TWI645969B - Multilayer graphene soft board transfer method and graphene soft board group - Google Patents

Abstract

A multi-layer graphene soft board transfer method and a graphene soft board group. The multi-layer graphene flexible board transfer method comprises the step A: providing a transfer unit and a soft board unit, the transfer unit comprising a metal substrate mainly composed of a transition metal, and a layer disposed on the metal substrate a graphene film having a plurality of graphene layers stacked on each other on the metal substrate, the soft board unit comprising a flexible substrate, and a bonding layer disposed on the flexible substrate, the bonding layer and The metal substrate has an adhesion force of 0.2 kgf/cm or more; Step B: bonding the adhesion layer to the graphene film; Step C: reducing the metal substrate after oxidation; and Step D: peeling off the metal substrate. The present invention can completely transfer the graphene film from the metal substrate to the flexible board unit.

Description

Multilayer graphene soft board transfer method and graphene soft board group

The invention relates to a method and a finished product for graphene and soft board, in particular to a multi-layer graphene soft board transfer method and a graphene soft board group.

Graphene is a two-dimensional material composed of carbon atoms. Because of its excellent electrical, mechanical, thermal and optical properties, the preparation of graphene and its related applications have become a research hotspot.

There are quite a number of methods for preparing graphene, including mechanical stripping, epitaxial growth, chemical vapor deposition, and the like. The mechanical peeling method is a method of simply removing the graphite material by mechanical force to obtain graphene, and the method is relatively simple but not suitable for mass production. Although the epitaxial growth method can produce graphene of high quality, it also has disadvantages that are not suitable for mass production. The chemical vapor deposition method is a method in which a carbon source is first formed into a gas and deposited on a metal substrate of a transition metal such as nickel or copper to form graphene. Since the chemical vapor deposition method has the advantages of easy control of the uniformity and thickness of the produced graphene, it is currently a method mainly used for preparing graphene. Based on the characteristics of the chemical vapor deposition method, the obtained graphene is formed on the metal substrate described above, and therefore it is necessary to further apply a graphene film composed of a single layer or a plurality of graphene layers to the through-transfer method. Various flexible substrates are used to further fabricate various components.

At present, the conventional graphene transfer method can be classified into a wet transfer method and a dry transfer method. In the wet transfer method, after the metal substrate is etched, the remaining graphene film is supported by the polymer film and transferred to a flexible substrate. Since the process requires the use of an etchant to remove the metal substrate, in addition to the greater environmental burden, the metal substrate cannot be reused and additional cost is incurred. In addition, after the transfer by the wet transfer method, there is also a problem of polymer residual glue, and problems such as cracking and wrinkling of the graphene film.

In the dry transfer method, a layer of a polymer material is provided on a flexible substrate, and the graphene film is bonded to the adhesive layer and then hot pressed, and then mechanically separated from the metal substrate. The dry transfer method solves the problem of cost loss and environmental protection of the metal substrate, and can be applied to the roll-to-roll process, and has a quantitative production prospect.

At present, in the dry transfer method, when a graphene film composed of a multilayer graphene is transferred, the graphene film is not well transferred from a metal substrate to a flexible substrate. The graphene film after transfer tends to be damaged and has poor electrical properties, which is not conducive to commercial applications and needs to be improved.

A first object of the present invention is to provide a multilayer graphene flexible board transfer method capable of overcoming at least one of the disadvantages of the prior art.

The multilayer graphene soft board transfer method comprises the steps of: providing a transfer unit and a soft plate unit, the transfer unit comprising a metal substrate mainly composed of a transition metal, and a layer disposed on the metal substrate a graphene film having a plurality of graphene layers stacked on each other on the metal substrate, the soft board unit comprising a flexible substrate, and a bonding layer disposed on the flexible substrate, the bonding layer The bonding force with the metal substrate is 0.2 kgf/cm or more; Step B: bonding the bonding layer and the graphene film; Step C: oxidizing the metal substrate, and forming the metal substrate and the After the metal oxide between the graphene films, the metal oxide is reduced to a metal; and step D: the metal substrate is peeled off.

The present invention mainly improves the adhesion between the underlayer and the metal substrate, and reduces the force between the graphene film and the metal substrate through the step C, so that the graphene film can be smoothly transferred to On the transfer unit. Therefore, if the adhesion between the adhesive layer and the metal substrate is less than 0.2 kgf/cm, or the metal substrate is not oxidized and then reduced, the graphene film cannot be completely transferred to the flexible substrate, so that the graphene The film is damaged after transfer, and does not have continuous electrical conductivity and has no commercial use value.

