WO2012102574A2 - Procédé de préparation de graphène, électrode transparente contenant ce graphène, couche active et dispositif d'affichage, dispositif électronique, dispositif photovoltaïque, batterie, cellule solaire et cellule solaire à colorant qui emploient ce graphène - Google Patents

Procédé de préparation de graphène, électrode transparente contenant ce graphène, couche active et dispositif d'affichage, dispositif électronique, dispositif photovoltaïque, batterie, cellule solaire et cellule solaire à colorant qui emploient ce graphène Download PDF

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Publication number
WO2012102574A2
WO2012102574A2 PCT/KR2012/000635 KR2012000635W WO2012102574A2 WO 2012102574 A2 WO2012102574 A2 WO 2012102574A2 KR 2012000635 W KR2012000635 W KR 2012000635W WO 2012102574 A2 WO2012102574 A2 WO 2012102574A2
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Prior art keywords
metal foil
graphene
target substrate
raw material
carbon raw
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PCT/KR2012/000635
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English (en)
Korean (ko)
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WO2012102574A3 (fr
Inventor
권순용
김성엽
곽진성
Original Assignee
국립대학법인 울산과학기술대학교 산학협력단
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Publication of WO2012102574A2 publication Critical patent/WO2012102574A2/fr
Publication of WO2012102574A3 publication Critical patent/WO2012102574A3/fr

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2022—Light-sensitive devices characterized by he counter electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/66007—Multistep manufacturing processes
    • H01L29/66075—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials
    • H01L29/66227—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials the devices being controllable only by the electric current supplied or the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched, e.g. three-terminal devices
    • H01L29/66409—Unipolar field-effect transistors
    • H01L29/66477—Unipolar field-effect transistors with an insulated gate, i.e. MISFET
    • H01L29/66742—Thin film unipolar transistors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/78603—Thin film transistors, i.e. transistors with a channel being at least partly a thin film characterised by the insulating substrate or support
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/78684—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising semiconductor materials of Group IV not being silicon, or alloys including an element of the group IV, e.g. Ge, SiN alloys, SiC alloys
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/60—Forming conductive regions or layers, e.g. electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • Transparent electrode comprising the same, the active layer, a display device having the same. It relates to an electronic device, an optoelectronic device, a battery, a solar cell and a dye-sensitized solar cell.
  • various devices such as a display element, a light emitting diode, a solar cell, and the like transmit light to form an image or generate power, so that a transparent electrode capable of transmitting light is used as an essential component.
  • a transparent electrode capable of transmitting light is used as an essential component.
  • 5 Indium Tin Oxide ( ⁇ ⁇ ) is the most known as such a transparent electrode. It is widely used.
  • indium tin oxide has a problem that the higher the consumption of indium, the higher the price, the lower the economic feasibility, the global reserve of indium is depleted, especially the chemical and electrical characteristics of the transparent electrode made of indium material0 As it is known to exist, efforts are being made to find an electrode material that can replace it. In addition. Electronic devices and semiconductor devices generally use silicon as an active layer. As a specific example, a thin film transistor will be described.
  • a general thin film transistor is composed of a multilayer and includes a semiconductor layer, an insulating layer, a protective layer, an electrode layer, and the like. Each charge constituting the thin film transistor is formed by sputtering or chemical vapor deposition (CVD), followed by film formation by lithography. Thin film transistors that are widely used at present are semiconductor layers, which are conducting channels through which electrons flow, and have an amorphous silicon layer. The display has been limited due to the low electron mobility of the amorphous silicon layer.
  • the phase shows a carrier mobility of about 1,000 cmWs at. I want to solve this problem.
  • a protective layer and an amorphous silicon insect are sequentially coated on a substrate, and then crystallized with a laser to form a polysilicon layer as an active layer.
  • the protective and amorphous silicon insects are coated by radio frequency (RF) sputtering.
  • RF sputtering is not only very slow in coating speed but also uneven in thickness, forming a layer sensitive to changes in laser energy density.
  • RF sputtering is not only very slow in coating speed but also uneven in thickness, forming a layer sensitive to changes in laser energy density.
  • chemical vapor deposition may be used to form the protective layer and the polysilicon active layer.
  • the glass substrate should be annealed at a high temperature and used with a laser.
  • Hydrogen which causes fatal problems, is introduced into the thin film, requiring an additional annealing process to remove hydrogen. It is difficult to form polysilicon insects of uniform electrical properties. Faster and better device fabrication requires the use of new materials to replace them.
  • the present invention provides a transparent electrode having improved chemical, electrical, and optical properties including the graphene.
  • a display device comprising the transparent electrode and the active layer.
  • the metal foil is Ni. Co, Fe, Pt. Au, Al. Cr. Cu. Mg. Mn. Mo, Rh. Si, Ta, Ti. W. U, V. Zr. Zn. Sr. Y. Nb. Tc. Ru, Pel, Ag, Cd, In. Re, 0s. Ir. It may be a metal consisting of Pb or a combination thereof.
  • the temperature rise temperature of step (b) may be 50 ° C to 3,000 ° C.
  • the temperature holding time of step (b) may be 10 seconds to 10 hours.
  • the temperature increase rate of step (b) may be 0.1 ° C / sec to 500 7 seconds.
  • the carbon raw material is a gas phase. Liquid phase. Solid phase or a combination thereof.
  • the carbon raw material is a gas phase
  • the temperature of the step (e) may be a temperature from 1.500 ° C.
  • the carbon raw material is a gaseous phase
  • the temperature holding time of the step (e) may be 1 second to 100 hours.
  • the carbon raw material is a gas phase
  • the temperature increase rate of step (e) may be o.rc / sec to 500 ° C / sec.
  • the carbon raw material is a liquid or solid phase, the temperature rising temperature of the step (e) is room temperature ⁇ )
  • the carbon raw material may be a liquid phase or a solid phase, and the winning time of the step (e) may be 1 second to 100 hours.
  • the carbon raw material may be a liquid phase or a solid phase, and the multiplication rate of the step (e) may be 0.1 ⁇ 7 sec to 50 CTC / sec.
  • the method may further include forming a graphene sheet using the graphene formed in the step (g).
