KR20130092216A - Method for manufacturing graphene film - Google Patents

Abstract

PURPOSE: A manufacturing method of a graphene film provided here is characterized in remarkably reducing damage to graphene layers when separating catalyst metal films. CONSTITUTION: A manufacturing method of a graphene film comprises the steps of: (111) preparing a material to which a first and a second catalyst metal films are adhered, (121) forming a first and a second graphene layers on the surface of the first and the second catalyst metal films, (131) forming a first and a second carrier layers on the surface of the first and the second graphene layers, (141) sticking a first and a second release tapes on the surface of the first and the second carrier layers, (151) separating the first and the second catalyst metal films to preparing a first and a substrates, (161) removing the first catalyst metal film on the first substrate, (171) transcribing a graphene film on the surface of the first graphene layer, (181) removing the first release tape adhered to the first carrier layer, and (191) removing the first carrier layer on first graphene layer to produce a graphene film. [Reference numerals] (111) Preparing a material a first and a second catalyst metal films are attached to each other; (121) Forming a first and a second graphene layers on the surface of the first and the second catalyst metal films; (131) Forming a first and a second carrier layers on the surface of the first and the second catalyst metal films; (141) Attaching a first and a second release tapes on the surface of the first and the second catalyst metal films; (151) Separating the first and the second catalyst metal films to prepare a first and a second substrates; (161) Removing the first catalyst metal film formed on the first substrate; (171,181) Removing the first release tape attached on the first carrier layer; (191) Finishing a graphene film by removing the first carrier formed on the first graphene layer; (AA) Start; (BB) End

Description

Graphene film manufacturing method {method for manufacturing graphene film}

The present invention relates to a polymer compound, and more particularly to a method for producing a graphene film composed of graphene.

With the development of science and technology, the development of new materials using nanotechnology is actively progressing. Among them, research on carbon-containing materials such as carbon nanotubes, diamonds, graphite, graphenes, and the like has been intensively studied in the field of nanotechnology. Such materials may be used in field effect transistors, biosensors, nanocomposites, quantum devices, and the like.

Graphene is a two-dimensional carbon allotrope and has very useful properties unlike conventional materials. One notable feature is that when electrons move in graphene, they flow as if the mass of the electrons is zero. This means that the electrons flow at the speed at which light in the vacuum moves, ie at the speed of light. Graphene has an electron mobility of up to 200,000 cm2 / Vs. Graphene exhibits an unusual half-integer quantum Hall effect on electrons and holes, and a fractional quantum Hall effect when suspended in the air.

In addition, since the graphene has an electrical characteristic that changes according to the crystal orientation of the graphene having a given thickness, the user can express the electrical characteristic in a selection direction and thus can easily design the device. The electrical properties of these graphenes are in contrast to carbon nanotubes (CNTs), in which the metallic and semiconducting electrical properties vary depending on chirality and diameter. In the case of CNTs, the process of separating the CNTs in order to use specific semiconductor and metal properties is difficult. In addition, graphene is advantageous in terms of economics as compared to CNTs that undergo purification after synthesis. Therefore, graphene can be effectively used for carbon-based electric or electromagnetic devices. Graphene is more excellent in impact resistance and flexibility than oxide transparent electrodes such as ITO materials, and has high transparency and high electrical conductivity.

A method for producing a graphene film is disclosed in Korean Patent Application Publication (# 2011-0079532). The disclosed patent discloses a graphene film manufacturing method using a roll-to-roll process, and when the graphene film is manufactured according to this method, the graphene may be damaged.

The present invention provides a graphene film production method that can safely produce a graphene film without damage.

The present invention to achieve the above object,

(a) preparing a material to which the first and second catalytic metal films are adhered to each other; (b) forming first and second graphene layers on the surfaces of the first and second catalytic metal films; (c) forming first and second carrier layers on the surfaces of the first and second graphene layers; (d) adhering first and second release tapes to surfaces of the first and second carrier layers; (e) separating the first and second catalyst metal films to provide first and second substrates; (f) removing the first catalytic metal film formed on the first substrate; (g) transferring the graphene film on the surface of the first graphene layer; (h) removing the first release tape adhered to the first carrier layer; And (i) provides a graphene film manufacturing method comprising the step of completing the graphene film by removing the first carrier layer formed on the first graphene layer.

