KR20170032796A - Method for preparing graphene using aromatic and aliphatic derivative compound and method for fabricating electronic device comprising the same - Google Patents

Abstract

The present invention comprises the following steps: (a) forming an organic layer on a metal catalyst; and (b) heat treating the metal catalyst having an organic layer formed to form graphene on the metal catalyst, wherein the organic layer relates to a method for preparing the graphene comprising aromatic and aliphatic derivative compounds. The method for preparing the graphene of the present invention uses the organic layer comprising the aromatic and aliphatic derivative compounds, which enables the growth of the graphene at a low temperature, thereby increasing production efficiency and reducing production costs. In addition, the method of the present invention can manufacture the graphene having excellent quality such as superior field-effect mobility by significantly reducing defects of the graphene.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing graphene using an aromatic derivative compound and an aliphatic derivative compound, and a method of manufacturing an electronic device including the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a method for producing graphene using an aromatic derivative compound and an aliphatic derivative compound, and a method for producing an electronic device including the same. More particularly, the present invention relates to a method for producing graphene using an organic layer comprising an aromatic derivative compound and an aliphatic derivative compound, A method of producing graphene using aromatic derivative compounds and aliphatic derivative compounds capable of increasing production efficiency and reducing production costs, and a method of manufacturing an electronic device including the same.

Graphite is a material having a typical layered structure, and graphenes of a two-dimensional plate-like structure in which carbon atoms are connected in a hexagonal shape are laminated. Graphene is a single flat sheet composed of three carbon atoms bonded by SP ² hybrid orbital bond, and has a hexagonal honeycomb-like crystal lattice.

In graphite, the bond between the carbon atoms in the graphene constituting each layer is very strong as a covalent bond, but the bond between graphene and graphene is weaker than the covalent bond as a van der Waals bond.

Graphene is a single layer of graphite, ie, a (0001) plane monolayer of graphite. Since grains and graphene bond in graphite is weak as described above, graphene having a very thin two-dimensional structure Can exist.

These graphenes have found very useful properties that are different from conventional materials. The most notable feature is that when electrons move from graphene, the mass of electrons flows like zero, which means that electrons flow at the rate at which light travels in vacuum, that is, the flux. These graphenes also have an unusual half-integer quantum Hall effect on electrons and holes.

Graphene, a carbonaceous honeycomb structure, has a strength of more than 200 times stronger than steel, more than 100 times more conductive than copper, and more than twice the thermal conductivity of diamond, making it ideal for use in displays, energy, It is widely regarded as the 'new material of dream'.

In the case of carbon nanotubes similar to graphene, the yield of the carbon nanotubes is very low when they are purified after synthesis. Therefore, even when synthesized using cheap materials, the final product is expensive, while graphite is very cheap , Single-walled carbon nanotubes are characterized not only by their chirality and diameters but also by their bandgaps, even though they have the same semiconductor characteristics. Therefore, the single-walled carbon nanotubes are characterized by having a specific semiconductor property or In order to utilize the metallic properties, it is necessary to separate all the single-walled carbon nanotubes, which is known to be very difficult.

On the other hand, in the case of graphene, since the electrical characteristics change according to the crystal orientation of the graphene of a given thickness, the user can express the electrical characteristics in the selection direction, and thus the device can be easily designed. The characteristics of such graphene can be very effectively used for carbon-based electric devices or carbon-based electromagnetic devices in the future.

Due to such excellent characteristics of graphene, it is attracting attention as a substitute material for next generation silicon and ITO (INDIUM TIN OXIDE) transparent electrode.

Methods for obtaining graphene include mechanical peeling, chemical peeling, SiC crystal pyrolysis, peeling-re-insert-expansion, chemical vapor deposition, and epitaxy synthesis.

The mechanical stripping method is based on the adhesion of scotch tape. When a cellophane tape is attached to a graphite sample and then the cellophane tape is peeled off, graphene detached from the graphite is attached to the surface of the cellophane tape. However, in the case of such a mechanical stripping method, the graphene which has fallen off is not uniform in a shape in which the paper is torn, and its size is only a micrometer level, and it is impossible to obtain a large area graphene, And there is a problem in that it is not suitable for research requiring a lot of samples.

The chemical peeling method is a method of oxidizing graphite and crushing it through ultrasonic waves to make graphene oxide dispersed in an aqueous solution, and then reducing the graphene grains again with a reducing agent such as hydrazine. However, since the oxidized graphene is not completely reduced and only about 70% of the oxidized graphene is reduced, many defects remain in the graphene, resulting in poor physical and electrical properties inherent to graphene.

The SiC crystal pyrolysis method is based on the principle that SiC is decomposed on the surface when SiC single crystal is heated, and Si is removed and graphene is formed by the remaining carbon (C). However, in the case of such a pyrolysis method, the SiC single crystal used as a starting material is very expensive, and it is very difficult to obtain graphene in a large area.

In the stripping-reinsertion-expansion method, when fuming sulfuric acid is inserted into graphite and then placed in a furnace at a very high temperature, graphite is expanded by the gas as the sulfuric acid is expanded, and the graphite is dispersed in a surfactant such as TBA, . In this peeling-re-insertion-expansion method, the actual graphene yield is very low and the interlayer contact resistance is large due to the surfactant used, so that satisfactory electrical characteristics are not obtained.

