Transfer method of three-dimensional graphene crystal film

Abstract

The invention discloses a transfer method of a three-dimensional graphene crystal film, and relates to the technical field of graphene materials, clean, green, complete and substrate-selectable transfer of the three-dimensional graphene crystal film can be realized, and the principle is that after ultrapure water is immersed in holes of the three-dimensional graphene crystal film, low-temperature phase change of the ultrapure water is realized through low-temperature freezing, and the three-dimensional graphene crystal film is obtained. And constructing a composite material of the ice / three-dimensional graphene crystal film, completing stripping of the growth substrate, transferring the growth substrate to the surface of a target substrate, and finally removing water molecules through heating to complete the transfer process.

Description

Technical Field

[0001] The invention relates to the technical field of graphene materials, and in particular to a method for transferring a three-dimensional graphene crystal film. Background Art

[0002] As a typical two-dimensional material, graphene has a high specific surface area, excellent electron mobility, good mechanical strength and high stability, which has set off a research boom in two-dimensional materials. At present, the common methods for preparing graphene are chemical vapor deposition, redox method, mechanical exfoliation, silicon carbide pyrolysis method and laser induction method. Among them, the laser induction method is a method that can directly grow graphene in situ on the surface of a carbon-containing substrate under an air atmosphere. The graphene prepared by this method has a three-dimensional interconnected network structure, and the three-dimensionally grown three-dimensional graphene crystal film also avoids the layered stacking problem of traditional graphene. At present, three-dimensional graphene crystal films have been used in fields such as supercapacitors and sensors.

[0003] In order to further expand the application of three-dimensional graphene crystal films, it is necessary to adapt suitable substrates for different application scenarios, so the transfer of three-dimensional graphene crystal films is particularly important. The current transfer methods include polydimethylsiloxane (PDMS) transfer method, low-temperature assisted transfer method and mechanical pressing method. Among them, the PDMS transfer method and low-temperature assisted transfer method use PDMS or gel as the transfer medium, and the transfer process is achieved by impregnating the transfer medium into the holes of the three-dimensional graphene crystal film and then solidifying it. This process has the problem of transfer medium residue causing the three-dimensional holes of graphene to be blocked and the target substrate cannot be selected; while the mechanical pressing method is to achieve the bonding of graphene and the transfer substrate through external pressure. The problem with this process is that the three-dimensional structure of graphene will collapse under the action of external force. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide a method for transferring a three-dimensional graphene crystal film, which can realize the clean, green, complete and substrate-selective transfer of the three-dimensional graphene crystal film. The principle is that after ultrapure water is immersed in the holes of the three-dimensional graphene crystal film, the low-temperature phase change of the ultrapure water is realized through low-temperature freezing, and a composite material of ice / three-dimensional graphene crystal film is constructed. The growth substrate is peeled off and transferred to the target substrate surface, and finally the water molecules are removed by heating to complete the transfer process.

[0005] The technical problem to be solved by the present invention is achieved by adopting the following technical solutions:

[0006] A method for transferring a three-dimensional graphene crystal film comprises the following steps:

[0007] Step S1, in-situ growing a three-dimensional graphene crystal film on the surface of a carbon-containing substrate by laser irradiation to obtain a three-dimensional graphene crystal film / carbon-containing substrate composite material;

[0008] Step S2, adding ultrapure water to the surface of the three-dimensional graphene crystal film of the composite material obtained in step S1 until the surface is completely covered by the ultrapure water, thereby obtaining a water / three-dimensional graphene crystal film / carbon-containing substrate composite material;

[0009] Step S3, covering the surface of the water layer of the composite material obtained in step S2 with a protective layer to obtain a composite material of protective layer / water / three-dimensional graphene crystal film / carbon-containing substrate;

[0010] Step S4, placing the composite material obtained in step S3 into a freezer to obtain a composite material of protective layer / ice / three-dimensional graphene crystal film / carbon-containing substrate;

[0011] Step S5, peeling off the carbon-containing substrate in the composite material obtained in step S4 to obtain a protective layer / ice / three-dimensional graphene crystal film composite material;

[0012] Step S6, placing the composite material obtained in step S5 on a target substrate coated with an adhesive layer to obtain a composite material of protective layer / ice / three-dimensional graphene crystal film / adhesive layer / target substrate;

[0013] Step S7, taking the composite material obtained in step S6 out of the freezer and putting it into an oven to obtain a composite material of protective layer / three-dimensional graphene crystal film / adhesive layer / target substrate;

[0014] Step S8, peeling off the protective layer in the composite material obtained in step S7, obtaining a three-dimensional graphene crystal film / adhesive layer / target substrate composite material, and completing the transfer of the three-dimensional graphene crystal film.

