WO2014019387A1 - Method for transferring graphene film using electrostatic protection film as medium - Google Patents

Method for transferring graphene film using electrostatic protection film as medium Download PDF

Info

Publication number
WO2014019387A1
WO2014019387A1 PCT/CN2013/074835 CN2013074835W WO2014019387A1 WO 2014019387 A1 WO2014019387 A1 WO 2014019387A1 CN 2013074835 W CN2013074835 W CN 2013074835W WO 2014019387 A1 WO2014019387 A1 WO 2014019387A1
Authority
WO
WIPO (PCT)
Prior art keywords
graphene
film
protective film
electrostatic
electrostatic protective
Prior art date
Application number
PCT/CN2013/074835
Other languages
French (fr)
Chinese (zh)
Inventor
邱玉锐
谭化兵
王振中
Original Assignee
无锡格菲电子薄膜科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 无锡格菲电子薄膜科技有限公司 filed Critical 无锡格菲电子薄膜科技有限公司
Publication of WO2014019387A1 publication Critical patent/WO2014019387A1/en

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
    • B32B37/025—Transfer laminating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2313/00—Elements other than metals
    • B32B2313/04—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/10—Batteries

Definitions

  • the invention relates to a method for transferring a graphene film, in particular to a method for transferring a single layer or a plurality of graphene films by using an electrostatic protective film as a medium, and belongs to the field of conductive film materials.
  • Graphene film has high light transmittance and high carrier mobility, and has great application prospects in electronic devices and solar cells.
  • the primary problem is to prepare a large-sized graphene film and transfer it to a suitable target substrate.
  • the transfer technique of graphene film is a method of transferring graphene between different substrates, usually by transferring graphene from the growth liner to the target substrate.
  • the transfer technology of graphene film is a key factor restricting the development of graphene film.
  • the ideal transfer technology should have the following characteristics: 1) It can keep graphene intact and no damage during the transfer process; (2) It has no pollution to graphene (including doping); (3) The process is stable and reliable, and has strong applicability and stability.
  • the 'corrosive matrix method' is a widely used method for transferring graphene by using polymethyl methacrylate (PMMA). Transfer medium such as heat release tape, and the metal growth substrate is etched away with a chemical reagent to transfer the graphene to the target substrate.
  • PMMA polymethyl methacrylate
  • Polymethyl methacrylate (PMMA) transferred graphene has low electrical resistance and good stability, which is a commonly used method in scientific research; but PMMA The process of transferring graphene is complicated, the transfer period is long, it is difficult to operate, and it is easy to be broken, which has certain limitations in transferring large-area graphene.
  • the heat release tape transfer method realizes the transfer of large-area graphene to the flexible substrate.
  • the cost of the technology is high, and the adhesive on the tape is liable to remain on the surface of the graphene, which is difficult to clean and affects the quality of the graphene.
  • the non-transfer medium 'corrosion matrix method' utilizes the characteristics that the multi-layer graphene has higher strength than the single-layer graphene, and the method can be used to transfer the multilayer graphene. This method is simpler in process and has therefore been developed. This method is only suitable for small-area transfer, and the integrity and reliability of the transfer cannot be compared with the 'corrosion matrix method' with medium, so the method has great limitations in application.
  • the transfer technology of the existing graphene film the transferred graphene film has many problems such as residual impurities, high sheet resistance, poor stability and complicated process, so an efficient transfer of graphene film is developed.
  • the method is an urgent problem to be solved.
  • one of the objects of the present invention is to provide a transfer method which is low in cost, simple in operation, and capable of obtaining a high quality graphene film.
  • the method for transferring the graphene film according to the present invention is to use a static protective film as a medium to realize the transfer of graphene between different substrates by reasonably releasing static electricity.
  • a method for transferring a graphene film by using an electrostatic protective film as a medium wherein the graphene containing the growth substrate is bonded by electrostatic adsorption of the electrostatic protection film, and then the substrate is removed to obtain a single layer graphene /
  • the electrostatic protective film is combined, and finally the single-layer graphene/electrostatic protective film combination is attached to the target substrate, and the static electricity is removed to remove the electrostatic protective film to obtain a single-layer graphene film;
  • the method may also be a single layer of graphene / after obtaining a single layer graphene / electrostatic protective film combination
  • the electrostatic protective film combination is used instead of the electrostatic protective film, and the following two steps are repeated n-1 times on the new graphene containing the substrate: laminating the graphene/electrostatic protective film, removing the substrate; thereby preparing n
  • n is an integer of ⁇ 2, such as 2, 3, 4, 5, 6, and the like.
  • preparation 3 The method for layering the graphene film is: bonding the graphene containing the growth substrate by electrostatic adsorption of the electrostatic protection film, and then removing the substrate to obtain a graphene/electrostatic protective film combination; and then obtaining the graphene/