  • Step (b) is. Heat treating the metal foil to increase the grain size of the metal foil. Spontaneously forming a pattern on the metal foil; Heat treating the metal foil to increase the size of grains of the metal foil and patterning the metal foil; Alternatively, the metal foil may be patterned in advance, and then the metal foil may be heat-treated to increase the size of crystal grains of the metal foil.
  • the target substrate may be a flexible substrate.
  • A preparing a target substrate: (b) supplying a metal foil (foil) on the target substrate; (c) supplying a carbon raw material onto the metal foil; (d) the supplied carbon raw material. Heating the target substrate and the metal foil; (e) diffusing carbon atoms generated by thermal decomposition of the heated carbon raw material into the metal foil; And (f) forming graphene on the target substrate by carbon atoms diffused into the metal foil.
  • It provides a graphene manufacturing method comprising the step of forming a graphene.
  • a transparent electrode including graphene manufactured according to the above-described manufacturing method is provided.
  • a display device having the above-described transparent electrode is provided.
  • an electronic device having the above-described active worm is provided.
  • the display device may be a liquid crystal display device, an electronic paper display device, or an optoelectronic device.
  • the electronic device may be a transistor, a sensor or an organic or inorganic semiconductor device.
  • the anode; Hole transport layer; Light emitting layer; Provided is an optoelectronic device comprising an electron transport layer and a cathode, wherein the anode is the transparent electrode described above.
  • the optoelectronic device may further include an electron injection layer and a hole injection layer.
  • a battery having the above-mentioned transparent electrode.
  • the active layer in the solar cell having at least one active layer between the lower electrode layer and the upper electrode layer stacked on the substrate, is a solar cell that is the above-mentioned active charge.
  • a dye electrode comprising a semiconductor electrode, an electrolyte layer and a counter electrode, wherein the semiconductor electrode is composed of a transparent electrode and a light absorbing layer, the light absorbing layer comprises a nanoparticle oxide and a dye
  • the transparent electrode and the counter electrode provides a dye-sensitized solar cell which is the above-mentioned transparent electrode.
  • spontaneous patterning black of the metal foil can be adjusted in advance the shape and size of the graphene to be formed by using the metal foil pre-patterned through a patterning technique used in the past.
  • FIG. 1 is a flow chart of a method for producing graphene according to an aspect of the present invention.
  • Figure 2 is a flow chart of the manufacturing method of the graphene according to another aspect of the present invention.
  • 3 is an SEM image of nickel metal foil after heat treatment in Example 1.
  • FIG. 4 is in Example 1.
  • FIG. It is a distribution map of the average grain size of nickel metal foil after heat processing.
  • FIG. 5 is a 10 / zniXlO / zni AFM image of nickel metal foil after heat treatment in Example 1.
  • FIG. 6 is XRD measurement results of nickel metal foil before and after heat treatment in Example 1.
  • FIG. 7 is an optical micrograph of the graphene formed in Example 1.
  • FIG. 10 is a graph showing a change in intensity ratio (I D / I G ) between the D peak and the G peak in Raman spectroscopy measurement results according to post-heat treatment conditions after graphene formation.
  • target substrate 102 metal foil
  • graphene sheet is a graphene in which a plurality of carbon atoms are covalently linked to each other to form a polycyclic aromatic molecule, thereby forming a sheet form. It forms a six-membered ring as a basic repeating unit, but it is also possible to further include a five-membered ring and / or a seven-membered ring, so that the graphene sheet appears as a single group of covalently bonded carbon atoms (usually sp2 bonds).
  • the sheet may have various structures, and the structure may vary depending on the content of the 5- and / or 7-membered rings that may be included in the graphene.
  • the graphene sheet may be a single layer of the graphene as described above. It may be possible, however, that they can be stacked together to form a plurality of layers (generally 10 layers or less), two up to 100nm. A is formed, typically the side ends of the graphene are saturated with hydrogen atoms.
  • the contact between the graphene sheet is a surface contact, it shows a very low contact resistance value compared to the carbon nanotubes made of point contact, the graphene sheet can be configured very thin thickness to prevent problems due to surface roughness Can, It can be easily separated from inexpensive graphite, resulting in excellent economy.
  • the electrical characteristics change according to the crystal orientation of the graphene sheet having a given thickness, the electrical characteristics can be expressed in the direction selected by the user, and thus, the device can be easily designed.
  • Method for producing a graphene 105 according to an embodiment of the present invention comprises the steps of (a) preparing a substrate 101 and the metal foil (foil.
  • the graphene formed on the target substrate 101 may be obtained by etching the metal foil 10 2 with respect to the graphene formed between the target substrate 101 and the metal foil 102.
  • the graphene formed on the target substrate 101 may be obtained by performing the step of transferring the graphene formed on the back surface of the metal foil 102 to the target substrate 101.
  • the target substrate 101 is Si, Ge.
  • Group IV semiconductor substrates such as SiGe; GaN. A1N.
  • Group III-V compound semiconductor substrates such as GaAs, AlAs, GaP;
  • Group II-VI compound semiconductor substrates such as ZnS and ZnSe; ZnO.
  • Oxide semiconductor substrates such as MgO and sapphire; Glass, quartz.
  • Other non-conductive substrates such as Si0 2 : polymer.
  • Organic substrates such as liquid crystals; Generally display element. Photoelectric / electronic device. Substrates and transistors used in batteries or solar cells.
  • the substrate used for the sensor or the organic-inorganic semiconductor device is not limited.
  • the metal foil (foil. 102) is made of metal like thin paper, and generally has excellent flexibility.
  • the metal foil 102 is Ni. Co. Fe, Pt. An. Al. Cr, Cu. Mg. Mn. Mo. Rh. Si. Ta, Ti, W, U, V, Zr, Zn, Sr. It may be a metal consisting of Y, Nb, Tc, Ru, Pd, Ag, Cd, In, Re, 0s, Ir, Pb, or a combination thereof.
  • the metal foil 10 2 is formed by a commercially available metal foil or a conventional plating or vapor deposition method.
  • the metal foil may vary in thickness from several, ni to several mm, and the size of the metal foil grains may range from several hundred nni to several tens. Can be. If necessary, a metal foil 102 having a thickness of "m" or less may be manufactured and used. If the above range is satisfied, the graphene 105 may be formed by diffusion of the carbon atoms 104. .