The invention limits the adhesion between the bonding layer and the metal substrate, and does not limit the adhesion between the bonding layer and the graphene film, mainly because the thickness of the graphene film is too thin, and the bonding layer is measured at the present time point. The adhesion between graphene films is difficult. In addition, since the thickness of the graphene film is relatively thin, the bonding force of the bonding layer can penetrate the graphene film to act on the metal substrate. In other words, the stronger the force (adjacent force) between the adhesive layer and the metal substrate, the better the effect of the adhesive layer penetrating the graphene film, and the more effective the effect on the graphene layer, resulting in better Adhesion effect. Therefore, the transfer effect is ensured by limiting the adhesion between the adhesive layer and the metal substrate, and the reliability and reliability can be achieved while taking into consideration the operability in which control can be performed.

The numbers A to D of the foregoing steps are used to refer to the steps, and are not intended to limit the order of the steps. For example, in the implementation of the present invention, the step B and the step C can also be reversed, that is, the step C is first performed to oxidize and then reduced, and then the step B is applied to the subsequent layer and the graphene film. Wherein, if only the metal substrate is oxidized without reducing the oxidized metal oxide, the purpose of weakening the force between the graphene film and the metal substrate may be achieved, but the graphite after transfer The olefin film will still have electrical properties that are damaged without continuous conduction; if it is oxidized and subsequently reduced by electrolysis, the oxide layer can be removed and the upper graphene film can be released, and electrical conductivity with continuous conductivity can be prepared. Finished product.

Preferably, the metal substrate is formed into an oxide by placing the transfer unit or the transfer unit bonded to the flexible sheet unit in a solution having an oxidizing substance such as an alkali metal hydroxide, for example, Sodium hydroxide, potassium hydroxide, etc.; and the preferred method of reducing the metal oxide is to provide an electric current, but in practice, it can be re-soaked in a solution having the ability to reduce substances. As described above, if step C is performed first and then step B is performed, the transfer unit after the redox treatment may be dried and then attached.

The material of the flexible substrate can be selected from polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), and polycarbonate. Polycarbonate (PC), polysulfone (PSU), polyethersulfone (PES), and any combination of the foregoing.

The adhesive layer is formed as a colloid. The adhesive can include epoxy resin, polyvinyl alcohol (PVA), polymethylmethacrylate (PMMA), ethylene vinyl acetate (EVA), polyimine. , or any combination of the foregoing materials.

Preferably, the colloid is a thermosetting polyimine and is mainly composed of an epoxy resin and a polyimide. The epoxy resin is preferably from 10 parts by weight to 40 parts by weight based on 100 parts by total of the total weight of the polyimine.

The polyimine is a polyimine comprising a structure of the formula (1): .. formula (1);

Where i is a positive integer of 200 to 1000, and j is a positive integer of 1 to 200;

R ^{1 is} selected from the formulae (2) to (9): Formula (2); Formula (3); Formula (4); ....... (5); ....... (6); ......... Formula (7); ... of formula (8); . (9);

X ^{1 is} selected from the group consisting of -O-, -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -CO- and -SO ₂ -;

R ^{2 is} selected from the formulae (10) to (12): Formula (10); ..... equation (11); Formula (12);

Wherein X ^{2 is} selected from the group consisting of -O-, -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -CO-, -SO ₂ -, -S-, , and ;

R ⁴ is -OH or -COOH.

R ³ is: ;

k is an integer from 0 to 20.

The multi-layer graphene soft plate transfer method has the effect of completely transferring the graphene film composed of a plurality of graphene layers onto the soft plate unit, and manufacturing a multilayer graphene and having continuous conductivity. Electrical graphene soft board set.

A second object of the present invention is to provide a graphene soft board set that overcomes at least one of the disadvantages of the prior art.

The graphene soft board group comprises a flexible substrate, a layer of an adhesive layer, and a layer of graphene film. The adhesive layer is disposed on the flexible substrate. The graphene film is disposed on the adhesive layer, has electrical continuity of continuity, and includes a plurality of graphene layers stacked on each other.