According to the present invention, by forming graphene layers on catalyst metal layers formed on both surfaces of a material and forming carrier coating layers on the graphene layers, damage to the graphene layers may be significantly reduced when the catalyst metal layers are separated.

In addition, since the release tape is adhered to the substrate when the graphene film is transferred to the separated substrate, the operator may handle the substrate very smoothly.

1 is a flow chart schematically showing a graphene film manufacturing method according to an embodiment of the present invention.
2 to 11 are cross-sectional views sequentially showing a graphene manufacturing method according to the present invention.
12 shows a state in which the separated catalyst metal is damaged when the graphene film manufacturing method is performed in a roll-to-roll manner.

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. Like reference numerals in the drawings denote like elements.

1 is a flow chart schematically showing a graphene film manufacturing method according to an embodiment of the present invention, Figures 2 to 11 are cross-sectional views sequentially showing a graphene manufacturing method according to the present invention. Referring to FIG. 1, the present invention includes first to ninth steps. With reference to Figures 1 to 11 will be described in detail a graphene film manufacturing method according to the present invention.

In the first step 211, a material in which the first and second catalytic metal films 221 and 222 are bonded to each other is prepared.

Referring to FIG. 2, the first and second catalyst metal films 221 and 222 may be formed on both sides of a release film, and the first and second catalyst metal films 221 and 222 and the release film 211. Is configured in the form of a plate.

The first and second catalytic metal films 221 and 222 may be catalyst metals such as nickel (Ni), copper (Cu), cobalt (Co), iron (Fe), platinum (Pt), gold (Au), and aluminum (Al). ), Chromium (Cr), copper (Cu), magnesium (Mg), manganese (Mn), rhodium (Rh), silicon (Si), tantalum (Ta), titanium (Ti), tungsten (W), uranium It may be formed by at least one selected from the group consisting of (U), vanadium (V), and zirconium (Zr), and among them, copper is preferably provided at low cost and good conductivity.

As shown in FIG. 2, a release film 211 is provided between the first and second catalyst metal films 221 and 222 to separate the first and second catalyst metal films 221 and 222 from each other. The second catalytic metal films 221 and 222 may be safely separated without being damaged.

In order to form the first and second catalytic metal films 221 and 222 on both surfaces of the release film 211, a release film 211 is mounted in a chamber, and the catalyst metal is sputtered and an electron beam evaporation device ( The first and second catalytic metal films 221 and 222 may be formed by depositing on both surfaces of the release film 211 using an e-beam evaporator.

The thickness of the release film 211 may be formed of a thin film relatively thinner than the thicknesses of the first and second catalytic metal films 221 and 222. For example, the thickness of the release film 211 may be about 50 to 300 [mm]. The release film 211 is later separated from the first and second catalytic metal films 221 and 222, and then removed. The separation process of the release film 211 will be described later in the corresponding part.

The thicknesses of the first and second catalytic metal films 221 and 222 are thicker than the thickness of the release film 211. For example, the thicknesses of the first and second catalytic metal films 221 and 222 may be about 3, 5, 9, 12, 18, 25, 35, 70 [um], or the like. The numerical values of the first and second catalytic metal films 221 and 222 are non-limiting examples, and the thicknesses of the first and second catalytic metal films 221 and 222 may be variously selected and changed according to the manufacturer. The thickness of the first catalyst metal film 221 and the thickness of the second catalyst metal film 222 may be the same or different.

The release film 211 and the first and second catalytic metal films 221 and 222 may be removed by a chemical or mechanical method after the separation process. As the chemical removal method, for example, an etching process may be used, and as a mechanical method, a polishing process may be used.

As a second step 221, first and second graphene layers 231 and 232 are formed on surfaces of the first and second catalytic metal films 221 and 222.

Referring to FIG. 3, the first graphene layer 231 is formed on the surface of the first catalyst metal film 221, and the second graphene layer 232 is formed on the surface of the second catalyst metal film 222. The first and second graphene layers 231 and 232 may be formed by chemical vapor deposition or thermal chemical vapor deposition. In particular, the chemical vapor deposition method is a preferable process for forming the first and second graphene layers (231, 232) can proceed at low temperatures and mass production. Specific methods of forming the first and second graphene layers 231 and 232 on the surfaces of the first and second catalytic metal films 221 and 222 are as follows.

