KR20120023471A - Method of manufacturing large area graphene film and patterning graphene film - Google Patents

Abstract

PURPOSE: A method for manufacturing a large sized graphene film and a patterned graphene film is provided to cost-effectively mass-product large sized graphene films by reacting organic materials and graphite under the existence of polyphosphoric acid to obtain organic material-based functionalized graphene. CONSTITUTION: A method for manufacturing a large sized graphene film and a patterned graphene film includes the following: organic material-based functionalized graphene is prepared by reacting organic materials and graphite in a reacting medium containing polyphosphoric acid and phosphorus pentoxide and substituting the bonds of graphene in the graphite with the covalent bonds of the graphene and the organic materials; the organic material-based functionalized graphene is dispersed in an organic solvent of 0.001-100mg/ml concentration to obtain a dispersed solution; The dispersed solution is dropped or spin-coated on a substrate; and the substrate is dried. The organic materials include one or more functional groups selected from carboxylic acid group, amide group, sulfonic acid group, carbonyl chloride group, and carbonyl bromide group.

Description

Method of manufacturing large area graphene film and patterned graphene film {Method of manufacturing large area graphene film and patterning graphene film}

The present invention relates to a large-area graphene film and a method for producing a patterned graphene film and a graphene film prepared by these methods, more specifically, the presence of a weak acid, polyphosphoric acid (polyphosphoric acid, polyphosphoric acid), etc. A large-area graphene film comprising the steps of preparing an organic functionalized graphene or a graphene-grafted graphene polymer by dispersing the organic material with graphite, and then dispersing it in an organic solvent and then drying it after dropping or spin coating. And a graphene film produced by the method and a method for producing a patterned graphene film.

Here, "a large area graphene film" means a graphene film having an area of 0.1 cm 2 to 50 m 2, preferably 1 cm 2 to 1 m 2, and more preferably 9 cm 2 to 0.5 m 2.

In addition, the "patterned graphene film" means that a certain size of holes formed in the graphene film at regular intervals. In this case, the graphene film may occupy an area excluding the hole, and the graphene film may have a form of filling the hole only.

In general, graphite (graphite) is a material having a representative layered structure, a structure in which two-dimensional graphene (plateene) of plate-shaped carbon atoms connected in a hexagonal shape is laminated. Graphene is a representative single plate sheet composed of three carbon atoms bonded by SP ² hybrid orbital bonds, and is integrated in a hexagonal crystal lattice.

In graphite, the bond between carbon atoms in each layer of graphene is very strong as a covalent bond, but the bond between graphene and graphene is very weak compared to the covalent bond described above as a van der Waals bond.

Graphene refers to a single layer of graphite, that is, the (0001) plane monolayer of graphite, which has a very thin two-dimensional structure with a thickness of about 4 angstroms since the bond between graphene and graphene is weak as described above. There may be pins.

These graphenes have found very useful properties that differ from conventional materials.

The most notable feature is that when electrons move in graphene, the mass flows as if the mass of the electrons is zero, which means that the electrons flow at the speed of light travel in vacuum, that is, at the speed of light. In addition, such graphene is characterized by having an abnormal half-integer quantum hall effect on electrons and holes.

In addition, the electron mobility of the graphene is known to have a high value of about 20,000 to 50,000 cm 2 / Vs. Above all, in the case of carbon nanotubes similar to the graphene, since the yield is very low after the synthesis after purification, the final product is expensive even if synthesized using a cheap material, but graphite is very cheap. In the case of single-walled carbon nanotubes, not only the metal and semiconductor properties vary depending on the chirality and diameter, but also the band gaps are different even if they have the same semiconductor properties. In order to use the metallic properties, it is necessary to separate each single-walled carbon nanotube, which is known to be very difficult.

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

Due to such excellent characteristics of graphene, it is attracting attention as a material to replace the car wash silicon and ITO (INDIUM TIN OXIDE) transparent electrode.

In addition, graphene has the advantage that it is very easy to process one-dimensional or two-dimensional nano-pattern made of only a relatively light element of carbon, it can be used to control the semiconductor-conductor properties as well as the chemical bond of carbon Because of the diversity, it is possible to manufacture a wide range of functional devices such as sensors and memories, and many people are trying to obtain high quality graphene films easily in order to commercialize graphene.

As a result, various methods for obtaining graphene have been continuously reported since 2004, which are mainly mechanical peeling, chemical peeling, SiC crystal pyrolysis, peel-reinsertion-expansion, chemical vapor deposition and epitaxy. Synthetic methods;

The mechanical peeling method uses the adhesion of the Scotch tape. When the cellophane tape is attached to the graphite sample and then the cellophane tape is peeled off, the graphene separated from the graphite adheres to the surface of the cellophane tape. However, in the case of such mechanical peeling method, the separated graphene is not always in the shape of torn paper, its size is only micrometer, so it is impossible to obtain a large area of graphene, and the final yield is extremely low. The problem is that many samples are low and not suitable for the required study.

Chemical exfoliation is a method of oxidizing graphite and crushing it with ultrasonic waves to form graphene oxide dispersed in an aqueous solution, and then reducing it back to graphene using a reducing agent such as hydrazine. However, since the oxidized graphene is not completely reduced and only about 70% is reduced, many defects remain in the graphene, thereby degrading excellent physical and electrical properties inherent to graphene.

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

The exfoliation-reinsertion-expansion method involves inserting fuming sulfuric acid into graphite and placing it in a furnace at a very high temperature. As the sulfuric acid expands, the graphite expands by the gas and disperses it in a surfactant such as TBA, thereby making the graphene It is a method of manufacturing. The exfoliation-reinsertion-expansion also has a very low graphene yield, and due to the surfactants used, the interlayer contact resistance is large, thus failing to provide satisfactory electrical properties.

Chemical vapor deposition is a method of synthesizing graphene by using a transition metal that forms carbon and carbide alloys or adsorbs carbon well at a high temperature as a catalyst layer. This method is difficult to process, uses heavy metal catalysts, and there are many restrictions on mass production.

Epitaxy synthesis is based on the principle that carbon adsorbed or contained in crystals is grown to graphene along the surface of the substrate at high temperatures. The graphene prepared by this method has a relatively poor electrical property than graphene grown by mechanical peeling and chemical vapor deposition, and has a disadvantage in that the substrate is very expensive and the device is very difficult to manufacture.

Despite many efforts to produce a conventional graphene film as described above, there is a limit to the film size of the graphene that can be produced by this prior art, due to the cost problem of large-area graphene film In order to solve the problem that the manufacturing is limited, and also difficult to graphene patterning through a complex process, the present invention by reacting the organic material and graphite in the presence of a weak acid, polyphosphoric acid (polyphosphoric acid, polyphosphoric acid), etc. A large-area graphene film and a patterned graphene film comprising preparing a graphene functionalized with organic material or graphene grafted with a polymer, and dispersing it in an organic solvent, followed by dropping or spin coating and drying the graphene film. An object of the present invention is to provide a method for producing and a graphene film produced by these production methods.

The object of the present invention as described above,

(a) reacting graphite with an organic substance having at least one functional group selected from the group consisting of carboxylic acid groups, amide groups, sulfonic acid groups, carbonyl chloride groups and carbonyl bromide groups in a reaction medium containing high molecular weight phosphoric acid and phosphorus pentoxide; Graphene functionalized with an organic material is prepared by substituting the covalent bond between the graphene and the organic material with the bond between the graphenes forming the graphite, or

One monomer containing a benzene ring and having at least one functional group selected from the group consisting of a carboxylic acid group, an amide group, a sulfonic acid group, a carbonyl chloride group and a carbonyl bromide group in a reaction medium containing high molecular phosphoric acid and phosphorus pentoxide Preparing a graphene-grafted graphene by substituting covalent bonds between the polymer and graphene formed by condensation polymerization of the monomers by reacting graphite with the graphite;

(b) preparing a dispersion solution by dispersing the graphene functionalized with the organic material or the graphene grafted with the polymer in an organic solvent at a concentration of 0.001 mg / ml to 100 mg / ml;

(c) dropping or spin coating the dispersion solution onto a substrate; And

(d) drying the substrate several times in a cycle of tilting the substrate horizontally or inclining at an inclination of 0.1 ° to 60 ° in order from the group consisting of right, left, top and bottom, each time of the cycle The run time is achieved by a method of making a large area graphene film, comprising the step being 0.01 seconds to 5 minutes.