The graphene soft board group has the effect of having a plurality of layers of graphene layers having electrical continuity of continuous conductivity, which has commercial application value and can promote industrial development.

"Embodiment 1"

Referring to Figures 1 through 4, an embodiment 1 of the present invention comprises a preparation step S1, a bonding step S2, a redox step S3, and a stripping step S4.

<Preparation step S1>

A transfer unit 1, a soft board unit 2, and a roll-to-roll apparatus 3 are provided.

The transfer unit 1 includes a metal substrate 11 mainly composed of copper and having a foil shape, and a graphene film 12 provided on the metal substrate 11. The graphene film 12 has a plurality of graphene layers 121 stacked on each other on the metal substrate 11. The flexible board unit 2 includes a flexible substrate 21 and a bonding layer 22 disposed on the flexible substrate 21. The adhesion of the adhesive layer 22 to the metal substrate 11 was measured to be 0.25 kgf/cm. Next, a method of preparing the transfer unit 1 and the flexible sheet unit 2, a configuration of the roll-to-roll apparatus 3, and a method of testing the adhesion force of the adhesive layer 22 and the metal substrate 11 will be described.

※Transfer unit preparation ※

A copper foil having a thickness of 25 μm was prepared as the metal substrate 11. The metal substrate 11 was placed in a reaction chamber prepared for chemical vapor deposition, and the temperature was raised to 1030 ° C to introduce a reaction gas. The flow rate of the reaction gas was 800 sccm of argon, 10 sccm of hydrogen, and 4.5 sccm of methane. The reaction was maintained at 760 Torr and the reaction time was 20 minutes. After the completion of the reaction, argon gas was separately introduced, and the temperature was gradually lowered to room temperature in 40 minutes to obtain the transfer unit 1 including the graphene film 12 and the metal substrate 11.

※Soft board unit preparation ※

100 g of polyimine colloid was taken and mixed with 5 g of epoxy resin to form a colloid. The polyimine colloid includes a polyimine having a solid content of 50 g, and the preparation method of the polyimine is described later. According to the foregoing usage amount, the epoxy resin is 10 parts by weight (5 g / 50 g × 100% = 10%) based on 100 parts by weight of the total weight of the polyimine, and is purchased from South Asia Plastics Co., Ltd., model number 170 . The adhesive was applied to a flexible substrate 21 having a thickness of 25 μm and made of polyimine, and soft baked at 90 ° C to cause the subsequent colloid to become the adhesive layer 22 and the flexible sheet unit 2 was obtained.

※Polyimine synthesis ※

60 mmol of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (Formula I) with 10 mmol of 1,3-bis(3-aminopropyl)- 1,1,3,3-Tetramethyldioxane (Formula II) was added to 400 g of NMP solvent and stirred to dissolve. Next, 30 mM of bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (formula III) and 40 mM of bis (3,4-dicarboxyl) were added. Phenyl)ether dianhydride (formula IV), after stirring for 4 hours, was added to 80 g of xylene to raise the temperature to 180 ° C and stirred for 3 hours. After cooling, the polyimine was obtained. Formula Ⅰ; ... of formula Ⅱ; ...... Ⅲ formula; of formula IV;

※Volume-to-roll equipment ※

The roll-to-roll apparatus 3 includes a laminating device 31 and a stripping device 32. The bonding device 31 includes two hot pressing rollers 311 that are side by side but spaced apart from each other. The stripping device 32 includes two auxiliary rollers 321 arranged side by side but spaced apart from each other, and two take-up rollers 322 located downstream of the auxiliary rollers 321 and spaced apart from each other by a large distance. Since the technique of controlling the pressure, the temperature, and the number of revolutions of the rolls of the bonding apparatus 31 and the peeling apparatus 32 is a conventional technique, the description thereof will be omitted.

※Continue force test ※

The colloid is applied to the flexible substrate 21, and the metal substrate 11 is bonded to the adhesive body by hot pressing. After the curing, the adhesive is used as the adhesive layer 22, and then cut into test pieces, and the metal is tested by a tensile machine. The adhesion of the substrate 11 to the adhesive layer 22. The test method is carried out according to IPC-TM-650, test method No. 2.4.9.

It should be noted that in the present embodiment 1, the present embodiment 1 is implemented in the roll-to-roll apparatus 3 in order to demonstrate that the present invention is applicable to the roll-to-roll apparatus 3 with the advantage of quantifiable production. In other embodiments of the present invention, it is also possible to apply and peel off in a mechanical or other manner, in which case the roll-to-roll device 3 need not be provided in the preparation step S1.