The epitaxy method is based on the principle that the carbon contained in a crystal is adsorbed to a crystal at a high temperature or that the carbon contained therein is grown as graphene along the surface of the substrate. The graphene produced by this method has a disadvantage that it is relatively inferior to the graphene grown by the mechanical peeling method and the chemical vapor deposition method, and the substrate is very expensive and it is very difficult to manufacture the device.

The chemical vapor deposition method is a method of synthesizing graphene by using a transition metal which forms carbon or carbide alloy well at high temperature or adsorbs carbon well as a catalyst layer. This process is difficult and heavy metal catalysts are used, and there are many limitations in mass production.

U.S. Patent Publication No. 2010-0047154 discloses a method for mass-producing graphene ribbons, which comprises finely cutting graphite, infiltrating water into graphite chips that are chopped, freezing graphite impregnated with water, However, ultrasonic treatment and hydrophilic treatment are required at the time of manufacturing, and there is a limitation in that a ribbon-shaped graphene piece can be obtained instead of a graphene sheet.

 In order to reduce the process cost and simplify the process, a method has been developed in which an organic layer containing an aromatic derivative compound is formed on a catalyst layer and heat treated at a low temperature to produce graphene. However, such a method of manufacturing graphene has a problem that defects are generated in the produced graphene and the characteristics of the device are deteriorated when the graphene is applied to an electronic device such as a field effect transistor.

DISCLOSURE OF THE INVENTION An object of the present invention is to solve the problems described above, and it is possible to grow graphene at a low temperature using an organic layer containing an aromatic derivative compound and an aliphatic derivative compound, thereby increasing production efficiency and reducing production cost , And a method for producing graphene in which defects are remarkably reduced.

It is also an object of the present invention to provide an electronic device such as a field effect transistor in which device characteristics are greatly improved by applying such graphene.

According to an aspect of the present invention,

(a) forming an organic layer on a metal catalyst; And (b) heat treating the metal catalyst having the organic layer formed thereon to form graphene on the metal catalyst, wherein the organic layer comprises an aromatic derivative compound and an aliphatic derivative compound .

The aliphatic derivative compound is a substituted or unsubstituted C4 to C200 aliphatic compound. The substituent corresponding to the substitution may be at least one selected from the group consisting of a phosphoric acid group, a halogen group, a sulfone group, an amine group, a carboxyl group, a hydroxyl group and a silyl group.

The aromatic derivative compound is a substituted or unsubstituted C6 to C200 aromatic compound, and the substituent corresponding to the substitution may be a C6 to C200 aryl group or a C1 to C200 alkyl group.

Wherein the aliphatic derivative is selected from the group consisting of 1-octylphosphonic acid, hexylphosphonic acid, octadecylphosphonic acid, hexadecylamine, octylamine, May include at least one member selected from the group consisting of hexylamine, octanesulfonic acid, hexanesulfonic acid, 1-butylphosphonic acid, 1-tetrabutylphosphonic acid and triethylsilyl acetylene. have.

Wherein the aromatic derivative compound is 1,2,3,4-tetraphenylnaphthalene, anthracene, phenanthrene, 2,3-benzanthracene, 2,3- may include at least one selected from benzoanthracene, chrysene, pyrene, benzopyrene, coronene, corannulene, naphthacene, naphthalene and pentacene. have.

The content of the aliphatic derivative compound may be 1 to 30 wt% of the total weight of the organic layer.

The aliphatic derivative compound and the aromatic derivative compound may be solid at 30 DEG C or less.

The organic layer may be formed by coating a solution containing the aromatic derivative compound and the aliphatic derivative compound on the metal catalyst.

The solvent of the solution may be a cosolvent capable of simultaneously dissolving the aromatic derivative compound and the aliphatic derivative compound.

The co-solvent may include at least one selected from chloroform, acetonitrile, carbon tetrachloride, methylene chloride, tetrahydrofuran, diethoxyethanol, ethyl acetate, methyl ethyl ketone, benzene, toluene, methanol, ethanol, propanol and dichloromethane .

The coating may be performed with at least one selected from spin coating, inkjet coating, dip coating, drop casting and bar coating.

The metal catalyst may include at least one selected from the group consisting of nickel, iron, copper, platinum, palladium, ruthenium and cobalt.

The heat treatment of step (b) may be performed at 300 to 800 < 0 > C.

The heat treatment may be performed under an atmospheric pressure of 1 x 10 < ^-3 > to 1 Torr.

The heat treatment may be performed for 30 minutes to 3 hours.

According to another aspect of the present invention,

A method of manufacturing an electronic device including the method of manufacturing the graphene is provided.

The electronic device may be any one selected from a field effect transistor, an electrode, a touch panel, an electroluminescent display, a backlight, a radio frequency identification tag, a solar cell module, an electronic paper, a TFT for a flat display, and a TFT array.

The electronic device may be a field effect transistor.

The method of producing graphene of the present invention is capable of growing graphene at a low temperature by forming an organic layer containing a compound and an aliphatic derivative compound in aromatic derivation, thereby increasing the production efficiency and reducing the production cost have.

In addition, it is possible to produce graphene with excellent quality with excellent field effect mobility by significantly reducing defects of graphene.

In addition, it can be applied to various electronic devices such as field effect transistors, electrodes, touch panels, electroluminescent displays, backlights, RFID tags, solar cell modules, There is an effect that can be.

