO2012036537A2 publication Critical patent/WO2012036537A2/fr
Publication of WO2012036537A3 publication Critical patent/WO2012036537A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—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
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02524—Group 14 semiconducting materials
    • H01L21/02527—Carbon, e.g. diamond-like carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
    • H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/16—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only elements of Group IV of the Periodic System
    • H01L29/1606—Graphene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
    • H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
    • H01L29/51—Insulating materials associated therewith
    • H01L29/518—Insulating materials associated therewith the insulating material containing nitrogen, e.g. nitride, oxynitride, nitrogen-doped material

Definitions

  • the present invention relates to a graphene manufacturing apparatus, a manufacturing method using a flash lamp or a laser beam, and a graphene manufactured by using the same, and more particularly, to graphene having a large area using a flash lamp or a laser beam. It relates to a graphene manufacturing method, a manufacturing apparatus and a graphene produced using the same that can be economically produced.
  • Graphene refers to a planar monolayer structure in which carbon atoms are filled into a two-dimensional (2D) lattice, which forms the basis for all other dimensional graphite materials. That is, the graphene may be a basic structure of graphite stacked in a fullerene, a one-dimensional nanotube, or a three-dimensional structure.
  • 2D two-dimensional
  • graphene has unique physical properties due to its honeycomb crystal structure, two interpenetrating triangular sub lattice structures, and the thickness of one atomic size. Note that for example a zero bandgap is shown.
  • graphene has unique charge transport characteristics, which causes graphene to exhibit a unique phenomenon that has not been observed in the past.
  • the semi-integer quantum Hall effect, the bipolar supercurrent transistor effect, and the like are examples, and this is also considered to be due to the unique structure of the graphene described above.
  • Boron nitride is also a material having the same crystal structure as graphene, and attracts attention as the main material of the electronic device, but the boron nitride layer is laminated only in the same manner as chemical vapor deposition.
  • the organic solvent method is a technique for preventing aggregation between graphenes by using mutual energy between graphene-organic solvents at a level similar to mutual energy between graphene-graphene sheets.
  • the graphene sizes obtained in the prior arts 1 and 2 are only in the nanometer to micrometer level. Therefore, the prior arts 1 and 2 have a problem that they are not suitable for producing a large area of graphene.
  • Another method for producing graphene is a mechanical microfractionation method of physically peeling a graphene sheet from graphite by a tape or the like, and repeating and laminating it on a silicon substrate (prior art 3).
  • the size of the graphene obtained in the prior art 3 is only a few tens to hundreds of micron units, this also has a problem that is not suitable for producing a large-area graphene film.
  • Recently reported large-area graphene manufacturing method by chemical vapor deposition has the disadvantage of requiring a complicated process and expensive equipment.
  • the presently disclosed prior art has the limitation that it takes considerable time or is not economically suitable for producing large-area graphene film.
  • the problem to be solved by the present invention is to provide a graphene manufacturing apparatus and method capable of producing large-area graphene in a more economical manner than the prior art.
  • Another object of the present invention is to provide a graphene semiconductor device manufactured by the above-described method and apparatus.
  • the method comprises the steps of contacting the reaction gas on the substrate surface; Heating the substrate by irradiating light with a flash lamp or by irradiating a laser beam onto a region of the substrate to which the reaction gas is contacted; And transferring the substrate to grow a graphene layer repeatedly heating the other region of the substrate in sequence.
  • the present invention is a graphene manufacturing method, the method comprising the steps of irradiating light or a laser beam to the substrate with a flash lamp in a mixed gas atmosphere of carbon-containing gas and hydrogen; And it provides a graphene manufacturing method comprising the step of growing a graphene layer on the substrate.
  • the present invention is a graphene manufacturing method, the method comprises the steps of forming a graphene layer by irradiating a first light to the substrate with a flash lamp or a laser; And patterning the graphene by removing the irradiated graphene layer by irradiating the graphene layer with a flash lamp or a laser with a second light to provide the graphene semiconductor device manufacturing method.