  • the grains of the metal foil 10 2 are relatively small in size, and when the heat treatment is performed in a specific atmosphere such as ultra-high vacuum or hydrogen atmosphere to increase the size of the metal foil 10 2, You can increase the size.
  • the heat treatment step for increasing the size of the crystal grains of the metal foil 102 may be performed separately from the target substrate 101.
  • damage to the target substrate 101 due to the heat treatment step can be minimized.
  • Heat treatment conditions at this time may be as follows.
  • the elevated temperature may be 50 ° C to 3000 ° C. 500 ° C to 2000 ° C or more specifically 500 ° C to 1500 ° C.
  • the elevated temperature may vary depending on the type of metal foil. The temperature below the melting point of the metal foil can be considered as the maximum temperature.
  • the temperature increase time may be 1 second to 10 hours, 1 second to 1 hour, or more specifically 1 second to 30 minutes.
  • the temperature retention time may be 10 seconds to 10 hours, 30 seconds to 5 hours or more specifically 1 minute to 3 hours.
  • the rate of temperature increase may be o.rc / sec to 50o ° C / sec, o.rc / sec to scrc / sec or more specifically 0.5 ° C / sec to 10 ° C / sec.
  • W is vacuum
  • black is Ar.
  • Inert gases such as N 2 and 3 ⁇ 4. Inflow of gaseous phases such as 0 2 is possible, and combinations thereof are possible, and inflow of 3 ⁇ 4 may be useful for increasing grain size.
  • the grain size in the metal foil is generally increased by several hundreds, "m to hundreds of microwatts.
  • the metal foil 102 having the increased size of the crystal grains may be supplied onto the target substrate 101.
  • the step of increasing the size of the crystal grains of the metal foil 102 may use a method of simultaneously heat-treating the metal foil 102 and the target substrate 101.
  • the heat treatment conditions at this time may vary depending on the type of the target substrate.
  • the target substrate is an inorganic material such as a semiconductor substrate such as Si or GaAs or an insulator substrate such as Si0 2 .
  • the elevated temperature is 400 ° C to 1400 ° C. 400 ° C to 1200 ° C or more specifically 600 ° C to 1200 ° C.
  • the temperature increase time is 1 second to 10 hours. 1 second to 1 hour or more specifically 3 seconds to 30 minutes.
  • the temperature raising time may be 10 seconds to 10 hours, 30 seconds to 3 hours or more specifically 1 minute to 1 hour.
  • the rate of temperature increase may be o.rc / sec to Kxrc / sec, o., Rc / sec to 3o ° c / sec or more specifically o.5 ° c / sec to io ° c / sec.
  • the elevated temperature environment allows for the introduction of vacuum or inert gases such as Ar, N 2 , and gaseous phases such as 3 ⁇ 4, 0 2 , and combinations thereof, and increases grain size. Inflow of H 2 may be useful.
  • the temperature rise temperature may be 30 ° C to 500 ° C, 30 ° C to 400 ° C or more specifically 50 to 300 ° C.
  • the temperature increase time is 1 second to 10 hours. 1 second to 30 minutes or more specifically 3 seconds to 10 minutes.
  • Temperature retention time is 10 seconds to 10 hours, 30 seconds to 5 hours or more specifically
  • the rate of temperature increase may be o.rc / sec to ioo ° c / sec, o.:rc/sec to 3 (rc / sec or more specifically 0.5 kPa sec to 10T sec.
  • the elevated temperature environment may be vacuum or inert gas such as Ar, N 2 and 3 ⁇ 4.
  • the grain size of the metal foil generally grows to 2 to 1000 times.
  • the metal foil 102 having the increased size of the crystal grains may be supplied onto the target substrate 101.
  • the carbon raw material 103 may be supplied onto the metal foil 102.
  • the carbonaceous material ( ⁇ ' ⁇ supplied in step (si)) may be a gaseous phase, a liquid phase, a solid phase, or a combination thereof. More specifically, the gaseous carbonaceous material 103 may include methane, ethane, propane, Butane, isobutane, pentane, isopentane, neopentane, nucleic acid, heptane octane, nonane, decane, metene, ethene propene, butene, pentene, hackene, heptene, octene, nonene, decene ethyne propyne, butyne pentine, nucleosin Cyclomethane Cycloethane, cyclobutane, methylcyclopropane, cyclopentane, methylcyclobutane ⁇ ethy
  • the size of the solid carbon source is 1 ⁇ to 100 cm, lnm to 1 ⁇ or more specifically 1 ⁇ to 100 / ⁇ ⁇
  • the elevated temperature of step (e) (S105) is from 1,500 ° C, 30 ° C to 1,000 ° C or more. more specifically, may be 50 ° C to 800 ° C. This is significantly lower than the temperature of the graphene 105, the temperature of the thin film prepared according to a general chemical vapor deposition process. cost to the process of the above temperature range w Standing can be prevented from the deformation of the target substrate 101 due to the glass hamye temperature higher than the conventional process. In the case of elevated temperature Depending on the target substrate 101, the maximum elevated temperature can be reduced.
  • the room temperature generally means a temperature of an environment in which the manufacturing method is performed.
  • the range of room temperature can be changed by seasons, locations, internal conditions, and the like.
  • the temperature increase time is 1 second to 10 hours, 1 second to 1 hour or more specifically
  • the temperature holding time is 1 second to 100 hours. 1 second to 10 hours or more specifically 5 seconds to 3 hours.
  • the temperature increase rate may be 0.117 seconds to 500 ° C / second, 0.3 ° C / second to 300 ° C / second, or more specifically 0.5 ° C / second to 100 ° C / second.
  • the elevated temperature may be more suitable when the carbon raw material 103 is liquid or solid.
  • the elevated temperature may be room temperature to 1,500 ° C, 300 to 1,200 ° C or more specifically 500 to 1,000 ° C.
  • the time may be 1 second to 10 hours, 1 second to 1 hour, or more specifically 2 seconds to 30 minutes.
  • the temperature retention time may be 1 second to 100 hours, 1 second to 10 hours, or more specifically 1 minute to 5 hours.
  • the rate of temperature increase may be o.rc / sec to 50 ° C./sec, o.:rc/sec to 30 ° C./sec, or more specifically 0.5 ° C./sec to 100 ° C / sec.