The material on which the first and second catalytic metal films 221 and 222 are formed is mounted in a chamber for chemical vapor deposition or a chamber for thermochemical vapor deposition. Subsequently, a hydrocarbon (CH4) gas is charged into the chamber at a predetermined concentration, and thermal energy is supplied into the chamber to separate carbon (C) atoms and hydrogen (H) atoms from the hydrocarbon. Then, carbon atoms and hydrogen atoms are separated by the thermal energy, and the separated carbon atoms are deposited on the surfaces of the first and second catalytic metal films 221 and 222 to form first and second graphene layers 231 and 232. do.

A process of surface treating the surfaces of the first and second catalytic metal films 221 and 222 by first injecting hydrogen (H 2) gas into the chamber before the thermal energy is injected into the chamber while the material is mounted in the chamber. You can proceed further. By surface treating the first and second catalytic metal films 221 and 222, the first and second graphene layers 231 and 232 may be more firmly formed on the surfaces of the first and second catalytic metal films 221 and 222. Can be.

In the present embodiment, a case where the hydrocarbon gas is introduced into the carbon source has been described, but the present invention is not limited thereto. For example, one or more selected from the group containing carbon atoms such as carbon monoxide, ethane, ethylene, ethanol, acetylene, propane, propylene, butane, butadiene, pentane, pentene, cyclopentadiene, hexane, cyclohexane, benzene and toluene can be used. have.

Before the first and second graphene layers 231 and 232 are formed on the surfaces of the first and second catalytic metal films 221 and 222, pretreatment is first performed on the surfaces of the first and second catalytic metal films 221 and 222. can do. The pretreatment process is a process for removing foreign matter present on the surfaces of the first and second catalytic metal films 221 and 222. For example, hydrogen (H 2) gas may be used. The surface of the first and second catalytic metal films 221 and 222 may be kept clean by supplying the hydrogen gas. In another embodiment, the solution may be used to pretreat the surfaces of the first and second catalytic metal films 221 and 222. For example, an acid solution or an alkaline solution may be used to clean the surfaces of the first and second catalytic metal films 221 and 222.

As described above, the first and second graphene layers 231 and 232 are formed on both surfaces of the material by using a material in which the first and second catalytic metal films 221 and 222 are disposed on both surfaces of the release film 211. It can be formed, the production efficiency of the graphene film (205 in Fig. 10) is greatly increased. In addition, in the process of separating the first and second catalyst metal films 221 and 222 from each other, the release film 211 is also easily removed together with the first and second catalyst metal films 221 and 222, thereby forming both surfaces of the material. The graphene film 205 of FIG. 10 may be obtained without sacrificing any one of the first and second graphene layers 231 and 232 formed therein.

In addition, the present invention forms the first and second graphene layers 231 and 232 on the first and second catalytic metal films 221 and 222 formed on both surfaces of the material, and on the first and second graphene layers 231 and 232. By forming the first and second carrier layers 241 and 242, damage to the first and second graphene layers 231 and 232 may be significantly reduced when the first and second catalyst metal layers 221 and 222 are separated.

In a third step 231, first and second carrier layers 241 and 242 are formed on surfaces of the first and second graphene layers 231 and 232.

Referring to FIG. 4, a first carrier layer is formed on the surface of the first graphene layer 231, and a second carrier layer 242 is formed on the surface of the second graphene layer 232. The first and second carrier layers 241 and 242 may be formed of one of a liquid material, for example, a solder resist, a photoresist, and a photo solder resist. The liquid material may be used to form the first and second carrier layers 241 and 242 using one of a screen printing method and a roll coating method. In the case of using the screen printing method, it is preferable to perform curing for about 5 minutes at 150 to 180 [° C] after screen printing.

In another embodiment, a carrier film, such as polydimethylsiloxane, polyethylene terephthalate, polyimide film, Various materials such as polyurethane film, glass, and the like may be used, and a heat release film that loses adhesive strength when a certain temperature is reached may be used.

