WO2013019021A2 - Graphene laminate including dopant and manufacturing method thereof - Google Patents

Graphene laminate including dopant and manufacturing method thereof Download PDF

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WO2013019021A2
WO2013019021A2 PCT/KR2012/005945 KR2012005945W WO2013019021A2 WO 2013019021 A2 WO2013019021 A2 WO 2013019021A2 KR 2012005945 W KR2012005945 W KR 2012005945W WO 2013019021 A2 WO2013019021 A2 WO 2013019021A2
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graphene
layer
dopant
graphene laminate
polymer
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French (fr)
Korean (ko)
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WO2013019021A3 (en
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권오관
최정옥
정준호
최면천
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주식회사 엘엠에스
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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    • B82—NANOTECHNOLOGY
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    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
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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
    • C01B32/186—Preparation by chemical vapour deposition [CVD]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
    • B32B2457/208—Touch screens

Definitions

  • the present invention relates to a graphene laminate with reduced sheet resistance and a method of manufacturing the same.
  • Graphene is a term made by combining the suffix -ene, which means a molecule having a double bond of graphite, which means graphite, and a two-dimensional allotrope of carbon, which has hexagonal lattice. do.
  • the infinite plane of graphene represents an energy-free region of electrons where the valence and conduction bands meet. Looking at the properties of the graph in more detail as follows.
  • the thickness of the graphene layer is about 0.34 nm, which corresponds to one carbon atom, and has a very useful property different from existing materials.
  • carrier mobility in monolayer graphene is up to 200,000 cm 2 / Vs, which is 100 times higher than silicon at room temperature, far beyond the 70,000 cm 2 / Vs of InSb.
  • the electrical resistance at room temperature is as small as 2/3 of copper, and has a current density of 100 million to 200 million A / cm 2 , and can withstand about 100 times the current density of the amount flowing through copper. Due to such excellent physical properties, the graphene layer has a very high application potential as an electronic device material, and is applicable to transistors, lasers, touch panels, organic light emitting devices, solar cells, or electrodes of secondary batteries.
  • the graphene layer transferred onto the substrate may be easily influenced by external physical and chemical environments, thereby changing the sheet resistance, which is important for graphene electrode applications.
  • the sheet resistance change acts as a cause of inhibiting physical properties and large area when forming various elements such as transparent electrodes.
  • the present invention provides a graphene laminate with reduced sheet resistance and a method of manufacturing the same.
  • the present invention provides a graphene laminate and a method of manufacturing the same, which are not affected by external environmental factors and maintain sheet resistance and light transmittance without a separate sealing process.
  • Graphene laminate according to the present invention is a substrate; A dopant-containing polymer layer; And a graphene layer. In addition, it provides a method for producing the graphene laminate.
  • the graphene laminate according to the present invention may have low sheet resistance and high light transmittance, and thus may be utilized in various forms of electronic devices.
  • FIG. 1 is a schematic view showing a laminated structure for the graphene laminate according to an embodiment of the present invention
  • FIGS. 2 and 3 are each a process chart showing a graphene transfer method according to an embodiment of the present invention.
  • FIG. 4 is a cross-sectional view illustrating a graphene stack structure including a graphene layer according to an embodiment of the present invention.
  • 5 and 6 are graphs showing the results of measuring the light transmittance of the graphene laminate according to an embodiment of the present invention, respectively.
  • Graphene laminate according to the present invention, the substrate; A dopant-containing polymer layer; And a graphene layer.
  • the graphene laminate according to the present invention includes a dopant and has a sheet resistance value of 600 ⁇ / sq or less, specifically 10 ⁇ / sq to 400 ⁇ / sq.
  • the graphene laminate may be utilized in various electronic devices such as transparent electrodes due to the low sheet resistance value.
  • the polymer layer is polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, fluorine, acrylic, polyvinyl acetate, polyamide, polyacetal, polycarbonate, polyphenylene oxide It may include one or more of a polyester, a polysulfone, a polyimide, a phenolic, urea, melamine, alkyd, unsaturated polyester, epoxy, silicon, acrylic and polyurethane. As the polymer, a thermosetting or thermoplastic polymer may be applied without particular limitation.
  • the polymer layer may include a conductive polymer.
  • Conductive polymers include, for example, polyacetylene, polydiacetylene, polyphenylene, polyaniline, polythiophene, polyphenylenevinylene, polythiophenevinylene, polypyrrole, polyfluorene and PEDOT: PSS (Poly (3 , 4-ethylenedioxythiophene) poly (styrenesulfonate)) may include any one or more.
  • the polymer layer may include a photocurable polymer.
  • a polymer layer may be formed through a UV curing process.
  • the photocurable polymer may be polymerized with one or more monomers of the following Chemical Formulas 1 to 3. .
  • n is an integer of 3 to 20.
  • the polymer layer may be an adhesive polymer including a repeating structure of one or more of the following Chemical Formulas 4 to 7.
  • R 1 is an alkyl group of C5 to C30
  • R 2 is an alkyl group of C5 to C20; Or a C6 to C30 aryl group having a substituted or unsubstituted C1 to C20 alkyl group,
  • R 3 is an alcohol group; Halogen group; Or a C1 to C10 alkyl group including any one or more of an alcohol group, a carboxyl group, a sulfonic acid group, an amine group, a carbonyl group, a cyano group, and a halogen group at the terminal of the substituent,
  • R 4 is a C1 to C10 alkyl group including a linear or branched chain type
  • X 1 to X 4 are each independently hydrogen or an alkyl group of C1 to C5,
  • n is an integer of 0-10.
  • the number of repetitions of the structure shown in Chemical Formulas 4 to 7 above is not particularly limited. This is because the repeating structures of Formulas 4 to 7 form a polymer layer.
  • the number of repetitions of the structure of Chemical Formulas 4 to 7 may be independently 1 to 1,000,000 range, but is not limited thereto.
  • the adhesive polymer not only has excellent adhesive properties with the graphene layer, but also due to such excellent adhesive properties, it is possible to improve the stability of the graphene layer with respect to transfer efficiency and external environmental factors of graphene.
  • the polymer layer may have a glass transition temperature of minus 10 °C to image 100 °C.
  • the glass transition temperature is a range that can increase the adhesion with the substrate and the graphene layer. If the glass transition temperature is less than minus 10 °C, the mechanical properties of the polymer layer is poor, the graphene layer transferred to the polymer layer can be easily damaged. If the glass transition temperature exceeds 100 °C image between the polymer layer and the graphene It is difficult to contact the interface of the adhesive force can be reduced.
  • the dopant according to the present invention is not particularly limited, but may preferably include a P-type dopant.
  • the dopant is included in the polymer layer and has an effect of lowering sheet resistance.
  • the dopant may include one or more of halogen oxide, sulfur oxide, metal halide, nitrogen oxide, metal peroxide, benzoquinone compound and dibromoanthracene.
  • Halogen oxides, sulfur oxides, metal halides, nitrogen oxides, metal peroxides, benzoquinone compounds, and dibromoanthracene are very effective materials for doping P-type dopants. Also affects.
  • By controlling the work function of the graphene thin film by doping with a P-type dopant it is possible to manufacture a functionalized graphene transparent electrode.
  • such graphene transparent electrode has excellent light transmittance, sheet resistance value and flexibility can be used in various transparent electrode applications.
  • the halogen oxide may include at least one of iodine oxide and chlorine oxide.
  • the iodine-based oxide may include at least one of iodilbenzene, iodoxybenzoic acid, and des-martin periodinan.
  • the chlorine-based oxide may include one or more of NaClO, NaClO 2 , NaClO 3 , NaClO 4 , AgClO 3 and AgClO 4 .
  • the sulfur oxide may include one or more of (CH 3 ) 2 SO, KHSO 5 , KHSO 4 , K 2 SO 4 , FSO 3 H and CF 3 SO 3 H.
  • the metal halide may be a metal salt including one or more of silver ions, gold ions, cerium ions, iron ions, molybdenum ions, tungsten ions, tin ions, ruthenium ions, and tantalum ions.
  • the metal halides are FeCl 3 , MoCl 5 , WCl 5 , SnCl 4 , MoF 5 , RuF 5 , TaBr 5 , SnI 4 , HAuCl 4 , AuCl 3 , (NH 4 ) 2 Ce (SO 4 ) 3 and (NH 4 ) And at least one of 2 Ce (NO 3 ) 6 .
  • the nitrogen oxides are AgNO 3 , NO 2 F, NO 2 Cl, N 2 O 5 , NO 2 BF 4 , CH 3 NO 2 , C 6 H 5 NO 2 , CH 3 ONO, NO (SbCl 6 ), NOBF 4 , It may comprise one or more of NOClO 4 , NOSO 4 H, C 6 H 5 NO, NOCl, NOF and NOBr.
  • metal peroxide may include KMnO 4, BaMnO 4, one or more of OsO 4.
  • benzoquinone-based compound may include one or more of benzoquinone, tetrachlorobenzoquinone, dichlorodicyanobenzoquinone and tetracyanoquinomethane.
  • the content of the dopant according to the present invention may be 0.01 to 20 wt%, preferably 0.1 to 10 wt%, based on the dopant-containing polymer layer.
  • the content of the dopant is less than 0.01wt%, the sheet resistance reduction effect is insignificant, and when it exceeds 20wt%, the film flatness may decrease.
  • the material constituting the substrate is not particularly limited, and for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyethersulfone (PES), polycyclic olefin (PCO), poly And one or more of acrylate (PA), polyetheretherketone (PEEK), and polyimide (PI).
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • PC polycarbonate
  • PES polyethersulfone
  • PCO polycyclic olefin
  • PA acrylate
  • PEEK polyetheretherketone
  • PI polyimide
  • FIG. 1 is a schematic diagram showing a laminated structure of a graphene-coated substrate according to an embodiment of the present invention. Referring to FIG. 1, it can be seen that the substrate 10, the polymer layer 20 including the dopant, and the graphene layer 30 are sequentially stacked on the substrate 10.
  • the present invention provides a method for producing the graphene laminate.
  • the manufacturing method For example, the manufacturing method,
  • the type and content of the dopant and the polymer used in the manufacturing method are as described above.
  • the content of the dopant may be 0.01 to 20 wt%, preferably 0.1 to 10 wt%, based on the dopant-containing polymer layer.
  • a dry or wet transfer method may be used depending on a method of removing a metal catalyst layer.
  • a roll-to-roll method may be used.
  • the dry transfer method has the advantage that the graphene layer formed on the metal catalyst layer can be directly transferred onto the target substrate without including a solution process using a solvent or water.
  • the present invention does not exclude a wet process.
  • the metal catalyst layer can be removed using an etching solution.
  • the roll-to-roll system can be used, for example.
  • the metal catalyst layer and the graphene layer are separated by a roll-to-roll method. .
  • the metal catalyst layer can be removed using, for example, an etchant.
  • the metal catalyst layer may be removed using an etching solution.