  • the present invention also provides a graphene manufacturing method, the method comprising the steps of providing a SiC substrate; Irradiating light with a flash lamp or irradiating a laser beam onto a region on the SiC substrate and heating the light; And transferring the substrate, thereby repeatedly heating another region of the substrate to grow graphene.
  • the present invention is a graphene manufacturing apparatus, the apparatus comprises a chamber in which a substrate on which graphene is to be grown; An inlet part through which a reaction gas flows into one side of the substrate; A vacuum unit for applying a vacuum to the chamber; And a light source provided at an upper end of the chamber to irradiate light to the substrate.
  • graphene growth gas is reacted using heat of a flash lamp or a laser beam irradiated with a large area to grow graphene without a metal catalyst on a substrate.
  • the flexible substrate is transferred in a roll-to-roll manner, graphene is grown, and only the reaction gas is configured differently, thereby making a large amount of graphene semiconductor devices without mechanical deformation of graphene.
  • Figure 1a is a schematic diagram of a graphene manufacturing apparatus according to an embodiment of the present invention.
  • Figure 1b is a schematic diagram of a graphene manufacturing apparatus applied in a roll-to-roll method to the apparatus of Figure 1a.
  • 2 to 4 is a step-by-step cross-sectional view and a front view of a graphene manufacturing method according to an embodiment of the present invention.
  • 5 to 9 are step-by-step views illustrating a method of continuously growing a boron nitride layer and graphene in the apparatus shown in FIGS. 1A and 1B.
  • 10 to 14 illustrate a method of fabricating a nanoribbon-type graphene semiconductor device using a flash lamp of the device shown in FIGS. 1A and 1B.
  • 15 to 21 are views illustrating a method of manufacturing a graphene transistor according to an embodiment of the present invention.
  • 22 to 24 are steps illustrating a graphene manufacturing method according to another embodiment of the present invention.
  • 25 to 30 are views illustrating a graphene manufacturing method according to another embodiment of the present invention.
  • 31A and 31B are schematic views of a chamber for producing graphene of FIG. 25.
  • the graphene manufacturing method and apparatus manufacture graphene using a flash lamp that generates light energy according to an applied electrical energy.
  • graphene instead of focusing local energy (more precisely local thermal energy) by a laser that irradiates light at the nanosecond level, graphene is used by using a flash lamp that can supply heat energy in microseconds to milliseconds longer than lasers.
  • the advantages of the flash lamp that is, a large irradiation area, millisecond level of irradiation time, low production cost, it is possible to produce large area graphene.
  • the graphene growth method according to the present invention grows the graphene in a roll-to-roll manner, thereby significantly increasing the graphene production (growth) rate.
  • Figure 1a is a schematic diagram of a graphene manufacturing apparatus according to an embodiment of the present invention.
  • the graphene manufacturing apparatus according to the present invention is a chamber form, the substrate is provided with a graphene to be grown in the chamber.
  • the graphene manufacturing apparatus according to the present invention is provided on the top of the chamber, and includes a plurality of flash lamps that can supply heat energy by light.
  • the plurality of flash lamps are preferably spaced at predetermined intervals to irradiate light to all areas of the substrate provided on the front surface.
  • the manufacturing apparatus is provided on both sides of the substrate 10 and the substrate to be deposited, the graphene is grown, the inlet 20 through which the reaction gas for graphene growth and the vacuum unit to which the vacuum is applied ( 30).
  • the reaction gas includes various components such as methane and hydrogen, and the reaction gas is heated on the substrate 10 by thermal energy applied by a plurality of flash lamps (flash lamp bulbs) 40. It is decomposed and grown into graphene.
  • the substrate 10 may be made of a stable plastic substrate even at a relatively low temperature.
  • Figure 1b is a schematic diagram of a graphene manufacturing apparatus applied in a roll-to-roll method to the apparatus of Figure 1a.