The manufacturing method of the large-area graphene film may further include the following step (e) after the step (d):

(e) annealing temperatures of 500 ° C. to 3000 ° C. for 5 minutes to 12 hours under an inert gas atmosphere selected from the group consisting of helium, neon, argon, krypton, xenon, radon, nitrogen, ammonia, methane, hydrogen and mixtures thereof. And annealing at the annealing temperature for 5 minutes to 24 hours.

Method for producing the large area graphene film. The method may further include the following steps immediately before, immediately after, or immediately before and after step (e):

(c) dropping or spin coating the dispersion solution onto a substrate; And

(d) drying the substrate several times in a cycle of tilting the substrate horizontally or inclining at an inclination of 0.1 ° to 60 ° in order from the group consisting of right, left, top and bottom, each time of the cycle The run time is 0.01 seconds to 5 minutes.

In the manufacturing method of the large-area graphene film, the spin coating is performed at a speed of 100rpm to 10000rpm.

In the manufacturing method of the large-area graphene film, the drying of the step (d) is performed under a temperature of -100 ℃ to 600 ℃ and a pressure of -5 atm to 5 atm.

In the method for producing the large-area graphene film, the substrate is selected from the group consisting of glass, quartz, silicon, copper, aluminum, gold, platinum, silver, zinc and oxides thereof.

In the method for producing the large-area graphene film, the organic solvent is water, methanol, ethanol, isopropyl alcohol, en-propanol, en-butanol, 1-butanol, 2-butanol, isobutyl alcohol, tetrabutyl alcohol, Isoamyl alcohol, 1-octanol, toluene, benzene, pentane, hexane, heptane, cyclopentane, cyclohexane, benzene, toluene, xylene, dioxane, m-cresol, ethyl acetate, carbon disulfide, dimethyl sulfoxide, dichloromethane , Dichloroethane, dichlorobenzene, chloroform, carbon tetrachloride, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, diethyl ether, tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl Formamide, acetic acid, formic acid, acetonitrile, dimethyl sulfoxide, petroleum ether, diethylamine, diethyl ether, triethylamine, tetrabutylmethyl ether, dimethoxy Ethane, benzyl acetate, 1-chlorobutane, ethyl acetate and mixtures thereof.

In addition, the object of the present invention is achieved by the large-area graphene film produced by the method for producing a large-area graphene film of the present invention described above.

In addition, the object of the present invention

(a) reacting graphite with an organic substance having at least one functional group selected from the group consisting of carboxylic acid groups, amide groups, sulfonic acid groups, carbonyl chloride groups and carbonyl bromide groups in a reaction medium containing high molecular weight phosphoric acid and phosphorus pentoxide; Graphene functionalized with an organic material is prepared by substituting the covalent bond between the graphene and the organic material with the bond between the graphenes forming the graphite, or

One monomer containing a benzene ring and having at least one functional group selected from the group consisting of a carboxylic acid group, an amide group, a sulfonic acid group, a carbonyl chloride group and a carbonyl bromide group in a reaction medium containing high molecular phosphoric acid and phosphorus pentoxide Preparing a graphene-grafted graphene by substituting covalent bonds between the polymer and graphene formed by condensation polymerization of the monomers by reacting graphite with the graphite;

(b) a concentration of 0.001 mg / ml to 100 mg / ml of the graphene functionalized with the organic material or the graphene grafted with the polymer in a mixture of organic solvent 1 and organic solvent 2 in a volume ratio of 1: 0.001 to 1: 1000 Preparing a dispersion solution by dispersing with a solvent, wherein the density of the organic solvent 2 is equal to or greater than that of the organic solvent 1;

(c) dropping or spin coating the dispersion solution onto a substrate; And

(d) drying the substrate several times in a cycle of tilting the substrate horizontally or inclining at an inclination of 0.1 ° to 60 ° in order from the group consisting of right, left, top and bottom, each time of the cycle Run time is 0.01 seconds to 5 minutes

It comprises, by a method of producing a patterned graphene film.

In addition, the object of the present invention,

(a) reacting graphite with an organic substance having at least one functional group selected from the group consisting of carboxylic acid groups, amide groups, sulfonic acid groups, carbonyl chloride groups and carbonyl bromide groups in a reaction medium containing high molecular weight phosphoric acid and phosphorus pentoxide; Graphene functionalized with an organic material is prepared by substituting the covalent bond between the graphene and the organic material with the bond between the graphenes forming the graphite, or

One monomer containing a benzene ring and having at least one functional group selected from the group consisting of a carboxylic acid group, an amide group, a sulfonic acid group, a carbonyl chloride group and a carbonyl bromide group in a reaction medium containing high molecular phosphoric acid and phosphorus pentoxide Preparing a graphene-grafted graphene by substituting covalent bonds between the polymer and graphene formed by condensation polymerization of the monomers by reacting graphite with the graphite;

(b) dispersing the graphene functionalized with the organic material or the graphene grafted with the polymer at a concentration of 0.001 mg / ml to 100 mg / ml in organic solvent 1 to prepare a dispersion solution;

(c) dropping or spin coating the dispersion solution on a substrate in a confined area;

(d) vaporizing and applying the organic solvent 2 to the substrate in a gaseous state, wherein the density of the organic solvent 2 is equal to or greater than that of the organic solvent 1; And

(e) horizontally drying or repeatedly drying the cycle of inclining at an inclination of 0.1 ° to 60 ° in order from the group consisting of right, left, top and bottom, each time of the cycle Run time is 0.01 seconds to 5 minutes

It comprises, by a method of producing a patterned graphene film.

The method for producing a patterned graphene film of the present invention may further include the following step (f) after the step (e):

(f) annealing temperatures of 500 ° C. to 3000 ° C. for 5 minutes to 12 hours under an inert gas atmosphere selected from the group consisting of helium, neon, argon, krypton, xenon, radon, nitrogen, ammonia, methane, hydrogen and mixtures thereof. And annealing at the annealing temperature for 5 minutes to 24 hours.

In the method for producing a patterned graphene film of the present invention, the spin coating is performed at a speed of 100rpm to 10000rpm.

In the method for producing a patterned graphene film of the present invention, the drying step is carried out under a temperature of -100 ℃ to 600 ℃ and a pressure of -5 atm to 5 atm.

In the method for producing a patterned graphene film of the present invention, the substrate is selected from the group consisting of glass, quartz, silicon, copper, aluminum, gold, platinum, silver, zinc and oxides thereof.

In the method for producing a patterned graphene film of the present invention, the organic solvent 1 and the organic solvent 2 is water, methanol, ethanol, isopropyl alcohol, en-propanol, en-butanol, 1-butanol, 2-butanol, respectively Isobutyl alcohol, tetrabutyl alcohol, isoamyl alcohol, 1-octanol, toluene, benzene, pentane, hexane, heptane, cyclopentane, cyclohexane, benzene, toluene, xylene, dioxane, m-cresol, ethyl acetate, Carbon disulfide, dimethyl sulfoxide, dichloromethane, dichloroethane, dichlorobenzene, chloroform, carbon tetrachloride, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, diethyl ether, tetrahydrofuran, dimethylformamide, dimethylacetamide , N-methylpyrrolidone, dimethylformamide, acetic acid, formic acid, acetonitrile, dimethyl sulfoxide, petroleum ether, diethylamine, diethyl ether, triethylamine , Tetrabutylmethyl ether, dimethoxyethane, benzyl acetate, 1-chlorobutane, ethyl acetate and mixtures thereof.

In addition, an object of the present invention is achieved by a patterned graphene film, produced by the method for producing the patterned graphene film.

According to the present invention, the manufacturing step itself is very simple and easy to implement, it is possible to produce a high quality graphene film or a patterned graphene film at low cost.

Figure 1 shows a manufacturing process of the graphene grafted polymer according to Example 1 of the present invention.
Figure 2 shows the TGA results comparing the thermal properties of the graphene grafted graphene polymer according to Example 1 of the present invention with graphite. (Heat rate: 10 ℃ / min)
Figure 3 is a graph showing the TGA results of the thermal properties of the graphene grafted to the edge of the polymer according to Example 1 of the present invention compared with graphite. (Heat rate: 1 ℃ / min)
Figure 4 shows an AFM image of graphene grafted to the edge of the polymer according to Example 1 of the present invention.
Figure 5 shows a TEM image of graphene grafted on the edge of the polymer according to Example 1 of the present invention.
FIG. 6 shows an SEM image of a large area graphene film on a silicon substrate after annealing obtained in Example 2. FIG.
FIG. 7 shows an AFM image of a large area graphene film on a silicon substrate after annealing obtained by Example 2. FIG.
Figure 8 shows an image showing the overall process of Example 2 and Example 3.
FIG. 9 shows an image in which a graphene film patterned on the OHP film obtained in Example 3 is transferred.
FIG. 10 shows an AFM image of a patterned graphene film obtained as a result of Example 4. FIG.