  • the metal catalyst layer is not particularly limited, and for example, a copper foil or a nickel thin film may be used.
  • the etchant is not particularly limited as long as it can remove the metal catalyst layer, for example, acid, hydrofluoric acid (HF), buffered oxide etchant (BOE), ferric chloride (FeCl 3 ) solution, and ferric nitrate (Fe). (NO 3 ) 3 ) solution and one or more of ammonium persulfate ((NH 4 ) 2 S 2 O 8 ).
  • the polymer is not particularly limited, and a thermoplastic polymer may be used.
  • a separate curing process is not required, but when a thermosetting or photocurable polymer is used, a curing process of applying heat or irradiating UV may be included.
  • the graphene layer formed on the metal catalyst layer and the polymer-coated substrate including the dopant may be laminated and may include a thermal or UV curing process.
  • the graphene layer used in the present invention may have a structure formed on both sides of the metal catalyst layer, after laminating a substrate coated with a dopant-containing polymer, respectively, on the outer surface of the graphene layer formed on both sides of the metal catalyst layer, to remove the metal catalyst layer Process may be included.
  • This is advantageous in that two graphene laminates can be formed through a single manufacturing process, thereby doubling the manufacturing efficiency. Even in this case, a separate curing process may be performed depending on the type of polymer used.
  • it may include a thermal or UV curing process.
  • FIGS. 2 and 3 schematically show a method of manufacturing a graphene laminate according to an embodiment of the present invention, respectively.
  • a polymer layer 20 is formed by applying a polymer including a dopant to one surface of the substrate 10. Then, the metal catalyst layer 40 on which the graphene layer 30 is formed is laminated. In this case, the polymer layer 20 and the graphene layer 30 are in direct contact with each other, and may be in close contact with a roller or the like to increase adhesion. Although it may vary depending on the components constituting the polymer layer, when the polymer is photocurable, it may include a process of curing through UV irradiation. Then, the metal catalyst layer 40 is removed. Removal of the metal catalyst layer 40 may be performed through a roll-to-roll process.
  • the metal catalyst layer 40 can be removed using an etchant.
  • the kind of etching liquid which can be used is not specifically limited.
  • 3 shows a process chart of the graphene transfer method according to another embodiment.
  • 3 discloses a method in which both graphene layers 31 and 32 formed on both surfaces of the metal catalyst layer 40 can be utilized.
  • Two substrates 11 and 12 having the dopant-containing polymer layers 21 and 22 are laminated on the upper and lower graphene layers 31 and 32 of the metal catalyst layer 40, respectively.
  • the process of irradiating heat or UV may be further processed.
  • the metal catalyst layer is removed using a roll-to-roll or etching solution, two laminated structures consisting of the substrate 10, the dopant containing polymer layers 21 and 22 and the graphene layers 31 and 32 are obtained.
  • This method compared with the conventional graphene transfer method can improve the process efficiency twice, and can minimize the amount of graphene lost in the transfer process.
  • the present invention also provides an intermediate structure of the graphene laminate formed during the transfer process.
  • the intermediate structure is a state before the metal catalyst layer is removed.
  • the graphene laminate may include a structure in which a substrate, a polymer layer including a dopant, a graphene layer, a metal catalyst layer, a graphene layer, a polymer layer including a dopant, and a substrate are sequentially stacked.
  • 4 shows an example of a graphene laminate.
  • the laminate has a symmetrical structure based on the copper foil 40 which is a metal catalyst layer.
  • the substrate 11, the dopant-containing polymer layer 21, and the graphene layer 31 are sequentially stacked, and the metal catalyst layer 40 is formed on the graphene layer 31.
  • the graphene layer 32, the dopant-containing polymer layer 22, and the substrate 10 are sequentially formed on the metal catalyst layer 40.
  • the present invention provides an electrode or a conductive thin film comprising the graphene laminate described above.
  • the electrode or the conductive thin film may be utilized in various types of electronic devices without particular limitation.
  • the electronic device may be applied as a transistor, a laser device, a touch panel, an organic light emitting device, a solar cell, or an electrode of a secondary battery.
  • the dopant-containing solution was applied to a PET substrate (thickness 75 ⁇ m) by spin coating, and dried at 70 ° C. for 1 hour to produce a thin film having a thickness of about 1 ⁇ m on the PET substrate.
  • Copper foil (thickness 25 ⁇ m, purity 99.8%), which is a metal catalyst having a size of 5 cm ⁇ 5 cm, was charged to a quartz tube for producing a graphene layer.
  • the graphene layer formed on the copper foil was laminated on a PET substrate coated with a polymer containing a dopant. Specifically, the surface where the graphene is formed on the copper foil and the surface on which the dopant-containing polymer is applied to the PET substrate are faced to each other, and the PET substrate and the graphene layer are laminated by applying pressure. Then, a graphene laminate including a copper foil was formed through a UV curing process. The graphene laminate including the copper foil was prepared using a 0.1 M (NH 4 ) 2 S 2 O 8 aqueous solution to remove the graphene laminate from the copper foil.
  • Example 2 was prepared in the same manner as in Example 1, except that 10g of the monomer represented by the formula (8) and 3g of the monomer represented by the following formula (3) used in Example 1.
  • a graphene laminate was manufactured in the same manner as in Example 1, except that 0.1 wt% of FeCl 3 was used as the dopant.
  • This Example was prepared in the same manner as in Example 1 except that KMnO 4 0.1wt% as a dopant was prepared.
  • This example uses NaClO as a dopant.
  • a graphene laminate was manufactured in the same manner as in Example 1, except that 0.1 wt% was used.
  • Comparative Example 1 is a graphene laminate containing no dopant, except that the dopant application process of Example 1, a graphene laminate was prepared in the same manner as in Example 1.
  • Comparative Example 2 is a graphene laminate containing no dopant, except that the dopant application process of Example 1, a graphene laminate was prepared in the same manner as in Example 2.
  • the sheet resistance of the graphene laminates prepared in Example 1 and Comparative Example 1 is shown in Tables 1 and 2 by measuring an arbitrary 9 section with a 4-point probe.
  • Table 1 Measure Sheet resistance ( ⁇ / sq) One 298 2 302 3 288 4 274 5 278 6 264 7 277 8 254 9 279
  • the measurement 1 to 9 means any 9 intervals.
  • Table 1 shows the sheet resistance values of Example 1, and the average sheet resistance values of 279 ⁇ / sq on average.
  • the sheet resistance of Comparative Example 1 disclosed in Table 2 represents an average of 828 ⁇ / sq, and it was confirmed that the sheet resistance was reduced to about 1/3 due to the use of the dopant tetracyanoquinomethane.
  • Table 3 shows the sheet resistance of Example 2, and the average sheet resistance of 351 ⁇ / sq.
  • the sheet resistance value of Comparative Example 2 disclosed in Table 4 was found to be an average of 832 ⁇ / sq. Through this, it was confirmed that the sheet resistance value was reduced to about 2/5 due to the use of the dopant tetracyanoquinomidimethane. In addition, it was confirmed that using the monomer of the formula (11) than the monomer of the formula (3) is more effective in lowering the sheet resistance value.
  • Tables 5 to 7 show sheet resistance values of Examples 3 to 5, respectively, and average sheet resistance values of 407 ⁇ / sq, 550 ⁇ / sq, and 506 ⁇ / sq, respectively. It can be seen that a slight difference occurs in the sheet resistance value depending on the type of dopant. From the above results, it was confirmed that the sheet resistance value was lowered to about 3/5 or less when the dopant was used as compared with the case where the dopant was not used.
  • the light transmittance of the graphene laminates prepared in Examples 1 and 2 was measured. Specifically, the light in the UV / visible region was irradiated and the amount of transmitted light was measured in%.
  • Figure 5 shows the light transmittance measurement results for the graphene laminate prepared in Example 1. Referring to FIG. 5, it was confirmed that the light transmittance of 97% or more in the entire wavelength band region, and the light transmittance of 97.83% for the light of 550 nm wavelength.
  • Figure 6 shows the light transmittance measurement results for the graphene laminate prepared in Example 2. Referring to FIG. 6, light transmittance of 97% or more was exhibited in the entire wavelength band, and light transmittance of 97.67% was observed for light having a wavelength of 550 nm.
  • the graphene laminate including the dopant of the present invention has excellent light transmittance in addition to the sheet resistance reduction effect.

Abstract

The present invention relates to a graphene laminate including a structure where a substrate, a polymer layer including a dopant, and a graphene layer are subsequently laminated, and a manufacturing method thereof, wherein the graphene laminate has low surface resistance and high optical transmittance and thus can be used for various electrical devices, and the like.

Description

도펀트 포함 그래핀 적층체 및 그 제조방법Graphene Laminates with Dopants and Manufacturing Method Thereof
본 발명은 면저항이 감소된 그래핀 적층체 및 그 제조방법에 관한 것이다. The present invention relates to a graphene laminate with reduced sheet resistance and a method of manufacturing the same.
그래핀(graphene)이란 흑연을 의미하는 그라파이트(graphite)와 탄소(carbon)의 이중결합을 가진 분자를 뜻하는 접미사 -ene을 결합해서 만든 용어로서 육각형의 격자를 가진 탄소의 2차원적인 동소체를 의미한다. 그래핀의 무한한 평면은 원자가띠와 전도띠가 만나는 전자가 없는 에너지 영역을 보인다. 그래핀의 성질을 보다 구체적으로 살펴보면 아래와 같다.Graphene is a term made by combining the suffix -ene, which means a molecule having a double bond of graphite, which means graphite, and a two-dimensional allotrope of carbon, which has hexagonal lattice. do. The infinite plane of graphene represents an energy-free region of electrons where the valence and conduction bands meet. Looking at the properties of the graph in more detail as follows.
그래핀층의 두께는 탄소원자 1개에 해당하는 약 0.34nm로 기존의 물질과 다른 매우 유용한 특성을 가지고 있다. 특히, 단층 그래핀 내에 캐리어 이동도는 실온에서 실리콘에 비하여 100배나 높은 최대 20만cm2/Vs이 되어 종래 최대로 알려진 인듐 안티몬(InSb)의 7.7만cm2/Vs를 훨씬 넘어선다. 또한 실온에서의 전기 저항치도 구리의 2/3로 작으며, 1억~2억A/cm2의 전류밀도를 가져 구리에 흐르는 양의 약 100배의 전류밀도에 견딜 수 있다. 이러한 우수한 물성으로 인해, 그래핀층은 전자 소자용 재료로서 매우 높은 응용 가능성을 가지고 있으며, 트랜지스터, 레이저, 터치패널, 유기발광소자, 태양전지 또는 이차전지의 전극 등으로 응용이 가능하다. The thickness of the graphene layer is about 0.34 nm, which corresponds to one carbon atom, and has a very useful property different from existing materials. In particular, carrier mobility in monolayer graphene is up to 200,000 cm 2 / Vs, which is 100 times higher than silicon at room temperature, far beyond the 70,000 cm 2 / Vs of InSb. In addition, the electrical resistance at room temperature is as small as 2/3 of copper, and has a current density of 100 million to 200 million A / cm 2 , and can withstand about 100 times the current density of the amount flowing through copper. Due to such excellent physical properties, the graphene layer has a very high application potential as an electronic device material, and is applicable to transistors, lasers, touch panels, organic light emitting devices, solar cells, or electrodes of secondary batteries.