  • the desired graphene 105 is stably controlled as the temperature and temperature are adjusted. It becomes possible to manufacture. In addition, the thickness of the graphene 105 may be adjusted by adjusting the temperature and time.
  • the pyrolyzed carbon atoms 104 present on the metal foil 10 2 may diffuse into the metal foil 102 (S105).
  • the principle of diffusion is spontaneous diffusion by a gradient of carbon concentration.
  • the solubility of carbon in metals is typically up to several percent. Due to the catalytic effect of the metal foil 102, the individual carbon atoms 104 pyrolyzed at low temperatures dissolve into the metal foil 102. The dissolved carbon atoms 104 are diffused by the concentration gradient on one surface of the metal foil 102 and then diffused into the metal foil 102. When the solubility of the carbon atoms 104 in the lower surface of the target substrate 101 in the metal foil 102 reaches a predetermined value, the graphene 105, which is stable, precipitates on the other surface of the metal foil 102. Therefore, the graphene 105 is formed between the target substrate 101 and the metal foil 102.
  • the metal foil 102 and the carbon raw material 103 are adjacent to each other, the decomposition of the carbon raw material KB is facilitated due to the catalytic action of the metal foil 102, and as a result, the carbon atoms decomposed when forming the metal-carbon system 104. ) May be spontaneously diffused by a concentration gradient through a dislocation or grain boundary, which is a source of line or planar defects, which are present in a large amount in the polycrystalline metal foil 102.
  • the carbon atoms 104 that spontaneously diffuse and reach the target substrate 101 may diffuse along the interface between the target substrate 101 and the metal foil 102 to form the graphene 105.
  • the diffusion mechanism in the metal foil 102 of the carbon atom 104 is It may vary depending on the type and heating conditions.
  • the filling of the graphene 105 formed by adjusting the temperature increase time and the temperature increase rate can be controlled. This control can produce a multilayer graphene 105 sheet.
  • the graphene 105 sheet may have a thickness ranging from O.lnm, which is a single layer of graphene 105, to about 100 nm, preferably 0.1 to ⁇ , and more preferably 0.1 to 5 ⁇ . It is possible to have. If the thickness is greater than 100 nm, it is defined as graphite rather than graphene 105, which is outside the scope of the present invention.
  • the metal foil 102 is removed. In the case of the metal foil 102 which is not partially removed, it can be completely removed by an organic solvent or the like. In this process, the remaining carbon raw material 103 may also be removed.
  • Organic solvents that can be used are hydrochloric acid. nitric acid. Sulfuric acid. Iron chloride. Pantan. Cyclopentane, hexane. Cyclonucleic acid. benzene. Toluene. 1,4—dioxane, methylene chloride (CHC1 3 ), diethyl ether. Dichloromethane, tetrahydrofuran, ethyl acetate, acetone.
  • the metal foil 102 is patterned before the carbon raw material 103 is supplied, it is possible to produce a sheet of the graphene 105 of a desired shape.
  • the patterning method may be any general method used in the art, and is not described separately.
  • the spontaneous patterning method of the metal foil 102 can be used by pre-heating heat treatment of supplying the carbon raw material 103.
  • a thin metal foil 102 is a high temperature
  • heat treatment it is possible to convert the two-dimensional thin film into the three-dimensional structure by active movement of the metal atoms, and by using this, selective graphene 105 deposition on the target substrate 101 is possible.
  • the target substrate 101 may be a flexible substrate.
  • the metal foil 102 may also be flexible, the curved graphene 105 may be formed on the flexible target substrate 101.
  • the flexible substrate is polystyrene, polyvinyl chloride, nylon, polypropylene. Acryl ⁇ phenol, melamine, epoxy, polycarbonate, polymethyl methacrylate. Polymethyl (meth) acrylate. Plastics, such as polyethyl methacrylate and polyethyl (meth) acrylate, and liquid crystal. Glass, quartz, rubber. Paper and so on. This is not restrictive.
  • the manufacturing method is a step of (d) heating the target substrate and the metal foil (S204) and (d) supplying a carbon raw material on the metal foil in the method for producing a graphene according to an embodiment of the present invention described above (S205) There is a difference in the order of).
  • the temperature rise temperature of step (d) (S204) may be a room temperature to 1,500 ° C, 300 to 1,200 ° C or more specifically 300 to i, oo (rc. This is a graphene 105 according to the general chemical vapor deposition method
  • the temperature range is significantly lower than the temperature of the thin film manufacturing, and the increase of the temperature range is advantageous in view of cost as a process, and prevents deformation of the target substrate 101 due to high temperature.
  • the temperature increase time may be 1 second to 10 hours, 1 second to 1 hour, or more specifically 2 seconds to) minutes.
  • the temperature increase holding time may be 1 second to 100 hours, 1 second to 10 hours, or more specifically 1 minute to 3 hours.
  • the rate of temperature increase may be o.rc / sec to 500 ° C / sec or more specifically 0.5 ° C / sec to 100 ° C / sec.
  • the desired graphene 105 can be stably produced.
  • the thickness of the graphene 105 may be adjusted by adjusting the temperature and time.
  • the above matters relating to the conditions may be more suitable when the carbon raw material 103 is in the gas phase.
  • the liquid and / or Solid carbon sources can be used to produce large graphenes in the order of millimeters to centimeters or more at low temperatures.
  • the equipment used for the existing process temperature-sensitive Si process can be used as it is. have.
  • Method for producing a graphene according to another embodiment of the present invention (a) preparing a target substrate. (b) supplying a metal foil on the target substrate. (c) supplying a carbon raw material onto the metal foil. (d) heating the supplied carbon raw material, the target substrate and the metal foil. (e) diffusing carbon atoms generated by thermal decomposition of the heated carbon raw material into the metal foil and (f) forming graphene on the target substrate by carbon atoms diffused into the metal foil.
  • the metal foil is supplied onto the object substrate. This allows the carbon material to be decomposed at a relatively low temperature due to the catalytic effect of the metal foil when the carbon material is supplied at a later stage. It provides a path through which the decomposed carbon raw material can diffuse as individual atoms to the target substrate. 2; ⁇
  • the elevated temperature of the step (cl) may be from room temperature to 1.500 ° C, 30 ° C to 1.000 ° C, 30 ° C to 800 ° C or more specifically 50 ° C to 600 ° C. This temperature is significantly lower than the silver content of graphene thin film manufacturing according to general chemical vapor deposition. The win of the temperature range is advantageous over conventional processes in terms of cost. The deformation of the target substrate due to the high temperature can be prevented. In the case of elevated temperature, the maximum elevated temperature may decrease depending on the target substrate.
