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WO2013019021A2 - Stratifié à base de graphène contenant un dopant et son procédé de fabrication - Google Patents

Stratifié à base de graphène contenant un dopant et son procédé de fabrication Download PDF

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Publication number
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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Prior art keywords
graphene
layer
dopant
graphene laminate
polymer
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Korean (ko)
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WO2013019021A3 (fr
Inventor
권오관
최정옥
정준호
최면천
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LMS Co Ltd
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LMS Co Ltd
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    • B82—NANOTECHNOLOGY
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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
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    • C—CHEMISTRY; METALLURGY
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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    • 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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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.

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Abstract

La présente invention concerne un stratifié à base de graphène ayant une structure formée par la stratification d'un substrat, d'une couche polymère contenant un dopant et d'une couche de graphène. L'invention concerne également un procédé de fabrication du stratifié à base de graphène. Le stratifié présente une faible résistance de surface et une transmission optique élevée, ce qui permet de l'utiliser, entre autres, dans divers dispositifs électriques.
PCT/KR2012/005945 2011-07-29 2012-07-26 Stratifié à base de graphène contenant un dopant et son procédé de fabrication Ceased WO2013019021A2 (fr)

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