TW201713595A - Roll to roll continuously fabricating method and fabricating apparatus for graphene film - Google Patents

Abstract

A roll to roll continuously fabricating method and fabricating apparatus for graphene film are provided. The roll to roll continuously fabricating apparatus for graphene film includes a supporting material provider, a catalyst forming chamber, a deposition chamber and a first roller. The supporting material provider is configured to accommodate a roll of heat resistant supporting material. The catalyst forming chamber is configured to form a catalyst layer on the heat resistant supporting material continuously provided from the supporting material provider. The deposition chamber is configured to form a graphene film on the catalyst layer. The first roller is configured to rewind the heat resistant supporting material with the graphene film formed thereon.

Description

Roll-to-roll continuous manufacturing method and production equipment of graphene film

The present invention relates to a roll-to-roll continuous manufacturing method and manufacturing apparatus, and more particularly to a roll-to-roll continuous manufacturing method and manufacturing apparatus for a graphene film.

Graphene is structurally stable and has only one carbon atom thickness. It is the thinnest but hardest two-dimensional nanomaterial. Graphene is almost completely transparent and absorbs only 2.3% of light. The thermal conductivity of graphene (5,300 W/m·K) is higher than that of carbon nanotubes (CNT) and diamond. The electron mobility of graphene at room temperature (15,000 cm ² /V·s) is higher than that of carbon nanotubes or germanium crystals, and the resistivity is lower than that of copper or silver, which is only about 10 ^-6 Ω·cm, which is the lowest resistivity at present. The material is highly flexible and has low reflectivity, so it is the first choice for soft electronic materials such as transparent touch elements and solar cells.

Techniques for preparing graphene films include Mechanical Exfoliation, Epitaxial Growth, Chemical Vapor Deposition (CVD), and Reduction from Graphene Oxides. ) and other methods. The mechanical peeling method and the epitaxial growth method can produce a graphene film of a better quality, but it is not possible to synthesize a graphene film over a large area. The oxidation reduction and thinning graphene chemical reduction method mainly first oxidizes graphite and then restores its conductivity by high temperature reduction, but not all of the graphene oxide can be effectively reduced, so the quality is poor. Chemical vapor deposition produces a large area of graphene film on the surface of the transition metal. However, the material of the support material is PET or copper foil, which is not resistant to the high temperature of the chemical vapor deposition process, and thus is limited to the area of the support material and can only produce a small piece of graphene film.

The invention provides a roll-to-roll continuous manufacturing method and manufacturing device of a graphene film, which can solve the problem that the area of the graphene film produced in the prior art is too small.

The roll-to-roll continuous production method of the graphene film of the present invention comprises the following steps. A catalyst is formed on the high temperature resistant support material by continuously forming a cavity from a high temperature resistant support material through a catalyst. The high temperature resistant support material formed with the catalyst layer is passed through a deposition chamber to form a graphene film on the catalyst layer.

In an embodiment of the present invention, the roll-to-roll continuous production method of the graphene film further comprises: separating the graphene film from the high temperature resistant support material after forming the graphene film, and recovering the high temperature resistant support material into a roll.

In an embodiment of the invention, the method of separating the graphene film from the high temperature resistant support comprises the following steps. A laminated film is attached to the graphene film. The catalyst layer is removed to separate the graphene film from the high temperature resistant support material and transfer to the bonded film.

In an embodiment of the invention, a method of forming a graphene film in a deposition chamber includes performing a chemical vapor deposition process.

In an embodiment of the invention, the high temperature resistant support material is a titanium foil.

In an embodiment of the invention, the high temperature resistant support material is resistant to 1300 ° C or higher.

In an embodiment of the invention, the material of the catalyst layer is copper, nickel or a copper-nickel alloy.

The roll-to-roll continuous production apparatus of the graphene film of the present invention comprises a support material supply unit, a catalyst forming chamber, a deposition chamber and a first winding unit. The support material supply unit is for accommodating a roll of high temperature resistant support material. The catalyst forming chamber is for forming a catalyst layer on the high temperature resistant support material continuously provided by the support material supply unit. The deposition chamber is used to form a graphene film on the catalyst layer. The first winding unit is configured to wind up a high temperature resistant support material formed with a graphene film.

In an embodiment of the invention, the deposition chamber is a high temperature chemical vapor deposition chamber.

In an embodiment of the invention, the roll-to-roll continuous manufacturing apparatus of the graphene film further comprises a roll-to-roll bonding unit for attaching a bonding film on the graphene film.

In an embodiment of the present invention, the roll-to-roll continuous manufacturing apparatus of the graphene film further includes an etching unit for etching and removing the catalyst layer to separate the graphene film from the high temperature resistant support material and shifting to the bonding. membrane.