BRIEF DESCRIPTION OF THE DRAWINGS FIG.
Figure 2 is an example of graphene formed using a solid organic layer.
FIG. 3 is a graph showing the Raman spectrum of graphene produced by the manufacturing method of the present invention and the graphene produced by the conventional manufacturing method, and the result of calculating the defect frequency.
4 is a HRTEM photograph of graphene prepared according to Example 5, Comparative Example 1 and Comparative Example 3. Fig.
5 shows p-GCMS measurement results of graphene prepared according to Example 5, Example 6, Comparative Example 1 and Comparative Example 2. Fig.
6 shows the results of measurement of carrier mobility of the field-effect transistor manufactured according to Example 11 and Comparative Example 4. Fig.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention.

However, the following description does not limit the present invention to specific embodiments. In the following description of the present invention, detailed description of related arts will be omitted if it is determined that the gist of the present invention may be blurred .

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises ", or" having ", and the like, specify that the presence of stated features, integers, steps, operations, elements, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, or combinations thereof.

The term "substituted" as used herein means that at least one hydrogen atom is replaced by a substituent selected from the group consisting of deuterium, C1 to C30 alkyl groups, C3 to C30 cycloalkyl groups, C2 to C30 heterocycloalkyl groups, C1 to C30 halogenated alkyl groups, C6 to C30 aryl groups, C1 to C30 heteroaryl groups, C1 to C30 alkoxy groups, C2 to C30 alkenyl groups, C2 to C30 alkynyl group, C6 to C30 aryloxy group, a silyloxy _{(-OSiH 3), -OSiR 1 H} 2 (R 1 is a C1 to C30 alkyl groups or C6 to C30 aryl _{group), -OSiR 1 R 2 H (} R 1 and R ₂ are each independently a C1 to C30 alkyl or C6 to C30 aryl _{group), -OSiR 1 R 2 R 3} , (R 1, R 2, and R ₃ each independently represent a C1 to C30 alkyl group or a C6 to C30 aryl group), a C1 to C30 acyl group, a C2 to C30 acyloxy group, a C2 to C30 heteroaryloxy group, a C1 to C30 sulfonyl group, a C1 to C30 alkylthiol group , A C6 to C30 arylthiol group, a C1 to C30 heterocyclothiol group, a C1 to C30 phosphoric acid amide group, a silyl group (- SiH ₃ , -SiR ₁ H ₂ , -SiR ₁ R ₂ H, and -SiR ₁ R ₂ R ₃ , wherein R ₁ , R ₂ , and R ₃ are each independently a C 1 to C 30 alkyl group or a C 6 to C 30 An aryl group), an amine group (-NRR ', where R and R' are each independently a substituent selected from the group consisting of a hydrogen atom, a C1 to C30 alkyl group, and a C6 to C30 aryl group), a carboxyl group, A cyano group, a nitro group, an azo group, and a hydroxy group.

The carbon number range of the alkyl group or aryl group in the above "substituted or unsubstituted C1 to C200 alkyl group" or "substituted or unsubstituted C6 to C200 aryl group" Quot; means the total number of carbon atoms constituting the alkyl moiety or the aryl moiety when it is considered to be " substituted ". For example, a phenyl group substituted with a butyl group at the para position means an aryl group having 6 carbon atoms substituted with a butyl group having 4 carbon atoms.

In the present specification, the term "combination thereof" means that two or more substituents are bonded to each other via a linking group or two or more substituents are condensed and bonded.

As used herein, "hydrogen" means monohydrogen, double hydrogen, or tritium, unless otherwise defined.

As used herein, unless otherwise defined, the term "alkyl group" means an aliphatic hydrocarbon group.

The alkyl group may be a "saturated alkyl group" which does not contain any double or triple bonds.

The alkyl group may be an "unsaturated alkyl group" comprising at least one double bond or triple bond.

"Alkynylene group" means a functional group in which at least two carbon atoms are composed of at least one carbon-carbon double bond, and "alkynylene group" means that at least two carbon atoms have at least one carbon- Quot; means a functional group formed by bonding. The alkyl group, whether saturated or unsaturated, can be branched, straight chain or cyclic.

The alkyl group may be a C1 to C200 alkyl group. More specifically, the alkyl group may be a C1 to C200 alkyl group, a C1 to C100 alkyl group, a C1 to C50 alkyl group, a C1 to C30 alkyl group, a C1 to C20 alkyl group, a C1 to C10 alkyl group or a C1 to C6 alkyl group.

For example, the C1 to C4 alkyl groups may have 1 to 4 carbon atoms in the alkyl chain, i.e., the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of methyl, ethyl, propyl, iso-propyl, n-butyl, Indicating that they are selected from the group.

Specific examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, ethenyl group, Butyl group, cyclopentyl group, cyclohexyl group, and the like.

An "amine group" includes an amino group, an arylamine group, an alkylamine group, an arylalkylamine group, or an alkylarylamine group, and may be represented by -NRR ', wherein R and R' , A C1 to C30 alkyl group, and a C6 to C30 aryl group.

"Cycloalkyl group" includes monocyclic or fused-ring polycyclic (i. E., Rings that divide adjacent pairs of carbon atoms) functional groups.

"Heterocycloalkyl group" means that the cycloalkyl group contains 1 to 4 hetero atoms selected from the group consisting of N, O, S and P in the cycloalkyl group, and the remainder is carbon. When the heterocycloalkyl group is a fused ring, at least one ring of the fused rings may contain from 1 to 4 heteroatoms.