  • the plastic substrate 10 may continuously move according to the rotation of the roll 60 provided below. Accordingly, the substrate 10 may move the light irradiation area from the fixed flash lamp 40, thereby growing the graphene at a very high speed even on a large area substrate. Therefore, in the present invention, the substrate 10 is laminated on a stage (not shown) formed between the roll and the roll which is the rotational transfer means, and the substrate 10 is moved according to the movement of the stage.
  • Graphene manufacturing apparatus further comprises a plurality of flash lamp 40 for generating light energy in accordance with the applied electrical energy spaced apart from the substrate 10.
  • the flash lamp uses a xenon (Xe) lamp, but the scope of the present invention is not limited thereto.
  • the graphene manufacturing apparatus may further include a reflecting means 50 provided at the rear end of the flash lamp to reflect the light irradiated to the front side to the front side, and in one embodiment of the present invention, the reflecting means ( 50 may be a curved mirror having a predetermined radius of curvature, but the scope of the present invention is now not limited.
  • Reference numeral 70 denotes a lamp irradiation area which schematically indicates an area irradiated on the substrate 10 by the flash lamp.
  • the graphene manufacturing apparatus of Figure 1a is equally applicable. Therefore, a graphene manufacturing method will be described based on the roll-to-roll type graphene manufacturing apparatus of FIG. 1B.
  • FIG. 2 to 4 is a step-by-step cross-sectional view and a front view of a graphene manufacturing method according to an embodiment of the present invention.
  • a plastic substrate is provided as the flexible substrate 101 on which graphene is grown and manufactured.
  • the flexible substrate cannot be used as a substrate for graphene growth.
  • the flash lamp and the laser since the entire flexible substrate receives heat, the flexible substrate cannot be used as a substrate for graphene growth.
  • the flash lamp and the laser generate heat only on the surface, and heat is usually generated within several ⁇ m on the surface of the flexible substrate having various thicknesses such as 25 ⁇ m to 125 ⁇ m, in the present invention using a light source, Enable the use of a flexible substrate.
  • the thin silicon oxide deposited on the flexible substrate may prevent the heat generated during the irradiation of the flash lamp and the laser from being conducted to the flexible substrate. There will be.
  • the substrate 101 may be a substrate having a SiO 2 on the flexible plastic substrate, but the scope of the present invention is not limited thereto.
  • a sapphire (Al 2 O 3 ) substrate, a metallized silicon substrate, and copper may be used.
  • Cu foil, MgO substrate, Al 2 O 3 substrate, Si substrate or the like is also possible.
  • a catalyst metal layer such as copper or nickel may be additionally laminated on the substrate so that these metal layers may function as a catalyst for graphite of the reaction gas.
  • the use of such a catalytic metal layer may be selectively applied depending on the growth rate and quality of the substrate or graphene applied.
  • the stacking method of the catalyst metal layer may be a method such as a sputtering process.
  • hydrogen and methane gas are injected through the gas inlet 20 into the apparatus illustrated in FIG. 1B without a separate catalyst metal layer or the like deposited on a substrate, and irradiated with a flash lamp. do.
  • the introduced reaction gas is decomposed by heat irradiated from the flash lamp and grows into graphene. That is, as a reaction gas containing a carbon source (methane gas, CH 4 ) is injected into the apparatus, and light is irradiated to the substrate 101 using a flash lamp, thermal energy by light is transmitted to the substrate 101.
  • a reaction gas containing a carbon source methane gas, CH 4
  • Methane which is a gaseous species containing reactant gas, in particular carbon, which is in contact with the substrate 101, is decomposed so that carbon is deposited on the substrate 101 surface, and hydrogen provided to make a reducing atmosphere is discharged in gaseous form. do. Thereafter, the stacked carbon gradually grows as the process progresses, and is converted into the graphene layer 102 uniformly grown over the entire substrate. Thereafter, the substrate 101 may be continuously moved in a roll-to-roll manner to grow graphene on the entire surface of the substrate (see FIG. 4).