<Fitting step S2>

As shown in FIG. 3, a portion of the transfer unit 1 and a portion of the flexible panel unit 2 are first wound onto the bonding apparatus 31 to be fed. At the time of feeding, the graphene film 12 is fed in such a manner as to face the adhesive layer 22. Next, the transfer unit 1 and the flexible plate unit 2 are bonded together by the bonding apparatus 31 so that the graphene film 12 contacts the adhesive layer 22. The surface temperature of the hot pressing roller 311 is 100 ° C, and the pressure for the transfer unit 1 and the soft plate unit 2 is 2 kg/cm ² . After laminating, it was placed in an environment of 200 ° C for 1 hour, and the unattached portion was cut to obtain half of the finished product.

<Redox Step S3>

The semi-finished product is immersed in a sodium hydroxide aqueous solution having a concentration of 0.5 M to form the metal substrate 11 to form a metal oxide contacting the graphene film 12, and then a graphite electrode is inserted and electrically connected to the graphite electrode and the metal base. The material 11 is simultaneously applied with a voltage of +2 V to reduce the metal oxide to a metal to be desorbed from the graphene film 12. Since the metal substrate 11 is mainly composed of copper in the first embodiment, the metal oxide is copper oxide. The metal oxide is formed entirely between the graphene film 12 and the metal substrate 11 having a slightly reduced thickness after immersion.

<Peeling step S4>

The metal substrate 11 of the cut-off side of the cut product is torn apart, so that the metal substrate 11 can be separated separately, that is, the graphene film 12 is adhered to the back layer 22 to the metal substrate. 11 separation. Then, as shown in FIG. 4, the partially peeled semi-finished product is wound onto the stripping device 32, and the metal substrate 11 is opposed to the auxiliary roller 321 and the retracting roller 322. The graphene film 12 and the flexible plate unit 2 are continuously peeled off to obtain a separate metal substrate 11, and a graphene soft plate group 4 including the graphene film 12, the adhesive layer 22, and the flexible substrate 21. The roller of the peeling device 32 has a radius of 20 mm, a rotational speed of 2.4 mm/s, a peeling angle A1 of 90 degrees, and a tension of 0.19 N.

Next, the properties of the graphene soft board group 4 obtained by the use of Example 1 and the transfer effect were evaluated.

※Quality evaluation of finished products ※

Measurements were made with a four-point probe and a Hall gauge. In the measurement, the spatial coordinates of the graphene film 12 of the graphene soft plate group 4 relative to the flexible substrate 21 are first defined, and the graphene film 12 is divided into square blocks of different arrays, and the squares are respectively measured. The sheet resistance and carrier mobility of the block are electrically equivalent. If the sheet resistance difference of any two blocks in the square block is less than 15%, the sheet resistance uniformity is evaluated as Y. If the sheet resistance difference of any two blocks in the square block is greater than 15%, the sheet resistance is The uniformity was evaluated as N. If the square blocks have electrical conductivity, it is determined that the graphene film 12 has continuous electrical conductivity, and also represents that the graphene film 12 is completely transferred from the metal substrate 11 to the softness. Substrate 21. If one or more of the square blocks do not have electrical conductivity, it is determined that the graphene film 12 after transfer has cracks or holes, and does not have continuous electrical conductivity. The measurement results of the continuous conductivity are recorded in Table 1.

※Transfer effect evaluation ※

The PMMA material is applied onto the metal substrate 11 after peeling. At the time of coating, it is applied to the side of the metal substrate 11 where the graphene film 12 is provided. Then, the metal substrate is removed by an etching solution, and the residual graphene which may be adhered to the PMMA film is transferred to a SiO ₂ /Si substrate having a thickness of 300 nm, and the contrast formed by the reflected light of the SiO ₂ /Si substrate under an optical microscope is formed. To observe the distribution and amount of graphene fragments that may remain, and record the degree of residue in Table 1.

※Raman spectroscopy ※

The graphene soft plate group prepared in Example 1 was analyzed by a Raman spectrometer, and the analysis results are plotted in Fig. 5.