그래핀을 실제로 응용하기 위하여 대면적 또는 미세 패턴을 가지는 균일한 그래핀층을 제조하여야 한다. 이를 위해서, 다양한 연구가 진행된 바 있다. 예를 들어, 기계적 박리법, 화학기상증착(CVD)법, SiC 기판의 열분해법 및 산화 그래핀법 등이 있다. In order to actually apply graphene, a uniform graphene layer having a large area or a fine pattern should be manufactured. To this end, various studies have been conducted. For example, mechanical peeling, chemical vapor deposition (CVD), thermal decomposition of SiC substrates, graphene oxide, and the like.
그러나, 그래핀층을 기판상에 전사하게 되면 기판상에 전사된 그래핀층이 외부의 물리적, 화학적 환경에 쉽게 영향을 받아 그래핀 전극 응용에 중요한 면저항이 변화될 수 있다. 면저항 변화는 투명 전극과 같은 다양한 소자를 형성하는 경우에 물성 및 대면적화를 저해하는 원인으로 작용한다. 종래에는 이러한 외부 환경 요인에 의한 면저항 변화를 차단하기 위해서 별도의 밀봉 기술을 도입해야 하는 문제점이 있었다.However, when the graphene layer is transferred onto the substrate, the graphene layer transferred onto the substrate may be easily influenced by external physical and chemical environments, thereby changing the sheet resistance, which is important for graphene electrode applications. The sheet resistance change acts as a cause of inhibiting physical properties and large area when forming various elements such as transparent electrodes. Conventionally, in order to block the change in sheet resistance caused by such external environmental factors, there is a problem that a separate sealing technology must be introduced.
본 발명은 면저항이 감소된 그래핀 적층체 및 그 제조방법을 제공한다. 또한, 별도의 밀봉 공정 없이도 외부 환경 요인에 영향을 받지 않아 면저항 및 광투과도가 유지되는 그래핀 적층체 및 그 제조방법을 제공한다. The present invention provides a graphene laminate with reduced sheet resistance and a method of manufacturing the same. In addition, the present invention provides a graphene laminate and a method of manufacturing the same, which are not affected by external environmental factors and maintain sheet resistance and light transmittance without a separate sealing process.
본 발명에 따른 그래핀 적층체는 기판; 도펀트 포함 고분자층; 및 그래핀층을 포함한다. 또한, 상기 그래핀 적층체를 제조하는 방법을 제공한다.Graphene laminate according to the present invention is a substrate; A dopant-containing polymer layer; And a graphene layer. In addition, it provides a method for producing the graphene laminate.
본 발명에 따른 그래핀 적층체는 면저항이 낮고 광투과도가 높아 다양한 형태의 전자 소자 등에 활용 가능하다. The graphene laminate according to the present invention may have low sheet resistance and high light transmittance, and thus may be utilized in various forms of electronic devices.
도 1은 본 발명의 일실시예에 따른 그래핀 적층체에 대한 적층구조를 나타낸 모식도이다;1 is a schematic view showing a laminated structure for the graphene laminate according to an embodiment of the present invention;
도 2 및 3은 각각 본 발명의 일실시예에 따른 그래핀 전사 방법을 도시한 공정도이다.2 and 3 are each a process chart showing a graphene transfer method according to an embodiment of the present invention.
도 4는 본 발명의 일실시예에 따른 그래핀층을 포함하는 그래핀 적층구조를 나타낸 단면도이다. 4 is a cross-sectional view illustrating a graphene stack structure including a graphene layer according to an embodiment of the present invention.
도 5 및 6은 각각 본 발명의 일실시예에 따른 그래핀 적층체에 대한 광투과도를 측정한 결과를 나타낸 그래프이다.5 and 6 are graphs showing the results of measuring the light transmittance of the graphene laminate according to an embodiment of the present invention, respectively.
본 발명에 따른 그래핀 적층체는, 기판; 도펀트 포함 고분자층; 및 그래핀층을 포함한다.Graphene laminate according to the present invention, the substrate; A dopant-containing polymer layer; And a graphene layer.
본 발명에 따른 그래핀 적층체는 도펀트를 포함하고 있어 600Ω/sq 이하, 구체적으로 10Ω/sq 내지 400Ω/sq의 낮은 면저항 값을 가진다. 상기 그래핀 적층체는 이러한 낮은 면저항 값으로 인해 투명 전극과 같은 다양한 전자소자 등에 활용 가능하다.The graphene laminate according to the present invention includes a dopant and has a sheet resistance value of 600 Ω / sq or less, specifically 10 Ω / sq to 400 Ω / sq. The graphene laminate may be utilized in various electronic devices such as transparent electrodes due to the low sheet resistance value.
상기 고분자층은 폴리에틸렌계, 폴리프로필렌계, 폴리스틸렌계, 폴리염화비닐계, 폴리염화비닐리덴계, 불소계, 아크릴계, 폴리아세트산비닐계, 폴리아미드계, 폴리아세탈계, 폴리카보네이트계, 폴리페닐렌옥사이드계, 폴리에스테르계, 폴리술폰계, 폴리이미드계, 페놀계, 요소계, 멜라민계, 알키드계, 불포화 폴리에스테르계, 에폭시계, 규소계, 아크릴계 및 폴리우레탄계 중 하나 이상을 포함할 수 있다. 상기 고분자로는 열경화성 또는 열가소성 고분자를 특별한 제한 없이 적용 가능하다.The polymer layer is polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, fluorine, acrylic, polyvinyl acetate, polyamide, polyacetal, polycarbonate, polyphenylene oxide It may include one or more of a polyester, a polysulfone, a polyimide, a phenolic, urea, melamine, alkyd, unsaturated polyester, epoxy, silicon, acrylic and polyurethane. As the polymer, a thermosetting or thermoplastic polymer may be applied without particular limitation.
상기 고분자층은 전도성 고분자를 포함 할 수 있다. 전도성 고분자는, 예를 들어, 폴리아세틸렌, 폴리디아세틸렌, 폴리페닐렌, 폴리아닐린, 폴리티오펜, 폴리페닐렌비닐렌, 폴리티오펜비닐렌, 폴리피롤, 폴리플루오렌 및 PEDOT:PSS(Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate)) 중 어느 하나 이상을 포함할 수 있다. The polymer layer may include a conductive polymer. Conductive polymers include, for example, polyacetylene, polydiacetylene, polyphenylene, polyaniline, polythiophene, polyphenylenevinylene, polythiophenevinylene, polypyrrole, polyfluorene and PEDOT: PSS (Poly (3 , 4-ethylenedioxythiophene) poly (styrenesulfonate)) may include any one or more.
상기 고분자층은 광경화성 고분자를 포함할 수 있다. 예를 들어, 그래핀층과 도펀트를 포함하는 고분자 용액을 도포한 기판과 합지한 후, UV 경화 과정을 거쳐 고분자층을 형성할 수 있다. 예를 들어, 광경화성 고분자는 하기 화학식 1 내지 3 중 하나 이상의 모노머로 중합될 수 있다. .The polymer layer may include a photocurable polymer. For example, after laminating with a substrate coated with a polymer solution including a graphene layer and a dopant, a polymer layer may be formed through a UV curing process. For example, the photocurable polymer may be polymerized with one or more monomers of the following Chemical Formulas 1 to 3. .
[화학식 1][Formula 1]
Figure PCTKR2012005945-appb-I000001
Figure PCTKR2012005945-appb-I000001
[화학식 2][Formula 2]
Figure PCTKR2012005945-appb-I000002
Figure PCTKR2012005945-appb-I000002
[화학식 3][Formula 3]
Figure PCTKR2012005945-appb-I000003
Figure PCTKR2012005945-appb-I000003
상기 화학식 1 및 2에서, n은 3 내지 20의 정수이다. In Chemical Formulas 1 and 2, n is an integer of 3 to 20.
또한, 상기 고분자층은 하기 화학식 4 내지 7 중 하나 이상의 반복 구조를 포함하는 접착성 고분자일 수 있다. In addition, the polymer layer may be an adhesive polymer including a repeating structure of one or more of the following Chemical Formulas 4 to 7.
[화학식 4][Formula 4]
Figure PCTKR2012005945-appb-I000004
Figure PCTKR2012005945-appb-I000004
[화학식 5][Formula 5]
Figure PCTKR2012005945-appb-I000005
Figure PCTKR2012005945-appb-I000005
[화학식 6][Formula 6]
Figure PCTKR2012005945-appb-I000006
Figure PCTKR2012005945-appb-I000006
[화학식 7][Formula 7]
Figure PCTKR2012005945-appb-I000007
Figure PCTKR2012005945-appb-I000007
상기 화학식 4 내지 7에서, In Chemical Formulas 4 to 7,
R1은 C5 내지 C30의 알킬기이고,R 1 is an alkyl group of C5 to C30,
R2는 C5 내지 C20의 알킬기; 또는 C1 내지 C20의 알킬기가 치환 또는 비치환된 C6 내지 C30의 아릴기이고, R 2 is an alkyl group of C5 to C20; Or a C6 to C30 aryl group having a substituted or unsubstituted C1 to C20 alkyl group,
R3는 알코올기; 할로겐기; 또는 치환기의 말단에 알코올기, 카르복실기, 술폰산기, 아민기, 카보닐기, 시아노기 및 할로겐기 중 어느 하나 이상을 포함하는 C1 내지 C10의 알킬기이고,R 3 is an alcohol group; Halogen group; Or a C1 to C10 alkyl group including any one or more of an alcohol group, a carboxyl group, a sulfonic acid group, an amine group, a carbonyl group, a cyano group, and a halogen group at the terminal of the substituent,
R4는 직쇄(linear chain) 또는 측쇄(branched chain)형을 포함하는 C1 내지 C10의 알킬기이고, R 4 is a C1 to C10 alkyl group including a linear or branched chain type,
X1 내지 X4는 각각 독립적으로 수소 또는 C1 내지 C5의 알킬기이고,X 1 to X 4 are each independently hydrogen or an alkyl group of C1 to C5,
n은 0 내지 10의 정수이다.n is an integer of 0-10.