  • the room temperature generally means a temperature of an environment in which the manufacturing method is performed. Therefore, the range of room temperature may be changed by seasons, locations, internal conditions, and the like.
  • the temperature increase time may be 1 second to 10 hours, 1 second to 1 hour, or more specifically, 2 seconds to 20 minutes.
  • the win time can be 1 second to 100 hours, 1 second to 10 hours or more specifically 5 seconds to 3 hours.
  • the rate of temperature increase may be O.rC / sec to 500 ° C./sec, 0.3T sec to 3001 sec, or more specifically 0.5 ° C./sec to 100 ° C / sec.
  • the elevated temperature may be more suitable when the carbon raw material is a liquid phase or solid phase.
  • the carbon raw material when the carbon raw material is in the gas phase, the following temperature raising conditions are possible.
  • the elevated temperature may be from 1 to 500 ° C. 300 to 1.200 ° C or more specifically 500 to 1,000 ° C.
  • the temperature increase time is 1 second to 10 hours, 1 second to 1 hour or more specifically It may be from 2 seconds to 30 minutes.
  • the temperature holding time is 1 second to 100 hours. 1 second to 10 hours or more specifically 1 minute to 5 hours.
  • the temperature increase rate is from 0.1 ° C./s to 500 ° C./s. 0.3 ° C./sec. To 300 ° C./sec, or more specifically 0.5 ° C./sec. To 100 ° C./sec.
  • the thickness of the graphene may be adjusted by adjusting the degree of silver and time.
  • the metal foil is removed, and in the case of the metal foil not partially removed, the metal foil may be completely removed by an organic solvent.
  • the remaining carbon raw material can also be removed in this process.
  • the metal foil is patterned before supplying the carbon raw material, it is possible to produce a graphene sheet of a desired shape.
  • the patterning method may be any general method used in the art, and is not described separately.
  • the spontaneous patterning method of metal foil can be used by heat processing before a carbon raw material supply.
  • the thinly deposited metal foil 102 when the high temperature heat treatment is performed, it is possible to convert from the two-dimensional thin film to the three-dimensional structure by the active movement of the metal atoms. It becomes possible.
  • Another embodiment of the present invention further includes the step of increasing the size of the crystal grain of the metal foil by heat treatment of the metal foil after the supply of the metal foil in the step (b) when compared with the embodiment of the present invention.
  • the grains of the supplied metal foil are relatively small in size, and when the heat treatment is performed in a specific atmosphere such as ultra-high vacuum or hydrogen atmosphere to increase their size, the grain size is controlled and the size is increased. You can.
  • the heat treatment conditions at this time may also vary depending on the type of substrate.
  • the temperature rising temperature is 400 ° C to 1400 ° C, 400 ° C to 1200 ° C or more specifically 600 ° C to May be 1200 ° C.
  • the temperature increase time may be 1 second to 10 hours, 1 second to 1 hour, or more specifically 3 seconds to 30 minutes.
  • the temperature increase holding time may be 10 seconds to 10 hours,: "! 0 second to 3 hours, or more specifically 1 minute to 1 hour.
  • the rate of temperature increase may be 0.1 ° C./s to 100 ° C./s, 0.3T seconds to 30 ° C./s or more specifically 0.5 ° C./s to 10 ° C./s.
  • Temperature environment is vacuum, black is Ar.
  • Inert gases such as N 2 and gaseous inlets such as 3 ⁇ 4 ⁇ 0 2 are possible and mixtures thereof are possible, and inlets of 3 ⁇ 4 may be useful in increasing grain size.
  • Target substrate is polymer.
  • the temperature increase temperature may be 30 ° C to 500 ° C, 30 ° C to 400 ° C or more specifically 50 ° C to 30 CTC.
  • the temperature increase time may be 1 second to 10 hours, 1 second to) minutes or more specifically 3 seconds to 10 minutes.
  • Win time is 10 seconds to 10 hours, 30 seconds to 5 hours or more specifically
  • the rate of temperature increase may be o.rc / sec to ioo ° c / sec, o.:rc/sec to) ° c / sec or more specifically 0.5 ° C./sec to 10 ° C / sec.
  • the elevated temperature environment may be vacuum or Ar.
  • Inert gases such as N 2 , and
  • the size of grains in the metal foil is generally increased by 2 to 1000 times.
  • Liquid and / or solid carbon sources can be used to produce large graphenes on the order of several millimeters to several centimeters or more at low temperatures.
  • the carbon raw material used in the manufacturing method of the graphene according to the embodiment of the present invention is very cheap compared to the existing high-purity carbonized gas.
  • the elevated temperature of step (c) may be from room temperature to 1,500 ° C, 300 to 1,200 ° C or more specifically 300 to 1,000 ° C. This temperature is significantly lower than the silver content of graphene thin film manufacturing according to general chemical vapor deposition.
  • the temperature range of the temperature rising process is advantageous in terms of cost than the existing process, it is possible to prevent the deformation of the target substrate due to the high temperature.
  • the temperature increase time may be 1 second to 10 hours, 1 second to 1 hour, or more specifically 2 seconds to 30 minutes.
  • the temperature increase holding time may be 1 second to 100 hours, 1 second to 10 hours, or more specifically 1 minute to 3 hours.
  • the rate of temperature increase may be o.rc / sec to 500 ° C / sec or more specifically 0.5 ° C / sec to 100 ° C / sec.
  • the thickness of the graphene may be adjusted by adjusting the temperature and time.
  • Matters related to the temperature raising condition may be more suitable when the carbon raw material is in the gas phase.
  • the forming of the pen may include forming graphene on the back surface of the metal foil by carbon atoms diffused into the metal foil: and transferring the graphene formed on the back surface of the metal foil onto the target substrate.
  • Another embodiment of the present invention further includes the step of increasing the size of the crystal grains of the metal foil by heat treating the metal foil after the supply of the metal foil in the step (b).