  • the electrostatic protective film assembly is bonded to another graphene containing the growth substrate, and the substrate is again removed to obtain a two-layer graphene/electrostatic protective film combination; then the obtained two-layer graphene /
  • the electrostatic protective film combination is bonded to another graphene containing the growth substrate, and the substrate is removed again to obtain a three-layer graphene/electrostatic protective film combination; finally, three layers of graphene/ After the electrostatic protection film assembly is bonded to the target substrate, the electrostatic protection film is removed to obtain a three-layer graphene film.
  • the electrostatic protective film has electrostatic adsorption ability and can be attached to a smooth surface of the object. It has stable chemical properties and high mechanical strength, so it can be used as a transfer medium for transferring graphene by the 'corrosive matrix method'.
  • the invention utilizes the electrostatic adsorption capacity of the electrostatic protection film to firmly adhere the electrostatic protection film to the surface of the graphene containing the growth substrate; and after removing the substrate, the static electricity of the electrostatic protection film of the graphene is adsorbed The adsorption capacity is unchanged, and the surface of the graphene containing the substrate can be continuously adhered to obtain a multilayer graphene film. / A combination of electrostatic protective films. While the process of removing the substrate of the present invention is not particularly limited, any method which can remove the growth substrate can be used in the present invention.
  • the present invention removes the substrate by solvent etching, and the substrate is transferred to the target substrate after being etched; finally, the method for reducing the electrostatic adsorption force is used to transfer the graphene to a plurality of substrates.
  • the purpose of reducing the electrostatic adsorption force according to the present invention is to release the static electricity removing electrostatic film.
  • the method for reducing the electrostatic adsorption force is not particularly limited as long as the purpose of releasing the static electricity removing electrostatic film can be achieved, and those skilled in the art have the ability to obtain a reduction.
  • the method of electrostatic adsorption can be used in the present invention, such as baking, low-temperature cooling, etc., to discharge static electricity to remove the electrostatic protective film.
  • the method for transferring graphene by the electrostatic protective film provided by the invention has the characteristics of convenient use, simple operation, no residue, reusable use, and cost saving. Meanwhile, the method for transferring graphene by the electrostatic protective film provided by the present invention can be used for roll-to-roll ( Roll-to-roll technology transfer of graphene is beneficial to the large-scale production of graphene films.
  • Roll-to-roll technology described is prior art in the art, and those skilled in the art have the ability to obtain relevant knowledge.
  • a method for transferring a graphene film by using an electrostatic protective film as a medium comprises the following steps:
  • the graphene/electrostatic protective film in step (3) is the single layer graphene according to step (2) / Electrostatic protective film.
  • the present invention utilizes the electrostatic adsorption capacity of the electrostatic protection film to firmly bond the electrostatic protection film to the surface of the graphene containing the growth substrate. After the substrate is removed, the electrostatic adsorption property of the graphene-adsorbing electrostatic protective film is not changed, and the surface of the graphene containing the growth substrate can be continuously adhered.
  • step (2') is optionally carried out after step (2):
  • the graphene/electrostatic protective film of the step (3) is a step ( 2')
  • the multilayer graphene/electrostatic protective film; the graphene film is a multilayer graphene film.
  • the electrostatic protection film is a self-adhesive film which is known to those skilled in the art, and includes, but is not limited to, the material of the electrostatic protection film.
  • OPP electrostatic protective film PE (polyethylene) electrostatic protective film, PET (polyethylene terephthalate) electrostatic protective film, PVC (polyvinyl chloride) electrostatic protective film and PP (Polypropylene) Electrostatic protective film, etc.
  • the material of the electrostatic protective film is not particularly limited in the present invention, and any electrostatic protective film which can be obtained by the prior art or new technology can be used in the present invention.
  • the electrostatic protection film of the present invention is selected from the group consisting of PE (polyethylene) electrostatic protection film, PET (polyethylene terephthalate) electrostatic protective film, PVC (polyvinyl chloride) electrostatic protective film and PP (polypropylene) electrostatic protective film, preferably PET electrostatic protective film, PVC Any of the electrostatic protective films.
  • PE polyethylene
  • PET polyethylene terephthalate
  • PVC polyvinyl chloride
  • PP polypropylene
  • the target substrate of the graphene film transfer in the present invention is not limited, and any technology in the art can be selected according to its own needs and actual conditions.
  • the target substrate of the present invention is selected from the group consisting of glass, PET, silicon wafer, PI Any one of (polyimide), PVC, PE, PP, and PS (polystyrene) is preferably any of PP, PE, and silicon wafer.