<<Examples 2 to 4>>

Embodiments 2 to 4 are similar to the embodiment 1, and the differences are as follows:

In Example 2, 100 g of the polyimine colloid (containing 50 g of polyimine) was mixed with 20 g of the epoxy resin to form the colloid. Therefore, the epoxy resin was 40 parts by weight based on 100 parts by weight of the total weight of the polyimine. The adhesion of the adhesive layer 22 formed of the aforementioned colloid to the metal substrate 11 was 0.4 kgf/cm.

The adhesive of Example 3 contained only an epoxy resin and an appropriate amount of solvent, and the adhesion of the adhesive layer 22 of Example 3 to the metal substrate 11 was 0.9 kgf/cm.

In Example 4, each 100 g of the gum system contained 30 g of an ethylene/vinyl acetate copolymer, and the balance of Xylene solvent. The ethylene/vinyl acetate copolymer was purchased from Aldrich and the product model number was 34052. The adhesion between the adhesive layer 22 formed of the aforementioned colloid and the metal substrate 11 was 0.7 kgf/cm.

The properties of the finished products and the transfer effects of Examples 2 to 4 were evaluated as described in Example 1 and recorded in Table 1.

Comparative Examples 1 to 4

Comparative Examples 1 to 4 are similar to the first embodiment except that:

In Comparative Example 1, 100 g of the polyimine colloid (containing 50 g of polyimine) was mixed with 2.5 g of the epoxy resin to form the colloid. Therefore, the epoxy resin was 5 parts by weight based on 100 parts by weight of the total weight of the polyimine. The adhesion between the adhesive layer 22 formed of the aforementioned colloid and the metal substrate 11 was 0.08 kgf/cm. Raman spectroscopy analysis was carried out for Comparative Example 1, and the results were plotted in Fig. 5.

In Comparative Example 2, 100 g of the polyimine colloid (containing 50 g of polyimine) was mixed with 25 g of the epoxy resin to form the colloid. Therefore, the epoxy resin was 50 parts by weight based on 100 parts by weight of the total weight of the polyimine. The adhesion of the adhesive layer 22 formed of the aforementioned colloid to the metal substrate 11 was 0.19 kgf/cm.

In Comparative Example 3, 30 g of the ethylene/vinyl acetate copolymer and the balance of the solvent were contained per 100 g of the colloid. The adhesion force of the adhesive layer 22 of Comparative Example 3 to the metal base material 11 was 0.7 kgf/cm, and the redox step S3 was also omitted in Comparative Example 3.

The graphene film 12 of Comparative Example 4 contains only one layer of the graphene layer 121, and the colloid of Comparative Example 4 contains only an epoxy resin and an appropriate amount of solvent different from that of Example 3, and Comparative Example 4 The adhesion of the adhesive layer 22 to the metal substrate 11 was 0.9 kgf/cm. Since the technique of adjusting the amount of use of the epoxy resin to change the adhesion force is a general knowledge, the description is omitted here.

The properties of the finished products and the transfer effects of Comparative Examples 1 to 4 were also evaluated and recorded in Table 1.  <TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> Table 1 </td><td> Substance Type </td><td> Parts by Weight </td><td> Then force kgf/cm </td><td> graphene layer number</td><td> redox step </td><td> continuous conduction </td><td> Resistance uniformity</td><td> graphene residue</td></tr><tr><td> Example 1 </td><td> PI </td><td> 100 </td> <td> 0.25 </td><td> Multilayer</td><td> Y </td><td> Y </td><td> Y </td><td> N </td></ Tr><tr><td> Epoxy </td><td> 10 </td></tr><tr><td> Example 2 </td><td> PI </td><td> 100 </td><td> 0.4 </td><td> multi-layer</td><td> Y </td><td> Y </td><td> Y </td><td> N </ Td></tr><tr><td> Epoxy </td><td> 40 </td></tr><tr><td> Example 3 </td><td> Epoxy </td> <td> 0.9 </td><td> Multilayer</td><td> Y </td><td> Y </td><td> Y </td><td> N </td></ Tr><tr><td> Example 4 </td><td> EVA </td><td> 0.7 </td><td> Multilayer</td><td> Y </td><td> Y </td><td> Y </td><td> N </td></tr><tr><td> Comparative Example 1 </td><td> PI </td><td> 100 </td><td> 0.08 </td><td> Multilayer</td><td> Y </td><td> N </td><td> N </td><td> Y </td></tr><tr><td> Epoxy </td><td> 5 </td></tr><tr><td> Comparative Example 2 < /td><td> PI </td><td> 100 </td><td> 0.19 </td><td> multilayer </td><td> Y </td><td> N </td ><td> N </td><td> Y </td></tr><tr><td> Epoxy </td><td> 50 </td></tr><tr><td> Comparative Example 3 </td><td> EVA </td><td> 0.7 </td><td> Multilayer</td><td> N </td><td> N </td><td> N </td><td> Y </td></tr><tr><td> Comparative Example 4 </td><td> Epoxy </td><td> 0.9 </td><td> Single Layer </td><td> Y </td><td> N </td><td> N </td><td> Y </td></tr></TBODY></TABLE>< TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> Symbol abbreviations description</td></tr><tr><td> EVA.... ....... </td><td> Ethylene/Vinyl Acetate Copolymer</td></tr><tr><td> Epoxy........ </td><td > Epoxy Resin</td></tr><tr><td> PI............... </td><td> Polyimine </td>< /tr></TBODY></TABLE>