위 화학식 4 내지 7에 나타낸 구조의 반복 횟수는 특별히 제한되지 않는다. 이는 화학식 4 내지 7의 반복 구조들이 고분자층을 형성하기 때문이다. 예를 들어, 상기 화학식 4 내지 7의 구조의 반복 횟수는 각각 독립적으로 1 내지 1,000,000 범위일 수 있으나, 이에 제한되는 것은 아니다. 상기 접착성 고분자는 그래핀층과의 우수한 접착 특성을 가질 뿐만 아니라, 이러한 우수한 접착특성으로 인해 그래핀의 전사 효율 및 외부 환경 요인에 대해 그래핀층의 안정성을 향상시킬 수 있다. The number of repetitions of the structure shown in Chemical Formulas 4 to 7 above is not particularly limited. This is because the repeating structures of Formulas 4 to 7 form a polymer layer. For example, the number of repetitions of the structure of Chemical Formulas 4 to 7 may be independently 1 to 1,000,000 range, but is not limited thereto. The adhesive polymer not only has excellent adhesive properties with the graphene layer, but also due to such excellent adhesive properties, it is possible to improve the stability of the graphene layer with respect to transfer efficiency and external environmental factors of graphene.
상기 고분자층은 영하 10℃ 내지 영상 100℃의 유리전이온도를 가질 수 있다. 이러한 유리전이온도는 기판 및 그래핀층과의 접착력을 높일 수 있는 범위이다. 유리전이온도가 영하 10℃ 미만일 경우에는 고분자층의 기계적 물성이 떨어져 고분자층에 전사된 그래핀층이 쉽게 손상을 입을 수 있고, 유리전이온도가 영상 100℃를 초과할 경우에는 고분자층과 그래핀 사이의 계면 접촉이 어려워 접착력이 저하될 수 있다.The polymer layer may have a glass transition temperature of minus 10 ℃ to image 100 ℃. The glass transition temperature is a range that can increase the adhesion with the substrate and the graphene layer. If the glass transition temperature is less than minus 10 ℃, the mechanical properties of the polymer layer is poor, the graphene layer transferred to the polymer layer can be easily damaged. If the glass transition temperature exceeds 100 ℃ image between the polymer layer and the graphene It is difficult to contact the interface of the adhesive force can be reduced.
본 발명에 따른 도펀트는 특별히 제한되지 않으나, 바람직하게는 P형 도펀트를 포함할 수 있다. 상기 도펀트는 고분자층 내에 포함되어 면저항을 낮추는 효과를 갖는다. The dopant according to the present invention is not particularly limited, but may preferably include a P-type dopant. The dopant is included in the polymer layer and has an effect of lowering sheet resistance.
상기 도펀트는 할로겐 산화물, 황산화물, 금속 할라이드, 질소 산화물, 금속 과산화물, 벤조퀴논계 화합물 및 디브로모안트라센 중 하나 이상을 포함할 수 있다. 할로겐 산화물, 황산화물, 금속 할라이드, 질소 산화물, 금속 과산화물, 벤조퀴논계 화합물 및 디브로모안트라센은 P형 도판트 도핑에 매우 효과적인 물질로서, 그래핀 박막의 면저항 뿐만 아니라 일함수(Workfunction) 특성 변화에도 영향을 미친다. P형 도펀트로 도핑하여 그래핀 박막의 일함수를 조절하면, 기능화된 그래핀 투명전극으로의 제조가 가능하다. 또한, 이러한 그래핀 투명전극은 우수한 광투과도, 면저항값 및 유연성을 가지게 되어 다양한 투명전극 응용분야에서 사용할 수 있다.The dopant may include one or more of halogen oxide, sulfur oxide, metal halide, nitrogen oxide, metal peroxide, benzoquinone compound and dibromoanthracene. Halogen oxides, sulfur oxides, metal halides, nitrogen oxides, metal peroxides, benzoquinone compounds, and dibromoanthracene are very effective materials for doping P-type dopants. Also affects. By controlling the work function of the graphene thin film by doping with a P-type dopant, it is possible to manufacture a functionalized graphene transparent electrode. In addition, such graphene transparent electrode has excellent light transmittance, sheet resistance value and flexibility can be used in various transparent electrode applications.
상기 할로겐 산화물은 요오드계 산화물 및 염소계 산화물 중 하나 이상을 포함할 수 있다. 상기 요오드계 산화물은 아이오딜벤젠, 아이오독시벤조산 및 데스-마틴 퍼아이오디난 중 하나 이상을 포함할 수 있다. 또한, 상기 염소계 산화물은 NaClO, NaClO2, NaClO3, NaClO4, AgClO3 및 AgClO4 중 하나 이상을 포함할 수 있다. The halogen oxide may include at least one of iodine oxide and chlorine oxide. The iodine-based oxide may include at least one of iodilbenzene, iodoxybenzoic acid, and des-martin periodinan. In addition, the chlorine-based oxide may include one or more of NaClO, NaClO 2 , NaClO 3 , NaClO 4 , AgClO 3 and AgClO 4 .
상기 황산화물은 (CH3)2SO, KHSO5, KHSO4, K2SO4, FSO3H 및 CF3SO3H 중 하나 이상을 포함할 수 있다. The sulfur oxide may include one or more of (CH 3 ) 2 SO, KHSO 5 , KHSO 4 , K 2 SO 4 , FSO 3 H and CF 3 SO 3 H.
상기 금속 할라이드는 은이온, 금이온, 세륨이온, 철이온, 몰리브덴이온, 텅스텐이온, 주석이온, 루테늄이온 및 탄탈륨이온 중 하나 이상을 포함하는 금속염일 수 있다. 또한 금속 할라이드는 FeCl3, MoCl5, WCl5, SnCl4, MoF5, RuF5, TaBr5, SnI4, HAuCl4, AuCl3, (NH4)2Ce(SO4)3 및 (NH4)2Ce(NO3)6 중 하나 이상을 포함할 수 있다.The metal halide may be a metal salt including one or more of silver ions, gold ions, cerium ions, iron ions, molybdenum ions, tungsten ions, tin ions, ruthenium ions, and tantalum ions. In addition, the metal halides are FeCl 3 , MoCl 5 , WCl 5 , SnCl 4 , MoF 5 , RuF 5 , TaBr 5 , SnI 4 , HAuCl 4 , AuCl 3 , (NH 4 ) 2 Ce (SO 4 ) 3 and (NH 4 ) And at least one of 2 Ce (NO 3 ) 6 .
상기 질소산화물은 AgNO3, NO2F, NO2Cl, N2O5, NO2BF4, CH3NO2, C6H5NO2, CH3ONO, NO(SbCl6), NOBF4, NOClO4, NOSO4H, C6H5NO, NOCl, NOF 및 NOBr 중 하나 이상을 포함할 수 있다. The nitrogen oxides are AgNO 3 , NO 2 F, NO 2 Cl, N 2 O 5 , NO 2 BF 4 , CH 3 NO 2 , C 6 H 5 NO 2 , CH 3 ONO, NO (SbCl 6 ), NOBF 4 , It may comprise one or more of NOClO 4 , NOSO 4 H, C 6 H 5 NO, NOCl, NOF and NOBr.
상기 금속 과산화물은 KMnO4, BaMnO4, OsO4 중 하나 이상을 포함할 수 있다. It said metal peroxide may include KMnO 4, BaMnO 4, one or more of OsO 4.
또한, 상기 벤조퀴논계 화합물은 벤조퀴논, 테트라클로로벤조퀴논, 디클로로디시아노벤조퀴논 및 테트라시아노퀴노디메탄 중 하나 이상을 포함할 수 있다. In addition, the benzoquinone-based compound may include one or more of benzoquinone, tetrachlorobenzoquinone, dichlorodicyanobenzoquinone and tetracyanoquinomethane.
본 발명에 따른 도펀트의 함량은, 도펀트 포함 고분자층을 기준으로, 0.01 내지 20wt%일 수 있으며, 바람직하게는 0.1~10wt% 범위일 수 있다. 도펀트의 함량이 0.01wt% 미만 일때는 면저항 감소 효과가 미비하고, 상기 20wt% 초과하는 경우에는 막 평탄성이 저하될 수 있다.The content of the dopant according to the present invention may be 0.01 to 20 wt%, preferably 0.1 to 10 wt%, based on the dopant-containing polymer layer. When the content of the dopant is less than 0.01wt%, the sheet resistance reduction effect is insignificant, and when it exceeds 20wt%, the film flatness may decrease.
기판을 구성하는 소재는 특별히 제한되지 않으며, 예를 들어 폴리에틸렌테레프탈레이트(PET), 폴리에틸렌나프탈레이트(PEN), 폴리카보네이트(PC), 폴리에테르설폰(PES), 폴리사이클릭올레핀(PCO), 폴리아크릴레이트(PA), 폴리에테르에테르케톤(PEEK) 및 폴리이미드(PI) 중 하나 이상을 포함할 수 있다.The material constituting the substrate is not particularly limited, and for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyethersulfone (PES), polycyclic olefin (PCO), poly And one or more of acrylate (PA), polyetheretherketone (PEEK), and polyimide (PI).
도 1은 본 발명의 일실시예에 따른 그래핀이 코팅된 기판의 적층구조를 나타낸 모식도이다. 도 1을 참조하면, 기판(10), 기판(10) 상에 도펀트가 포함된 고분자층(20) 및 그래핀층(30)이 순차적으로 적층된 구조임을 알 수 있다. 1 is a schematic diagram showing a laminated structure of a graphene-coated substrate according to an embodiment of the present invention. Referring to FIG. 1, it can be seen that the substrate 10, the polymer layer 20 including the dopant, and the graphene layer 30 are sequentially stacked on the substrate 10.
본 발명은 상기 그래핀 적층체를 제조하는 방법을 제공한다. 예를 들어, 상기 제조방법은,The present invention provides a method for producing the graphene laminate. For example, the manufacturing method,
(a) 기판상에 도펀트를 포함하는 고분자를 도포하는 단계;(a) applying a polymer comprising a dopant on a substrate;
(b) 금속 촉매층 상에 형성된 그래핀층과 도펀트를 포함하는 고분자가 도포된 기판을 합지하는 단계; 및(b) laminating a substrate coated with a polymer including a graphene layer and a dopant formed on the metal catalyst layer; And
(c) 금속 촉매층을 제거하는 단계를 포함할 수 있다.  (c) removing the metal catalyst layer.
본 제조방법에서 사용되는 도펀트 및 고분자의 종류와 함량은 앞서 설명한 바와 같다. 예를 들어, 도펀트의 함량은, 도펀트 포함 고분자층을 기준으로, 0.01 내지 20wt%일 수 있으며, 바람직하게는 0.1~10wt% 범위일 수 있다.The type and content of the dopant and the polymer used in the manufacturing method are as described above. For example, the content of the dopant may be 0.01 to 20 wt%, preferably 0.1 to 10 wt%, based on the dopant-containing polymer layer.
본 발명에 따른 그래핀 적층체의 제조방법은, 금속 촉매층을 제거하는 방식에 따라 건식 또는 습식 전사방법을 사용할 수 있다. 건식 전사방법으로는 예를 들어, 롤투롤 방식이 사용될 수 있다. 건식 전사방법은, 용제나 물을 사용하는 용액공정을 포함하지 않고 금속 촉매층에 형성된 그래핀층을 목적 기판상에 직접 건식 전사할 수 있다는 장점이 있다. 또한, 본 발명은 습식 공정을 제외하는 것은 아니다. 예를 들어, 에칭액을 이용하여 금속 촉매층을 제거할 수 있다. In the method for producing a graphene laminate according to the present invention, a dry or wet transfer method may be used depending on a method of removing a metal catalyst layer. As the dry transfer method, for example, a roll-to-roll method may be used. The dry transfer method has the advantage that the graphene layer formed on the metal catalyst layer can be directly transferred onto the target substrate without including a solution process using a solvent or water. In addition, the present invention does not exclude a wet process. For example, the metal catalyst layer can be removed using an etching solution.