The present invention prepares graphene functionalized with organics or graphene grafted with polymers in the presence of a weak acid, polyphosphoric acid (polyphosphoric acid) and the like, and disperses it in an organic solvent and drops it. It relates to a method for producing a large-area graphene film comprising the step of drying after ping or spin coating, and a method for producing a patterned graphene film and a graphene film produced by these methods. Hereinafter, the present invention will be described in detail.

The manufacturing method of the large-area graphene film of the present invention,

(a) reacting graphite with an organic substance having at least one functional group selected from the group consisting of carboxylic acid groups, amide groups, sulfonic acid groups, carbonyl chloride groups and carbonyl bromide groups in a reaction medium containing high molecular weight phosphoric acid and phosphorus pentoxide; Graphene functionalized with an organic material is prepared by substituting the covalent bond between the graphene and the organic material with the bond between the graphenes forming the graphite, or

One monomer containing a benzene ring and having at least one functional group selected from the group consisting of a carboxylic acid group, an amide group, a sulfonic acid group, a carbonyl chloride group and a carbonyl bromide group in a reaction medium containing high molecular phosphoric acid and phosphorus pentoxide Preparing a graphene-grafted graphene by substituting covalent bonds between the polymer and graphene formed by condensation polymerization of the monomers by reacting graphite with the graphite;

(b) preparing a dispersion solution by dispersing the graphene functionalized with the organic material or the graphene grafted with the polymer in an organic solvent at a concentration of 0.001 mg / ml to 100 mg / ml;

(c) dropping or spin coating the dispersion solution onto a substrate; And

(d) drying the substrate several times in a cycle of tilting the substrate horizontally or inclining at an inclination of 0.1 ° to 60 ° in order from the group consisting of right, left, top and bottom, each time of the cycle Run time is 0.01 seconds to 5 minutes

It includes.

Graphene functionalized with the organic material of step (a) is selected from the group consisting of carboxylic acid group, amide group, sulfonic acid group, carbonyl chloride group and carbonyl bromide group in a reaction medium containing high molecular weight phosphoric acid and phosphorus pentoxide The organic material having at least two functional groups is reacted with graphite to prepare a bond between the graphenes forming the graphite with a covalent bond between the graphene and the organic material.

The polymer phosphoric acid is a weak acid, the pH is 1 to 4, more preferably 2 to 3. The polymer phosphoric acid does not weaken the inherent properties of graphite because it functions as a weak acid but does not affect the original structure of the graphite. In addition, these polymer phosphates are easy to remove because they are soluble in water.

The phosphorus pentoxide is a dehydrating agent that removes water generated by the reaction of organic matter and graphite. Since phosphorus pentoxide reacts with water and is converted into polymer phosphoric acid, it has the advantage of being easy to remove because it does not affect other reactions and dissolves well in water except promoting the reaction of graphite and organic matter.

The reaction medium comprises the aforementioned polymeric phosphoric acid in an amount of 65% to 85% by weight, preferably in an amount of 74% to 83% by weight, and phosphorus pentoxide in an amount of 15% to 35% by weight, preferably Preferably in an amount from 17% to 26% by weight.

The functional group of the organic substance having the functional group is at least one selected from the group consisting of a carboxylic acid group, an amide group, a sulfonic acid group, a carbonyl chloride group and a carbonyl bromide group.

Preferably, the functional group of the organic material is at least one selected from the group consisting of -COOH, -CONH ₂ , -CONR'H, -CONR'R ", -SO ₃ H, -COCl and -COBr, wherein R 'And R' are each independently an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms or an aralkyl group having 6 to 10 carbon atoms, and the alkyl group, aryl group or Aralkyl groups are unsubstituted, halo, nitro, amino, cyano, mercapto, hydroxy, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, formyl, having 1 to 4 carbon atoms And substituted with a substituent selected from the group consisting of alkylcarbonyl, phenyl, benzoyl, phenoxy and combinations thereof.

The organic substance having the functional group may be an alkan having 1 to 5 carbon atoms having the functional group, an alkene having 2 to 5 carbon atoms, an alkene having 2 to 5 carbon atoms, and 3 to 10 carbon atoms. A cycloalkane having 6 to 15 carbon atoms or an aryl compound having 6 to 15 carbon atoms or an aralkyl compound having 6 to 15 carbon atoms, wherein the alkane, alkene, alkyne, cycloalkane, aryl compound, or aralkyl compound is substituted Halo, nitro, amino, cyano, mercapto, hydroxy, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, formyl, alkylcarbonyl having 1 to 4 carbon atoms, It is substituted with a substituent selected from the group consisting of phenyl, benzoyl, phenoxy, and combinations thereof.

Preferably, the organic material is unsubstituted, halo, nitro, amino, cyano, mercapto, hydroxy, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, formyl, 1 carbon Benzoic acid substituted with a substituent selected from the group consisting of 4 to 4 alkylcarbonyl, phenyl, benzoyl, phenoxy and combinations thereof.

More preferably, the organic material is 3-aminobenzoic acid, 4-aminobenzoic acid, 4- (4-aminophenyl) benzoic acid, 4- (3-aminophenyl) benzoic acid, 5-aminoisophthalic acid, 4- (4-amino Phenoxy) benzoic acid, 4- (3-aminophenoxy) benzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2-phenoxybenzoic acid, 3-phenoxybenzoic acid, 4-phenoxybenzoic acid, 3,5-diphenoxybenzoic acid, 5-phenoxyisophthalic acid, 4-phenyl- (4-phenoxy benzoic acid), 4-phenoxy- (4-phenylbenzoic acid), 4-ethylbenzoic acid, 2-ethylbenzoic acid and 4 -Any one compound selected from the group consisting of ethylphenoxybenzoic acid.

In the reaction medium containing the polymeric phosphoric acid and phosphorus pentoxide, the organic material and the graphite are reacted in a weight ratio of 2: 1 to 1: 5, preferably in a weight ratio of 3: 2 to 1: 3.

At this time, the reaction temperature is 100 to 160 ℃, preferably 120 to 140 ℃, if the reaction temperature is less than 100 ℃ there is a problem that the reaction does not occur, if the reaction temperature exceeds 160 ℃ a lot of side reactions There is.

The reaction time is 12 hours to 120 hours, preferably 60 hours to 84 hours. When the reaction time is less than 12 hours, the reaction is not completed, and when the reaction time exceeds 120 hours, no further reaction proceeds.

0.01-40 parts by weight of graphite is added to 100 parts by weight of the reaction medium to carry out the reaction.

By the reaction of the organic material with the above-described graphite, graphene having an edge position functionalized with the organic material is produced. That is, in the reaction medium containing the polymer phosphoric acid and phosphorus pentoxide, the bond of the edge position between the graphene, which is each layer of the graphite to form the graphite by reacting the graphite with the organic substance, is replaced by the covalent bond between the functional group of the organic substance and the graphene edge carbon. Organic matter bound to the graphene of the graphite acts as a wedge serves to peel the graphene from the graphite.

As such, when the organic material and the graphite are reacted in the reaction medium containing the polymer phosphoric acid and phosphorus pentoxide, the graphene functionalized at the edge is produced as described above, but the polymer product of the phosphoric acid and phosphorus pentoxide, including the graphite and the organic material which are not reacted in the reaction product, is This coexists.

In order to remove the polymeric phosphoric acid, phosphorus pentoxide, and unreacted organics from the reaction product in which various compounds coexist, the reaction product is washed with water, followed by washing with alcohol such as methanol. Thereafter, the washings may be dried using a method such as freeze drying.

When lyophilization is performed, the resulting edge position is dried while maintaining the space between the functionalized graphenes, and thus, when the lyophilisate obtained through the lyophilization is dissolved in the solvent again, the solvent is more likely to be functionalized between the graphenes. It can penetrate and, as a result, the functionalized graphene melts better, making the subsequent process easier.

In the freeze-dried product, since the unreacted graphite and the graphene functionalized at the edge are mixed, the dried material is dispersed in a solvent and centrifuged to separate the graphene functionalized at the edge. Alternatively, the dried material is dispersed in a solvent and filtered after sonication to separate graphene having a functionalized edge position.

