JP6124300B2 - Method for producing graphene laminate and method for producing transparent electrode using the graphene laminate - Google Patents

Description

  The present invention relates to a method for producing a graphene laminate for use in a transparent conductive film and the like, and a method for producing a transparent electrode using the graphene laminate.

Conductive planar crystals with SP ² bonded carbon atoms are called “graphene”. The graphene is described in detail in Non-Patent Document 1. Graphene is the basic unit of various forms of crystalline carbon films. Examples of crystalline carbon films using graphene include single-layer graphene using one layer of graphene, nanographene that is a stack of several to ten layers of nanometer-sized graphene, and a graphene stack of several to several tens of layers Are carbon nanowalls (see Non-Patent Document 2) that are oriented at an angle close to perpendicular to the substrate surface.

A crystalline carbon film made of graphene is expected to be used as a transparent conductive film or a transparent electrode because of its high light transmittance and electrical conductivity. Furthermore, the carrier mobility of electrons and holes in graphene may be up to 200,000 cm ² / Vs, which is 100 times higher than that of silicon at room temperature. Development of ultra-high-speed transistors aiming at terahertz (THz) operation utilizing the characteristics of this graphene is also underway.
As for the method for producing a graphene film, a method of peeling from natural graphite, a method of desorbing silicon by high-temperature heat treatment of silicon carbide, and a method of forming on various metal surfaces have been developed. Recently, a method of forming graphene by chemical vapor deposition (CVD) on the copper foil surface has been developed (see Non-Patent Documents 3 and 4). This graphene film formation method using a copper foil as a substrate is based on a thermal CVD method, in which methane gas, which is a raw material gas, is thermally decomposed at about 1000 ° C. to form one to several layers of graphene on the copper foil surface Is formed.

  This graphene film formation by the thermal CVD method has a problem that the synthesis temperature is a high temperature process of about 1000 ° C. and the process time is long. The present inventors have realized a technique for forming a graphene film at a lower temperature in a shorter time by plasma CVD using microwave surface wave plasma on a copper foil substrate, and a touch panel using a large-area transparent conductive carbon film Has also been prototyped (Non-Patent Document 5). In addition, a small amount of carbon contained in the metal base material is deposited on the surface of the base material by heating, and further, plasma treatment using hydrogen gas is performed under reduced pressure to grow graphene on the surface of the base material. It has also been proposed to obtain a transparent conductive film (Patent Document 2).

  A graphene film using a CVD method is formed on a catalyst metal, and cannot be used as a device as it is. For this reason, various transfer methods have been proposed. For example, in Patent Document 1, a binder layer such as a siloxane compound, an acrylic compound, or an epoxy compound is formed on a graphene film formed on a catalyst metal, and the graphene film is fixed to a transfer material such as PET. . Next, a technique for obtaining a sheet in which a graphene film is formed on a transfer material via a binder layer by dissolving and removing the catalyst metal from the graphene film with an etching solution such as an acid has been proposed.

  Non-Patent Document 4 reports a method in which a catalyst metal is dissolved and removed from a graphene film formed on the catalyst metal and then transferred to another substrate. That is, a thin resin solution in which polymethyl methacrylate (PMMA) or the like is dissolved in anisole is applied onto the graphene surface, and after drying, this is immersed in an etching solution to remove the catalyst metal and retained in the resin layer. A graphene film is obtained, attached to another substrate such as silicon, and the resin layer is removed with a solvent such as acetone, whereby the graphene film is transferred onto the substrate.

  Patent Document 3 solves the problem that the shape of the surface of the catalytic metal is transferred to the graphene laminate, which is a problem of the conventional method of forming the binder layer on the graphene film, and is a highly transparent graphene laminate with less haze The object is to provide a technique for forming a body. And in this patent document, after forming the graphene film on the catalyst metal by the CVD method, the catalyst metal is removed by etching, and in the method for producing the graphene film, a film having an adhesive surface is prepared, Before removing the catalytic metal, the above problem is solved by providing a step of temporarily fixing the adhesive surface of the film to the whole and / or part of the surface of the graphene film.