In an embodiment of the invention, the roll-to-roll continuous manufacturing apparatus of the graphene film further includes a second winding unit for winding the high temperature resistant support material separated from the graphene film.

Based on the above, in the roll-to-roll continuous production method and manufacturing apparatus of the graphene film of the present invention, a high-temperature resistant support material and a roll-to-roll continuous process are used, so that a large-area graphene film can be produced and the yield is improved.

The above described features and advantages of the invention will be apparent from the following description.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a roll-to-roll continuous production apparatus of a graphene film according to an embodiment of the present invention. Referring to FIG. 1 , the roll-to-roll continuous manufacturing apparatus 100 of the graphene film of the present embodiment includes a support material supply unit 110 , a catalyst forming cavity 120 , a deposition chamber 130 , and a first winding unit 140 . The support material supply unit 110 is for accommodating a roll of the high temperature resistant support material 10. The catalyst forming chamber 120 is for forming a catalyst layer 20 on the high temperature resistant support material 10 continuously provided by the support material supply unit 110. The deposition chamber 130 is used to form a graphene film 30 on the catalyst layer 20. The first winding unit 140 is configured to wind up the high temperature resistant support material 10 on which the graphene film 30 is formed.

The high temperature resistant support member 10 can be pulled from the support material supply unit 110 and pulled out from the state of being wound into a roll. The high temperature resistant support material 10 is continuously pulled through the catalyst forming cavity 120 and the deposition cavity 130 by the first winding unit 140, and the catalyst layer 20 and the graphene are sequentially formed on the high temperature resistant support material 10. Membrane 30. Finally, the first winding unit 140 collects the high temperature resistant support material 10 together with the catalyst layer 20 and the graphene film 30 thereon in a roll for storage and transportation. In the roll-to-roll continuous production apparatus 100 of the graphene film of the present embodiment, the support material supply unit 110 provides the high-temperature resistant support material 10, so that the large-area graphene film 30 can be formed continuously through the deposition chamber 130, and there is no Not resistant to high temperature deposition processes. In addition, since the roll-to-roll continuous production apparatus 100 of the graphene film of the present embodiment provides a roll-to-roll transfer mechanism of the high-temperature resistant support material 10, the process time of the graphene film 30 is greatly shortened and the yield is improved.

2 is a schematic view of a roll-to-roll continuous production apparatus of a graphene film according to another embodiment of the present invention. Referring to FIG. 2, the roll-to-roll continuous manufacturing apparatus 200 of the graphene film of the present embodiment has a plurality of selectively selectable process units compared to the roll-to-roll continuous production apparatus 100 of FIG. The device 100 can also selectively mate with some of these process units, and the invention is not limited thereto. The roll-to-roll continuous manufacturing apparatus 200 of the graphene film of the present embodiment includes a support material supply unit 210, a catalyst forming chamber 220, a deposition chamber 230, a cooling roller 250, a first winding unit 240, and a roll pair. The roll bonding unit 260, an etching unit 270 and a second winding unit 280.

Here, the roll-to-roll continuous production method of the graphene film according to an embodiment of the present invention is described by the roll-to-roll continuous production apparatus 200, but the roll-to-roll continuous production apparatus 200 is not limited to a roll capable of performing only the graphene film. The roll-to-roll continuous production method of the graphene film of the present embodiment is not limited to being performed only on the roll-to-roll continuous production apparatus 200. The roll-to-roll continuous production method of the graphene film of the present embodiment includes at least the following steps. First, a high temperature resistant support material 10 is continuously drawn from a roll of high temperature resistant support material 10 and a cavity 220 is formed through a catalyst to form a catalyst layer 20 on the high temperature resistant support material 10. Next, the high temperature resistant support material 10 on which the catalyst layer 20 is formed is passed through a deposition chamber 230 to form a graphene film 30 on the catalyst layer 20. Finally, the graphene film 30 is separated from the high temperature resistant support material 10, and the high temperature resistant support material 10 is recovered into a roll.

In the roll-to-roll continuous production method of the graphene film of the present embodiment, the high-temperature resistant support member 10 is used, so that the high temperature at the time of depositing the graphene film 30 can be withstood, which is advantageous for increasing the area of the graphene film 30. In addition, the high-temperature resistant support material 10 is in a state of being wound from the beginning of the process, and finally is in a state of being wound, that is, the method adopts a roll-to-roll process, and the process time is short and the output is high. In addition, the high temperature resistant support material 10 can be recycled at the end, which helps to reduce the process cost.

Hereinafter, in the description of the roll-to-roll continuous production apparatus 200, details of other optional steps and steps of the roll-to-roll continuous production method of the graphene film of the present invention will be described.