The solvent depends on the type of organic matter bound to the edge position in the graphene where the edge position is functionalized. Such solvents are water, methanol, ethanol, isopropyl alcohol, en-propanol, en-butanol, 1- Butanol, 2-butanol, isobutyl alcohol, tetrabutyl alcohol, isoamyl alcohol, 1-octanol, toluene, benzene, pentane, hexane, heptane, cyclopentane, cyclohexane, benzene, toluene, xylene, dioxane, m- Cresol, ethyl acetate, carbon disulfide, dimethyl sulfoxide, dichloromethane, dichloroethane, dichlorobenzene, chloroform, carbon tetrachloride, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, diethyl ether, tetrahydrofuran, dimethylform Amide, dimethylacetamide, N-methylpyrrolidone, dimethylformamide, acetic acid, formic acid, acetonitrile, dimethyl sulfoxide, petroleum ether, Ethylamine, di is selected from ethyl ether, triethylamine, tetra-butyl methyl ether, dimethoxy ethane, benzyl acetate, 1-chlorobutane, the group consisting of ethyl acetate, and mixtures thereof.

The centrifugation is performed at a speed of 1,000 rpm to 15,000 rpm, preferably at a speed of 7,000 rpm to 12,000 rpm, for 30 seconds to 20 minutes, and preferably for 2 to 15 minutes, so that the edge position is functionalized. To separate. If the centrifugation speed is less than 1,000 rpm, or if the centrifugation time is less than 30 seconds, the separation is not performed properly, and if the centrifugation speed exceeds 15,000 rpm or the centrifugation time exceeds 20 minutes, the centrifuge tube There is a risk of breaking.

The graphene grafted with the polymer of step (a) includes a benzene ring in a reaction medium containing polymer phosphoric acid and phosphorus pentoxide, and includes a carboxylic acid group, an amide group, a sulfonic acid group, a carbonyl chloride group, and a carbonyl bromide By reacting at least one monomer having at least one functional group selected from the group consisting of a group and graphite, the bond between the graphenes forming the graphite is replaced by a covalent bond between the polymer and graphene formed by condensation polymerization of the monomer. do.

The polymer phosphoric acid is a weak acid, the pH is 1 to 4, more preferably 2 to 3. The polymer phosphoric acid does not weaken the inherent properties of graphite because it functions as a weak acid but does not affect the original structure of the graphite. In addition, these polymer phosphates are easy to remove because they are soluble in water.

The phosphorus pentoxide is a dehydrating agent that removes water generated by the reaction between the polymer and phosphoric acid. Since phosphorus pentoxide reacts with water and is converted into polymer phosphoric acid, it has an advantage that it is easy to remove because it does not affect other reactions and is well dissolved in water except for promoting the reaction between graphite and polymer.

The reaction medium comprises the aforementioned polymeric phosphoric acid in an amount of 65% to 85% by weight, preferably in an amount of 74% to 83% by weight, and phosphorus pentoxide in an amount of 15% to 35% by weight, preferably Preferably in an amount from 17% to 26% by weight.

The monomer includes a benzene ring and has the functional group, alkanes having 1 to 5 carbon atoms, alkenes having 2 to 5 carbon atoms, alkynes having 2 to 5 carbon atoms, and 3 carbon atoms. A cycloalkane having from 10 to 10 carbon atoms, an aryl compound having 6 to 15 carbon atoms or an aralkyl compound having 6 to 15 carbon atoms, wherein the alkane, alkene, alkyne, cycloalkane, aryl compound, or aralkyl Compounds are unsubstituted, halo, nitro, amino, cyano, mercapto, hydroxy, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, formyl, alkyl having 1 to 4 carbon atoms And substituted with a substituent selected from the group consisting of carbonyl, phenyl, benzoyl, phenoxy, and combinations thereof.

Preferably, the monomer is unsubstituted, halo, nitro, amino, cyano, mercapto, hydroxy, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, formyl, 1 carbon atom. It is to include a benzoyl group substituted with a substituent selected from the group consisting of 4 to 4 alkylcarbonyl, phenyl, benzoyl, phenoxy and combinations thereof.

More preferably, the monomer is 3-aminobenzoic acid, 4-aminobenzoic acid, 4- (4-aminophenyl) benzoic acid, 4- (3-aminophenyl) benzoic acid, 5-aminoisophthalic acid, 4- (4-amino Phenoxy) benzoic acid, 4- (3-aminophenoxy) benzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2-phenoxybenzoic acid, 3-phenoxybenzoic acid, 4-phenoxybenzoic acid, 4- (2,6-dimethylphenoxy) benzoic acid, 3,5-diphenoxybenzoic acid, 5-phenoxyisophthalic acid, 4-phenyl- (4-phenoxy benzoic acid), 4-phenoxy- (4-phenylbenzoic acid ), 4-ethylbenzoic acid, 2-ethylbenzoic acid and 4-ethylphenoxybenzoic acid.

In the reaction medium containing the polymeric phosphoric acid and phosphorus pentoxide, the monomers and graphite are added in a weight ratio of 20: 1 to 1: 1, preferably in a weight ratio of 13: 1 to 6: 1, more preferably in a ratio of 11: 1 to 8: 1. React in weight ratio. When using 2 or more types of monomers as a monomer, it is preferable to use each monomer in the same molar ratio.

The reaction temperature is 100 to 160 ℃, preferably 120 to 140 ℃, when the reaction temperature is less than 100 ℃ there is a problem that the polymerization of the monomer and the reaction between the polymer and the graphite formed by polymerization of the monomer does not occur, the reaction temperature is If it exceeds 160 ℃ there is a problem that a lot of side reactions occur.

The reaction time is 12 hours to 120 hours, preferably 60 hours to 84 hours. When the reaction time is less than 12 hours, the reaction is not completed, and when the reaction time exceeds 120 hours, no further reaction proceeds.

0.01-40 parts by weight of graphite is added to 100 parts by weight of the reaction medium to carry out the reaction.

By the reaction of the monomer and graphite, the monomer is first electrophilic substitution condensation polymerization to form a polymer, and the polymer is reacted with graphite to produce graphene grafted with a polymer. In other words, in the reaction medium containing the polymer phosphoric acid and phosphorus pentoxide, the bond between the polymer formed by the electrophilic substitution condensation polymerization of the monomer and the graphene, which is each layer forming the graphite by the reaction of graphite, is shared between the polymer and the graphene edge carbon. Substituted with a bond, the polymer bonded to the graphene of the graphite in this way acts as a wedge serves to peel off the graphene grafted with the polymer from the graphite.

As described above, the polymer-grafted graphene is produced in the reaction medium containing the polymer phosphoric acid and phosphorus pentoxide, but the polymer phosphoric acid and phosphorus pentoxide coexist in the reaction product, including graphite and monomers which are not reacted.

In order to remove the polymeric phosphoric acid, phosphorus pentoxide, and unreacted monomers from the reaction product in which various compounds coexist, the reaction product is washed with water, followed by washing with alcohol such as methanol. Thereafter, the washings may be dried using a method such as freeze drying.

When lyophilization is carried out, the polymer is dried while maintaining the space between the grafted graphenes as it is. Thus, when the freeze-dried product obtained through the lyophilization is dissolved in a solvent again, the solvent is grafted to the graphene. It can penetrate the liver better and, as a result, the graphene grafted with the polymer melts better, making the subsequent process easier.

Since the freeze-dried product is in a state in which unreacted graphite and a graphene grafted with a polymer are mixed, the dry matter is dispersed in a solvent and centrifuged to separate the graphene grafted with a polymer. Alternatively, the dried material is dispersed in a solvent and filtered after sonication to separate the graphene grafted graphene.

The solvent depends on the type of polymer bound to the edge position in the graphene grafted graphene, such solvent is water, methanol, ethanol, isopropyl alcohol, en-propanol, en-butanol, 1- Butanol, 2-butanol, isobutyl alcohol, tetrabutyl alcohol, isoamyl alcohol, 1-octanol, toluene, benzene, pentane, hexane, heptane, cyclopentane, cyclohexane, benzene, toluene, xylene, dioxane, m- Cresol, ethyl acetate, carbon disulfide, dimethyl sulfoxide, dichloromethane, dichloroethane, dichlorobenzene, chloroform, carbon tetrachloride, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, diethyl ether, tetrahydrofuran, dimethylform Amide, dimethylacetamide, N-methylpyrrolidone, dimethylformamide, acetic acid, formic acid, acetonitrile, dimethyl sulfoxide, petroleum ether, die Amine, diethyl ether, triethylamine, tetra-butyl methyl ether, dimethoxy ethane, benzyl acetate, 1-chlorobutane, is selected from the group consisting of ethyl acetate, and mixtures thereof.