As described above, various proposals have been made as a method of transferring a graphene film formed on a film formation substrate such as a catalyst metal to PET or the like.
However, the sheet resistance of graphene transferred to PET, etc. is about 500Ω / □, which is insufficient as a transparent conductive film that requires high electrical conductivity such as a touch panel, so another element is added to graphene. A method of doping is proposed.

  For example, Non-Patent Document 6 discloses that after fixing a graphene film on a PET substrate using an epoxy resin, a 20 mmol / L nitromethane solution of gold chloride is applied to the graphene on the PET substrate, so that the electric power is reduced to about 250Ω / □. It has been proposed to increase conductivity. However, doping using gold (III) chloride has a great effect on improving electrical conductivity, but the transparency decreases due to the light yellow dopant, and gold chloride aggregates over time, It is difficult to change the color to reddish purple as seen in colloidal gold, and the nitromethane solvent is a highly flammable organic solvent and has a relatively high reactivity with the resin.

  Non-Patent Document 7 shows a technique of doping with concentrated nitric acid instead of gold chloride nitromethane solution. In this document, in addition to concentrated nitric acid, the results of doping with nitromethane solution, concentrated nitric acid nitromethane solution, gold chloride nitromethane solution, chloroauric acid aqueous solution, chloroauric acid nitromethane solution, sulfuric acid, nitromethane sulfate solution, hydrochloric acid, nitromethane hydrochloride solution are included. It is shown. Concentrated nitric acid is colorless and transparent and has no change in transmittance before and after doping, but it cannot be used for substrates and adhesive layers that react with concentrated nitric acid. It is a difficult point that an effect falls.

JP 2009-298683 A Japanese Patent Application No. 2013-120761 International Publication No. 2012/153684

Kumi Yamada, Chemistry and Industry, 61 (2008) pp.1123-1127. Y. Wu, P. Qiao, T. Chong, Z. Shen, Adv. Mater. 14 (2002) pp. 64-67. Alfonso Reina, Xiaoting Jia, John Ho, Daniel Nezich, Hyungbin Son, Vladimir Bulovic, Mildred S. Dresselhaus, Jing Kong, Nano letters, 9 (2009) pp. 30-35. Xuesong Li, Yanwu Zhu, Weiwei Cai, Mark Borysiak, Boyang Han, David Chen, Richard D. Piner, Luigi Colombo, Rodney S. Ruoff, Nano Letters, 9 (2009) pp. 4359-4363. Jaeho Kim, Masatou Ishihara, Yoshinori Koga, Kazuo Tsugawa, Masataka Hasegawa, and Sumio Iijima, Appl.Phys.Lett., 98 (2011) pp.091502_1-3. Toshiyuki Kobayashi, Masashi Bando, Nozomi Kimura, Keisuke Shimizu, Koji Kadono, Nobuhiko Umezu, Kazuhiko Miyahara, Shinji Hayazaki, Sae Nagai, Yukiko Mizuguchi, Yosuke Murakami, and Daisuke Hobara, Appl. Phys. Lett., 102 (2013) pp. 023112_1-3. Sukang Bae, Hyeongkeun Kim, Youngbin Lee, Xiangfan Xu, Jae-Sung Park, Yi Zheng, Jayakumar Balakrishnan, Tian Lei, Hye Ri Kim, Young Il Song, Young-Jin Kim, Kwang S. Kim, Barbaros Oe zyilmaz, Jong- Hyun Ahn, Byung Hee Hong, and Sumio Iijima, Nature Nanotechnol., 5 (2010) 574-578.

The above-described doping method using a gold chloride nitromethane solution or concentrated nitric acid is considered promising as a method for enhancing the electrical conductivity of graphene as a transparent conductive film.
However, since all the methods dope graphene onto a transparent substrate such as PET after the transfer, the substrate or the adhesive layer needs to be made of a material having high chemical resistance, and the passage of time At the same time, it has been found that there are problems such as the effect of doping fading or discoloration.