"An aromatic group" means a functional group in which all elements of a functional group in the form of a ring have a p-orbital, and these p-orbital forms a conjugation. Specific examples thereof include an aryl group and a heteroaryl group.

An "aryl group" includes a monocyclic or fused ring polycyclic (i. E., A ring that divides adjacent pairs of carbon atoms) functional groups.

"Heteroaryl group" means that the aryl group contains 1 to 4 hetero atoms selected from the group consisting of N, O, S and P, and the remainder is carbon. When the heteroaryl group is a fused ring, at least one ring of the fused rings may contain from 1 to 4 heteroatoms.

In the aryl group and the heteroaryl group, the number of atoms in the ring is the sum of carbon number and non-carbon atom number.

When used in combination, such as "alkylaryl" or "arylalkyl group ", the terms alkyl and aryl of each of the above have the meanings and contents indicated above.

The term "arylalkyl group " means an aryl substituted alkyl radical, such as benzyl, and is included in the alkyl group.

The term "alkylaryl group " means an alkyl substituted aryl radical and is included in the aryl group.

BRIEF DESCRIPTION OF THE DRAWINGS FIG.

Hereinafter, a method for producing graphene of the present invention will be described in detail with reference to FIG. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

First, an organic layer is formed on the metal catalyst (step a).

The metal catalyst plays a role of growing a graphene layer, and nickel, iron, copper, platinum, palladium, ruthenium, cobalt and the like can be applied. In addition, any metal that can induce growth of graphene can be applied.

The metal catalyst may be formed by sputtering, thermal evaporation, electron beam evaporation, or the like, but is not limited thereto.

The metal catalyst may be formed to a thickness of 10 to 1000 nm, preferably 100 to 600 nm, more preferably 300 to 500 nm

The organic layer includes an aromatic derivative compound and an aliphatic derivative compound.

The aliphatic derivative compound may be a substituted or unsubstituted C4 to C200 aliphatic compound, and the substituent corresponding to the substitution may be a phosphoric acid group, a halogen group, a sulfonic group, an amine group, a hydroxyl group, a silyl group, or the like.

When the carbon number of the aliphatic derivative compound is unsubstituted, it is preferably C100 to C200, more preferably C150 to C200.

When substituted, the carbon number range of the aliphatic derivative compound is preferably C4 to C100, more preferably C4 to C50, and still more preferably C4 to C20.

Since the aliphatic derivative compound is in a solid phase because it is advantageous for low-temperature graphene growth, it may be preferable to have a substituent.

The aliphatic derivative compound is preferably selected from 1-octylphosphonic acid, hexylphosphonic acid, octadecylphosphonic acid, hexadecylamine, octylamine, hexylamine, octanesulfonic acid, hexanesulfonic acid, 1-butylphosphonic acid , 1-tetrabutylphosphonic acid, triethylsilyl acetylene, and the like, and more preferably 1-octylphosphonic acid.

The aromatic derivative compound may be a substituted or unsubstituted C6 to C200 aromatic compound, and the substituent corresponding to the substitution may be a C6 to C200 aryl group or a C1 to C200 alkyl group.

When the carbon number of the aromatic derivative compound is unsubstituted, it is preferably C100 to C200, more preferably C150 to C200.

When substituted, the carbon number range of the aromatic derivative compound may preferably be C6 to C100, more preferably C6 to C50, and still more preferably C6 to C30.

The substituent of the aromatic derivative compound is preferably a C6 to C100 aryl group or a C1 to C100 alkyl group, more preferably a C6 to C50 aryl group or a C1 to C50 alkyl group, still more preferably a C6 to C30 aryl group or a C1 to C30 aryl group, Alkyl group.

The aromatic derivative compound is also preferably in a solid form.

The aromatic derivative compound may be 1,2,3,4-tetraphenylnaphthalene, anthracene, phenanthrene, 2,3-benzoanthracene, chrysene, pyrene, benzopyrene, Naphthalene, pentacene, and the like, preferably 1,2,3,4-tetraphenylnaphthalene.

The content of the aliphatic derivative compound may be 1 to 30 wt%, preferably 1 to 28 wt%, more preferably 1 to 25 wt% of the total weight of the organic layer.

The aliphatic derivative compound and the aromatic derivative compound are preferably solid at 30 DEG C or lower and may be advantageous for low-temperature graphene growth.

The organic layer may be formed by coating a solution containing the aromatic derivative compound and the aliphatic derivative compound on the metal catalyst.

The solvent of the solution is a co-solvent capable of solubilizing the aromatic derivative compound and the aliphatic derivative compound at the same time. The solvent of the solution is a co-solvent which can simultaneously dissolve the aromatic derivative compound and the aliphatic derivative compound, , Toluene, methanol, ethanol, propanol, dichloromethane and the like, preferably chloroform.

The coating may be performed by spin coating, inkjet coating, dip coating, drop casting, bar coating or the like, but is not limited thereto.

Finally, the metal catalyst having the organic layer formed thereon is heat-treated to form graphene on the metal catalyst (step b).

The heat treatment in step b may be performed at 300 to 800 ° C, preferably at 350 to 650 ° C, more preferably at 380 to 620 ° C.