In this embodiment, the catalyst forming chamber 220 is divided into a cleaning chamber 222 and three sputtering chambers 224, but the number of sputtering chambers 224 may be more or less. The high temperature resistant support material 10 continuously provided by the support material supply unit 210 sequentially passes through the cleaning chamber 222 and the three sputtering chambers 224. The cleaning chamber 222 has an ion source 222A for providing ion bombardment of the high temperature resistant support material 10. The sputtering chamber 224 has a target holder 224A for placing a catalyst target 20A. The high temperature resistant support material 10 is cleaned before the formation of the catalyst layer 20, and the process yield can be improved. The cleaning method is such that the ions provided by the ion source 222A bombard the high temperature resistant support material 10 in a vacuum high temperature environment. Thereby, the possibility of recycling and recycling of the high-temperature resistant support material 10 can also be improved. The material of the catalyst target 20A of the present embodiment is, for example, copper. The method of forming the catalyst layer 20 in this embodiment is to perform a sputtering process in a vacuum high temperature environment, but the present invention is not limited thereto. A heating roller 226 is further disposed in the catalyst forming chamber 220 of the embodiment. The high-temperature-resistant support member 10 continuously supplied from the support member supply unit 210 sequentially passes through the cleaning chamber 222 and the sputtering chamber 224 in a state of being attached to the surface of the heating roller 226, so that the yield of forming the catalyst layer 20 can be improved.

The deposition chamber 230 of this embodiment is a high temperature chemical vapor deposition chamber. A method of forming the graphene film 30 in the deposition chamber 230 is, for example, a chemical vapor deposition process. For example, high-carbon compounds such as methane (CH ₄ ), ethane (C ₂ H ₆ ), and ethylene (C ₂ H ₄ ) are decomposed under high temperature (about 1300 ° C) and filled with hydrogen and argon. The carbon molecules form a graphene film 30 on the surface of the catalyst layer 20. Since the chemical vapor deposition is carried out in an environment of about 1300 ° C, the selection of the high temperature resistant support material 10 is considered to be a material resistant to 1300 ° C or higher, such as a titanium foil, and the titanium foil is also ductile and elastic. Good advantage. Of course, when the process temperature of the chemical vapor deposition is changed, the material selection of the high temperature resistant support material 10 can be changed accordingly.

The roll-to-roll continuous production apparatus 200 of the graphene film of the present embodiment further includes a cooling roller 250. The high temperature resistant support material 10 leaving the deposition chamber 230 is cooled by the surface of the cooling roller 250 and then wound by the first winding unit 240. The cooling roller 250 is similar to the heating roller 226 in that the high temperature resistant support material 10 is wound around the roller and then left to complete the cooling or heating. The high temperature resistant support material 10 on which the catalyst layer 20 and the graphene film 30 are sequentially formed may be wound by the first winding unit 240 for storage and transportation to the next production line.

The roll-to-roll continuous manufacturing apparatus 200 of the present embodiment further includes a roll-to-roll bonding unit 260 for attaching a bonding film 40 to the graphene film 30. For example, the high temperature resistant support material 10 having the graphene film 30 wound by the first winding unit 240 is placed on a roller, and the rolled film 40 is placed on the other roller. The bonding film 40 can be attached to the graphene film 30 by pressing and rotating the two rollers. The material of the bonding film 40 is, for example, polyethylene terephthalate (PET), Cyclic Olefin Copolymers (COC), Cyclic Olefin Polymers (COP), Polyimine ( Materials such as PI), acryl (PMMA), polycarbonate (PC), glass, etc., which are also coated with an adhesive to adhere to the graphene film 30. In the present embodiment, the high-temperature resistant support material 10 in which the graphene film 30 is formed is wound by the first winding unit 240, and then supplied to the roll-to-roll bonding unit 260 and bonded to the bonding film 40. However, the first winding unit 240 may be skipped, and the roll-to-roll bonding unit 260 may be bonded to the bonding film 40 directly after the graphene film 30 is formed.

The roll continuous manufacturing apparatus 200 of the present embodiment further includes an etching unit 270 for etching and removing the catalyst layer 20 to separate the graphene film 30 from the high temperature resistant support material 10 and transfer it to the bonding film 40. Since the catalyst layer 20 is to be removed and the bonding film 40, the graphene film 30 and the high temperature resistant support material 10 are to be retained, the etching unit 270 performs a selective etching process. The etching solution for the selective etching process includes, but is not limited to, CuCl ₂ , FeCl ₃ , NH ₃ , (NH ₄ ) ₂ S ₂ O ₈ , CrO ₃ , H ₂ SO ₄ , H ₂ O, C ₆ H ₈ O ₇ , At least one of HCl and H ₂ O ₂ . Specifically, the etching solution used in the present embodiment is a combination of C ₆ H ₈ O ₇ and H ₂ O ₂ .