  The present invention has been made in view of the circumstances as described above, solves the above problems, and can form a graphene film doped with any substrate to increase the electrical conductivity, Furthermore, it aims at providing the method of maintaining the effect.

  As a result of intensive studies to achieve the above object, the present inventors have directly doped a graphene film temporarily fixed on the slightly adhesive sheet using a doping solution that does not chemically react with the slightly adhesive sheet. It was found that the above-described problems in the prior art can be solved by applying the graphene to a transparent substrate such as PET after applying and enhancing the electrical conductivity. It has also been found that the doping effect can be sustained by providing a dopant fixed layer made of a substance that forms a self-assembled monolayer on the doped layer.

The present invention has been completed based on these findings, and is as follows.
[1] A method for producing a graphene laminate, wherein a graphene film is temporarily fixed on a slightly adhesive sheet, and then the graphene film is treated with a doping solution that does not chemically react with the slightly adhesive sheet.
[2] The method for producing a graphene laminate according to [2], wherein the chemically non-reactive doping solution is an isopropyl alcohol solution of gold (III) chloride.
[3] The method for producing a graphene laminate according to [1] or [2], further comprising adsorbing a self-assembled monolayer.
[4] The method for producing a graphene laminate according to any one of [1] to [3], wherein the graphene film is patterned and then temporarily fixed on the slightly adhesive sheet.
[5] The method for producing a graphene laminate according to any one of [1] to [3], wherein the graphene film is temporarily fixed on the slightly adhesive sheet, and then the graphene film is patterned.
[6] a slightly adhesive sheet;
A graphene film temporarily fixed to the slightly adhesive sheet;
A graphene laminate comprising a layer in which the graphene film is doped with a dopant.
[7] The graphene laminate according to [6], further comprising a dopant fixed layer made of a substance that forms a self-assembled monolayer on the doped layer.
[8] The graphene laminate according to [6] or [7], wherein the graphene film is patterned.
[9] After the surface on which the doped graphene layer or the dopant fixed layer of the graphene laminate according to any one of [6] to [8] is formed is attached to a transparent transfer material, A method of forming a transparent electrode, comprising: forming a transparent electrode doped on a transfer material by removing the slightly adhesive sheet.
[10] A transparent electrode formed by transferring the graphene laminate according to any one of [6] to [8] except for the slightly adhesive sheet to a transparent transfer material, the transfer material And a graphene layer doped between the graphene film and the transparent electrode.

  According to the method of the present invention, the conventional problem of doping graphene with a gold chloride nitromethane solution or concentrated nitric acid after transfer is solved, and before or after transferring graphene to a transparent substrate such as PET. Also, the graphene can be doped to increase electrical conductivity. The transparent electrode formed by transferring the graphene laminate of the present invention to the transfer material has a doped graphene layer between the transfer material and the graphene film, so that the effect of doping is maintained. be able to. Furthermore, by providing the dopant fixed layer of the present invention, the effect of doping the graphene stack can be maintained. Therefore, by using a highly conductive graphene laminate in which the electrical conductivity of graphene is increased by the method of the present invention, a transparent conductive film for touch panel use, a semiconductor device or an electronic device such as a transistor or an integrated circuit, a large area Application to necessary transparent electrodes, electrochemical electrodes, biodevices, etc. becomes possible.

Schematic showing an example of the structure of a substrate for film formation and a graphene film formed on the substrate Schematic showing an example of the structure of a sheet having a smooth and slightly adhesive surface Schematic showing a state in which a sheet having a smooth and slightly adhesive surface is temporarily fixed together with bubbles on at least a part of a graphene film formed by a CVD method Schematic showing a process of temporarily fixing a sheet having a smooth and slightly adhesive surface to at least a part of a graphene film formed by a CVD method without bubbles In an exemplary embodiment, a schematic diagram illustrating a graphene laminate in which a film-forming substrate is removed by etching and a graphene film is temporarily fixed without bubbles on a sheet having a smooth and slightly adhesive surface. Schematic showing a graphene stack with a doping layer applied to the graphene stack Schematic showing a graphene stack with a dopant pinned layer on a graphene stack with a doping layer Schematic showing a patterned electrode produced by transferring a graphene stack with a doping layer to another transfer material The figure which shows typically the microwave surface wave plasma processing apparatus used for the present Example

Hereinafter, the present invention will be described with reference to the drawings.
FIG. 1 is a schematic view showing a film-forming substrate (100) and a graphene film (101) formed on the substrate according to the present invention. As shown in FIG. 1, a graphene film is formed on the surface of the film-forming substrate.