The centrifugation is performed at a speed of 1,000 rpm to 15,000 rpm, preferably at a speed of 7,000 rpm to 12,000 rpm, for 30 seconds to 20 minutes, and preferably for 2 to 15 minutes, so that the edge position is functionalized. To separate. If the centrifugation speed is less than 1,000 rpm, or if the centrifugation time is less than 30 seconds, the separation is not performed properly, and if the centrifugation speed exceeds 15,000 rpm or the centrifugation time exceeds 20 minutes, the centrifuge tube There is a risk of breaking.

In step (b), the graphene functionalized with the organic material or the graphene grafted with the polymer is in a concentration of 0.001 mg / ml to 100 mg / ml in an organic solvent, preferably 0.1 mg / ml to 10 mg / ml. Dispersing at a concentration of, more preferably, 0.5 mg / ml to 5 mg / ml to prepare a dispersion solution.

The organic solvent is water, methanol, ethanol, isopropyl alcohol, en-propanol, en-butanol, 1-butanol, 2-butanol, isobutyl alcohol, tetrabutyl alcohol, isoamyl alcohol, 1-octanol, toluene, benzene , Pentane, hexane, heptane, cyclopentane, cyclohexane, benzene, toluene, xylene, dioxane, m-cresol, ethyl acetate, carbon disulfide, dimethyl sulfoxide, dichloromethane, dichloroethane, dichlorobenzene, chloroform, carbon tetrachloride, acetone , Methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, diethyl ether, tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylformamide, acetic acid, formic acid, acetonitrile, dimethyl sulfoxide Said, petroleum ether, diethylamine, diethyl ether, triethylamine, tetrabutylmethyl ether, dimethoxyethane, benzyl acetate, 1-chlorobutane, ethyl acetate Yite and mixtures thereof, but is not limited thereto.

Step (c) is to drop or spin coat the dispersion solution on a substrate.

The substrate is selected from the group consisting of glass, quartz, silicon, copper, aluminum, gold, platinum, silver, zinc and oxides thereof, but is not limited thereto. In addition, the size of such a substrate is 0.1 cm 2 to 50 m 2.

The speed of the spin coating is 100 rpm to 10000 rpm, preferably 300 rpm to 4000 rpm, more preferably 500 rpm to 1500 rpm.

The step (d) may be performed by leveling the substrate horizontally or by selecting an order from the group consisting of right, left, top, and bottom, inclination of 0.1 ° to 60 °, inclination of 0.5 ° to 45 °, more preferably Preferably, the cycle of inclining at an inclination of 1 ° to 30 ° is repeatedly carried out several times, wherein a single execution time of the cycle is 0.01 second to 5 minutes.

This drying is carried out at a temperature of -100 ° C. to 600 ° C., preferably at a temperature of 0 ° C. to 450 ° C., more preferably at a temperature of 20 ° C. to 200 ° C. and a pressure of -5 atm to 5 atm, preferably at -2 atm. To 2 atm.

Method for producing a large-area graphene film of the present invention, after the step (d) may further comprise the following step (e):

(e) for 5 minutes to 12 hours under an inert gas atmosphere selected from the group consisting of helium, neon, argon, krypton, xenon, radon, nitrogen, ammonia, methane, hydrogen and mixtures thereof, preferably 1 hour to 6 hours. For an hour, more preferably 3 to 6 hours, annealing temperatures of 500 ° C. to 3000 ° C., preferably annealing temperatures of 500 ° C. to 1200 ° C., more preferably 600 ° C. to 950 ° C. Annealing at said annealing temperature for 5 minutes to 24 hours, preferably for 30 minutes to 6 hours, more preferably for 1 to 3 hours.

As the inert gas, for example, helium, neon, argon, krypton, xenon, radon, nitrogen and mixtures thereof are used as the main gas, and thus the group consisting of ammonia, hydrogen, methane and mixtures thereof. It may be used by further mixing selected from.

The manufacturing method of the large-area graphene film of the present invention may further include the following steps immediately before, immediately after, or immediately after and immediately after the step (e).

(c) dropping or spin coating the dispersion solution onto a substrate; And

(d) drying the substrate several times in a cycle of tilting the substrate horizontally or inclining at an inclination of 0.1 ° to 60 ° in order from the group consisting of right, left, top and bottom, each time of the cycle The run time is 0.01 seconds to 5 minutes.

These steps (c) and (d) are as described above.

Method for producing a patterned graphene film of the present invention

(a) reacting graphite with an organic substance having at least one functional group selected from the group consisting of carboxylic acid groups, amide groups, sulfonic acid groups, carbonyl chloride groups and carbonyl bromide groups in a reaction medium containing high molecular weight phosphoric acid and phosphorus pentoxide; Graphene functionalized with an organic material is prepared by substituting the covalent bond between the graphene and the organic material with the bond between the graphenes forming the graphite, or

One monomer containing a benzene ring and having at least one functional group selected from the group consisting of a carboxylic acid group, an amide group, a sulfonic acid group, a carbonyl chloride group and a carbonyl bromide group in a reaction medium containing high molecular phosphoric acid and phosphorus pentoxide Preparing a graphene-grafted graphene by substituting covalent bonds between the polymer and graphene formed by condensation polymerization of the monomers by reacting graphite with the graphite;

(b) a concentration of 0.001 mg / ml to 100 mg / ml of the graphene functionalized with the organic material or the graphene grafted with the polymer in a mixture of organic solvent 1 and organic solvent 2 in a volume ratio of 1: 0.001 to 1: 1000 Preparing a dispersion solution by dispersing with a solvent, wherein the density of the organic solvent 2 is equal to or greater than that of the organic solvent 1;

(c) dropping or spin coating the dispersion solution onto a substrate; And

(d) drying the substrate several times in a cycle of tilting the substrate horizontally or inclining at an inclination of 0.1 ° to 60 ° in order from the group consisting of right, left, top and bottom, each time of the cycle Run time is 0.01 seconds to 5 minutes

It includes.

The graphene functionalized with the organic material of step (a) and the graphene grafted with the polymer are the same as described in the description of the method for producing the large-area graphene of the present invention.

In the step (b), the graphene functionalized with the organic material or the graphene grafted with the polymer is 1: 0.001 to 1: 1000 volume ratio of the organic solvent 1 and the organic solvent 2, preferably 1: 0.01 to 1: 100. Concentrations from 0.001 mg / ml to 100 mg / ml, preferably from 0.1 mg / ml to 10 mg / ml, more preferably 0.5 mg in a mixture of volume ratios, more preferably from 1: 0.5 to 1:50 Dispersing at a concentration of / ml to 5mg / ml to prepare a dispersion solution, wherein the density of the organic solvent 2 is equal to or greater than that of the organic solvent 1.

The organic solvent 1 and the organic solvent 2 are each independently water, methanol, ethanol, isopropyl alcohol, en-propanol, en-butanol, 1-butanol, 2-butanol, isobutyl alcohol, tetrabutyl alcohol, isoamyl alcohol, 1-octanol, toluene, benzene, pentane, hexane, heptane, cyclopentane, cyclohexane, benzene, toluene, xylene, dioxane, m-cresol, ethyl acetate, carbon disulfide, dimethyl sulfoxide, dichloromethane, dichloroethane, Dichlorobenzene, chloroform, carbon tetrachloride, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, diethyl ether, tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylformamide, acetic acid , Formic acid, acetonitrile, dimethyl sulfoxide, petroleum ether, diethylamine, diethyl ether, triethylamine, tetrabutylmethyl ether, dimethoxyethane, benzyl acetate Tate, 1-chlorobutane, ethyl acetate and mixtures thereof, but as described above, the density of the organic solvent 2 is equal to or greater than the density of the organic solvent 1.

Step (c) is to drop or spin coat the dispersion solution on a substrate.

The substrate is selected from the group consisting of glass, quartz, silicon, copper, aluminum, gold, platinum, silver, zinc and oxides thereof, but is not limited thereto. In addition, the size of such a substrate is 0.1 cm 2 to 50 m 2.

The speed of the spin coating is 100 rpm to 10000 rpm, preferably 500 rpm to 5000 rpm, more preferably 800 rpm to 1500 rpm.

The step (d) is inclined from 0.1 to 60 degrees, preferably from 0.5 to 45 degrees, more preferably in the order of horizontally or in the group consisting of right, left, top and bottom. Preferably a step of drying the cycle of inclining at an inclination of 1 ° to 30 ° several times, wherein the one running time of the cycle is 0.01 seconds to 5 minutes. Such drying is carried out at temperatures of -100 ° C. to 600 ° C., preferably at temperatures of 0 ° C. to 450 ° C., more preferably at temperatures of 20 ° C. to 200 ° C. and at pressures of −5 atm to 5 atm, preferably at −1 atm. To 1 atm.