The continuous roll making apparatus 200 of the present embodiment further includes a second winding unit 280 for winding the high temperature resistant support material 10 separated from the graphene film 30 and transferring the graphene onto the bonding film 40. The film 30 is also wound separately. Therefore, the wound high temperature resistant support material 10 can be moved to the support material supply unit 210 for recycling. Further, the graphene film 30 transferred to the bonding film 40 may be in the form of a roll or a tube, or may be first cut and stored in a sheet form.

In summary, in the roll-to-roll continuous manufacturing method and manufacturing apparatus of the graphene film of the present invention, since the high-temperature resistant support material is used, the area of the graphene film which is not resistant to high temperature in the prior art can be solved. The problem. In addition, the present invention also adopts a roll-to-roll continuous process, which has the advantages of short process time and large output.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

10‧‧‧High temperature support material
20‧‧‧ catalyst layer
20A‧‧‧ Catalyst Target
30‧‧‧Graphene film
40‧‧‧Finished film
100,200‧‧‧Roll-to-roll continuous production equipment for graphene film
110, 210‧‧‧Support material supply unit
120, 220‧‧‧ catalyst formation cavity
130, 230‧‧‧ deposition chamber
140, 240‧‧‧ first winding unit
222‧‧‧Clean chamber
222A‧‧‧Ion source
224‧‧‧Spray chamber
226‧‧‧heating roller
250‧‧‧Cooling roller
260‧‧‧Volume-to-roll fitting unit
270‧‧‧etching unit
280‧‧‧Second winding unit

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a roll-to-roll continuous production apparatus of a graphene film according to an embodiment of the present invention. 2 is a schematic view of a roll-to-roll continuous production apparatus of a graphene film according to another embodiment of the present invention.

10‧‧‧High temperature support material

20‧‧‧ catalyst layer

30‧‧‧Graphene film

100‧‧‧Roll-to-roll continuous production equipment for graphene film

110‧‧‧Support material supply unit

120‧‧‧Catalyst forming cavity

130‧‧‧Deposition chamber

140‧‧‧First winding unit

Claims (10)

A roll-to-roll continuous manufacturing method of a graphene film, comprising: continuously drawing a high temperature resistant support material from a roll of high temperature resistant support material and forming a cavity through a catalyst to form a catalyst layer on the high temperature resistant support material; And passing the high temperature resistant support material formed with the catalyst layer through a deposition chamber to form a graphene film on the catalyst layer. The method for continuously producing a roll-to-roll of a graphene film according to claim 1, further comprising separating the graphene film from the high temperature resistant support material after forming the graphene film, and recovering the high temperature resistant support material Into a volume. The method for continuously producing a roll-to-roll of a graphene film according to claim 2, wherein the method for separating the graphene film from the high temperature resistant support comprises: laminating a film on the graphene film And removing the catalyst layer to separate the graphene film from the high temperature resistant support material and transferring to the bonded film. A roll-to-roll continuous production method of a graphene film according to claim 1, wherein the method of forming the graphene film in the deposition chamber comprises performing a chemical vapor deposition process. The roll-to-roll continuous production method of the graphene film according to the first aspect of the invention, wherein the high temperature resistant support material is a titanium foil. The method for continuously producing a roll-to-roll of a graphene film according to claim 1, wherein the high temperature resistant support material is resistant to 1300 ° C or higher. The method for continuously producing a roll-to-roll of a graphene film according to claim 1, wherein the material of the catalyst layer is copper, nickel or a copper-nickel alloy. A roll-to-roll continuous manufacturing apparatus for graphene film, comprising: a support material supply unit for accommodating a roll of high temperature resistant support material; a catalyst forming cavity for continuously providing the high temperature resistance in the support material supply unit Forming a catalyst layer on the support material; a deposition chamber for forming a graphene film on the catalyst layer; and a first winding unit for winding the high temperature resistant support material on which the graphene film is formed. The roll-to-roll continuous production apparatus of the graphene film according to claim 8, wherein the deposition chamber is a high temperature chemical vapor deposition chamber. The roll-to-roll continuous manufacturing apparatus for a graphene film according to the eighth aspect of the invention, further comprising: a roll-to-roll bonding unit for bonding a bonding film on the graphene film; And etching to remove the catalyst layer to separate the graphene film from the high temperature resistant support material to the bonding film; and a second winding unit for winding and separating the graphene film This high temperature resistant support material.