[0015] The beneficial effects of the present invention are:

[0016] 1) The present invention uses ultrapure water as the transfer medium, which has the advantages of being clean, environmentally friendly and easily available;

[0017] 2) The present invention realizes the transfer of three-dimensional graphene crystal film only by using the phase change of water, and the process is simple and easy to operate;

[0018] 3) The present invention does not have any transfer medium residue before and after the transfer, thus meeting the cleanliness requirements of the three-dimensional graphene crystal film transfer;

[0019] 4) The target substrate in the present invention can be freely selected to meet the needs of different usage scenarios;

[0020] 5) The present invention has low requirements on equipment and can lower the application threshold of three-dimensional graphene crystal film by transferring over a large area, thus generating greater economic and social benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1It is a schematic diagram of the process of transferring the three-dimensional graphene crystal film in the present invention;

[0022] Figure 2 This is a scanning electron microscope image of the three-dimensional graphene crystal film prepared in Example 1;

[0023] Figure 3 This is a scanning electron microscope image of the in-situ growth of the three-dimensional graphene crystal film prepared in Example 1 on the polyimide surface;

[0024] Figure 4 This is a scanning electron microscope image of the three-dimensional graphene crystal film prepared in Example 1 transferred to the polyethylene terephthalate (PET) surface;

[0025] Figure 5 This is the Raman spectrum of the three-dimensional graphene crystal film prepared in Example 1 transferred to the PET surface. DETAILED DESCRIPTION

[0026] In order to make the technical means, creative features, objectives and effects achieved by the present invention easy to understand, the present invention is further described below in conjunction with specific embodiments and diagrams.

[0027] like Figure 1 As shown, the present invention provides a method for transferring a three-dimensional graphene crystal film, comprising the following steps:

[0028] Step S1, in-situ growing a three-dimensional graphene crystal film on the surface of a carbon-containing substrate by laser irradiation to obtain a three-dimensional graphene crystal film / carbon-containing substrate composite material;

[0029] Step S2, adding ultrapure water to the surface of the three-dimensional graphene crystal film of the composite material obtained in step S1 until the surface is completely covered by the ultrapure water, thereby obtaining a water / three-dimensional graphene crystal film / carbon-containing substrate composite material;

[0030] Step S3, covering the surface of the water layer of the composite material obtained in step S2 with a protective layer to obtain a composite material of protective layer / water / three-dimensional graphene crystal film / carbon-containing substrate;

[0031] Step S4, placing the composite material obtained in step S3 into a freezer to obtain a composite material of protective layer / ice / three-dimensional graphene crystal film / carbon-containing substrate;

[0032] Step S5, peeling off the carbon-containing substrate in the composite material obtained in step S4 to obtain a protective layer / ice / three-dimensional graphene crystal film composite material;

[0033] Step S6, placing the composite material obtained in step S5 on a target substrate coated with an adhesive layer to obtain a composite material of protective layer / ice / three-dimensional graphene crystal film / adhesive layer / target substrate;

[0034] Step S7, taking the composite material obtained in step S6 out of the freezer and putting it into an oven to obtain a composite material of protective layer / three-dimensional graphene crystal film / adhesive layer / target substrate;

[0035] Step S8, peeling off the protective layer in the composite material obtained in step S7, obtaining a three-dimensional graphene crystal film / adhesive layer / target substrate composite material, and completing the transfer of the three-dimensional graphene crystal film.

[0036] Furthermore, the carbon-containing substrate is selected from one or more combinations of carbon chain polymers, heterochain polymers, alicyclic polymers, aromatic polymers, fruits and vegetables, and animal fur.

[0037] Furthermore, the three-dimensional graphene crystal film is selected from a combination of one or more of a three-dimensional few-layer graphene crystal film, a three-dimensional multi-layer graphene crystal film, a three-dimensional single-crystal graphene crystal film, and a three-dimensional polycrystalline graphene crystal film.

[0038] Furthermore, the protective layer is pretreated before covering the water layer. The pretreatment includes sandblasting, grinding, laser treatment, plasma treatment, pickling, chemical treatment, etc., in order to increase the surface roughness.

[0039] Furthermore, bubbles should be avoided at the interface between the protective layer and the water layer. The residual bubbles will cause holes to be generated during the phase change of water, thereby endangering the integrity of the graphene film transfer.

[0040] Furthermore, the protective layer is selected from a glass sheet, a metal sheet, a metal oxide sheet, a plastic sheet or a sheet material with a rigid structure.

[0041] Furthermore, the temperature of the freezer is -200 to 0° C., and the composite material obtained in step S3 is placed in the freezer for 1 to 24 hours.