Referring to Table 1, it can be found from the experimental results of Examples 1 to 4 that as long as the force between the adhesive layer 22 and the metal substrate 11 is 0.2 kgf/cm or more and is treated by the redox step S3, regardless of the formation of the adhesive layer The adhesive of 22 is a mixed glue, Epoxy glue or EVA glue, which can achieve excellent transfer effect and the finished product after transfer can have continuous electrical conductivity and resistance uniformity. That is, the graphene film 12 can be completely transferred from the metal substrate 11 to the soft plate unit 2, so that the graphene film 12 after transfer has continuous electrical conductivity and uniform electric resistance distribution.

From the comparison of Examples 1 to 4 with Comparative Examples 1 and 2, it was found that when the amount of the epoxy resin used was less than 10 parts by weight as shown in Comparative Example 1, or more than 40 parts by weight as shown in Comparative Example 2. The force between the adhesive layer 22 and the metal substrate 11 is less than 0.2 kgf/cm, and the transfer cannot be completely performed, that is, the graphene film 12 partially remains on the metal substrate 11, so that the transferred graphite The olefin film 12 does not have electrical continuity of continuous conductivity due to defects, and the resistance uniformity of the graphene film 12 is not good. Graphene FPC groups refer to FIG. 5, Example 1 was 4, the Raman shift at about 1375cm ^-1, 1625 cm ^-1, 2875cm ^-1, etc., and, ethylenically signal representative of the presence of peaks of graphite (at circle However, in the graphene soft board group 4 prepared in Comparative Example 1, since the graphene film 12 after the transfer was defective, only the background signal of the layer 22 was not at 1375 cm ^-1 , 1625 cm ^{- 1} , and the peak signal of graphene appears at 2875cm ^-1 and so on.

From the comparison of Examples 1 to 4 and Comparative Example 3, it was found that even if the force between the adhesive layer 22 and the metal substrate 11 is more than 0.2 kgf/cm, it is not possible without the oxidation reduction step S3. A complete transfer effect is obtained, so that the graphene film 12 after transfer does not have electrical continuity of continuous conductivity. From the comparison of Examples 1 to 4 and Comparative Example 4, it was found that the present invention is only applicable to multilayer graphene transfer, and if the present invention is applied to single-layer graphene transfer, the transferred graphene film 12 will also be It does not have the continuity of electrical continuity due to damage.

In summary, the multi-graphene layer 121 soft board transfer method has the effect of: by limiting the adhesion of the adhesive layer 22 to the metal substrate 11 by more than 0.2 kgf / cm, and the metal substrate 11 and graphene The contact surface contacted by the film 12 is oxidized and reduced, and the graphene film 12 composed of the multilayer graphene layer 121 can be completely transferred from the metal substrate 11 to the flexible plate unit 2, and the continuous conductive property is included. A graphene soft board group 4 of a multilayer graphene having electrical and resistance uniformity. The graphene soft board group 4 has an effect of promoting the industrial development by having a plurality of layers of the graphene layer 121 having electrical continuity of continuous conductivity.

The above is only the embodiment of the present invention, and the scope of the present invention is not limited thereto. The simple equivalent changes and modifications made by the content of the patent application and the contents of the patent specification of the present invention are still the patents of the present invention. Covered by the scope.