건식 전사방법을 사용하는 경우에는, 예를 들어 롤투롤 방식을 사용할 수 있다. 구체적으로는, 상기 (c) 단계는, 금속 촉매층 상에 형성된 그래핀층과 도펀트를 포함하는 고분자가 도포된 기판을 상호 접촉하도록 합지한 후, 롤투롤 방식에 의해 금속 촉매층과 그래핀층을 분리하게 된다. When using the dry transfer method, the roll-to-roll system can be used, for example. Specifically, in the step (c), after laminating the graphene layer formed on the metal catalyst layer and the polymer-coated substrate including the dopant to contact each other, the metal catalyst layer and the graphene layer are separated by a roll-to-roll method. .
습식 전사방법을 사용하는 경우에는, 예를 들어 에칭액을 이용하여 금속 촉매층을 제거할 수 있다. 구체적으로는, 상기 (c) 단계는, 금속 촉매층 상에 형성된 그래핀층과 도펀트를 포함하는 고분자가 도포된 기판을 상호 접촉하도록 합지한 후, 에칭액을 이용하여 금속 촉매층을 제거할 수 있다. 상기 금속 촉매층은 특별히 제한되지 않으며, 예를 들어 구리 호일 또는 니켈 박막 등이 사용될 수 있다. 상기 에칭액은 금속 촉매층을 제거할 수 있는 경우라면 특별히 제한되지 않으며, 예를 들어 산, 불산(HF), BOE(buffered oxide etchant), 염화제2철(FeCl3) 용액, 질산제2철(Fe(NO3)3) 용액 및 과황산암모늄((NH4)2S2O8) 중 하나 이상을 이용하여 수행될 수 있다.In the case of using the wet transfer method, the metal catalyst layer can be removed using, for example, an etchant. Specifically, in the step (c), after laminating the graphene layer formed on the metal catalyst layer and the polymer-coated substrate including the dopant to contact each other, the metal catalyst layer may be removed using an etching solution. The metal catalyst layer is not particularly limited, and for example, a copper foil or a nickel thin film may be used. The etchant is not particularly limited as long as it can remove the metal catalyst layer, for example, acid, hydrofluoric acid (HF), buffered oxide etchant (BOE), ferric chloride (FeCl 3 ) solution, and ferric nitrate (Fe). (NO 3 ) 3 ) solution and one or more of ammonium persulfate ((NH 4 ) 2 S 2 O 8 ).
본 발명에서 사용되는 고분자의 종류에 따라서 별도의 경화 과정을 거칠 수 있다. 본 발명에서 고분자는 특별히 제한되지 않으며, 열가소성 고분자가 사용될 수 있으며 이 경우에는 별도의 경화 과정이 요구되지 않지만, 열경화성 또는 광경화성 고분자가 사용될 경우에는 열을 가하거나 UV를 조사하는 경화 과정이 포함될 수 있다. 예를 들어, 상 기 (b) 단계에서, 금속 촉매층 상에 형성된 그래핀층과 도펀트를 포함하는 고분자가 도포된 기판을 합지하고 열 또는 UV 경화 과정을 포함할 수 있다.Depending on the type of polymer used in the present invention may be subjected to a separate curing process. In the present invention, the polymer is not particularly limited, and a thermoplastic polymer may be used. In this case, a separate curing process is not required, but when a thermosetting or photocurable polymer is used, a curing process of applying heat or irradiating UV may be included. have. For example, in step (b), the graphene layer formed on the metal catalyst layer and the polymer-coated substrate including the dopant may be laminated and may include a thermal or UV curing process.
또한, 본 발명에서 사용되는 그래핀층은 금속 촉매층의 양면에 형성된 구조일 수 있으며, 금속 촉매층의 양면에 형성된 그래핀층의 외면에 각각 도펀트 포함 고분자가 도포된 기판을 합지한 후, 금속 촉매층을 제거하는 과정을 포함할 수 있다. 이는 1 회의 제조공정을 통해 2 개의 그래핀 적층체를 형성할 수 있다는 점에서, 제조 효율을 2배로 높일 수 있다는 장점이 있다. 이 경우에도, 사용되는 고분자의 종류에 따라서 별도의 경화 과정을 거칠 수 있다. 예를 들어, 금속 촉매층의 양면에 형성된 그래핀층의 외면에 각각 도펀트 포함 고분자가 도포된 기판을 합지한 후, 열 또는 UV 경화 과정을 포함할 수 있다.In addition, the graphene layer used in the present invention may have a structure formed on both sides of the metal catalyst layer, after laminating a substrate coated with a dopant-containing polymer, respectively, on the outer surface of the graphene layer formed on both sides of the metal catalyst layer, to remove the metal catalyst layer Process may be included. This is advantageous in that two graphene laminates can be formed through a single manufacturing process, thereby doubling the manufacturing efficiency. Even in this case, a separate curing process may be performed depending on the type of polymer used. For example, after laminating a substrate coated with a dopant-containing polymer on each of the outer surfaces of the graphene layer formed on both surfaces of the metal catalyst layer, it may include a thermal or UV curing process.
도면을 통해 본 발명의 일실시예에 따른 그래핀 적층체를 제조하는 방법을 보다 상세히 살펴본다.Look at in more detail the method for producing a graphene laminate according to an embodiment of the present invention through the drawings.
도 2 및 3은 각각 본 발명의 일실시예에 따른 그래핀 적층체의 제조방법을 모식적으로 나타내었다.2 and 3 schematically show a method of manufacturing a graphene laminate according to an embodiment of the present invention, respectively.
도 2를 참조하면, 기판(10)의 일면에 도펀트가 포함된 고분자를 도포하여 고분자층(20)을 형성한다. 그런 다음, 그래핀층(30)이 형성된 금속 촉매층(40)을 합지한다. 이 때에는, 고분자층(20)과 그래핀층(30)이 직접 접촉하도록 하며, 부착력을 높이기 위해 롤러 등을 이용하여 밀착시킬 수 있다. 고분자층을 구성하는 성분에 따라 달라질 수 있으나, 고분자가 광경화성인 경우에는 UV 조사를 통해 경화시키는 과정을 포함할 수 있다. 그런 다음, 금속 촉매층(40)을 제거하게 된다. 금속 촉매층(40) 제거는 롤투롤 공정을 통해 수행될 수 있다. 이때 고분자층(20)의 접착력에 의해 금속 촉매층을 분리시키더라도 그래핀층(30)은 기판(10)에 남게 된다. 혹은, 에칭액을 사용하여 금속 촉매층(40)을 제거할 수 있다. 사용 가능한 에칭액의 종류는 특별히 제한되지 않는다. 금속 촉매층(40)이 제거된 후에는, 기판(10), 도펀트 포함 고분자층(20) 및 그래핀(30)으로 이루어진 적층 구조가 남게 된다.Referring to FIG. 2, a polymer layer 20 is formed by applying a polymer including a dopant to one surface of the substrate 10. Then, the metal catalyst layer 40 on which the graphene layer 30 is formed is laminated. In this case, the polymer layer 20 and the graphene layer 30 are in direct contact with each other, and may be in close contact with a roller or the like to increase adhesion. Although it may vary depending on the components constituting the polymer layer, when the polymer is photocurable, it may include a process of curing through UV irradiation. Then, the metal catalyst layer 40 is removed. Removal of the metal catalyst layer 40 may be performed through a roll-to-roll process. At this time, even though the metal catalyst layer is separated by the adhesive force of the polymer layer 20, the graphene layer 30 remains on the substrate 10. Alternatively, the metal catalyst layer 40 can be removed using an etchant. The kind of etching liquid which can be used is not specifically limited. After the metal catalyst layer 40 is removed, a lamination structure of the substrate 10, the dopant-containing polymer layer 20, and the graphene 30 remains.
도 3에는 또 다른 하나의 실시예에 따른 그래핀 전사방법의 공정도를 나타내었다. 도 3은 금속 촉매층(40)의 양면에 형성된 그래핀층(31, 32)을 모두 활용할 수 있는 방법을 개시한 것이다. 도펀트 포함 고분자층(21, 22)이 형성된 두 개의 기판(11, 12)을 금속 촉매층(40)의 상하부 그래핀층(31, 32)에 각각 합지하게 된다. 필요에 따라서는, 열 또는 UV를 조사하는 과정을 더 거칠 수 있다. 그런 다음, 롤투롤 또는 에칭액을 이용하여 금속 촉매층을 제거하면, 기판(10), 도펀트 포함 고분자층(21, 22) 및 그래핀층(31, 32)으로 이루어진 적층구조가 2 개 얻어진다. 이러한 방법은, 기존의 그래핀 전사방법과 비교하여 공정 효율을 2배 향상시킬 수 있으며, 전사과정에서 소실되는 그래핀의 양을 최소화할 수 있다.3 shows a process chart of the graphene transfer method according to another embodiment. 3 discloses a method in which both graphene layers 31 and 32 formed on both surfaces of the metal catalyst layer 40 can be utilized. Two substrates 11 and 12 having the dopant-containing polymer layers 21 and 22 are laminated on the upper and lower graphene layers 31 and 32 of the metal catalyst layer 40, respectively. If necessary, the process of irradiating heat or UV may be further processed. Then, when the metal catalyst layer is removed using a roll-to-roll or etching solution, two laminated structures consisting of the substrate 10, the dopant containing polymer layers 21 and 22 and the graphene layers 31 and 32 are obtained. This method, compared with the conventional graphene transfer method can improve the process efficiency twice, and can minimize the amount of graphene lost in the transfer process.
본 발명은 또한, 상기 전사과정에서 형성되는 그래핀 적층체의 중간 구조를 제공한다. 상기 중간구조는 금속 촉매층이 제거되기 전의 모습이다. 예를 들어, 그래핀 적층체는 기판, 도펀트 포함 고분자층, 그래핀층, 금속 촉매층, 그래핀층, 도펀트 포함 고분자층 및 기판이 순차적으로 적층된 구조를 포함할 수 있다. 도 4에는 그래핀 적층체의 일례를 도시하였다. 상기 적층체는 금속 촉매층인 구리 호일(40)을 기준으로 대칭 구조를 형성하고 있다. 기판(11), 도펀트 포함 고분자층(21) 및 그래핀층(31)이 순차 적층되고, 그래핀층(31) 위에 금속 촉매층(40)이 형성된 구조이다. 또한, 금속 촉매층(40) 상에는 그래핀층(32), 도펀트 포함 고분자층(22) 및 기판(10)이 순차적으로 형성된 구조이다.The present invention also provides an intermediate structure of the graphene laminate formed during the transfer process. The intermediate structure is a state before the metal catalyst layer is removed. For example, the graphene laminate may include a structure in which a substrate, a polymer layer including a dopant, a graphene layer, a metal catalyst layer, a graphene layer, a polymer layer including a dopant, and a substrate are sequentially stacked. 4 shows an example of a graphene laminate. The laminate has a symmetrical structure based on the copper foil 40 which is a metal catalyst layer. The substrate 11, the dopant-containing polymer layer 21, and the graphene layer 31 are sequentially stacked, and the metal catalyst layer 40 is formed on the graphene layer 31. In addition, the graphene layer 32, the dopant-containing polymer layer 22, and the substrate 10 are sequentially formed on the metal catalyst layer 40.