  • An inert gas such as Ar gas may be supplied together with or separately from the hydrogen gas. The supply of such inert gas may serve as a purge gas to contribute to more uniform graphene growth.
  • Another embodiment of the present invention is to manufacture a graphene semiconductor device using the device shown in Figure 1b, which will be described in detail below.
  • FIG. 5 to 9 are step-by-step views illustrating a method of continuously growing a boron nitride layer (BN) and graphene in the device shown in FIG. 1B.
  • NH 3 , B 2 H 6 gas is injected into the apparatus of FIG. 1B on which the flexible substrate 201 movable in a roll-to-roll manner is deposited. Thereafter, a flash lamp is irradiated to make a boron nitride layer (BN layer) 202 on the substrate.
  • NH 3 gas is flowed to the nitrogen supply
  • B 2 H 6 gas is flowed to the boron source.
  • all gases containing Boron such as BCl 3 and BF 3
  • all gases including N may be used.
  • the present invention also discloses a technique for preparing a graphene layer in the form of nanoribbons with a flash lamp to form a band gap of graphene. That is, as the source, gate, and drain electrodes are connected through the nanoribbon-type graphene sheet, and a voltage is applied to the gate electrode, a transistor device having electrons flows into the nanoribbon-type graphene.
  • the problem is that there is a technical limitation in that the nano-sized ribbon-shaped graphene must be precisely manufactured on the substrate, but the present invention effectively solves the problem according to the prior art by using a flash lamp.
  • FIG. 10 to 14 illustrate a method of manufacturing a nanoribbon-type graphene semiconductor device using a flash lamp of the apparatus shown in FIG. 1.
  • the graphene layer 302 is grown with a flash lamp on the flexible substrate 301, which is done in the device shown in FIG. 1B.
  • oxygen is injected into the device to pattern the graphene layer 302, and light is irradiated with a flash lamp. .
  • the carbon of the graphene layer 302 irradiated with light from the flash lamp is activated to react with and remove oxygen. Thereafter, as shown in FIG.
  • Oxygen in the present invention means not only a gas atmosphere consisting of oxygen, but also collectively refers to a gas atmosphere containing oxygen, all belonging to the scope of the present invention.
  • the interval of graphene (20 nm or less) must be narrow.
  • An embodiment of the present invention achieves this shape of semiconductor graphene using a mask and a flash lamp.
  • a ribbon-shaped second mask M2 for patterning graphene in a ribbon shape (a wide end and a narrow middle part) is stacked on the graphene layer 320 region shown in FIG. 12.
  • the width of the ribbon is preferably 20nm or less, whereby the graphene has the characteristics as a semiconductor.
  • the second mask is a light blocking mask for blocking light from the flash lamp irradiated in the same manner as the first mask.
  • the graphene layer 302 of the region where the second mask is not formed is removed, thereby forming a ribbon-type graphene layer 303.
  • the graphene layer 303 having a narrow width in the ribbon form has semiconductor characteristics.
  • the present invention further provides a technique of doping boron and nitrogen by flowing an impurity doping gas such as B 2 H 6 or NH 3 .
  • an impurity doping gas such as B 2 H 6 or NH 3 .
  • FIG. 15 to 21 illustrate a method of manufacturing a graphene transistor on a flexible substrate according to an embodiment of the present invention.
  • the semiconductor graphene layer 303 desired for manufacturing the P-type semiconductor graphene among the formed semiconductor graphene layers 303 is exposed to the outside, and impurity doping is required. All of the remaining graphene layer 303 is not laminated to block the light.
  • a gas (B 2 H 6 ) containing boron, which is a dopant for forming a P-type semiconductor is injected into the apparatus together with hydrogen, and light is irradiated with a flash lamp.
  • boron is doped into the semiconductor graphene layer 303 which is not covered by the third mask layer M3, so that the boron-doped P-type graphene layer 304 is formed on the flexible substrate 301.
  • Nitrogen doping of the plurality of unit graphene devices formed on the substrate is performed in the same manner. To do this, another doping gas containing NH 3 and methane is flowed onto the substrate, and the device region to be doped is light-treated with a flash lamp. ( Figures 16-18).