In order to form a carrier layer using the carrier film, a plurality of injection nozzles are arranged on the back of the carrier film while the graphene layer and the carrier film are arranged side by side, and the air is injected to the carrier film with the plurality of injection nozzles. To apply pneumatic pressure. Then, the carrier film is pushed toward the graphene layer by the pneumatic pressure applied by the plurality of injection nozzles, so that the carrier film adheres to the graphene layer. In this case, the method may further include heating air to pressurize the carrier film. The method further includes heating the air applied to the carrier film, so that the carrier film and the graphene layer adhere to each other better because the air heats the carrier film while simultaneously applying air pressure to the carrier film. The heating of the carrier film also increases the flexibility in contact between the interface of the carrier film and the graphene layer. Therefore, even if the carrier film or the graphene layer has a variety of surface conditions, such as irregularities, curved surfaces or patterns are formed on the surface of the carrier film or graphene layer can be flexibly coped.

In a fourth step 241, the first and second release tapes 251 and 252 are adhered to the surfaces of the first and second carrier layers 241 and 242.

Referring to FIG. 5, the first release tape 251 is adhered to the surface of the first carrier layer 241, and the second release tape 252 is adhered to the surface of the second carrier layer 242. The first and second release tapes 251 and 252 may be attached to the first and second carrier layers 241 and 242 by a roll coating method. The first and second release tapes 251 and 252 include heat-peelable tape, UV (Ultraviolet) tape, photoresist, water-soluble polyurethane resin, water-soluble epoxy resin, water-soluble acrylic resin, water-soluble natural polymer resin, water-based adhesive, alcohol release tape , Vinyl acetate emulsion adhesive, hot melt adhesive, visible light curable adhesive, infrared curable adhesive, electron beam curable adhesive, polybenizimidazole (PBI) adhesive, polyimide adhesive, silicone adhesive, imide adhesive, bisaleimide (BMI) adhesive, modified epoxy resin It may include one selected from the group.

The first and second release tapes 251 and 252 may be bonded after surface treatment of the first and second carrier layers 241 and 242. That is, by performing a surface treatment that roughly forms the surface of the first and second carrier layers 241 and 242, the first and second release tapes 251 and 252 and the first and second carrier layers 241 and 242 are formed. Adhesion is strengthened.

As described above, since the first and second release tapes 251 and 252 are adhered to the substrate, an operator handles the substrate when the substrate is separated into two and the graphene film 261 is transferred to the separated substrate. handling can be done very smoothly.

In a fifth step 251, the first and second catalyst metal layers are separated to include the first and second substrates 201 and 202.

Referring to FIG. 6, the first substrate 201 is formed by sequentially stacking a first carrier layer 241, a first graphene layer 231, and a first catalyst metal film 221 on a first release tape 251. The second substrate 202 has a structure in which the second carrier layer 242, the second graphene layer 232, and the second catalyst metal film 222 are sequentially stacked on the second release tape 252. Have

To separate the first and second substrates 201 and 202, while holding one of the first and second substrates 201 and 202 fixed, one end of the other is pulled upward or downward and the first and second substrates 201 and 202 are separated. One of the substrates 201 and 202 is separated from the release film 211, and the release film 211 is attached to the other substrate. Therefore, the release film 211 can be separated from the first substrate 201 or the second substrate 202 in the above manner.

In the present embodiment, a case where a physical force is applied to one end of one of the first and second substrates 201 and 202 is described, but the present invention is not limited thereto. For example, a physical force may be applied at both ends of the first and second substrates 201 and 202 or in all directions to simultaneously separate the first and second substrates from the release film 211.

When the heat release tape is used as the release film 211, the first and second substrates can be separated from the release film 211 by applying predetermined heat.

In a sixth step 261, the first catalyst metal film 221 formed on the first substrate 201 is removed.

Referring to FIG. 7, the first catalyst metal film 221 formed on the first substrate 201 is removed, and the first release tape 251, the first carrier layer 241, and the first carrier 201 are removed from the first substrate 201. Only the graphene layer 231 remains.

In the following processes, since the process of the first substrate 201 and the process of the second substrate 202 may be performed simultaneously or separately, the first substrate 201 may be used for convenience of description. Only the process related to) will be described.