  As the film forming substrate, at least one selected from metals such as copper (Cu), iron (Fe), nickel (Ni), and aluminum (Al) can be used. The substrate is preferably a thin film or foil having a thickness of about 1 nm to 10 mm, preferably 500 nm to 0.1 mm.

  A CVD method is used as a method for forming a graphene film on a substrate for film formation. For example, a thermal CVD method in which a raw material gas is introduced in the presence of a catalytic metal and the raw material gas is thermally decomposed, or a microwave is used. There is a surface wave microwave plasma chemical vapor deposition (CVD) method in which treatment is performed by plasma, but the film forming method is not limited as long as the graphene film can be formed on the catalyst substrate.

  In order to perform a CVD process for forming a graphene film without changing the surface shape of the film-forming substrate and without causing evaporation of the catalytic metal substrate, the melting point of the film-forming substrate (for example, copper It is effective to treat at a sufficiently lower temperature than the melting point of 1080 ° C.

FIG. 2 is a schematic view showing an example of the structure of a sheet having a smooth and slightly adhesive surface according to the present invention.
The smooth and slightly adhesive surface only needs to be on at least one surface of the sheet (201), and as shown in the figure, when one surface has adhesive force, It is desirable that the adhesive surface is covered with a peelable protective material (release liner) (202) in order to prevent adhesion of foreign matters such as dust and unintentional objects. When sticking, the release liner is peeled off. The thickness of the slightly adhesive sheet (201) is 1 μm to 5 mm, preferably 20 μm to 1 mm.

  A sheet having a smooth and slightly adhesive surface must be non-reactive with organic solvents. For example, slight adhesion composed entirely and / or partially of siloxane (polydimethylsiloxane), acrylic (acrylic ester copolymer, etc.), rubber (synthetic rubber, etc.), urethane (urethane resin, etc.) A sheet can be used.

  3 and 4 show a smooth and slightly adhesive surface on at least a part of the graphene film (101) formed by the CVD method on the film forming substrate (100) in the present invention. FIG. 2 is a schematic diagram showing a step of bonding a sheet (hereinafter, also simply referred to as a “slightly adhesive sheet”) (201).

The adhesive surface of the slightly adhesive sheet (201) is bonded to the graphene film (101), and is bonded to the opposite side of the film forming substrate (100). When the graphene film formed on the substrate for film formation and the slightly adhesive sheet (201) are bonded together, as shown in FIG. 3, if bubbles (301) or foreign substances enter the adhesive surface, The film does not stick.
Therefore, it is important to adhere carefully so that bubbles and foreign substances do not enter.

FIG. 5 is a schematic diagram showing a graphene laminate comprising a sheet (201) having a smooth and slightly adhesive surface and a graphene film (101) after the film-forming substrate is removed in the present invention. FIG.
In order to remove the substrate for film formation, there are etching methods such as a wet method and a dry method. In wet etching, a graphene film (101) formed on a substrate for film formation as illustrated in FIG. 4 is used as an etching solution such as an acid or a corrosive solution (such as a ferric chloride aqueous solution or an ammonium persulfate aqueous solution). There is a method of immersing a laminate to which a slightly adhesive sheet (201) is adhered. In wet etching, if a gas is generated during etching, peeling of the graphene film from the slightly adhesive sheet may be induced. Therefore, an etching solution that generates a gas must be avoided.