본 발명은 앞서 설명한 그래핀 적층체를 포함하는 전극 또는 전도성 박막을 제공한다. 상기 전극 또는 전도성 박막은 특별한 제한 없이 다양한 형태의 전자 소자에 활용될 수 있다. 또한, 상기 전자 소자는 트랜지스터, 레이저 소자, 터치패널, 유기발광소자, 태양전지 또는 이차전지의 전극 등으로 응용 가능하다. The present invention provides an electrode or a conductive thin film comprising the graphene laminate described above. The electrode or the conductive thin film may be utilized in various types of electronic devices without particular limitation. In addition, the electronic device may be applied as a transistor, a laser device, a touch panel, an organic light emitting device, a solar cell, or an electrode of a secondary battery.
이하 실시예를 들어 본 발명을 더 상세히 설명한다. 본 발명의 실시예는 발명의 상세한 설명을 위한 것일 뿐, 이에 의해 권리범위를 제한하려는 것은 아니다.The present invention will be described in more detail with reference to the following examples. The embodiments of the present invention are only for the detailed description of the present invention, and are not intended to limit the scope thereof.
실시예 1 Example 1
하기 화학식 8로 표시되는 모노머 10g과 화학식 9로 표시되는 모노머 3g, 희석제 2g 및 광개시제 0.1g(CIBA사, 제품번호 184)을 혼합하고, 여기에 도펀트로 테트라시아노퀴노디메탄 0.1wt%를 혼합하여 용액을 제조하였다.10 g of the monomer represented by the following formula (8), 3 g of the monomer represented by the formula (9), 2 g of diluents and 0.1 g of photoinitiator (CIBA, product no. To prepare a solution.
[화학식 8] [Formula 8]
Figure PCTKR2012005945-appb-I000008
Figure PCTKR2012005945-appb-I000008
[화학식 9][Formula 9]
Figure PCTKR2012005945-appb-I000009
Figure PCTKR2012005945-appb-I000009
그런 다음, PET 기판(두께 75μm)에 상기 도펀트 포함 용액을 스핀 코팅 방법으로 도포한 후, 70℃에서 1시간 건조 시켜 PET 기판에 약 1μm 두께의 박막을 제작 하였다.Thereafter, the dopant-containing solution was applied to a PET substrate (thickness 75 μm) by spin coating, and dried at 70 ° C. for 1 hour to produce a thin film having a thickness of about 1 μm on the PET substrate.
그래핀층 제작을 위하여 5cm x 5cm 크기를 갖는 금속 촉매인 구리 호일(두께 25μm, 순도 99.8%)을 석영 튜브에 장입하였다. 먼저 산화막 제거를 위하여 1000℃에서 H2/Ar = 10/50sccm으로 20분간 흘려주었다. 그런 다음, 동일 온도를 유지하면서 CH4/H2/Ar = 20/10/50sccm을 30분간 흘려주어 구리 호일 표면상에 그래핀층을 형성한 후, Ar = 50sccm 흘려주면서 3.6℃/sec 속도로 냉각하여 그래핀층이 형성된 구리 호일을 제조하였다.Copper foil (thickness 25 μm, purity 99.8%), which is a metal catalyst having a size of 5 cm × 5 cm, was charged to a quartz tube for producing a graphene layer. First, to remove the oxide film was flowed for 20 minutes at 1000 ℃ H 2 / Ar = 10 / 50sccm. Then, CH 4 / H 2 / Ar = 20/10 / 50sccm was flowed for 30 minutes while maintaining the same temperature to form a graphene layer on the surface of the copper foil, followed by cooling at 3.6 ° C / sec while flowing Ar = 50sccm. To prepare a copper foil having a graphene layer.
구리 호일에 형성된 그래핀층을 도펀트가 포함된 고분자가 도포된 PET 기판상에 합지하였다. 구체적으로는, 구리 호일에 그래핀이 형성된 면과 PET 기판에 도펀트 포함 고분자가 도포된 면을 마주보도록 하고, 압력을 가하여 PET 기판과 그래핀층을 합지 시켰다. 그런 다음, UV 경화 과정을 거쳐 구리 호일을 포함하는 그래핀 적층체를 형성하였다. 상기 구리 호일이 포함된 그래핀 적층체를 0.1M의 (NH4)2S2O8 수용액을 이용하여 구리 호일이 제거된 그래핀 적층체를 제조하였다.The graphene layer formed on the copper foil was laminated on a PET substrate coated with a polymer containing a dopant. Specifically, the surface where the graphene is formed on the copper foil and the surface on which the dopant-containing polymer is applied to the PET substrate are faced to each other, and the PET substrate and the graphene layer are laminated by applying pressure. Then, a graphene laminate including a copper foil was formed through a UV curing process. The graphene laminate including the copper foil was prepared using a 0.1 M (NH 4 ) 2 S 2 O 8 aqueous solution to remove the graphene laminate from the copper foil.
실시예 2 Example 2
본 실시예는 실시예 1에서 사용된 상기 화학식 8로 표시되는 모노머 10g과 하기 화학식 3으로 표시되는 모노머 3g을 사용한 것을 제외하고는, 실시예 1과 동일한 방법으로 그래핀 적층체를 제조하였다.This Example was prepared in the same manner as in Example 1, except that 10g of the monomer represented by the formula (8) and 3g of the monomer represented by the following formula (3) used in Example 1.
[화학식 3] [Formula 3]
Figure PCTKR2012005945-appb-I000010
Figure PCTKR2012005945-appb-I000010
실시예 3Example 3
본 실시예는 도펀트로 FeCl3 0.1wt%를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 그래핀 적층체를 제조하였다. In this example, a graphene laminate was manufactured in the same manner as in Example 1, except that 0.1 wt% of FeCl 3 was used as the dopant.
실시예 4Example 4
본 실시예는 도펀트로 KMnO4 0.1wt%를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 그래핀 적층체를 제조하였다. This Example was prepared in the same manner as in Example 1 except that KMnO 4 0.1wt% as a dopant was prepared.
실시예 5Example 5
본 실시예는 도펀트로 NaClO 0.1wt%를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 그래핀 적층체를 제조하였다. This example uses NaClO as a dopant. A graphene laminate was manufactured in the same manner as in Example 1, except that 0.1 wt% was used.
비교예 1Comparative Example 1
본 비교예 1은 도펀트를 포함하지 않는 그래핀 적층체로, 실시예 1의 도펀트 적용 공정을 제외 하고는, 실시예 1과 동일한 방법으로 그래핀 적층체를 제조하였다.Comparative Example 1 is a graphene laminate containing no dopant, except that the dopant application process of Example 1, a graphene laminate was prepared in the same manner as in Example 1.
비교예 2Comparative Example 2
본 비교예 2는 도펀트를 포함하지 않는 그래핀 적층체로, 실시예 1의 도펀트 적용 공정을 제외 하고는, 실시예 2과 동일한 방법으로 그래핀 적층체를 제조하였다.Comparative Example 2 is a graphene laminate containing no dopant, except that the dopant application process of Example 1, a graphene laminate was prepared in the same manner as in Example 2.
실험예 1: 면저항 측정 실험Experimental Example 1: Sheet Resistance Measurement Experiment
1. 실시예 1 및 비교예 1의 면저항 측정1. Measurement of sheet resistance of Example 1 and Comparative Example 1
실시예 1 및 비교예 1에서 제조된 그래핀 적층체에 대한 면저항은 4-탐침 면저항 측정기(4-point probe)로 임의의 9구간을 측정하여 표 1과 2에 각각 나타내었다. The sheet resistance of the graphene laminates prepared in Example 1 and Comparative Example 1 is shown in Tables 1 and 2 by measuring an arbitrary 9 section with a 4-point probe.
표 1
측정 면저항(Ω/sq)
1 298
2 302
3 288
4 274
5 278
6 264
7 277
8 254
9 279
Table 1
Measure Sheet resistance (Ω / sq)
One 298
2 302
3 288
4 274
5 278
6 264
7 277
8 254
9 279
* 상기 측정 1 ~ 9는 임의의 9 구간을 의미함.* The measurement 1 to 9 means any 9 intervals.
표 2
측정 면저항(Ω/sq)
1 852
2 823
3 850
4 632
5 790
6 894
7 871
8 843
TABLE 2
Measure Sheet resistance (Ω / sq)
One 852
2 823
3 850
4 632
5 790
6 894
7 871
8 843
표 1은 실시예 1의 면저항 값을 나타낸 것으로, 평균 279Ω/sq의 평균 면저항 값을 나타내었다. 이에 비해, 표 2에 개시된 비교예 1의 면저항 값은 평균 828Ω/sq을 나타내어, 도펀트인 테트라시아노퀴노디메탄의 사용으로 인해 면저항 값이 약 1/3 수준으로 감소되는 것을 확인하였다.Table 1 shows the sheet resistance values of Example 1, and the average sheet resistance values of 279 Ω / sq on average. In comparison, the sheet resistance of Comparative Example 1 disclosed in Table 2 represents an average of 828 Ω / sq, and it was confirmed that the sheet resistance was reduced to about 1/3 due to the use of the dopant tetracyanoquinomethane.
2. 실시예 2 및 비교예 2의 면저항 측정2. Measurement of sheet resistance of Example 2 and Comparative Example 2
실시예 2 및 비교예 2에서 제조된 그래핀 적층체에 대한 면저항 값을 표 3과 4에 각각 나타내었다. The sheet resistance values of the graphene laminates prepared in Example 2 and Comparative Example 2 are shown in Tables 3 and 4, respectively.