The heat treatment may be performed under an atmospheric pressure of 1 × 10 ^-3 to 1 Torr, preferably at a pressure of 0.5 × 10 ^-1 to 0.5 Torr, more preferably 0.8 × 10 ^-1 to 0.3 Torr . However, the present invention is not limited thereto under the atmospheric pressure condition of the heat treatment.

The heat treatment may be performed for 30 minutes to 3 hours, preferably 45 minutes to 2 hours 30 minutes, more preferably 1 hour to 2 hours. However, the heat treatment time of the present invention is not limited thereto. The heat treatment time may vary depending on the heat treatment temperature or the atmospheric pressure condition of the heat treatment.

As described above, when an organic layer comprising the aromatic derivative compound and the aliphatic derivative compound is formed on the metal catalyst to produce graphene, it is possible to produce graphene of excellent quality with little defect.

Optionally, after step b, a polymeric support layer may be formed on said graphene (step c).

Also, graphene can be obtained by removing the metal catalyst from the product of step b without passing through step c after step b (step d).

If the polymer support layer is formed through step c, the metal catalyst may be removed from the product of step c to obtain graphene having the polymer support layer (step e).

The graphene produced according to the above steps can be applied to various electronic devices and can be applied to necessary electronic devices by transferring a graphene layer to a desired substrate.

In detail, after forming the laminated structure of the metal catalyst / graphene / polymer support layer according to steps a to e, the metal catalyst may be removed to leave only the graphene / polymer support layer.

At this time, the polymer scaffold may include an acrylate-based polymer material including polymethylmethacrylate (PMMA), a variety of commercial polymer materials, and a silicone polymer. After transferring the graphene to the desired substrate using the graphene / polymer support layer, the polymer support layer may be removed. The solvent used for removing the polymer support layer may be an organic solvent such as chloroform, toluene, Or a possible inorganic solvent can be used.

As described above, the graphene sheet transferred to a target substrate can be applied to a flexible electronic device, a transparent electronic device, and the like, and more particularly to a field effect transistor, a touch panel, an electroluminescent display, a backlight, ) Tags, solar cell modules, electronic paper, TFTs for flat panel displays, TFT arrays, and the like.

2 is a schematic view of graphene prepared by forming an organic layer containing an aliphatic derivative compound and an aromatic derivative compound on a metal catalyst.

Hereinafter, with reference to FIG. 2, a description will be given of the reason why defects are caused in manufacturing graphene.

Figures 2 (a) and 2 (b) are graphenes prepared using only aromatic derivative compounds. When graphene is produced using only the aromatic derivative compound, the orientation direction of the aromatic derivative compound is not constant, so that defects may occur (Fig. 2 (a)). In addition, defects may also be caused by the molecular structure inherent in aromatic derivative compounds (Fig. 2B).

On the other hand, when an aliphatic derivative compound is prepared using an aromatic derivative compound (Fig. 2 (c)), a small carbon fragment is located at the defect position. Accordingly, when graphene is formed by forming an organic layer containing an aliphatic derivative compound and an aromatic derivative compound together, it is possible to produce a single-layer graphene of excellent quality with few defects.

[Example]

Hereinafter, preferred embodiments of the present invention will be described. However, this is for illustrative purposes only, and thus the scope of the present invention is not limited thereto.

Example  One: Grapina  Produce

2.04 mg of 1-octylphosphonic acid (OPA) and 100 mg of 1,2,3,4-tetraphenyl naphthalene (TPN) were dissolved in 10 ml of chloroform as a solvent to obtain 1-octylphosphonic acid and 1,2,3,4- -Tetraphenyl naphthalene in a weight ratio of 2:98 (OPA 2 wt%). The mixed solution was spin-coated on a copper substrate at 2,000 rpm to prepare a copper substrate having an organic layer formed thereon. The copper substrate on which the organic layer was formed was placed in a quartz tube under a condition of 1.5 × 10 ^-1 Torr. The surface of the copper substrate on which the organic layer was formed was heat-treated at 400 캜 for 1 hour and 30 minutes to prepare graphene.

Example 2: Preparation of graphene

Graphene was prepared in the same manner as in Example 1, except that the surface of the copper substrate on which the organic layer was formed was heat-treated at 600 ° C instead of heat-treating at 400 ° C.

Example 3: Preparation of graphene

Octylphosphonic acid and 1,2,3,4-tetraphenylnaphthalene in a weight ratio of 2:98 (OPA 2 wt%) was replaced by 1-octylphosphonic acid and 1,2,3,4-tetraphenylnaphthalene Was used as a mixed solution having a weight ratio of 4.8: 95.2 (OPA: 4.8 wt%).

Example 4: Preparation of graphene

Octylphosphonic acid and 1,2,3,4-tetraphenylnaphthalene in a weight ratio of 2:98 (OPA 2 wt%) was replaced by 1-octylphosphonic acid and 1,2,3,4-tetraphenylnaphthalene Except that the surface of the copper substrate on which the organic layer was formed was subjected to heat treatment at 600 ° C instead of heat treatment at 400 ° C, Graphene.