  • the grains of the supplied metal foil are relatively small in size, and when the heat treatment is performed in a specific atmosphere such as ultra-high vacuum or hydrogen atmosphere to increase their size, the grain size is controlled and the size is increased. You can.
  • the heat treatment conditions at this time may also vary depending on the type of substrate.
  • the temperature rising temperature is 400 ° C. to 1400 ° C., 400 ° C to 1200 ° C. or more specifically 600 ° C. to 1200 May be ° C.
  • the temperature increase time may be 1 second to 10 hours, 1 second to 1 hour, or more specifically 3 seconds to 30 minutes.
  • the temperature retention time is 10 seconds to 10 hours. 30 seconds to 3 hours or more specifically
  • the temperature increase rate is from o.rc / sec to ioo ° c / sec. o.:rc/sec to 3 (rc / sec or more specifically 0.5 ° C / sec to 10 ° C / sec.
  • the temperature rise environment is vacuum. Or inert gases such as Ar, N 2 and. Inflow of gaseous phases such as 0 2 is possible and mixtures thereof are possible, and inflow of 3 ⁇ 4 may be useful in increasing grain size.
  • the elevated temperature is from 30 ° C to 500 ° C.
  • It may be 30 ° C to 400 ° C or more specifically 50 ° C to 300 ° C.
  • the temperature increase time may be 1 second to 10 hours, 1 second to 30 minutes, or more specifically 3 seconds to 10 minutes.
  • the temperature retention time may be 10 seconds to 10 hours 30 seconds to 5 hours or more specifically 1 minute to 1 hour.
  • the rate of temperature increase may be o.rc / sec to lootvsec, o.:rc/sec to 3 (rc / sec or more specifically 0.5T sec to 10 ° C / sec.
  • the elevated temperature environment may be vacuum, black, inert gas such as Ar, N 2 and 3 ⁇ 4, as described above.
  • the metal foil When the metal foil is heat-treated by the above method, it is generally in the metal foil
  • the grain size grows from 2 to 1000 times.
  • Liquid and / or solid carbon sources can be used to produce large graphenes on the order of several millimeters to several centimeters or more at low temperatures.
  • the equipment used for the existing process temperature-sensitive Si process can be used as it is. Can be.
  • the carbon raw material used in the manufacturing method of the graphene according to an embodiment of the present invention is very cheap compared to the existing high purity carbon gas.
  • a transparent electrode comprising graphene 105 prepared according to the method described above.
  • the graphene 105 sheet is used as a transparent electrode.
  • the transparent electrode thus has excellent electrical properties. That is, high conductivity, low contact resistance value, and the like, and the graphene 105 sheet is very thin and flexible, making it possible to produce a bendable transparent electrode.
  • the transparent electrode has excellent conductivity as the graphene 105 sheet is used. Of course. Accordingly, since the desired conductivity can be represented only by a thin thickness, transparency is improved.
  • the transparency of the transparent electrode is preferably from 60 to 99.9%, the sheet resistance of ⁇ / sq. To 2000a / sq. Is preferred.
  • the transparent electrode according to the present invention employing the graphene 105 obtained by the manufacturing method according to an embodiment of the present invention can be manufactured in a simple process, as well as excellent economical efficiency. It has high conductivity and excellent film uniformity. In particular, it can be produced in a large area at a low temperature, and the thickness of the graphene 105 sheet can be freely adjusted, so it is easy to control the transmittance. In addition, since it is flexible, it is easy to handle and can be used in a field requiring a bendable transparent electrode. As a field in which the transparent electrode including the graphene 105 sheet is utilized.
  • Various display elements for example, in the field of batteries, including liquid crystal display devices, electronic paper display devices, organic and inorganic photoelectric devices, and battery fields.
  • the transparent electrode according to the present invention when used for the display element. It is possible to bend the display element freely, thereby increasing convenience, and in the case of a solar cell, the transparent electrode according to the present invention can have various curved structures according to the direction of light movement, thereby enabling efficient use of light. It is possible to improve the light efficiency.
  • the thickness of the transparent electrode When using the graphene 105 sheet-containing transparent electrode according to an embodiment of the present invention in a variety of devices. It is preferable to adjust the thickness suitably in consideration of transparency. For example, to form a transparent electrode with a thickness of 0.1 to 100 ⁇ If possible, when the thickness of the transparent electrode exceeds 100 nm, transparency may be deteriorated and light efficiency may be deteriorated, and when the thickness is less than O.lnm. It is not preferable because the sheet resistance may be too low or the film of the graphene 105 sheet may become uneven.
  • An example of a solar cell employing a graphene 105 sheet-containing transparent electrode according to an embodiment of the present invention is a dye-sensitized solar cell, and the dye-sensitized solar cell includes a semiconductor electrode, an electrolyte charge, and a counter electrode.
  • the semiconductor electrode is made of a conductive transparent substrate and a light absorbing insect. It is completed by coating a colloidal solution of nanoparticle oxide on a conductive glass substrate, heating it in a high temperature electric furnace, and then adsorbing a dye.
  • a graphene 105 sheet-containing transparent electrode according to the present invention is used as the conductive transparent substrate.
  • Such a transparent electrode can be obtained by directly forming the graphene 105 sheet on a transparent substrate according to an embodiment of the present invention, and as the transparent substrate, for example, polyethylene terephthalate, polycarbonate. Polyimide. Transparent polymeric materials or glass substrates such as polyamide or polyethylenenaphthalate or copolymers thereof can be used. This also applies to the counter electrode as it is.
  • the transparent electrode In order to form a structure capable of bending the dye-sensitized solar cell, for example, a cylindrical structure, it is preferable that in addition to the transparent electrode, the counter electrode and the like are all soft together.
  • the nanoparticle oxide used in the solar cell is preferably an n-type semiconductor in which conduction band electrons become carriers and provide an anode current under optical excitation as semiconductor fine particles.
  • the said metal oxide is not limited to these. These can be used individually or in mixture of 2 or more types.
  • Such semiconductor fine particles preferably have a large surface area in order for the dye adsorbed on the surface to absorb more light, and for this purpose, the particle size of the semiconductor fine particles is preferably about 20 ⁇ or less.
  • the dye may be used without limitation as long as it is generally used in the solar cell or photovoltaic field, ruthenium complex is preferred.