FIG. 6 is a schematic view showing a graphene laminated body in which a layer doped with a dopant (hereinafter also referred to as “doping layer”) (601) is applied to the graphene film in the present invention.
In order to form the doping layer, there are doping methods such as a wet method and a dry method. As an example, graphene of a graphene laminate comprising a sheet (201) having a smooth and slightly adhesive surface and a graphene film (101) in which a dopant such as gold chloride, iron chloride, and palladium chloride is dissolved in a solvent Apply to the surface. As a coating method, generally known methods include spin coating and dipping. When an excessive doping solution is attached, it is preferable to blow off the excessive solution by blowing compressed air or the like.

FIG. 7 is a schematic view showing a graphene laminate in which a dopant fixed layer (701) is applied to a graphene laminate provided with a doping layer in the present invention.
A self-assembled monolayer can be used for the dopant fixed layer. Self-assembled monolayers include organic sulfur molecules, organic selenium molecules, organic tellurium molecules, nitrile compounds, monoalkyl silanes, carboxylic acids, phosphonic acids, phosphate esters, organic silane molecules, unsaturated hydrocarbons, alcohols, and aldehydes. , Alkyl bromides, unsaturated hydrocarbons, diazo compounds, alkyl iodides, and the like. Preferably, organic sulfur molecules such as acetic acid thiol and undecane thiol and organic silane molecules such as trichloro (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) silane are suitable. In order to form a self-assembled monolayer, there are a method of immersing in a generally known solution and a method of exposing to vapor, but not limited thereto.

  FIG. 8 is a schematic view showing a patterned electrode produced by transferring a graphene stack with a doping layer to another transfer material (801) in one exemplary embodiment of the present invention. is there. As shown in the figure, the patterned electrode formed by transferring the graphene laminate of the present invention to a transfer material has a doping layer (601) between the transfer material (801) and the graphene film (101). Therefore, the doping effect can be maintained.

  The material to be transferred is a base material characterized in that the interaction force between the transfer surface and the graphene laminate is stronger than the interaction force between the graphene laminate and the slightly adhesive sheet (201). Such a material to be transferred may be a material having a strong interaction force itself or a material to which an interaction force is applied by surface processing. The surface processing includes methods such as application of a curable resin, melting of the surface, and formation of a fine structure, but the method is not limited thereto.

Although the method of producing a pattern electrode is illustrated below, if a similar electrode is produced, a method will not be this limit.
First, the film-forming substrate (100) on which the graphene film (101) is formed is cut into an electrode shape. For cutting, there are methods such as cutting with a blade, punching with a die having a patterned electrode shape, and cutting with a laser cutting technique. A film-forming substrate on which a transparent conductive carbon film cut into an electrode shape is formed is pressure-bonded to a slightly adhesive sheet (201) having the cross-sectional structure of FIG. The film-forming substrate on the slightly adhesive sheet is removed and doping is performed. If necessary, a dopant fixed layer may be formed.

  A graphene laminate in which a graphene film is patterned into an electrode shape is bonded to the transfer material (801), and the interaction between the graphene laminate and the transfer material is kept stronger than that of the slightly adhesive sheet. . By removing the slightly adhesive sheet, a patterned electrode is formed on the transfer material.

  Further, as a method of forming a patterned graphene film on the slightly adhesive sheet, an unnecessary graphene film may be removed from the graphene stack by ozone or oxygen plasma.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited to this Example.

First, the evaluation method used in the examples will be described.
<Measurement of electrical conduction characteristics>
The sheet resistance of the graphene laminate produced by the method of the present invention was measured to evaluate the electric conduction characteristics. The sheet resistance was measured by a four-end needle method using a fine pitch four-probe probe (spring material contact type) manufactured by Kiyota Manufacturing & NTT Advanced Technology.