In addition, another method for producing a patterned graphene film of the present invention

(a) reacting graphite with an organic substance having at least one functional group selected from the group consisting of carboxylic acid groups, amide groups, sulfonic acid groups, carbonyl chloride groups and carbonyl bromide groups in a reaction medium containing high molecular weight phosphoric acid and phosphorus pentoxide; Graphene functionalized with an organic material is prepared by substituting the covalent bond between the graphene and the organic material with the bond between the graphenes forming the graphite, or

One monomer containing a benzene ring and having at least one functional group selected from the group consisting of a carboxylic acid group, an amide group, a sulfonic acid group, a carbonyl chloride group and a carbonyl bromide group in a reaction medium containing high molecular phosphoric acid and phosphorus pentoxide Preparing a graphene-grafted graphene by substituting covalent bonds between the polymer and graphene formed by condensation polymerization of the monomers by reacting graphite with the graphite;

(b) dispersing the graphene functionalized with the organic material or the graphene grafted with the polymer at a concentration of 0.001 mg / ml to 100 mg / ml in organic solvent 1 to prepare a dispersion solution;

(c) dropping or spin coating the dispersion solution on a substrate in a confined area;

(d) vaporizing and applying the organic solvent 2 to the substrate in a gaseous state, wherein the density of the organic solvent 2 is equal to or greater than that of the organic solvent 1; And

(e) horizontally drying or repeatedly drying the cycle of inclining at an inclination of 0.1 ° to 60 ° in order from the group consisting of right, left, top and bottom, each time of the cycle Run time is 0.01 seconds to 5 minutes

It includes.

The graphene functionalized with the organic material of step (a) and the graphene grafted with the polymer are the same as described in the description of the method for producing the large-area graphene of the present invention.

In step (b), the graphene functionalized with the organic material or the graphene grafted with the polymer is in a concentration of 0.001 mg / ml to 100 mg / ml in organic solvent 1, preferably 0.1 mg / ml to 10 mg /. A dispersion solution is prepared by dispersing at a concentration of ml, more preferably at a concentration of 0.5 mg / ml to 5 mg / ml.

The organic solvent 1 is water, methanol, ethanol, isopropyl alcohol, en-propanol, en-butanol, 1-butanol, 2-butanol, isobutyl alcohol, tetrabutyl alcohol, isoamyl alcohol, 1-octanol, toluene, Benzene, pentane, hexane, heptane, cyclopentane, cyclohexane, benzene, toluene, xylene, dioxane, m-cresol, ethyl acetate, carbon disulfide, dimethyl sulfoxide, dichloromethane, dichloroethane, dichlorobenzene, chloroform, carbon tetrachloride, Acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, diethyl ether, tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylformamide, acetic acid, formic acid, acetonitrile, dimethyl Sulfoxide, petroleum ether, diethylamine, diethyl ether, triethylamine, tetrabutylmethyl ether, dimethoxyethane, benzyl acetate, 1-chlorobutane, ethyl acetate Byte and but selected from the group consisting of and mixtures thereof, and the like.

Step (c) is the step of dropping or spin coating the dispersion solution on a substrate in a sealed place.

By "closed place" is meant a place where there is no wind flow and a certain amount of vapor pressure of the solvent exists.

The substrate is selected from the group consisting of glass, quartz, silicon, copper, aluminum, gold, platinum, silver, zinc and oxides thereof, but is not limited thereto. In addition, the size of such a substrate is 0.1 cm 2 to 50 m 2.

The speed of the spin coating is 100 rpm to 10000 rpm, preferably 500 rpm to 5000 rpm, more preferably 800 rpm to 1500 rpm.

In step (d), the organic solvent 2 is vaporized and applied to the substrate in a gaseous state.

The organic solvent 2 is water, methanol, ethanol, isopropyl alcohol, en-propanol, en-butanol, 1-butanol, 2-butanol, isobutyl alcohol, tetrabutyl alcohol, isoamyl alcohol, 1-octanol, toluene, Benzene, pentane, hexane, heptane, cyclopentane, cyclohexane, benzene, toluene, xylene, dioxane, m-cresol, ethyl acetate, carbon disulfide, dimethyl sulfoxide, dichloromethane, dichloroethane, dichlorobenzene, chloroform, carbon tetrachloride, Acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, diethyl ether, tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylformamide, acetic acid, formic acid, acetonitrile, dimethyl Sulfoxide, petroleum ether, diethylamine, diethyl ether, triethylamine, tetrabutylmethyl ether, dimethoxyethane, benzyl acetate, 1-chlorobutane, ethyl acetate Sites, and as being selected from the group consisting of and mixtures thereof, and the density of the organic solvent 2 is not less than the density of the first organic solvent.

One example of a method in which the organic solvent 2 is vaporized and applied to the substrate in a gaseous state is to apply a temperature to a boiling point with respect to the solvent, and then moves and applies the solvent, which has become a gaseous state, along the tube to the substrate. At this time, the distance between the end of the tube and the substrate is 0.1cm to 5cm.

When the organic solvent 2 is applied, the volume ratio of the organic solvent 2 to the organic solvent 1 is 1: 0.001 to 1: 1000, preferably 1: 0.01 to 1: 100, and more preferably 1: 0.5 to 1: Perform at a rate of 50.

The application rate is preferably 0.0001 ml / s to 1 ml / s.

The step (e) is inclined from 0.1 ° to 60 °, preferably from 0.5 ° to 45 °, more preferably in the order of leveling the substrate or ordering from the group consisting of right, left, top and bottom. Preferably a step of drying the cycle of inclining at an inclination of 1 ° to 30 ° several times, wherein the one running time of the cycle is 0.01 seconds to 5 minutes. Such drying is carried out at a temperature of -100 ° C to 600 ° C, preferably at a temperature of 0 ° C to 450 ° C, more preferably at a temperature of 20 ° C to 200 ° C and a pressure of -5 atm to 5 atm, preferably -2atm to Under pressure of 2 atm.

Method for producing a patterned graphene film of the present invention may further comprise the following step (f) after step (e):

(f) for 5 minutes to 12 hours under an inert gas atmosphere selected from the group consisting of helium, neon, argon, krypton, xenon, radon, nitrogen, ammonia, methane, hydrogen and mixtures thereof, preferably 1 hour to 6 hours. For an hour, more preferably 3 to 6 hours, annealing temperature of 500 ° C. to 3000 ° C., preferably annealing temperature of 500 ° C. to 1200 ° C., more preferably 600 ° C. to 950 ° C. Annealing at an annealing temperature for 5 minutes to 24 hours, preferably for 0.5 to 6 hours, more preferably for 1 to 3 hours.

As the inert gas, for example, helium, neon, argon, krypton, xenon, radon, nitrogen and mixtures thereof are used as the main gas, and thus the group consisting of ammonia, hydrogen, methane and mixtures thereof. It may be used by further mixing selected from.

Hereinafter, the present invention will be described in detail with reference to the following examples, but these examples are only presented to more clearly understand the present invention, and are not intended to limit the scope of the present invention. It will be determined within the scope of the technical idea of the claims.

Example  1: A polymer obtained by reacting graphite with 4-ethylbenzoic acid in a reaction medium containing polymeric phosphoric acid and phosphorus pentoxide Grafted Graphene  Produce

Sigma-Aldrich Corporation polyphosphoric acid to _{(115% H 3 PO 4 basis} ) a polymeric acid (PPA) and phosphorus pentoxide (P ₂ O ₆₎ graphite 5g and 4-ethyl benzoic acid 5g in the reaction medium, each containing 200g 250g and 50g Put and reacted at 130 ℃ for 72 hours. In the above reaction, 4-ethyl benzoic acid is first polymerized to form ethyl benzo (ether-ketone), and the formed ethyl benzo (ether-ketone) reacts with graphite to bond the edge positions between the graphenes forming the graphite. The polymer was grafted to the edge position of graphene by substitution with a covalent bond between carbon at the edge of the polymer and carbonyl group of the polymer (see FIG. 1).

After the reaction was terminated, the graphene grafted the polymer at the edge position was precipitated in water, and recovered again and treated with Soxhlet for 3 days in water and methanol for 3 days, and the polymer phosphoric acid and phosphorus pentoxide And unreacted substances such as unreacted ethylbenzoic acid were removed.

Thereafter, graphene (4-ethylbenzoic acid-g-graphite, EBA-g-graphite) grafted with polymer at the edge position, isolated from the above unreacted material, was lyophilized.