[0042] Furthermore, the bonding layer is coated by one or more of spin coating, roll coating, screen printing and spray coating.

[0043] Furthermore, the adhesive layer is selected from one or more combinations of acrylic adhesive, polyvinyl alcohol adhesive, epoxy resin adhesive, polyvinyl acetate adhesive, phenolic resin adhesive, polyurethane adhesive, chloroprene rubber adhesive, and acrylate adhesive.

[0044] Furthermore, the target substrate is selected from one or more combinations of metals, metal oxides, polymers, semiconductors, glass, cloth, silicone, plastics, and wood products.

[0045] Furthermore, the temperature of the oven is 20 to 120° C., and the composite material obtained in step S6 is placed in the oven for 1 to 24 hours.

[0046] Example 1

[0047] In this embodiment, a polyimide film is selected as the carbon-containing substrate, glass is selected as the protective layer, acrylic adhesive is selected as the bonding layer, and PET is selected as the target substrate.

[0048] Step S1, in-situ growing a three-dimensional graphene crystal film on the surface of a polyimide film by laser irradiation to obtain a three-dimensional graphene crystal film / polyimide composite material;

[0049] Step S2, adding ultrapure water to the surface of the three-dimensional graphene crystal film of the composite material obtained in step S1 until the surface is completely covered by the ultrapure water, thereby obtaining a water / three-dimensional graphene crystal film / polyimide composite material;

[0050] Step S3, covering the surface of the water layer of the composite material obtained in step S2 with frosted glass, avoiding bubbles at the interface between the glass and the water layer, and obtaining a glass / water / three-dimensional graphene crystal film / polyimide composite material;

[0051] Step S4, placing the composite material obtained in step S3 into a freezer and storing it at -20°C for 12 hours to obtain a glass / ice / three-dimensional graphene crystal film / polyimide composite material;

[0052] Step S5, peeling off the polyimide in the composite material obtained in step S4 to obtain a glass / ice / three-dimensional graphene crystal film composite material;

[0053] Step S6, placing the composite material obtained in step S5 on PET spin-coated with acrylic acid to obtain a glass / ice / three-dimensional graphene crystal film / acrylic acid / PET composite material;

[0054] Step S7, taking the composite material obtained in step S6 out of the freezer and putting it into an oven, heating it at 60° C. for 24 hours to obtain a glass / three-dimensional graphene crystal film / acrylic acid / PET composite material;

[0055] Step S8, peeling off the glass in the composite material obtained in step S7, obtaining a three-dimensional graphene crystal film / acrylic acid / PET composite material, and completing the transfer of the three-dimensional graphene crystal film.

[0056] Figure 2 This is a scanning electron microscope image of the three-dimensional graphene crystal film prepared in this embodiment. Figure 2 It can be seen that graphene presents a three-dimensional interconnected network structure.

[0057] Figure 3 This is a scanning electron microscope image of the three-dimensional graphene crystal film prepared in this embodiment grown in situ on the polyimide surface. Figure 3It can be seen that the three-dimensional graphene crystal film and the polyimide substrate are clearly delaminated, and the three-dimensional graphene crystal film has a thickness of micrometer scale.

[0058] Figure 4 This is a scanning electron microscope image of the three-dimensional graphene crystal film prepared in this embodiment transferred to the PET surface. Figure 4 It can be seen that the three-dimensional graphene crystal film basically maintains the morphology and structure before transfer, and is clearly stratified from the PET substrate.

[0059] Figure 5 This is the Raman spectrum of the three-dimensional graphene crystal film prepared in this example transferred to the PET surface. As can be seen from Figure 5, the 2D peak of graphene is sharp and obvious, indicating that the quality of graphene formation is high.

[0060] Example 2

[0061] In this embodiment, phenolic resin is selected as the carbon-containing substrate, and the other conditions are the same as those in Embodiment 1 to obtain a three-dimensional graphene crystal film / acrylic acid / PET composite material.

[0062] Example 3

[0063] In this embodiment, a copper sheet is selected as the protective layer, and the other conditions are the same as those in Embodiment 1 to obtain a three-dimensional graphene crystal film / acrylic acid / PET composite material.

[0064] Example 4

[0065] In this embodiment, the freezing temperature is -40°C, the holding time is 6 hours, and the other conditions are the same as those in Embodiment 1, to obtain a three-dimensional graphene crystal film / acrylic acid / PET composite material.

[0066] Example 5

[0067] In this embodiment, epoxy resin adhesive is selected as the bonding layer, and the other conditions are the same as those in Embodiment 1 to obtain a three-dimensional graphene crystal film / epoxy resin / PET composite material.