  • ruthenium complex RuL 2 (SCN) 2 , RuL 2 (H 2 0) 2 , RuL 3 , RuL 2 , and the like can be used (wherein L is 2,2′-bipyridyl-4,4′-dicar). Carboxylate and the like).
  • the dye is not particularly limited as long as it has a charge separation function and exhibits a sensitizing action.
  • xanthine-based pigments such as rhodamine B, rosebengal, eosin, and erythrosine, quinocyanine and kryptoshi Cyanine-based pigments such as. Phenosafranin, cabrio blue.
  • Basic dyes such as thiocin and methylene blue.
  • Porphyrin-based compounds such as chlorophyll, zinc porphyrin, magnesium porphyrin, and other azo pigments. Phthalocyanine compounds, Ru trisbipyridyl and other complex compounds, anthraquinone dyes, polycyclic quinone dyes and the like. These may be used alone or in combination of two or more thereof.
  • the thickness of the light absorbing insect including the nanoparticle oxide and the dye is 15 / m or less, preferably 1 to 15 / zm. Because the light absorption layer has a large series resistance for structural reasons and an increase in the series resistance causes a decrease in conversion efficiency, the film thickness is kept to 15 am or less, thereby maintaining the function while maintaining the function of the series resistance. of The fall can be prevented.
  • Examples of the electrolyte charge used in the dye-sensitized solar cell include a liquid electrolyte ionic liquid electrolyte, an ionic gel electrolyte, a polymer electrolyte, and a composite therebetween. Representatively, it is made of an electrolyte solution, and includes the light absorption layer, or is formed so that the electrolyte solution is infiltrated into the light absorption layer.
  • an electrolyte for example, an acetonitrile solution of iodine may be used, but the present invention is not limited thereto, and any electrolyte may be used without limitation as long as it has a hole conduction function.
  • the dye-sensitized solar cell may further include a catalyst layer, such a catalyst layer is platinum for promoting the redox reaction of the dye-sensitized solar cell.
  • a catalyst layer is platinum for promoting the redox reaction of the dye-sensitized solar cell.
  • Carbon, graphite, carbon nano-lube, carbon black, 1) -type semiconductors and composites thereof may be used, and they may be located between the electrolyte charge and the counter electrode. It is preferable that such a catalyst layer has increased surface area in a microstructure.
  • the carbon in the porous state can be formed by a method such as sintering carbon fine particles or firing an organic polymer.
  • the dye-sensitized solar cell as described above is excellent in conductivity and has excellent light efficiency and processability by employing a flexible graphene 105-containing transparent electrode.
  • the organic photoelectric device is if the current to the fluorescent or phosphorescent organic thin film. It is an active light emitting display device using a phenomenon in which light is generated while electrons and holes are combined in an organic layer.
  • an organic photoelectric device has an anode formed on an upper portion of a substrate, and a hole transport layer, a light emitting charge, an electron transport layer, and a cathode are sequentially formed on the anode.
  • an electron injection layer and a hole injection layer may be further provided, and a hole blocking insect, a buffer layer, etc. may be further provided as necessary.
  • the anode is preferably a transparent material having excellent conductivity, and the graphene 105 sheet-containing transparent electrode according to the present invention may be usefully used.
  • the material of the hole transport layer a material commonly used may be used, and preferably, polytriphenylamine may be used, but is not limited thereto.
  • the material of the electron transport layer a material that is commonly used may be used.
  • a material that is commonly used may be used.
  • polyoxadiazole may be used, but is not limited thereto.
  • a fluorescent or phosphorescent light emitting material which is generally used can be used without limitation. And it may further comprise one or more selected from the group consisting of a non-luminescent polymer matrix.
  • the polymer host, the low molecular host, and the non-luminescent polymer matrix may be used as long as they are commonly used when forming the light emitting layer for the organic electroluminescent device.
  • Poly (vinylcarbazole). Polyfluorene.
  • Poly (P-phenylene vinylene), polythiophene, and the like, and examples of low molecular weight hosts include CBP (4.4'-N.N'-dicarbazole-biphenyl), 4.4'-bis [9- (3, 6-biphenylcarbazolyl)]-1--1-, ⁇ -biphenyl ⁇ 4,4'—bis [9- (3,6-biphenylcarbazolyl)]-1-1. ⁇ -phenyl ⁇ , 9, 10—bis [(2'.7'-t-butyl) -9 ', 9''-spirobifhiorenylanthracene. Tetrafluorene and the like.
  • Non-luminescent polymer matrices include polymethylmethacrylate, polystyrene, and the like. It is not limited to this.
  • the above-mentioned light emitting layer is vacuum deposition method, sputtering method. Printing method, coating method. It may be formed by an inkjet method or the like.
  • Fabrication of the organic electroluminescent device according to an embodiment of the present invention does not require a special device or method, it can be manufactured according to the manufacturing method of the organic electroluminescent device using a conventional light emitting material.
  • the graphene prepared according to one embodiment of the present invention may be used as an active layer of the electronic device.
  • the active layer may be used in a solar cell.
  • the solar cell may include at least one active layer between the lower electrode layer and the upper electrode layer stacked on the substrate.
  • the substrate is, for example, a polyethylene terephthalate substrate.
  • the metal substrate may be selected from any one of gallium arsenide substrates.
  • the lower electrode layer is, for example, graphene sheet, indium-tin-oxide (IT0:
  • the electronic device is a transistor. Sensor or organic-inorganic semiconductor device.
  • Group III-V and II-VI compound semiconductor heterojunction structures were formed, and band gap engineering using the same resulted in limiting electron movement to two dimensions, thereby allowing high electron mobility of about 100 to 1,000 cnr / Vs.
  • the theoretical calculations show that graphene has a high electron mobility of 10,000 to 100,000 cniVVs.
  • the sensor can detect the minute change caused by the adsorption / desorption of molecules in one layer of graphene can have a superior sensing characteristics compared to the conventional sensor.
  • Graphene according to one embodiment of the present invention may be used in a battery.
  • the battery may be a lithium secondary battery.
  • Lithium secondary batteries can be classified into lithium secondary batteries, lithium ion polymer batteries, and lithium polymer batteries according to the type of separator and electrolyte used, and are cylindrical, rectangular, and coin-shaped according to their shape. It can be classified into pouch type and the like, and can be divided into bulk type and thin film type according to the size. Since the structure and manufacturing method of these batteries are well known in the art, detailed description thereof will be omitted.