Example 5: Preparation of graphene

Octylphosphonic acid and 1,2,3,4-tetraphenylnaphthalene in a weight ratio of 2:98 (OPA 2 wt%) was replaced by 1-octylphosphonic acid and 1,2,3,4-tetraphenylnaphthalene Was 9.1: 90.9 (OPA: 9.1 wt%). The graphene was prepared in the same manner as in Example 1,

Example 6: Preparation of graphene

Octylphosphonic acid and 1,2,3,4-tetraphenylnaphthalene in a weight ratio of 2:98 (OPA 2 wt%) was replaced by 1-octylphosphonic acid and 1,2,3,4-tetraphenylnaphthalene Except that the surface of the copper substrate on which the organic layer was formed was heat-treated at 600 ° C instead of heat-treating at 400 ° C, the same procedure as in Example 1 was repeated, except that the mixed solution was 9.1: 90.9 (OPA: 9.1 wt% Graphene.

Example 7: Preparation of graphene

Octylphosphonic acid and 1,2,3,4-tetraphenylnaphthalene in a weight ratio of 2:98 (OPA 2 wt%) was replaced by 1-octylphosphonic acid and 1,2,3,4-tetraphenylnaphthalene Was used as a mixed solution having a weight ratio of 16.6: 83.4 (OPA: 16.6 wt%).

Example 8: Preparation of graphene

Octylphosphonic acid and 1,2,3,4-tetraphenylnaphthalene in a weight ratio of 2:98 (OPA 2 wt%) was replaced by 1-octylphosphonic acid and 1,2,3,4-tetraphenylnaphthalene Except that the surface of the copper substrate on which the organic layer was formed was heat-treated at 600 ° C instead of heat-treating at 400 ° C. Graphene.

Example 9: Preparation of graphene

Octylphosphonic acid and 1,2,3,4-tetraphenylnaphthalene in a weight ratio of 2:98 (OPA 2 wt%) was replaced by 1-octylphosphonic acid and 1,2,3,4-tetraphenylnaphthalene (OPA 23 wt%) was used instead of the mixed solution of graphite powder and graphite powder.

Example 10: Preparation of graphene

Octylphosphonic acid and 1,2,3,4-tetraphenylnaphthalene in a weight ratio of 2:98 (OPA 2 wt%) was replaced by 1-octylphosphonic acid and 1,2,3,4-tetraphenylnaphthalene (OPA 23 wt%), and the surface of the copper substrate on which the organic layer was formed was subjected to heat treatment at 600 ° C instead of heat treatment at 400 ° C. Pin.

Comparative Example 1: Preparation of graphene

The procedure of Example 1 was repeated, except that 100 mg of 1,2,3,4-tetraphenylnaphthalene was replaced with 1,2,3,4-tetraphenylnaphthalene solution in 10 ml of chloroform in place of the mixed solution. Pin.

Comparative Example 2: Preparation of graphene

Instead of the mixed solution, 1,2,3,4-tetraphenylnaphthalene solution in which 100 mg of 1,2,3,4-tetraphenylnaphthalene was dissolved in 10 ml of chloroform was used and the surface of the copper substrate on which the organic layer was formed was heated to 400 ° C Graphene was prepared in the same manner as in Example 1, except that the heat treatment was performed at 600 占 폚 in place of the heat treatment in Example 1.

Comparative Example 3: Preparation of graphene

Grafting was carried out in the same manner as in Example 1, except that 1-octylphosphonic acid (100 mg) was used instead of the mixed solution, and 1-octylphosphonic acid solution in which 10 mL of chloroform was used.

The production conditions of the graphene produced according to Examples 1 to 10 and Comparative Examples 1 to 3 are summarized in Table 1 below. The content of 1-octylphosphonic acid or 1,2,3,4-tetraphenylnaphthalene is preferably in the range of 1 to 20% by weight based on the total weight of the organic layers (1-octylphosphonic acid and 1,2,3,4-tetraphenylnaphthalene) It has nothing to do with the content.

division Content of 1-octylphosphonic acid (wt%) Content of 1,2,3,4-tetraphenylnaphthalene (wt%) Heat treatment temperature (캜) Example 1 2 98 400 Example 2 2 98 600 Example 3 4.8 95.2 400 Example 4 4.8 95.2 600 Example 5 9.1 90.9 400 Example 6 9.1 90.9 600 Example 7 16.6 83.4 400 Example 8 16.6 83.4 600 Example 9 23 77 400 Example 10 23 77 600 Comparative Example 1 0 100 400 Comparative Example 2 0 100 600 Comparative Example 3 100 0 400

Device embodiment: Fabrication of field effect transistor

A polymer layer was coated on the graphene layer prepared in Example 5 with a support layer, and then copper was dissolved in an aqueous solution of ammonium persulfate to prepare a polymer layer / graphene laminate. Next, the polymer layer / graphene laminate was transferred onto a heavily doped Si substrate in which SiO ₂ was thermally grown to a thickness of 300 nm, and the polymer layer was removed by heat treatment at 250 ° C. Au electrodes were formed on the graphene / Si substrate on a graphene layer by a thermal deposition method through a patterned mask to produce a field effect transistor device.

device Comparative Example : Fabrication of Field Effect Transistor

A field effect transistor was fabricated in the same manner as in the device example except that graphene prepared according to Comparative Example 1 was used instead of graphene prepared according to Example 5.