[0068] Example 6

[0069] In this embodiment, copper foil is selected as the target substrate, and the other conditions are the same as those in Embodiment 1 to obtain a three-dimensional graphene crystal film / acrylic acid / copper foil composite material.

[0070] Example 7

[0071] In this embodiment, the heating temperature is 120° C., the holding time is 6 h, and the other conditions are the same as those in Embodiment 1, to obtain a three-dimensional graphene crystal film / acrylic acid / PET composite material.

[0072] The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention. It should be understood by those skilled in the art that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention to be protected. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. A method for transferring a three-dimensional graphene crystal film, characterized in that: The following steps are involved: Step S1, in-situ growing a three-dimensional graphene crystal film on the surface of a carbon-containing substrate by laser irradiation to obtain a three-dimensional graphene crystal film / carbon-containing substrate composite material; Step S2, adding ultrapure water to the surface of the three-dimensional graphene crystal film of the composite material obtained in step S1 until the surface is completely covered by the ultrapure water, thereby obtaining a water / three-dimensional graphene crystal film / carbon-containing substrate composite material; Step S3, covering the surface of the water layer of the composite material obtained in step S2 with a protective layer to obtain a composite material of protective layer / water / three-dimensional graphene crystal film / carbon-containing substrate; Step S4, placing the composite material obtained in step S3 into a freezer to obtain a composite material of protective layer / ice / three-dimensional graphene crystal film / carbon-containing substrate; Step S5, peeling off the carbon-containing substrate in the composite material obtained in step S4 to obtain a protective layer / ice / three-dimensional graphene crystal film composite material; Step S6, placing the composite material obtained in step S5 on a target substrate coated with an adhesive layer to obtain a composite material of protective layer / ice / three-dimensional graphene crystal film / adhesive layer / target substrate; Step S7, taking the composite material obtained in step S6 out of the freezer and putting it into an oven to obtain a composite material of protective layer / three-dimensional graphene crystal film / adhesive layer / target substrate; Step S8, peeling off the protective layer in the composite material obtained in step S7, obtaining a three-dimensional graphene crystal film / adhesive layer / target substrate composite material, and completing the transfer of the three-dimensional graphene crystal film.

2. The method for transferring a three-dimensional graphene crystal film according to claim 1, characterized in that: The carbon-containing substrate is selected from one or more combinations of carbon chain polymers, heterochain polymers, alicyclic polymers, aromatic polymers, fruits and vegetables, and animal fur.

3. The method for transferring a three-dimensional graphene crystal film according to claim 1, characterized in that: The three-dimensional graphene crystal film is selected from a combination of one or more of a three-dimensional few-layer graphene crystal film, a three-dimensional multi-layer graphene crystal film, a three-dimensional single-crystal graphene crystal film, and a three-dimensional polycrystalline graphene crystal film.

4. The method for transferring a three-dimensional graphene crystal film according to claim 1, characterized in that: The protective layer must be pretreated before covering the water layer. The pretreatment includes sandblasting, grinding, laser treatment, plasma treatment, pickling, and chemical treatment. Bubbles should be avoided at the interface between the protective layer and the water layer.

5. The method for transferring a three-dimensional graphene crystal film according to claim 1, characterized in that: The protective layer is selected from a glass sheet, a metal sheet, a metal oxide sheet, a plastic sheet or a sheet material with a rigid structure.

6. The method for transferring a three-dimensional graphene crystal film according to claim 1, characterized in that: The temperature of the freezer is -200 to 0° C., and the composite material obtained in step S3 is placed in the freezer for 1 to 24 hours.

7. The method for transferring a three-dimensional graphene crystal film according to claim 1, characterized in that: The bonding layer is coated in a manner selected from one or more combinations of spin coating, roll coating, screen printing, and spray coating.

8. The method for transferring a three-dimensional graphene crystal film according to claim 1, characterized in that: The adhesive layer is selected from one or more combinations of acrylic adhesive, polyvinyl alcohol adhesive, epoxy resin adhesive, polyvinyl acetate adhesive, phenolic resin adhesive, polyurethane adhesive, chloroprene rubber adhesive, and acrylate adhesive.

9. The method for transferring a three-dimensional graphene crystal film according to claim 1, characterized in that: The target substrate is selected from one or more combinations of metals, metal oxides, polymers, semiconductors, glass, cloth, silica gel, plastics, and wood products.

10. The method for transferring a three-dimensional graphene crystal film according to claim 1, characterized in that: The temperature of the oven is 20-120° C., and the composite material obtained in step S6 is placed in the oven for 1-24 hours.

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