(Example 1)
In this example, a dissolution test of gold (III) chloride as a dopant in various solvents and a chemical resistance test of a slightly adhesive sheet were performed.
In the slightly adhesive sheet, the release liner was removed from a siloxane-based slightly adhesive tape (E-MASK DW100, manufactured by Nitto Denko Corporation, adhesive strength: 2.04 gf / 25 mm) having slight adhesiveness only on one surface. A thing was used. The test results are shown in Table 1. The solubility of gold chloride (III) was determined by mixing gold chloride (III) powder with a gold chloride concentration of 20 mmol / L in a solvent and stirring with a magnetic stirrer for 10 minutes. Judged by the presence or absence of. The chemical resistance of the slightly adhesive sheet was judged from the surface state after 10 minutes after applying a solvent to the adhesive surface of the slightly adhesive sheet.

  As can be seen from the table above, among these solvents, only isopropyl alcohol can easily dissolve the gold (III) chloride powder and not damage the fine adhesive sheet coated with the siloxane-based adhesive. I understood.

(Example 2)
In this example, the graphene film was manufactured by performing the method described in Patent Document 2, that is, conducting heating and hydrogen plasma treatment of the electrolytic copper foil.
FIG. 9 is a diagram schematically showing the microwave surface wave plasma processing apparatus used in the present embodiment.
As shown in FIG. 9, the microwave surface wave plasma processing apparatus used in the present invention includes a metal processing vessel (910) having an open upper end, and a metal support member (904) at the upper end of the processing vessel (910). A quartz window (903) for introducing microwaves attached in an airtight manner, a rectangular microwave waveguide with a slot (902) attached to the top thereof, a power source for electric heating (907), etc. Has been.
An electrolytic copper foil base material is fixed as a metal base material (905) to a base material current heating electrode (906) provided inside the processing vessel (910), and current heating and hydrogen plasma treatment are performed. The processing procedure is as follows.

An electrolytic copper foil from which a rust inhibitor was removed with dilute sulfuric acid was placed on a substrate energization heating electrode (906) provided in a plasma generation chamber (901) in a microwave surface wave plasma processing vessel (910). Next, the reaction chamber was evacuated to 1 × 10 ⁻⁴ Pa or less through an exhaust pipe (908).

The height of the sample stage was adjusted so that the distance between the quartz window (903) and the electrolytic copper foil base material was about 8.5 cm.
Next, hydrogen gas was introduced into the treatment chamber through a treatment gas introduction pipe (909). The hydrogen gas flow rate was 30.0 SCCM. The pressure in the reaction chamber was maintained at 5 Pa using a pressure adjusting valve connected to the exhaust pipe (908).

  A direct current with a power output of 32.5 W for energization heating was applied to the copper foil base material to heat the substrate. The temperature of the substrate during processing was measured with a radiation thermometer through an observation window. The temperature rose to about 500 ° C. in about 5 minutes. The substrate temperature was stabilized and the substrate surface was cleaned by heating in hydrogen gas for 15 minutes. Thereafter, plasma was generated at a microwave power of 400 W to perform a hydrogen plasma treatment of the copper foil base material. The temperature of the substrate during the plasma treatment showed a value about 20% higher than that in the case of only current heating. When the base material during the hydrogen plasma treatment reaches a high temperature, the copper foil may be melted or further disappear due to evaporation. Therefore, it is important to carefully control the temperature of the substrate. As a result of the above hydrogen plasma treatment, a graphene film is formed on the copper foil base material. The plasma processing time is 30 seconds. The treated electrolytic copper foil base material was taken out from the plasma generation chamber after natural cooling. The graphene film on the electrolytic copper foil having the cross-sectional structure of the conceptual diagram shown in FIG.

  Next, after removing the release liner from the siloxane-based slightly adhesive tape described above, it was bonded to the graphene film formed on the electrolytic copper foil.

  The electrolytic copper foil was removed by etching in a 0.5 mol / L aqueous solution of ammonium persulfate and thoroughly washed with ion-exchanged water. The film was dried with a hot air dryer at 50 ° C. to obtain a graphene laminate temporarily fixed to the slightly adhesive tape.