  • boron is doped at both ends of the two left ends (304), and nitrogen is doped at both end areas (305).
  • the doped region ie, the center region of the ribbon
  • an insulating layer 306 such as HfO 2 is formed on the doped semiconductor graphene device region as a gate insulating film, and the source, gate, and drain electrodes of the unit graphene transistor are formed. (307). That is, the graphene transistor structure is formed by forming a gate electrode on the insulating layer 306 and source and drain electrodes on both ends of the graphene layer having a nano ribbon shape.
  • the P-type graphene transistor 308 and the N-type graphene transistor 309 may be selectively manufactured on the flexible substrate according to the type of impurities doped in the graphene layer.
  • FIG. 22 to 24 are steps illustrating a graphene manufacturing method according to another embodiment of the present invention.
  • a SiC substrate 401 containing carbon C in a substrate is used.
  • FIG. 23 light is irradiated onto a SiC substrate 401 by a flash lamp, from which heat is transferred to the substrate.
  • hydrogen may be injected in advance to make the chamber a reducing atmosphere.
  • the silicon of the SiC substrate is sublimated by the heat radiated from the flash lamp, and the carbon remaining on the substrate surface is grown on the surface in the form of graphene by the silicon sublimation.
  • a uniform graphene layer 302 (sheet) is grown on the entire substrate.
  • 25 to 30 are views illustrating a graphene manufacturing method according to another embodiment of the present invention, and illustrates a graphene forming method using a laser beam instead of the above-described flash lamp, which was used as a light source.
  • a sapphire (Al 2 O 3 ) substrate 101 is disclosed.
  • the substrate used in the present invention may be any substrate that can be subjected to a conventional semiconductor process, for example, a silicon substrate, a silicon oxide / silicon substrate, a metal deposited silicon substrate, a copper foil (Cu foil) and the like can also be used.
  • the laser beam is irradiated onto the substrate while simultaneously flowing a nitrogen-containing doping gas and a boron-containing doping gas on the substrate 101 (first laser beam irradiation).
  • the nitrogen-containing doping gas was ammonia (NH 3 )
  • the boron-containing doping gas was B 2 H 6 .
  • the scope of the present invention is not limited thereto, and various doping gases such as BCl 3 and BF 3 may be used.
  • the doping gas in the irradiated region is decomposed by the irradiated laser to form a boron nitride layer, which is caused by simultaneous decomposition of the boron-containing doping gas and the nitrogen-containing doping gas.
  • the boron nitride layer 102 ' is formed on the substrate 101.
  • the boron nitride layer forming region corresponds to the irradiation region of the laser beam.
  • the present invention provides a method of manufacturing a boron nitride layer 102 ', which is a lower substrate, on which a semiconductor device layer such as graphene is formed.
  • a general boron nitride layer is manufactured through a high thermal reaction such as plasma chemical vapor deposition, but the present invention forms the boron nitride layer 102 'on the substrate through a laser beam reaction rather than a high thermal reaction.
  • the boron nitride layer 102 ′ is formed on the entire substrate 101 by sequentially moving the laser beam irradiation region on the substrate 101. At this time, as described above, the nitrogen-containing doping gas and the boron-containing doping gas are continuously introduced.
  • an embodiment of the present invention forms a graphene semiconductor device on the boron nitride layer 102 'by using a laser beam on which the boron nitride layer 102' is formed, such a boron nitride layer-based graphene.
  • the fin semiconductor device has a considerably improved carrier mobility compared to the silicon substrate semiconductor device, and the present invention can manufacture a multilayer semiconductor device by irradiating the laser beam a plurality of times.
  • the reaction gas containing carbon flows on the boron nitride layer 102 ′, thereby contacting the boron nitride layer 102 ′.
  • the reaction gas includes an inert gas such as methane (CH 4 ), hydrogen (H 2 ) and argon (Ar).