[Test Example]

Test Example  1: an aliphatic derivative compound Grapina  Impact on Quality

FIG. 3 shows the results of Raman spectrum measurement and defect density calculation of graphene produced by the manufacturing method of the present invention and graphene produced by a conventional manufacturing method. FIG. 3 (a) shows the Raman spectrum of the graphene produced according to Comparative Example 2, and FIG. 3 (b) shows the Raman spectrum of the graphene prepared according to Example 6. FIG. FIG. 3 (c) is a graph showing the results of mapping of graphene produced according to Examples 1, 3, 5, 7, and 9 and Comparative Example 1 by Raman mapping, The average intensity of graphene produced by heat treatment at 400 < 0 > C, respectively. FIG. 3 (d) shows the calculation of the defect frequency based on the results of Raman mapping of the graphene produced according to Examples 1, 3, 5, 7, 9 and Comparative Example 1 It is. The defect frequency can be calculated according to the following equation (1).

[Formula 1]

n _D has a defect density, λ _L is the wavelength (488nm) of the laser used in the Raman map, I (D) is the intensity of the result of a Raman mapping D peak, I (G) is the intensity of the G peak.

Referring to (a) and (b) of Figure 3, the comparative example according to one of graphene manufacturing composite though at a lower temperature G peak of 400 ℃ is ^{- - (1 2700 cm) (} 1580 cm 1) and 2D peak It was observed that graphene was formed. However, a D peak (1350 cm ^-1 ) and a D 'peak (1617 cm ^-1 ), which are directly related to the defect of graphene, were also observed. The value of I (D ') / I (D) was 4 or more, indicating that graphene produced according to Comparative Example 1 had graphene but also vacancy-type defects . On the contrary, the graphene produced according to Example 6 showed a G peak and a 2D peak but did not show a D peak, indicating that the graphene was excellent in quality with little defects.

Referring to FIG. 3 (c), the average intensity of D peaks of graphene (0 wt%) prepared according to Comparative Example 1 and Comparative Example 2 was the highest, It was confirmed that the content of 1-octylphosphonic acid was increased in graphene (2.0 wt%) to graphene (9.1 wt%) prepared according to Example 5 and Example 6, and the average intensity of D peak was lowered there was. However, graphene (16.6 wt%) prepared according to Examples 7 and 8 or graphene (23.0 wt%) prepared according to Examples 9 and 10 were prepared according to Examples 5 and 6 The content of 1-octylphosphonic acid was higher than that of graphene (9.1 wt%), but the average intensity of the D peak was stronger, indicating that the defects were large.

Therefore, graphene (9.1 wt%) prepared according to Example 5 and Example 6 was found to be the least defective and high quality graphene.

Referring to FIG. 3 (d), as the content of 1-octylphosphonic acid increases from 0 wt% to 9.1 wt% at 400 ° C., the defect frequency gradually increases from 6.03 × ^{10 11} cm ^-2 to 9.52 × ^{10 10} cm ^-2 Respectively. As the content of 1-octylphosphonic acid increased from 0 wt% to 9.1 wt% at 600 ° C, the defect frequency gradually decreased from 2.54 × ^{10 11} cm ^-2 to 3.81 × ^{10 10} cm ^-2 .

This is in agreement with the results shown in FIG. 3 (c). It was found that when the content of 1-octylphosphonic acid was 9.1 wt%, the defects were the smallest and the quality of graphene was excellent.

Test Example 2: TEM photograph of graphene

4 is a high resolution transmission electron microscopy (HRTEM) image of graphene prepared according to Example 5, Comparative Example 1, and Comparative Example 3. FIG. 4 (a) shows graphene produced according to Comparative Example 1, FIG. 4 (b) shows graphene produced according to Comparative Example 3, and FIG. 4 (c) Of HRTEM.

Referring to FIG. 4A, it can be seen that the graphene produced according to Comparative Example 1 has a hexagonal structure of carbon atoms and a fast Fourier transform (FFT) pattern, so that a single layer of graphene is formed . However, vacancy-type defects were also observed in several places.

Referring to FIG. 4 (b), graphene produced according to Comparative Example 3 was observed only in amorphous carbon pieces. Therefore, it is judged that only a 1-octylphosphonic acid which is an aliphatic derivative compound can be used as a carbon source to form a single layer of graphene.

Referring to FIG. 4 (c), it can be seen that the graphene produced according to Example 5 has fewer porosity defects than the graphene produced according to Comparative Example 1.

Therefore, it was found that 1,2,3,4-tetraphenylnaphthalene, which is an aromatic derivative, and 1-octylphosphonic acid, which is an aliphatic derivative, are used together as an organic layer.

Test Example 3: Effect of growth temperature of graphene on the quality of graphene

FIG. 5 shows p-GCMS (pyrolysis gas chromatography mass spectroscopy) measurement results of graphene prepared according to Example 5, Example 6, Comparative Example 1 and Comparative Example 2. FIG. Cn represents a carbon fragment having n carbon atoms.

Referring to FIG. 5 (a), the graphene produced according to Comparative Example 1 showed a sharp peak at 35 min corresponding to 1,2,3,4-tetraphenylnaphthalene. Other peaks were not observed, indicating that 1,2,3,4-tetraphenyl naphthalene is thermally stable and behaves like a monomer during graphene synthesis at a copper surface at 400 ° C.

On the other hand, referring to FIG. 5 (b), graphene produced according to Example 5 exhibited other peaks of C4 to C8 as well as peaks at 35 min. This means that 1-octylphosphonic acid can easily break and provide a small carbon fraction when growing graphene at 400 < 0 > C. The concentration of small carbon fragments below C8 on the copper surface was 0.051%.