표 3
측정 면저항(Ω/sq)
1 375
2 345
3 327
4 311
5 328
6 346
7 371
8 348
9 355
TABLE 3
Measure Sheet resistance (Ω / sq)
One 375
2 345
3 327
4 311
5 328
6 346
7 371
8 348
9 355
표 4
측정 면저항(Ω/sq)
1 869
2 822
3 836
4 789
5 778
6 874
7 841
8 813
9 865
Table 4
Measure Sheet resistance (Ω / sq)
One 869
2 822
3 836
4 789
5 778
6 874
7 841
8 813
9 865
표 3은 실시예 2의 면저항 값을 나타낸 것으로, 평균 351Ω/sq의 평균 면저항 값을 나타내었다. 이에 비해, 표 4에 개시된 비교예 2의 면저항 값은 평균 832Ω/sq인 것으로 나타났다. 이를 통해, 도펀트 테트라시아노퀴노디메탄의 사용으로 인해 면저항 값이 약 2/5 수준으로 감소되었음을 확인하였다. 또한, 화학식 3의 모노머보다 화학식 11의 모노머를 사용하는 것이 면저항 값을 낮추는데 보다 효과적임을 확인 하였다. Table 3 shows the sheet resistance of Example 2, and the average sheet resistance of 351 Ω / sq. In comparison, the sheet resistance value of Comparative Example 2 disclosed in Table 4 was found to be an average of 832 Ω / sq. Through this, it was confirmed that the sheet resistance value was reduced to about 2/5 due to the use of the dopant tetracyanoquinomidimethane. In addition, it was confirmed that using the monomer of the formula (11) than the monomer of the formula (3) is more effective in lowering the sheet resistance value.
3. 실시예 3 내지 5의 면저항 측정3. Measurement of sheet resistance of Examples 3 to 5
실시예 3 내지 5에서 제조된 그래핀 적층체에 대한 면저항 값을 표 5 내지 7에 각각 나타내었다. The sheet resistance values of the graphene laminates prepared in Examples 3 to 5 are shown in Tables 5 to 7, respectively.
표 5
측정 면저항(Ω/sq)
1 426
2 400
3 444
4 449
5 353
6 403
7 399
8 392
9 396
Table 5
Measure Sheet resistance (Ω / sq)
One 426
2 400
3 444
4 449
5 353
6 403
7 399
8 392
9 396
표 6
측정 면저항(Ω/sq)
1 547
2 544
3 571
4 577
5 502
6 557
7 486
8 578
9 586
Table 6
Measure Sheet resistance (Ω / sq)
One 547
2 544
3 571
4 577
5 502
6 557
7 486
8 578
9 586
표 7
측정 면저항(Ω/sq)
1 501
2 550
3 439
4 546
5 509
6 513
7 486
8 482
9 524
TABLE 7
Measure Sheet resistance (Ω / sq)
One 501
2 550
3 439
4 546
5 509
6 513
7 486
8 482
9 524
상기 표 5 내지 7은 각각 실시예 3 내지 5의 면저항 값을 나타낸 것으로, 각각 평균 407Ω/sq, 550Ω/sq 및 506Ω/sq의 면저항 값을 나타내었다. 도펀트의 종류에 따라 면저항 값에 약간의 차이가 발생함을 알 수 있다. 위 결과를 통해 도펀트를 사용하지 않은 경우와 비교하여 도펀트를 사용한 경우에는 면저항 값이 약 3/5수준 이하로 낮아지는 것을 확인하였다.Tables 5 to 7 show sheet resistance values of Examples 3 to 5, respectively, and average sheet resistance values of 407 Ω / sq, 550 Ω / sq, and 506 Ω / sq, respectively. It can be seen that a slight difference occurs in the sheet resistance value depending on the type of dopant. From the above results, it was confirmed that the sheet resistance value was lowered to about 3/5 or less when the dopant was used as compared with the case where the dopant was not used.
실험예 2: 광투과도 측정 실험Experimental Example 2: Light Transmittance Measurement Experiment
실시예 1 및 2에서 제조된 그래핀 적층체에 대하여 광투과도를 측정하였다. 구체적으로는 UV/visible 영역의 광을 조사하고 투과된 광량을 %로 측정 하였다.The light transmittance of the graphene laminates prepared in Examples 1 and 2 was measured. Specifically, the light in the UV / visible region was irradiated and the amount of transmitted light was measured in%.
도 5에는 실시예 1에서 제조된 그래핀 적층체에 대한 광투과도 측정결과를 나타내었다. 도 5를 참조하면, 전 파장대 영역에서 97% 이상의 광투과도를 나타내며, 550 nm 파장의 광에 대해서는 97.83%의 광투과도를 나타내는 것으로 확인되었다. Figure 5 shows the light transmittance measurement results for the graphene laminate prepared in Example 1. Referring to FIG. 5, it was confirmed that the light transmittance of 97% or more in the entire wavelength band region, and the light transmittance of 97.83% for the light of 550 nm wavelength.
도 6에는 실시예 2에서 제조된 그래핀 적층체에 대한 광투과도 측정결과를 나타내었다. 도 6을 참조하면, 전 파장대 영역에서 97% 이상의 광투과도를 나타내며, 550 nm 파장의 광에 대해서 97.67%의 광투과도를 나타내는 것으로 확인되었다. Figure 6 shows the light transmittance measurement results for the graphene laminate prepared in Example 2. Referring to FIG. 6, light transmittance of 97% or more was exhibited in the entire wavelength band, and light transmittance of 97.67% was observed for light having a wavelength of 550 nm.
이를 통해, 본 발명의 도펀트 포함 그래핀 적층체는 면저항 감소 효과 이외에도 광투과도가 매우 우수한 것을 알 수 있다. Through this, it can be seen that the graphene laminate including the dopant of the present invention has excellent light transmittance in addition to the sheet resistance reduction effect.
10, 11, 12 : 기판        10, 11, 12: substrate
20, 21, 22 : 도펀트 포함 고분자층20, 21, 22: polymer layer containing a dopant
30, 31, 32 : 그래핀층30, 31, 32: graphene layer
40 : 금속 촉매층40: metal catalyst layer

Claims (35)

  1. 기판; 도펀트 포함 고분자층; 및 그래핀층을 포함하는 그래핀 적층체.Board; A dopant-containing polymer layer; And a graphene layer comprising a graphene layer.
  2. 제 1 항에 있어서,The method of claim 1,
    면저항이 600Ω/sq 이하인 그래핀 적층체.Graphene laminate with a sheet resistance of 600 Ω / sq or less.
  3. 제 1 항에 있어서,The method of claim 1,
    면저항이 10Ω/sq 내지 400Ω/sq인 그래핀 적층체.Graphene laminate having a sheet resistance of 10Ω / sq to 400Ω / sq.
  4. 제 1 항에 있어서,The method of claim 1,
    고분자층은 폴리에틸렌계, 폴리프로필렌계, 폴리스틸렌계, 폴리염화비닐계, 폴리염화비닐리덴계, 불소계, 아크릴계, 폴리아세트산비닐계, 폴리아미드계, 폴리아세탈계, 폴리카보네이트계, 폴리페닐렌옥사이드계, 폴리에스테르계, 폴리술폰계, 폴리이미드계, 페놀계, 요소계, 멜라민계, 알키드계, 불포화 폴리에스테르계, 에폭시계, 규소계, 아크릴계 및 폴리우레탄계 중 하나 이상을 포함하는 그래핀 적층체.The polymer layer is polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, fluorine, acrylic, polyvinyl acetate, polyamide, polyacetal, polycarbonate, polyphenylene oxide , Graphene laminate comprising at least one of polyester, polysulfone, polyimide, phenol, urea, melamine, alkyd, unsaturated polyester, epoxy, silicon, acrylic and polyurethane .
  5. 제 1 항에 있어서,The method of claim 1,
    고분자층은 전도성 고분자를 포함하는 그래핀 적층체.The polymer layer is a graphene laminate containing a conductive polymer.
  6. 제 5 항에 있어서,The method of claim 5,
    전도성 고분자는 폴리아세틸렌, 폴리디아세틸렌, 폴리페닐렌, 폴리아닐린, 폴리티오펜, 폴리페닐렌비닐렌, 폴리티오펜비닐렌, 폴리피롤, 폴리플루오렌 및 PEDOT:PSS 중 하나 이상을 포함하는 그래핀 적층체.The conductive polymer is a graphene lamination comprising at least one of polyacetylene, polydiacetylene, polyphenylene, polyaniline, polythiophene, polyphenylenevinylene, polythiophenvinylene, polypyrrole, polyfluorene and PEDOT: PSS sieve.
  7. 제 1 항에 있어서,The method of claim 1,
    고분자층은 하기 화학식 1 내지 3 중 하나 이상의 모노머 중합체를 포함하는 그래핀 적층체The polymer layer is a graphene laminate comprising at least one monomer polymer of the following Chemical Formulas 1 to 3
    [화학식 1][Formula 1]
    Figure PCTKR2012005945-appb-I000011
    Figure PCTKR2012005945-appb-I000011
    [화학식 2][Formula 2]
    Figure PCTKR2012005945-appb-I000012
    Figure PCTKR2012005945-appb-I000012
    [화학식 3][Formula 3]
    Figure PCTKR2012005945-appb-I000013
    Figure PCTKR2012005945-appb-I000013
    상기 화학식 1 및 2에서, n은 3 내지 20의 정수이다. In Chemical Formulas 1 and 2, n is an integer of 3 to 20.
  8. 제 1 항에 있어서,The method of claim 1,
    고분자층은 하기 화학식 4 내지 7 중 하나 이상을 포함하는 그래핀 적층체:The polymer layer is a graphene laminate comprising at least one of the following formulas 4 to 7:
    [화학식 4][Formula 4]
    Figure PCTKR2012005945-appb-I000014
    Figure PCTKR2012005945-appb-I000014
    [화학식 5][Formula 5]
    Figure PCTKR2012005945-appb-I000015
    Figure PCTKR2012005945-appb-I000015
    [화학식 6][Formula 6]
    Figure PCTKR2012005945-appb-I000016
    Figure PCTKR2012005945-appb-I000016
    [화학식 7][Formula 7]
    Figure PCTKR2012005945-appb-I000017
    Figure PCTKR2012005945-appb-I000017
    상기 화학식 4 내지 7에서, In Chemical Formulas 4 to 7,
    R1은 C5 내지 C30의 알킬기이고,R 1 is an alkyl group of C5 to C30,
    R2는 C5 내지 C20의 알킬기; 또는 C1 내지 C20의 알킬기가 치환 또는 비치환된 C6 내지 C30의 아릴기이고, R 2 is an alkyl group of C5 to C20; Or a C6 to C30 aryl group having a substituted or unsubstituted C1 to C20 alkyl group,
    R3는 알코올기; 할로겐기; 또는 말단에 알코올기, 카르복실기, 술폰산기, 아민기, 카보닐기, 시아노기 및 할로겐기 중 하나 이상을 포함하는 C1 내지 C10의 알킬기이고,R 3 is an alcohol group; Halogen group; Or a C1 to C10 alkyl group containing at least one of an alcohol group, a carboxyl group, a sulfonic acid group, an amine group, a carbonyl group, a cyano group and a halogen group at the terminal,
    R4는 직쇄(linear chain) 또는 측쇄(branched chain)형을 포함하는 C1 내지 C10의 알킬기이고, R 4 is a C1 to C10 alkyl group including a linear or branched chain type,
    X1 내지 X4는 각각 독립적으로 수소 또는 C1 내지 C5의 알킬기이고,X 1 to X 4 are each independently hydrogen or an alkyl group of C1 to C5,
    n은 0 내지 10의 정수이다. n is an integer of 0-10.