  • methane supplies carbon for graphene growth, and hydrogen prevents oxidation of graphene through a reducing atmosphere.
  • laser beam irradiation is performed on the substrate (more specifically, the boron nitride layer 102 ') in contact with the reaction gas (second laser beam irradiation).
  • the reaction gas in particular, the carbon-containing gas species (methane) of the reaction gas is decomposed by the laser beam irradiated thereby, and thus graphene grows only in the region to which the laser beam is irradiated.
  • methane gas having a femtosecond decomposition rate is effectively decomposed on the substrate (silicon oxide layer) by nanosecond laser beam irradiation, and carbon is deposited on the substrate.
  • the power of the laser beam was 2 to 100W
  • the line width of the laser beam was 2 to 4
  • the length was several centimeters.
  • the scope of the present invention is not limited to the types and conditions of the above-described laser beam, a solid state laser or the like may also be used.
  • the laser may use not only pulse laser but also CW (continuous wave) laser.
  • the substrate region irradiated with the laser beam rises to 900 to 2000 ° C., whereby the methane gas of the reaction gas in contact with the elevated temperature substrate is decomposed.
  • the scope of the laser beam used in the present invention includes any laser beam capable of raising the temperature of the irradiated substrate to the level of 900 to 2000 ° C regardless of its type and dimension.
  • the graphene layer 103 grows in one region of the substrate according to the laser beam irradiation, as described above.
  • the laser beam is irradiated to other regions other than one region of the substrate on which graphene is grown. That is, the present invention moves the growth and stacking region of the graphene layer 103 by moving the laser beam irradiated to the substrate, for this purpose, both the laser beam or the substrate itself can be moved.
  • the graphene manufacturing method according to the present invention has the advantage of precise control of the graphene growth region due to the small line width of the laser beam, and the graphene layer 103 grown horizontally by the laser beam irradiation is the boron nitride layer. It is formed on (102 '), thereby producing a large area of graphene.
  • the chamber 13 of the semiconductor device manufacturing apparatus is in the form of a vacuum chamber cut off from the outside, and includes a first hole to which a vacuum line (not shown) outside the chamber 13 is connected. 15 and the plate 17 on which the substrate w is placed.
  • the plate 17 may further include a heating means (not shown) for raising the temperature of the substrate, thereby increasing the temperature of the target layer (boron nitride layer or graphene) only by irradiation with a laser beam. As it rises, graphene properties can be improved.
  • the outer wall of the chamber 13 is further provided with another second hole 19 for supplying a reaction gas therein.
  • FIG. 31B is a schematic view of another chamber for graphene manufacture of FIG. 25.
  • the laser beam generated from the laser beam generator 21 passes through the optical system 23 and the mask stage 25 and is then irradiated into the chamber 27 in which the target substrate is placed.
  • the chamber 27 is a process chamber in which a substrate is placed, and a separate reaction gas supply system may be connected.
  • the semiconductor device manufacturing apparatus according to the present invention may further include a means for moving the substrate itself or a means for moving the laser beam for the large-area boron nitride layer or graphene growth. This allows for selective device layer growth in the desired area.
  • the semiconductor device manufacturing apparatus by sequentially moving the irradiation region of the laser beam sequentially, it is possible to induce continuous object layer growth on a large area substrate. That is, according to the semiconductor device manufacturing apparatus according to the present invention by adjusting the irradiation time and the moving speed of the irradiation area, the boron nitride layer or graphene device layer of uniform height can be continuously grown two-dimensionally.
  • the laser beam moving means or substrate means can be any means used in the art, all of which are within the scope of the present invention.
  • the present invention largely describes a graphene manufacturing method using a flash lamp or a laser beam as a light source.
  • the above-described embodiments describe the same graphene manufacturing method except that the light source uses a flash lamp or a laser beam. Therefore, the pattern of the graphene and the method of manufacturing the graphene semiconductor device accordingly may be equally applicable to the method using the above-described flash lamp using the laser beam.