The first catalyst metal film 221 formed on the first substrate 201 may be removed using an etching process. As the etching process, a wet process may be used. The etchant used in the etching process includes an acid, hydrogen fluoride (HF), buffered oxide etch (BOE), ferric chloride (FeCl3) solution, ferric nitrate (Fe (No3) 3) solution, and the like.

In the present embodiment, the wet etching process using the etching solution as a method of removing the first catalyst metal film 221 is described, but the present invention is not limited thereto. For example, a dry etching process may be applied as an etching process, or a process of removing the first catalytic metal film 221 using sputtering may be applied. When the first catalyst metal film 221 is removed, the first graphene layer 231 is exposed as shown in FIG. 7.

In a seventh step 271, the graphene film 261 is transferred onto the surface of the first graphene layer 231.

Referring to FIG. 8, the graphene film 261 is transferred so that the first substrate 201 may include a first release tape 251, a first carrier layer 241, a first graphene layer 231, and a graphene film 261. This has a form that is sequentially stacked. The graphene film 261 may be formed by transferring graphene to the surface of the first graphene layer 231 using a wet transfer method or a dry transfer method. Here, as a dry transfer method, an indirect transfer method using UV tape, a thermal reaction tape, or a thermal release tape may be used, or the graphene film 261 may be directly applied to the first graphene layer 231. Direct transfer methods of transferring may be used.

Before transferring the graphene film 261, first, the surface of the first graphene layer 231 may be plasma treated. Plasma treatment of the surface of the first graphene layer 231 improves the surface characteristics of the first graphene layer 231 so that the graphene film 261 is firmly bound to the first graphene layer 231.

In an eighth step 281, the first release tape 251 adhered to the first carrier layer 241 is removed.

Referring to FIG. 9, the first release tape 251 is removed to leave only the first carrier layer 241, the first graphene layer 231, and the release layer 211 on the first substrate 201. In order to remove the first release tape 251 adhered to the first substrate 201, one end of the first carrier layer 241 is grasped and the first release tape 251 is pulled upward or downward. Then, the first release data is separated from the first carrier layer 241 by the physical force.

In the present embodiment, a case where a physical force is applied to one end of the first carrier layer 241 is described, but the present invention is not limited thereto. For example, the first release tape 251 may be removed by applying a physical force at both ends or all sides of the first substrate 201 to which the first carrier layer 241 and the first release tape 251 are bonded.

In order to easily separate the first release tape 251 from the first carrier layer 241, the first release tape 251 may use a member having a weak bonding force with the first carrier layer 241.

In the case where the heat release tape is used as the first release tape 251, the first release tape 251 can be removed by applying a predetermined heat.

After removing the first release tape 251, the first substrate 201 may be further cleaned and dried.

As a ninth step 291, the graphene film 205 of FIG. 10 is completed by removing the first carrier layer 241 formed on the first graphene layer 231.

Referring to FIG. 10, the manufacture of the graphene film 205 is completed by removing the first carrier layer 241 formed on the first substrate 201. In order to remove the first carrier layer 241, an etching process and a physical removal method may be used.

When the first carrier layer 241 is formed of a liquid material, an etching process may be applied to remove the first carrier layer 241, and when the first carrier layer 241 is formed of a carrier film, In order to remove the first carrier layer 241, a physical removal method may be applied.

As the etching process, a wet process may be used. The etchant used in the etching process includes an acid, hydrogen fluoride (HF), buffered oxide etch (BOE), ferric chloride (FeCl3) solution, ferric nitrate (Fe (No3) 3) solution, and the like. In order to remove the first carrier layer 241, the present invention is not limited to the wet etching process. For example, a dry etching process may be applied as the etching process, or a process of removing the catalyst metal film using sputtering may be applied.

As the physical removal method, one end of the first graphene layer 231 is grasped and the carrier film is pulled upward or downward. Then, the carrier film is separated from the first graphene layer 231 by physical force.

In the present embodiment, a case where a physical force is applied to one end of the first graphene layer 231 is described, but the present invention is not limited thereto. For example, the carrier film may be removed by applying a physical force at both ends or all sides of the first substrate 201 to which the first graphene layer 231 and the carrier film are bonded.