  9. 제 1 항에 있어서,The method of claim 1,
    고분자층의 유리전이온도가 영하 10℃ 내지 영상 100℃ 범위인 그래핀 적층체.Graphene laminate of the glass transition temperature of the polymer layer ranges from minus 10 ℃ to image 100 ℃.
  10. 제 1 항에 있어서,The method of claim 1,
    도펀트는 P형 도펀트를 포함하는 그래핀 적층체.The dopant is a graphene laminate comprising a p-type dopant.
  11. 제 1 항에 있어서,The method of claim 1,
    도펀트는 할로겐 산화물, 황산화물, 금속 할라이드, 질소 산화물, 금속 과산화물, 벤조퀴논계 화합물 및 디브로모안트라센 중 하나 이상을 포함하는 그래핀 적층체.The dopant is a graphene laminate comprising at least one of halogen oxides, sulfur oxides, metal halides, nitrogen oxides, metal peroxides, benzoquinone compounds and dibromoanthracene.
  12. 제 11 항에 있어서,The method of claim 11,
    할로겐 산화물은 요오드계 산화물 및 염소계 산화물 중 하나 이상을 포함하는 그래핀 적층체.Halogen oxide is graphene laminate comprising at least one of iodine-based oxide and chlorine-based oxide.
  13. 제 12 항에 있어서,The method of claim 12,
    요오드계 산화물은 아이오딜벤젠, 아이오독시벤조산 및 데스-마틴 퍼아이오디난 중 하나 이상을 포함하는 그래핀 적층체.An iodine-based oxide is a graphene laminate comprising at least one of iodilbenzene, iodoxybenzoic acid and des-martin periodinan.
  14. 제 12 항에 있어서,The method of claim 12,
    염소계 산화물은 NaClO, NaClO2, NaClO3, NaClO4, AgClO3 및 AgClO4 중 하나 이상을 포함하는 그래핀 적층체.Chlorine oxide is a graphene laminate comprising one or more of NaClO, NaClO 2 , NaClO 3 , NaClO 4 , AgClO 3 and AgClO 4 .
  15. 제 11 항에 있어서,The method of claim 11,
    황산화물은 (CH3)2SO, KHSO5, KHSO4, K2SO4, FSO3H 및 CF3SO3H 중 하나 이상을 포함하는 그래핀 적층체.The sulfur oxide layer of graphene comprising at least one of (CH 3 ) 2 SO, KHSO 5 , KHSO 4 , K 2 SO 4 , FSO 3 H and CF 3 SO 3 H.
  16. 제 11 항에 있어서,The method of claim 11,
    금속 할라이드는 은이온, 금이온, 세륨이온, 철이온, 몰리브덴이온, 텅스텐이온, 주석이온, 루테늄이온 및 탄탈륨이온 중 하나 이상을 포함하는 금속염인 그래핀 적층체.The metal halide is a graphene laminate comprising a metal salt comprising at least one of silver, gold, cerium, iron, molybdenum, tungsten, tin, ruthenium and tantalum ions.
  17. 제 11 항에 있어서,The method of claim 11,
    금속 할라이드는 FeCl3, MoCl5, WCl5, SnCl4, MoF5, RuF5, TaBr5, SnI4, HAuCl4, AuCl3, (NH4)2Ce(SO4)3 및 (NH4)2Ce(NO3)6 중 하나 이상을 포함하는 그래핀 적층체.Metal halides are FeCl 3 , MoCl 5 , WCl 5 , SnCl 4 , MoF 5 , RuF 5 , TaBr 5 , SnI 4 , HAuCl 4 , AuCl 3 , (NH 4 ) 2 Ce (SO 4 ) 3 and (NH 4 ) 2 Graphene laminate comprising at least one of Ce (NO 3 ) 6 .
  18. 제 11 항에 있어서,The method of claim 11,
    질소산화물은 AgNO3, NO2F, NO2Cl, N2O5, NO2BF4, CH3NO2, C6H5NO2, CH3ONO, NO(SbCl6), NOBF4, NOClO4, NOSO4H, C6H5NO, NOCl, NOF 및 NOBr 중 하나 이상을 포함하는 그래핀 적층체.Nitrogen oxides are AgNO 3 , NO 2 F, NO 2 Cl, N 2 O 5 , NO 2 BF 4 , CH 3 NO 2 , C 6 H 5 NO 2 , CH 3 ONO, NO (SbCl 6 ), NOBF 4 , NOClO 4 , NOSO 4 H, C 6 H 5 NO, graphene laminate comprising at least one of NOCl, NOF and NOBr.
  19. 제 11 항에 있어서,The method of claim 11,
    금속 과산화물은 KMnO4, BaMnO4 및 OsO4 중 하나 이상을 포함하는 그래핀 적층체.Metal peroxides graphene laminate containing KMnO 4, BaMnO OsO 4 and one or more of the four.
  20. 제 11 항에 있어서,The method of claim 11,
    벤조퀴논계 화합물은 벤조퀴논, 테트라클로로벤조퀴논, 디클로로디시아노벤조퀴논 및 테트라시아노퀴노디메탄 중 하나 이상을 포함하는 그래핀 적층체.A benzoquinone compound is a graphene laminate comprising at least one of benzoquinone, tetrachlorobenzoquinone, dichlorodicyanobenzoquinone, and tetracyanoquinodimethane.
  21. 제 1 항에 있어서,The method of claim 1,
    도펀트의 함량은, 고분자층을 기준으로, 0.01 내지 20wt%인 그래핀 적층체.The content of the dopant is a graphene laminate of 0.01 to 20wt% based on the polymer layer.
  22. 제 1 항에 있어서,The method of claim 1,
    기판은 폴리에틸렌테레프탈레이트, 폴리에틸렌나프탈레이트, 폴리카보네이트, 폴리에테르설폰, 폴리사이클릭올레핀, 폴리아크릴레이트, 폴리에테르에테르케톤 및 폴리이미드 중 하나 이상을 포함하는 그래핀 적층체.The substrate is a graphene laminate comprising at least one of polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyethersulfone, polycyclic olefin, polyacrylate, polyetheretherketone and polyimide.
  23. (a) 기판상에 도펀트를 포함하는 고분자를 도포하는 단계;(a) applying a polymer comprising a dopant on a substrate;
    (b) 금속 촉매층 상에 형성된 그래핀층과 도펀트를 포함하는 고분자가 도포된 기판을 합지하는 단계; 및(b) laminating a substrate coated with a polymer including a graphene layer and a dopant formed on the metal catalyst layer; And
    (c) 금속 촉매층을 제거하는 단계를 포함하는 그래핀 적층체의 제조방법.(C) a method for producing a graphene laminate comprising the step of removing the metal catalyst layer.
  24. 제 23 항에 있어서,The method of claim 23,
    도펀트의 함량은, 고분자층을 기준으로 0.01 내지 20wt%인 그래핀 적층체의 제조방법.The content of the dopant is 0.01 to 20wt% of the graphene laminate based on the polymer layer.
  25. 제 23 항에 있어서,The method of claim 23,
    (c) 단계는 건식 전사방법에 의해 금속 촉매층을 제거하는 그래핀 적층체의 제조방법.Step (c) is a method for producing a graphene laminate to remove the metal catalyst layer by a dry transfer method.
  26. 제 25 항에 있어서,The method of claim 25,
    (c) 단계는, 롤투롤 방식에 의해 금속 촉매층과 그래핀층을 분리하는 그래핀 적층체의 제조방법.Step (c) is a graphene laminate manufacturing method of separating the metal catalyst layer and the graphene layer by a roll-to-roll method.
  27. 제 23 항에 있어서,The method of claim 23,
    (c) 단계는 습식 전사방법에 의해 금속 촉매층을 제거하는 그래핀 적층체의 제조방법.Step (c) is a method for producing a graphene laminate to remove the metal catalyst layer by a wet transfer method.
  28. 제 27 항에 있어서,The method of claim 27,
    (c) 단계는, 에칭액을 이용하여 금속 촉매층을 제거하는 그래핀 적층체의 제조방법.(c) step, the graphene laminate manufacturing method for removing the metal catalyst layer using an etching solution.
  29. 제 23 항에 있어서,The method of claim 23,
    (b) 단계에서, 금속 촉매층상에 형성된 그래핀층과 도펀트를 포함하는 고분자가 도포된 기판을 합지하고 열 또는 UV 경화 과정을 포함하는 그래핀 적층체의 제조방법.In the step (b), the graphene layer formed on the metal catalyst layer and a method of manufacturing a graphene laminate comprising laminating a substrate coated with a polymer comprising a dopant and a thermal or UV curing process.
  30. 제 23 항에 있어서,The method of claim 23,
    그래핀층이 형성된 금속 촉매층은 금속 촉매층의 양면에 그래핀층이 형성된 구조이며,The metal catalyst layer having the graphene layer formed thereon has a graphene layer formed on both sides of the metal catalyst layer,
    금속 촉매층의 양면에 형성된 그래핀층 각각의 외면에 도펀트를 포함하는 고분자가 도포된 기판을 합지한 후, 금속 촉매층을 제거하는 그래핀 적층체의 제조방법.Method of manufacturing a graphene laminate to remove the metal catalyst layer after laminating a substrate coated with a polymer containing a dopant on the outer surface of each graphene layer formed on both sides of the metal catalyst layer.
  31. 제 30 항에 있어서,The method of claim 30,
    금속 촉매층 양면에 형성된 그래핀층 각각의 외면에 도펀트를 포함하는 고분자가 도포된 기판을 합지한 후, 열 또는 UV 경화 과정을 포함하는 그래핀 적층체의 제조방법.After laminating a substrate coated with a polymer containing a dopant on the outer surface of each graphene layer formed on both sides of the metal catalyst layer, a method for producing a graphene laminate comprising a heat or UV curing process.
  32. 기판, 도펀트 포함 고분자층, 그래핀, 금속 촉매층, 그래핀, 도펀트 포함 고분자층 및 기판이 순차적으로 적층된 구조의 그래핀 적층체.A graphene laminate having a structure in which a substrate, a dopant-containing polymer layer, graphene, a metal catalyst layer, graphene, a dopant-containing polymer layer, and a substrate are sequentially stacked.
  33. 제 1 항에 따른 그래핀 적층체를 포함하는 전극 또는 전도성 박막.Electrode or conductive thin film comprising the graphene laminate according to claim 1.
  34. 제 33 항의 전극 또는 전도성 박막을 포함하는 전자 소자.An electronic device comprising the electrode or conductive thin film of claim 33.
  35. 제 34 항에 있어서,The method of claim 34, wherein
    상기 전자 소자는 트랜지스터, 레이저 소자, 터치패널, 유기발광소자, 태양전지 또는 이차전지인 전자 소자.The electronic device is a transistor, a laser device, a touch panel, an organic light emitting device, a solar cell or a secondary battery.
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