  • the lithium secondary battery includes a negative electrode, a positive electrode and a separator disposed between the negative electrode and the positive electrode, an electrolyte impregnated in the negative electrode, the positive electrode and the separator, and a battery container.
  • the sealing member which encloses the said battery container is comprised as a main part. These lithium secondary batteries are. cathode.
  • the positive electrode and the separator are sequentially stacked and then housed in a battery container in a state of being wound onto a spiral.
  • the positive electrode and the negative electrode may include a current collector, an active material, a binder, and the like.
  • Graphene according to an embodiment of the present invention described above may be used as the current collector.
  • the electron mobility is excellent, and thus the rate characteristic of the battery. Lifespan characteristics and the like can be improved.
  • the graphene according to one embodiment of the present invention is not limited to the above-mentioned uses, and any field and use that can use the characteristics of the graphene may be used.
  • graphene was formed on a Si0 2 / Si substrate using a liquid carbon raw material and nickel metal foil.
  • nickel metal foil a metal foil having a purity of 99.95% and a thickness of 1 // ⁇ purchased from Goodfellow was used. Size and orientation of average grain size of nickel metal foil In order to control, the nickel metal foil was heat-treated in a high purity hydrogen atmosphere at 1.100 for 1 hour in a high vacuum chamber.
  • FIG. 3 is an SEM image of nickel metal foil after heat treatment
  • FIG. 4 is a distribution diagram of average grain sizes of nickel metal foil after heat treatment.
  • Nickel metal foil before heat treatment exists in the same ratio between (111) and (200) planes. As a result of the heat treatment, it was confirmed that most nickel crystal grains were oriented in the (200) plane. After heat treatment, the nickel metal foil is placed on the target substrate, Si0 2 / Si. Supply carbon raw material on the metal foil.
  • Graphite powder was used as the carbon raw material.
  • Graphite powder was purchased from Aklrich (product 496596, batch number M BB1941), and the average particle size of graphite powder was less than 40 mm 3.
  • Graphite powder was mixed with ethane to form a slush form, and it was placed on nickel metal foil, dried at an appropriate temperature, and then fixed to the specimen using a jig made of a special material.
  • the specimen prepared in the above manner was put in an electric furnace and heat treated to allow carbon raw material to spontaneously diffuse through the nickel metal foil.
  • the heat treatment temperature was. The win took less than three minutes and argon Heated in atmosphere.
  • the temperature retention time was 1 hour.
  • the graphene was formed between the target substrate and the nickel metal foil.
  • a PMMA (poly (methyl methacrylate)) layer was formed on the graphene formed on the nickel metal foil by spin coating, and the nickel metal foil was etched.
  • the etching solution was used FeCl 3 aqueous solution.
  • the graphene was transferred to the SiO 2 / Si substrate using the resulting graphene / PMMA heterostructure.
  • Example 7 is an optical micrograph of the formed graphene.
  • Example 2 Preparation of Graphene
  • Example 1 the carbon raw material was added to the nickel metal foil, and then heat-treated at 160 0 C to perform a process of forming graphene between the nickel metal foil and the target substrate.
  • the sample fixed to the jig is introduced into a rapid thermal annealing (RTA) and heat treated at 400 for 1 minute. After that, as in Example 1, the back of the nickel metal foil I could confirm that graphene was formed.
  • the large area graphene formed was transferred to a SiO 2 / Si substrate using PMMA.
  • Graphene was prepared in the same manner as in Example 2 except that the graphene was formed in Example 2 and then heat-treated at 400 to 10 minutes in a rapid heat treatment machine. 9 is an optical micrograph of the formed graphene.
  • the thicker the thickness of the nickel metal foil was the more easily graphene was formed and the physical properties of the graphene were also reduced.
  • the thinner the thickness of the nickel metal foil was confirmed that there is a disadvantage that the experiment is not easy due to the flexibility of the metal foil itself.
  • FIG. 10 is a graph showing a change in intensity ratio (I D / I G ) between the D peak and the G peak in Raman spectroscopy measurement results according to post-heat treatment conditions after graphene formation.
  • I D / I G a change in intensity ratio
  • the post-heat treatment was performed at 400 0 C for 1 minute or 10 minutes, the ID / IG values were confirmed to have values of 0.2 (Example 2) and 0.1 (Example 3), respectively, thereby improving the physical properties of the graphene. It can be confirmed.

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Abstract

La présente invention concerne un procédé de préparation de graphène, une électrode transparente contenant ce graphène, une couche active et un dispositif d'affichage, un dispositif électronique, un dispositif photovoltaïque, une batterie, une cellule solaire et une cellule solaire à colorant qui emploient ce graphène. Le procédé de préparation de graphène comprend les étapes suivantes : (a) préparation d'un substrat cible et d'une feuille de métal; (b) augmentation de la taille des grains de la feuille de métal par traitement thermique de la feuille de métal; (c) amenée de la feuille de métal dans laquelle la taille des grains est augmentée jusqu'au substrat cible; (d) amenée d'un combustible carboné sur la feuille de métal; (d) chauffage dudit combustible carboné, du substrat et de la feuille de métal; (e) diffusion d'atomes de carbone, générés par la pyrolyse du combustible carboné chauffé, dans la feuille de métal; et (f) formation de graphène sur le substrat cible par les atomes de carbone diffusés dans la feuille de métal.
PCT/KR2012/000635 2011-01-28 2012-01-27 Procédé de préparation de graphène, électrode transparente contenant ce graphène, couche active et dispositif d'affichage, dispositif électronique, dispositif photovoltaïque, batterie, cellule solaire et cellule solaire à colorant qui emploient ce graphène WO2012102574A2 (fr)

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CN109888101A (zh) * 2019-02-19 2019-06-14 江苏赛清科技有限公司 一种碳基叠合太阳能电池及其制备方法
CN113555695A (zh) * 2021-07-14 2021-10-26 东南大学 Ku波段的高透明柔性动态调频吸波表面结构及其制备方法
CN114890410A (zh) * 2022-06-30 2022-08-12 常州二维碳素科技股份有限公司 一种高产率高质量石墨烯粉体的制备方法

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