S1‧‧‧Preparation steps

S2‧‧‧ fitting steps

S3‧‧‧ Redox step

S4‧‧‧ peeling step

1‧‧‧Transfer unit

11‧‧‧Metal substrate

12‧‧‧Graphene film

121‧‧‧graphene layer

2‧‧‧Soft board unit

21‧‧‧Soft substrate

22‧‧‧Next layer

3‧‧‧Volume-to-roll equipment

31‧‧‧Fitting device

311‧‧‧Hot roller

32‧‧‧ peeling device

321‧‧‧Auxiliary wheel

322‧‧‧ Rolling roller

4‧‧‧ Graphene soft board group

A1‧‧‧ peeling angle

Other features and effects of the present invention will be apparent from the following description of the drawings, wherein: FIG. 1 is a flow chart illustrating a multi-layer graphene soft board transfer method and a graphene soft board set of the present invention. Embodiment 1 FIG. 2 is an incomplete cross-sectional view showing a transfer unit and a flexible board unit used in the embodiment 1. FIG. 3 is an incomplete cross-sectional view showing that the embodiment 1 utilizes a fitting. The device is attached to the transfer unit and the flexible plate unit; FIG. 4 is an incomplete cross-sectional view illustrating that the first embodiment uses a peeling device to peel off a metal substrate of the transfer unit; and FIG. 5 is a Raman spectrum. The results of Raman spectroscopy analysis of the first embodiment and a comparative example 1 are shown.

Claims (7)

A multi-layer graphene soft board transfer method comprising: Step A: providing a transfer unit and a soft board unit, the transfer unit comprising a metal substrate mainly composed of a transition metal, and a layer disposed on the metal substrate a graphene film having a plurality of graphene layers stacked on each other on the metal substrate, the soft board unit comprising a flexible substrate, and a bonding layer disposed on the flexible substrate, the bonding layer The bonding force with the metal substrate is 0.2 kgf/cm or more; Step B: bonding the bonding layer and the graphene film; Step C: oxidizing the metal substrate, and forming the metal substrate and the After the metal oxide between the graphene films, the metal oxide is reduced to a metal; and step D: the metal substrate is peeled off. The multi-layer graphene soft board transfer method according to claim 1, wherein in the step B, the metal substrate is oxidized by an alkali metal hydroxide solution, and an electric current is supplied to the metal substrate to make the metal. Oxide reduction. The method for transferring a multilayer graphene soft board according to claim 1, wherein the material of the flexible substrate is mainly polyethylene terephthalate, polyethylene naphthalate, polyimine, polycarbonate , polyfluorene, polyether oxime, or any combination of the foregoing. The multilayer graphene soft board transfer method according to any one of claims 1 to 3, wherein the adhesive layer is formed by a colloid comprising epoxy resin, polyvinyl alcohol, polymethyl methacrylate Ethylene/vinyl acetate copolymer, polyimine, or a combination of any of the foregoing. The multilayer graphene soft board transfer method according to any one of claims 1 to 3, wherein the adhesive layer is formed by a colloid which is a thermosetting polyimine and is mainly composed of an epoxy resin. It is composed of polyimine, and the epoxy resin is 10 parts by weight to 40 parts by weight based on 100 parts by weight of the total weight of the polyimine. The multilayer graphene soft board transfer method according to claim 5, wherein the polyimine is a polyimine comprising a structure of the formula (1): .. of formula (1); wherein, i is an integer of 200 to 1000, j is an integer of 1 to 200; R & lt Formula ¹ selected from (2) to (9); Formula (2); Formula (3); Formula (4); ........ Formula (5); ........ Formula (6); ..........式(7); ... of formula (8); .. Formula (9); X ^{1 is} selected from, -O-, -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -CO-, and -SO ₂ -; R ^{2 is} selected from the formulae (10) to (12); Formula (10); ...... (11); Formula (12); wherein X ^{2 is} selected from the group consisting of -O-, -CH ₂ -, -C(CF ₃ ) ₂ -, -C(CH ₃ ) ₂ -, -CO-, -SO ₂ -, -S -, , and Wherein R ⁴ is -OH or -COOH; R ³ is: ; k is an integer from 0 to 20. A graphene soft board group comprising: a flexible substrate; a layer of an adhesive layer disposed on the flexible substrate; and a layer of graphene film disposed on the adhesive layer, having continuous electrical conductivity and including a plurality of layers of each other Stacked graphene layers.