Referring to FIG. 5 (C), it can be seen that the graphene produced according to Comparative Example 2 exhibits small carbon fragments like benzene unlike graphene grown at 400 ° C. (Comparative Example 1). The concentration of small carbon pieces was 0.0096%.

Referring to FIG. 5 (d), the graphene produced according to Example 6 was found to have a concentration of small carbon fragments which increased to about 10 times that of graphene grown at 400 ° C at 0.582% (Example 5) .

Therefore, it was found that the heat treatment at 600 占 폚 is advantageous for forming graphene of excellent quality, since the concentration of the small carbon pieces becomes very large at 600 占 폚 and the defects are rapidly reduced.

Test Example 4: Characterization of a field effect transistor

FIG. 6 is a result of measurement of carrier mobility of the field effect transistor manufactured according to the device embodiment and the device comparison example.

Referring to FIG. 6, the mobility of graphene is determined by fitting the R-VG curve obtained by measuring the resistance R at the gate voltage V _G of the field effect transistor to a constant mobility model. Respectively. The field effect transistor manufactured according to the comparative example showed a hole mobility of 200 cm ² / V · s and an electron mobility of 100 cm ² / V · s. In contrast, the field-effect transistor manufactured according to the embodiment of the present invention has a hole mobility of 1,000 cm ² / V · s and an electron mobility of 800 cm ² / V · s, and the mobility of graphene is increased about 5 times . This is considered to be the most excellent mobility among graphenes produced using a solid organic layer at a low temperature of about 600 ° C or lower as reported in the prior art.

Therefore, it has been found that the use of an aromatic derivative compound and an aliphatic derivative compound together as a solid organic layer greatly improves the electrical properties of graphene.

The scope of the present invention is defined by the appended claims rather than the detailed description and all changes or modifications derived from the meaning and scope of the claims and their equivalents are to be construed as being included within the scope of the present invention do.

Claims (18)

(a) forming an organic layer on a metal catalyst; And
(b) heat treating the metal catalyst having the organic layer formed thereon to form graphene on the metal catalyst,
Wherein the organic layer comprises an aromatic derivative compound and an aliphatic derivative compound. The method according to claim 1,
Wherein the aliphatic derivative compound is a substituted or unsubstituted C4 to C200 aliphatic compound and the substituent corresponding to the substitution is at least one selected from the group consisting of a phosphate group, a halogen group, a sulfone group, an amine group, a carboxyl group, a hydroxyl group and a silyl group Method of manufacturing graphene. The method according to claim 1,
Wherein the aromatic derivative compound is a substituted or unsubstituted C6 to C200 aromatic compound, and the substituent corresponding to the substitution is a C6 to C200 aryl group or a C1 to C200 alkyl group. 3. The method of claim 2,
Wherein the aliphatic derivative is selected from the group consisting of 1-octylphosphonic acid, hexylphosphonic acid, octadecylphosphonic acid, hexadecylamine, octylamine, And at least one member selected from the group consisting of hexylamine, octanesulfonic acid, hexanesulfonic acid, 1-butylphosphonic acid, 1-tetrabutylphosphonic acid and triethylsilyl acetylene ≪ / RTI > The method of claim 3,
Wherein the aromatic derivative compound is 1,2,3,4-tetraphenylnaphthalene, anthracene, phenanthrene, 2,3-benzanthracene, 2,3- and at least one selected from the group consisting of benzoanthracene, chrysene, pyrene, benzopyrene, coronene, corannulene, naphthacene, naphthalene and pentacene ≪ / RTI > The method according to claim 1,
Wherein the content of the aliphatic derivative compound is 1 to 30 wt% of the total weight of the organic layer. The method according to claim 1,
Wherein the aliphatic derivative compound and the aromatic derivative compound are solid at 30 DEG C or less. The method according to claim 1,
Wherein the organic layer is formed by coating a solution containing the aromatic derivative compound and the aliphatic derivative compound on the metal catalyst. 9. The method of claim 8,
Wherein the solvent of the solution is a cosolvent capable of simultaneously dissolving the aromatic derivative compound and the aliphatic derivative compound. 10. The method of claim 9,
The co-solvent is at least one selected from the group consisting of chloroform, acetonitrile, carbon tetrachloride, methylene chloride, tetrahydrofuran, diethoxy ethanol, ethyl acetate, methyl ethyl ketone, benzene, toluene, methanol, ethanol, propanol and dichloromethane By weight. 9. The method of claim 8,
Characterized in that the coating is carried out with at least one selected from spin coating, inkjet coating, dip coating, drop casting and bar coating. Method of manufacturing graphene. The method according to claim 1,
Wherein the metal catalyst comprises at least one selected from the group consisting of nickel, iron, copper, platinum, palladium, ruthenium and cobalt. The method according to claim 1,
Wherein the heat treatment of step (b) is carried out at 300 to 800 占 폚. 14. The method of claim 13,
Wherein the heat treatment is performed at a pressure of 1 x 10 < ^-3 > to 1 Torr. 14. The method of claim 13,
Wherein the heat treatment is performed for 30 minutes to 3 hours. A manufacturing method of an electronic device comprising the manufacturing method according to claim 1. 17. The method of claim 16,
Wherein the electronic device is any one selected from the group consisting of a field effect transistor, an electrode, a touch panel, an electroluminescent display, a backlight, a radio frequency identification tag, a solar cell module, / RTI > 18. The method of claim 17,
Wherein the electronic device is a field effect transistor.

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