Experimental Example  1: high molecular weight Grafted On graphene  About TGA  Experiment

Thermogravimetric analysis was performed on graphite, EBA-g-graphite prepared in Example 1 using a TA Hi-Res TGA 2950 thermogravimetric analyzer to confirm thermal properties.

The results are shown in FIGS. 2 and 3, where a in FIG. 2 shows a loss of mass with temperature in air, and b in FIG. 2 shows a loss of mass with temperature in a nitrogen atmosphere. The blue graph for shows the results of graphite and the red graph shows the results of EBA-g-graphite prepared in Example 1 at all times.

Referring to a of FIG. 2, the blue graph resulting from graphite started losing mass at about 650 ° C., but the EBA-g-graphite of Example 1 started losing mass at 400 ° C., which was about 250 ° C. lower than the graphite. You can check it. This shows that the polymers grafted on their edges are thermally more unstable than the structures of graphene or graphite and are removed at lower temperatures.

Figure 3 shows the mass loss in the air as compared to a of Figure 2 by slowing the heat rate (heat rate) by applying heat for a time (heat rate = 1 ℃ / min) that the heat can be sufficiently applied to the sample It is a measure of mass loss.

In FIG. 3, in which heat is sufficiently heated for a sufficient time to measure mass loss, it can be confirmed that the mass loss occurs about 100 ° C. to 150 ° C. faster than the graph a of FIG. 2.

In addition, in Figure 3 it can be seen that the EBA-g-graphite of Example 1 is more thermally stable than the graphite at a temperature higher than 540 ℃.

In addition, in FIG. 3, all of them are removed at about 800 ° C. When the annealing is performed in the presence of an inert gas, the graphene is not removed even at a high temperature and the organic or polymer grafted to the edge of the graphene is carbonized at a high temperature. Rearrangement occurs, which makes the structure stronger (not shown).

On the other hand, through the b graph of Figure 2, the result of measuring the mass loss in the nitrogen atmosphere it was confirmed that the removal of the mass gradually occurs as the temperature is increased without increasing EBA-g-graphite of Example 1 under the nitrogen atmosphere. Can be.

Experimental Example  2: high molecular weight Grafted On graphene  About AFM  And FE - TEM  image

Veeco Multimode V. Atomic force microscopy and FEI Tecnai G2 F30 S-Twin Field Emission Transmission Electron Microscope (operating voltage: 200 kV) An enlarged image of EBA-g-graphite was obtained.

The results are shown in FIG. 4 and FIG. 5. FIG. 4 is an image obtained from an atomic microscope. When checking the topographic height of the surface of FIG. 4, the height of the portion corresponding to the edge of the graphene surface is centered. It can be seen that generally 0.5 nm to 1 nm higher than the height of the surface. This supports the grafting of polymer onto the edges of flat graphite or graphene.

In addition, Figure 5 is an image obtained through a transmission electron microscope, Figure 5a shows a graphene graphed with a polymer grafted at its edge as a layer of graphene. Since graphene originally had a property of bending well, the flat and folded image can be confirmed through a of FIG. 5. In addition, b of FIG. 5 is an enlarged portion of a of FIG. 5, which also supports the grafting of the polymer at the edge.

Example  2: Example  Obtained from 1 EBA -g- graphite Functionalized with Graphene  After it is dissolved in dichloromethane On a substrate Dropped  After argon gas atmosphere at a temperature of 900 ℃ For 2 hours Annealed  Large area with electrical conductivity Graphene  Manufacture of film

After dissolving the EBA-g-graphite obtained in Example 1 in dichloromethane and sonication for 1 minute, using a filter paper with a hole size of 0.5 ㎛ of Teflon material, the graphite in the form of agglomerate and the edges were functionalized. It was separated from the pin.

Graphene (0.5mg / ml) solution grafted with polymer dissolved in dichloromethane was 25cm ² with HF cleaning. Drop five drops onto the silicon substrate. After that, the dropped silicon substrate is sealed, and the cycle of tilting at an angle of about 10 to 25 ° to the right, left, top, and bottom so as not to remain in one place is repeated by appropriately drying. The drying time was about 10 minutes, the drying temperature was room temperature, and the drying pressure was the dichloromethane vapor pressure produced in the enclosed space. After that, the graphene-loaded silicon substrate grafted with the well-dried polymer is raised to an annealing temperature of 900 ° C. for 4 hours under an argon atmosphere and annealed at 900 ° C. for 2 hours. Through this process, a graphene film having an average sheet resistance of l.75 kPa and an area of 9 cm ² was obtained.

Experimental Example  3: Example  2, large area Graphene  For film AFM  And FE - SEM  image

The characteristics of the large-area graphene film surface prepared in Example 2 were confirmed by using a LEO 1530FE Field Emission Scanning Electron Microscope and Veeco Multimode V. Atomic force microscopy.

6 shows an image of a scanning electron microscope of the large area graphene film of Example 2. FIG. a is an image before annealing, b is an image after annealing, and before annealing, the surface of the graphene film appears to be wrinkled on the surface, whereas b after image annealing is very smooth. Can be. As well as seeing the graphene film after annealing, it can be seen that the film is transparent. The thickness of this film is about 16 nm.

7 shows that the large area graphene film is very smooth in its surface after annealing with an atomic microscope image.

Example  3: Example  Large area obtained on silicon substrate via 2 Graphene  Film HF  Through etching OHP  With film Graphene  Which can be bent by moving the film Graphene  Film manufacturing

The large area graphene film obtained on the silicon substrate by Example 2 was coated with polymethacrylate (PMMA) solution. After the coating, the polymethacrylate (PMMA) is sufficiently dried for about 15 minutes, and then the silicon substrate with the graphene film is cut to an appropriate desired size. The cut silicon substrate is etched in 10% HF solution to prepare a free-standing graphene film after 30 seconds.

Such pre-standing graphene film may be transferred to an OHP film. After transferring to the OHP film, polymethacrylate (PMMA) coated on the graphene film was removed using acetone to obtain a large area graphene film on the OHP.

Experimental Example  4: process of etching and OHP Image showing the process of transferring to film

8 lists photographs showing the overall process of Example 2 and Example 3. The graphene dispersion solution grafted with the polymer of Example 1 dissolved in dichloromethane was dropped onto a silicon substrate (b), and then uniformly dispersed and dried (c). The well-dried substrate was heated to 900 ° C., annealing temperature for 4 hours, annealed at 900 ° C. for 2 hours (d), cut to desired size (e) and etched in an 8% HF solution (f) and freestanding. A graphene film having a free standing conductivity can be obtained.

FIG. 9 is a view of a graphene film obtained by transferring the freestanding graphene film obtained in FIG. 8 into an OHP film. The size is 2 inches by 2 inches.

Example  4: Example  The polymer obtained in 1 Grafted Graphene  Dichloromethane with a volume ratio of 15: 1 In dichlorobenzene  Dissolve Dropped  after Argon gas  In the atmosphere By niling Patterned Graphene  Manufacture film

After dissolving the graphene grafted graphene obtained in Example 1 in dichloromethane (15ml) was subjected to sonication for 1 minute. Thereafter, a filter paper having a pore size of 0.5 μm of Teflon was separated from the lumped graphite and the functionalized graphene.

Dichlorobenzene (1ml) was added to a graphene (0.5mg / ml) grafted graphene (0.5mg / ml) dispersion solution dissolved in dichloromethane (15ml), followed by HF cleaning 1cm ² One drop was dropped onto the silicon substrate. Thereafter, the dropped silicon substrate is left at room temperature for 24 hours while being leveled. Thereafter, the silicon substrate on which the patterned graphene film was loaded was raised to 900 ° C., an annealing temperature for 4 hours under an argon atmosphere, and annealed at 900 ° C. for 2 hours. This resulted in a patterned graphene film with uniform spacing and uniform pore size.

Experimental Example  5: Patterned Graphene  For film AFM  image

The surface of the patterned graphene film prepared in Example 4 was confirmed using Veeco Multimode V. Atomic force microscopy.

FIG. 10 is an atomic microscope image showing the surface of a graphene film patterned after annealing. The lifespan generated in the surface is due to dichlorobenzene. You can see that.

The present invention has been described above with reference to the illustrated examples, but this is only an example and the present invention can perform various modifications and other embodiments that are obvious to those skilled in the art. Understand the facts.