After removing the first carrier layer 241, the cleaning and drying of the graphene film 205 may be further performed.

Referring to FIG. 11, passivation layers 271 may be formed on both surfaces of the graphene film 205 of FIG. 10.

The protective layers 271 may be formed on both sides of the graphene film 205 of FIG. 10 by using a spin coating method, a spray method, a gravure printing method, or the like. As the passivation layers 271, a light transmissive and conductive polymer material such as PEDOT (poly (3,4-ethylenedioxythiophene)) may be used. Since PEDOT is an organic material, there is a strong affinity with graphene in addition to the above properties. As another embodiment of the passivation layers 271, a thiophene-based polymer, polypyrrole, polyaniline, a ferroelectric polymer such as PVDF (Polyvinylidene Fluoride), a ferroelectric inorganic such as PZT, or the like may be used. Since graphene is a two-dimensional bond of one layer of carbon atoms, it is difficult to compensate for defects from other atomic layers when damaged by scratches or pressure. Therefore, it is preferable to form the protective layers 271 for use in a device to which a constant pressure is applied, such as a touch screen.

(A), (b) & (c) of FIG. 12 show a state in which the separated catalyst metals are damaged when the graphene film manufacturing method is performed in a roll-to-roll manner.

The present invention forms first and second graphene layers 231 and 232 on the surfaces of the first and second catalytic metal films 221 and 222 formed on both surfaces of the release film 211, and the first and second graphene layers. By forming the first and second carrier coating layers 241 and 242 on the surface of the first and second catalyst metal layers 221 and 222, the first and second graphene layers 231 and 232 and the second and second graphene layers 231 and 232 are formed. Damage to the first and second catalytic metals 221 and 222 can be significantly reduced.

Although the present invention has been described with reference to the embodiments shown in the drawings, it is to be understood that various modifications and equivalent embodiments may be made by those skilled in the art without departing from the scope of the present invention. Accordingly, the true scope of the present invention should be determined by the technical idea of the appended claims.

201/202: first and second substrates, 205: graphene film
211: release film, 221/222: first and second catalytic metal films
231/232: first and second graphene layers, 241/242: first and second carrier layers
251/252: first and second release tapes, 261: graphene film
271: shields

Claims (10)

(a) preparing a material to which the first and second catalytic metal films are adhered to each other;
(b) forming first and second graphene layers on the surfaces of the first and second catalytic metal films;
(c) forming first and second carrier layers on the surfaces of the first and second graphene layers;
(d) adhering first and second release tapes to surfaces of the first and second carrier layers;
(e) separating the first and second catalyst metal films to provide first and second substrates;
(f) removing the first catalytic metal film formed on the first substrate;
(g) transferring the graphene film on the surface of the first graphene layer;
(h) removing the first release tape adhered to the first carrier layer; And
(i) removing the first carrier layer formed on the first graphene layer, thereby completing the graphene film. The method of claim 1,
Graphene film manufacturing method characterized in that it comprises a release film between the first and second catalytic metal film of step (a). The method of claim 1,
The first and second graphene layer of step (b) is a graphene film manufacturing method, characterized in that formed by chemical vapor deposition. The method of claim 1,
The first and second carrier layer of the step (c) is a graphene film manufacturing method, characterized in that it can be formed using one of the screen printing and roll coating. The method of claim 1,
The first and second release tapes of the step (d) is a graphene film manufacturing method, characterized in that the adhesive after the surface treatment of the first and second carrier layers. The method of claim 1,
Method of producing a graphene film, characterized in that one of the heat release tape and UV (Ultraviolet) tape can be used as the first and second release tape of the step (d). The method of claim 1,
The graphene film manufacturing method, characterized in that for transferring the graphene film after the plasma treatment of the surface of the first graphene layer of step (g). The method of claim 1,
And removing and rinsing and drying the first release tape of the step (h). The method of claim 1,
Method of producing a graphene film, characterized in that further comprising the step of washing and drying after removing the first carrier layer of step (i). The method of claim 1,
Graphene film manufacturing method further comprises the step of forming protective films on both sides of the graphene film completed in the step (i).

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