  • FIG. 32 is a diagram illustrating various configurations of a graphene semiconductor device according to the present invention, and shows that various types of semiconductor devices using graphene may be implemented.
  • the flash lamp since the flash lamp has a pulse duration of microseconds in milliseconds, thermal energy can be used for graphene growth longer than a pulse laser of nanoseconds.
  • the flash lamp can irradiate heat to a relatively larger area than the laser, there is an advantage that can reduce the process time when manufacturing a large area of graphene.
  • the flash lamp and the laser beam may each be selectively used as needed, and the present invention is characterized by presenting a method for producing such a light source and a graphene forming source gas.
  • the present invention using an optical means such as a lamp or a laser beam, and a roll-to-roll method can rapidly grow graphene on a flexible substrate.
  • graphene growth gas is reacted using heat of a flash lamp or a laser beam irradiated with a large area to grow graphene without a metal catalyst on a substrate.
  • the flexible substrate is transferred in a roll-to-roll manner, graphene is grown, and only the reaction gas is configured differently, thereby making a large amount of graphene semiconductor devices without mechanical deformation of graphene.

Abstract

L'invention concerne un procédé et un appareil permettant de fabriquer du graphène en utilisant une lampe flash ou un faisceau laser, ainsi que le graphène fabriqué par ceux-ci. L'appareil de la présente invention comprend : un compartiment dans lequel est disposé un substrat permettant de faire croître le graphène, une unité formant orifice d'entrée qui introduit un gaz de réaction sur un côté du substrat, une unité de vide qui applique du vide au compartiment et une lampe flash ou un dispositif laser disposé sur la partie supérieure du compartiment afin d'appliquer par illumination la lumière sur le substrat, le substrat étant transféré par un moyen de transfert à rouleaux. Le procédé et l'appareil permettant de fabriquer le graphène conformément à la présente invention génèrent une induction du gaz de réaction pour la croissance du graphène en utilisant la chaleur de la lumière illuminée sur une grande surface à partir de la lampe flash de façon à faire croître le graphène sur le substrat. De plus, pour faire croître le graphène sur celui-ci, un substrat souple est transféré par un système de transfert à rouleaux, et des composants à semiconducteur à base de graphène peuvent être produits en masse en faisant uniquement varier la composition du gaz de réaction sans déformer le graphène.
PCT/KR2011/006917 2010-09-17 2011-09-19 Appareil et procédé pour fabriquer du graphène en utilisant une lampe flash ou un faisceau laser et graphène fabriqué par ceux-ci WO2012036537A2 (fr)

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KR1020100091640A KR101198482B1 (ko) 2010-09-17 2010-09-17 플래쉬 램프를 이용한 그래핀 제조장치, 제조방법 및 이를 이용하여 제조된 그래핀
KR10-2010-0091640 2010-09-17
KR1020110006115A KR101172625B1 (ko) 2011-01-21 2011-01-21 레이저를 이용한 반도체 소자 제조방법, 이에 의하여 제조된 그래핀 반도체 및 그래핀 트랜지스터
KR10-2011-0006115 2011-01-21
KR10-2011-0062484 2011-06-27
KR1020110062484A KR101260606B1 (ko) 2011-06-27 2011-06-27 플래쉬 램프를 이용한 그래핀 제조장치, 제조방법 및 이를 이용하여 제조된 그래핀 반도체 소자

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CN104495821A (zh) * 2014-12-16 2015-04-08 重庆墨希科技有限公司 一种单层连续石墨烯薄膜卷材的制备方法及装置
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CN110155994A (zh) * 2019-04-04 2019-08-23 江苏大学 一种直接制备复合图案化石墨烯的装置及方法
CN110155994B (zh) * 2019-04-04 2023-01-17 江苏大学 一种直接制备复合图案化石墨烯的装置及方法
CN113380949A (zh) * 2021-06-07 2021-09-10 天津大学 瞬态电子器件的制备方法
CN113380949B (zh) * 2021-06-07 2023-04-07 天津大学 瞬态电子器件的制备方法

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