Claims (16)

(a) reacting graphite with an organic substance having at least one functional group selected from the group consisting of carboxylic acid groups, amide groups, sulfonic acid groups, carbonyl chloride groups and carbonyl bromide groups in a reaction medium containing high molecular weight phosphoric acid and phosphorus pentoxide; Graphene functionalized with an organic material is prepared by substituting the covalent bond between the graphene and the organic material with the bond between the graphenes forming the graphite, or
One monomer containing a benzene ring and having at least one functional group selected from the group consisting of a carboxylic acid group, an amide group, a sulfonic acid group, a carbonyl chloride group and a carbonyl bromide group in a reaction medium containing high molecular phosphoric acid and phosphorus pentoxide Preparing a graphene-grafted graphene by substituting covalent bonds between the polymer and graphene formed by condensation polymerization of the monomers by reacting graphite with the graphite;
(b) preparing a dispersion solution by dispersing the graphene functionalized with the organic material or the graphene grafted with the polymer in an organic solvent at a concentration of 0.001 mg / ml to 100 mg / ml;
(c) dropping or spin coating the dispersion solution onto a substrate; And
(d) drying the substrate several times in a cycle of tilting the substrate horizontally or inclining at an inclination of 0.1 ° to 60 ° in order from the group consisting of right, left, top and bottom, each time of the cycle Run time is 0.01 seconds to 5 minutes
Comprising, a large-area graphene film production method. The method of claim 1, further comprising the following step (e) after the step (d):
(e) annealing temperatures of 500 ° C. to 3000 ° C. for 5 minutes to 12 hours under an inert gas atmosphere selected from the group consisting of helium, neon, argon, krypton, xenon, radon, nitrogen, ammonia, methane, hydrogen and mixtures thereof. And annealing at the annealing temperature for 5 minutes to 24 hours. The method of claim 2, further comprising the following steps immediately before, immediately after, or immediately after and immediately after the step (e).
(c) dropping or spin coating the dispersion solution onto a substrate; And
(d) drying the substrate several times in a cycle of tilting the substrate horizontally or inclining at an inclination of 0.1 ° to 60 ° in order from the group consisting of right, left, top and bottom, each time of the cycle The run time is 0.01 seconds to 5 minutes. The method according to any one of claims 1 to 3, wherein the spin coating is performed at a speed of 100 rpm to 10000 rpm. The large-area graphene film of any one of claims 1 to 3, wherein the drying of the step (d) is performed at a temperature of -100 ° C to 600 ° C and a pressure of -5 atm to 5 atm. Method of preparation. The large area according to claim 1, wherein the substrate is selected from the group consisting of glass, quartz, silicon, copper, aluminum, gold, platinum, silver, zinc and oxides thereof. Method for producing graphene film. The organic solvent of claim 1, wherein the organic solvent is water, methanol, ethanol, isopropyl alcohol, en-propanol, en-butanol, 1-butanol, 2-butanol, isobutyl alcohol, tetra Butyl alcohol, isoamyl alcohol, 1-octanol, toluene, benzene, pentane, hexane, heptane, cyclopentane, cyclohexane, benzene, toluene, xylene, dioxane, m-cresol, ethyl acetate, carbon disulfide, dimethyl sulfoxide , Dichloromethane, dichloroethane, dichlorobenzene, chloroform, carbon tetrachloride, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, diethyl ether, tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrroli Don, dimethylformamide, acetic acid, formic acid, acetonitrile, dimethyl sulfoxide, petroleum ether, diethylamine, diethyl ether, triethylamine, tetrabutylmethyl ether, dimethoxye Tan, benzyl acetate, 1-chlorobutane, ethyl acetate and a mixture thereof, the method for producing a large-area graphene film. A large-area graphene film produced by the method of any one of claims 1 to 3. (a) reacting graphite with an organic substance having at least one functional group selected from the group consisting of carboxylic acid groups, amide groups, sulfonic acid groups, carbonyl chloride groups and carbonyl bromide groups in a reaction medium containing high molecular weight phosphoric acid and phosphorus pentoxide; Graphene functionalized with an organic material is prepared by substituting the covalent bond between the graphene and the organic material with the bond between the graphenes forming the graphite, or
One monomer containing a benzene ring and having at least one functional group selected from the group consisting of a carboxylic acid group, an amide group, a sulfonic acid group, a carbonyl chloride group and a carbonyl bromide group in a reaction medium containing high molecular phosphoric acid and phosphorus pentoxide Preparing a graphene-grafted graphene by substituting covalent bonds between the polymer and graphene formed by condensation polymerization of the monomers by reacting graphite with the graphite;
(b) a concentration of 0.001 mg / ml to 100 mg / ml of the graphene functionalized with the organic material or the graphene grafted with the polymer in a mixture of organic solvent 1 and organic solvent 2 in a volume ratio of 1: 0.001 to 1: 1000 Preparing a dispersion solution by dispersing with a solvent, wherein the density of the organic solvent 2 is equal to or greater than that of the organic solvent 1;
(c) dropping or spin coating the dispersion solution onto a substrate; And
(d) drying the substrate several times in a cycle of tilting the substrate horizontally or inclining at an inclination of 0.1 ° to 60 ° in order from the group consisting of right, left, top and bottom, each time of the cycle Run time is 0.01 seconds to 5 minutes
Comprising a method for producing a patterned graphene film. (a) reacting graphite with an organic substance having at least one functional group selected from the group consisting of carboxylic acid groups, amide groups, sulfonic acid groups, carbonyl chloride groups and carbonyl bromide groups in a reaction medium containing high molecular weight phosphoric acid and phosphorus pentoxide; Graphene functionalized with an organic material is prepared by substituting the covalent bond between the graphene and the organic material with the bond between the graphenes forming the graphite, or
One monomer containing a benzene ring and having at least one functional group selected from the group consisting of a carboxylic acid group, an amide group, a sulfonic acid group, a carbonyl chloride group and a carbonyl bromide group in a reaction medium containing high molecular phosphoric acid and phosphorus pentoxide Preparing a graphene-grafted graphene by substituting covalent bonds between the polymer and graphene formed by condensation polymerization of the monomers by reacting graphite with the graphite;
(b) dispersing the graphene functionalized with the organic material or the graphene grafted with the polymer at a concentration of 0.001 mg / ml to 100 mg / ml in organic solvent 1 to prepare a dispersion solution;
(c) dropping or spin coating the dispersion solution on a substrate in a confined area;
(d) vaporizing and applying the organic solvent 2 to the substrate in a gaseous state, wherein the density of the organic solvent 2 is equal to or greater than that of the organic solvent 1; And
(e) horizontally drying or repeatedly drying the cycle of inclining at an inclination of 0.1 ° to 60 ° in order from the group consisting of right, left, top and bottom, each time of the cycle Run time is 0.01 seconds to 5 minutes
Comprising a method for producing a patterned graphene film. The method of claim 9 or 10, further comprising the following step (f) after the step (e):
(f) annealing temperatures of 500 ° C. to 3000 ° C. for 5 minutes to 12 hours under an inert gas atmosphere selected from the group consisting of helium, neon, argon, krypton, xenon, radon, nitrogen, ammonia, methane, hydrogen and mixtures thereof. And annealing at the annealing temperature for 5 minutes to 24 hours. The method of claim 9, wherein the spin coating is performed at a speed of 100 rpm to 10000 rpm. The method of claim 9, wherein the drying step is performed at a temperature of −100 ° C. to 600 ° C. and a pressure of −5 atm to 5 atm. The patterned graphene film of claim 9 or 10, wherein the substrate is selected from the group consisting of glass, quartz, silicon, copper, aluminum, gold, platinum, silver, zinc and oxides thereof. Way. The method of claim 9 or 10, wherein the organic solvent 1 and the organic solvent 2 are each independently water, methanol, ethanol, isopropyl alcohol, en-propanol, en-butanol, 1-butanol, 2-butanol, isobutyl Alcohol, tetrabutyl alcohol, isoamyl alcohol, 1-octanol, toluene, benzene, pentane, hexane, heptane, cyclopentane, cyclohexane, benzene, toluene, xylene, dioxane, m-cresol, ethyl acetate, carbon disulfide, Dimethyl sulfoxide, dichloromethane, dichloroethane, dichlorobenzene, chloroform, carbon tetrachloride, acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, diethyl ether, tetrahydrofuran, dimethylformamide, dimethylacetamide, N- Methylpyrrolidone, dimethylformamide, acetic acid, formic acid, acetonitrile, dimethyl sulfoxide, petroleum ether, diethylamine, diethyl ether, triethylamine, tetrabutylmethyl The method of Le, dimethoxy ethane, benzyl acetate, 1-chlorobutane, ethyl acetate and mixtures thereof which is selected from the group, patterned graphene films. The patterned graphene film produced by the manufacturing method of claim 9 or 10.

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