Doping gold chloride to the graphene laminate temporarily fixed to the slightly adhesive tape is performed by immersing the graphene laminate in an isopropyl alcohol solution of gold (III) chloride for 5 minutes and removing the excess solution with compressed air. It was. As the gold (III) chloride, an isopropyl alcohol solution having a concentration of 0.2, 2, 5, 10 mmol / L was used, and the sheet resistance before and after doping was measured.
The results are shown in the table below.

  As can be seen from the above table, according to the present invention, doping can be performed while the graphene film is temporarily fixed to the slightly adhesive sheet, and electrical conductivity can be enhanced.

Example 3
In this example, a dopant fixed layer was formed on the graphene laminate produced by the same method as in Example 2 to suppress discoloration.

  A graphene film temporarily fixed on a slightly adhesive tape is doped with gold chloride, and then with a petri dish containing trichloro (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) silane (hereinafter referred to as chlorosilane) The gas phase adsorption treatment was performed for 1 hour in a vacuum desiccator. Similarly, 10-carboxy-1-decanethiol (hereinafter referred to as acetate thiol) diluted with isopropyl alcohol to a concentration of 2 mmol / L was adsorbed on a graphene film sample doped with gold chloride by spin coating. As a comparative sample, a sample in which no dopant fixed layer was formed was also prepared. The following table shows the results of evaluating the sheet resistance of these samples before doping with gold chloride, and the sheet resistance and color after the doping and dopant fixed layer forming treatment. The evaluation after the formation of the dopant fixed layer is after one month.

  As can be seen from the table above, according to the present invention, it has been found that the surface treatment technique suppresses the color change while maintaining the doping effect as compared with the conventional technique.

  According to the present invention, it is possible to supply a graphene laminated body whose electrical conductivity is increased by doping and to maintain the effect thereof. Therefore, a transparent conductive film for touch panel use, a semiconductor device such as a transistor or an integrated circuit, or an electronic device It is a very important technology that can be used for all devices, equipment, and applied products that use graphene such as transparent electrodes, electrochemical electrodes, and biodevices that require a large area.

DESCRIPTION OF SYMBOLS 100: Base material for film-forming 101: Graphene film 201: Slightly adhesive sheet 201: Release liner 301: Bubble 601: Doping layer 701: Dopant fixed layer 801: Transfer material 901: Plasma generation chamber 902: Rectangular microwave conduction with slot Wave tube 903: Quartz window for introducing microwaves 904: Metal support member for supporting the quartz window 905: Metal base material 906: Electrode for base material heating heating 907: Power source for current heating 908: Exhaust pipe 909: Plasma Processing gas introduction pipe 910: Processing vessel 911: Current introduction terminal

Claims (9)

A method for producing a graphene laminate, comprising: temporarily fixing a graphene film on a slightly adhesive sheet; and then treating the graphene film with an isopropyl alcohol solution of gold (III) chloride . The method for producing a graphene laminate according to claim 1, further comprising adsorbing a self-assembled monolayer. 3. The method for producing a graphene laminate according to claim 1, wherein after the graphene film is patterned, the graphene film is temporarily fixed on the slightly adhesive sheet. 3. The method for producing a graphene laminate according to claim 1, wherein the graphene film is patterned after temporarily fixing the graphene film on the slightly adhesive sheet. A slightly adhesive sheet,
A graphene film temporarily fixed to the slightly adhesive sheet;
A layer in which the graphene film is doped with a dopant;
A graphene laminate comprising: The graphene laminate according to claim 5 , further comprising a dopant fixed layer made of a material that forms a self-assembled monolayer on the doped layer. The graphene laminate according to claim 5 or 6 , wherein the graphene film is patterned. The surface of the graphene laminate according to any one of claims 5 to 7 , wherein the doped graphene layer or the dopant fixed layer is formed, is bonded to a transparent transfer material, and then the slightly adhesive sheet A transparent electrode formed by doping is formed on the transfer material by removing the electrode. A transparent electrode formed by transferring the graphene laminate according to any one of claims 5 to 7 to a transparent transfer material excluding the slightly adhesive sheet, wherein the transparent electrode is formed between the transfer material and the graphene film. A transparent electrode characterized by having a graphene layer doped with.

Images