  • Steps of the invention (1) The graphene-containing graphene is prepared by the prior art, and the preparation methods are well known to those skilled in the art, and typical but non-limiting examples are vapor deposition methods and the like.
  • step 1 The adhesion of the electrostatic protection film to the graphene surface including the substrate means that the electrostatic protection film is adhered to the non-substrate side of the graphene film, and the electrostatic protection film / graphene is obtained after the bonding is completed.
  • the combination of the substrates has a structure of a substrate, a graphene, and an electrostatic protection film from bottom to top.
  • Steps of the invention The method of removing the growth substrate may be performed by, but not limited to, wet etching.
  • the wet etching method uses the etching solution to obtain the electrostatic protective film / graphene obtained in the step (1) /
  • the growth substrate in the substrate is removed, and the selection of the etching solution should also be related to the material of the substrate.
  • Etching should be a skill skilled by those skilled in the art, including which material to choose which etching solution.
  • Typical but non-limiting examples of etching liquids are copper chloride, ferric chloride, ferric nitrate, nitric acid, and Hydrogen peroxide - Sulfuric acid, ammonia base, persulfate, etc.
  • the selection of the specific etching liquid and the selection of the etching step can be selected by those skilled in the art according to actual conditions.
  • the etching liquid of the step (2) of the present invention is selected from the group consisting of ferric chloride (FeCl 3 ), ferric nitrate (Fe(NO 3 ) 3 ), nitric acid (HNO 3 ), ammonium persulfate ((NH 4 ) 2 Any one or a combination of at least two of S 2 O 8 ) and potassium persulfate (K 2 S 2 O 8 ), such as FeCl 3 /(NH 4 ) 2 S 2 O 8 , K 2 S 2 O 8 /HNO 3 , K 2 S 2 O 8 /(NH 4 ) 2 S 2 O 8 , HNO 3 /FeCl 3 /HNO 3 and the like.
  • the attachment of an electrostatic protection film to a target substrate is well known to those skilled in the art, and typical but non-limiting examples are graphene/ The electrostatic protective film combination is transferred to the target substrate and baked. It should be apparent to those skilled in the art that the graphene/electrostatic protective film is attached to the target substrate, and the graphene / The graphene layer of the electrostatic protection film is bonded to the target substrate, that is, the bonded structure is a target substrate, a multilayer (or single layer) graphene film, and an electrostatic protection film in this order from bottom to top.
  • step (3) The method of releasing static electricity is any one of baking and cryogenic cooling.
  • the baking temperature is 40 to 200 ° C, for example, 42 to 188 ° C, 51 to 173 ° C, 66 ⁇ 141 °C, 48 °C, 89 °C, 129 °C, 145 °C, 160 °C, 183 °C, 195 °C, etc., preferably 50 ⁇ 180 °C, further preferred 70 to 150 ° C, particularly preferably 100 to 120 ° C.
  • the cooling temperature is -210 to 0 °C, for example -210 to -5 °C, -200 to -10 °C, -164 ⁇ -23 °C, -2 °C, -22 °C, -50 °C, -80 °C, -111 °C, -135 °C, -160 °C, -193 °C, etc., preferably -200 to -5 ° C, further preferably -160 to -20 ° C, particularly preferably -100 to -50 ° C.
  • step (1) and step (3) are related to the 'fit' process. Since the electrostatic protection film itself has self-adhesiveness, the bonding process requires no bubbles, and if there are bubbles, the physical and chemical properties of the graphene film, especially the electrical properties, are greatly affected. Therefore, a bonding process capable of adhering a graphene film to an electrostatic protection film and bonding a graphene film to a target substrate well can be used in the present invention.
  • the step ( 1) and steps (3) The bonding method described above is any one of manual bonding and machine film bonding, and is preferably applied by a machine film. Machines described as machine-coated films are also well known to those skilled in the art, and typical, but non-limiting examples are electrostatic protective film laminators, laminators, and the like.
  • the film speed of the machine film is 0 to 2000 mm/min, for example, 1 ⁇ 2000 mm/min, 5 ⁇ 1980 mm/min, 150 ⁇ 2000 mm/min, 11 mm/min, 80 mm/min, 280 Mm/min, 778 mm/min, 1635 mm/min, 1880 mm/min, 1973 mm/min, etc., preferably 10 ⁇ 180 mm/min Further, it is preferably 20 to 150 mm/min, particularly preferably 30 to 140 mm/min.
  • the film temperature of the machine film adhered in the step (3) of the present invention is 0 to 200 ° C, for example, 1-199 ° C, 18-187 °C, 50-150 °C, 2 °C, 13 °C, 45 °C, 89 °C, 110 °C, 165 °C, 189 °C, 197 °C, etc., preferably 3 ⁇ 198 °C, further preferably 20 to 80 °C, particularly preferably 40 to 70 °C.
  • the method for transferring a graphene film by using an electrostatic protection film as described in the present invention includes the following steps:
  • the graphene/electrostatic protective film in step (3) is the single layer graphene according to step (2) / An electrostatic protective film; the graphene film is a two-layer graphene film.
  • the steps of preparing a single-layer graphene film are steps (1), (2), (3). ), that is, the bonding of the electrostatic protection film and the graphene film including the growth substrate is performed only once; and the step of preparing the multilayer graphene film is to perform steps (1), (2), (2'), (3) ), that is, multiple electrostatic protection films (or electrostatic protection film / A combination of a graphene bond and a graphene film comprising a growth substrate.
  • the 'multiple times' can be selected by a person skilled in the art according to actual conditions (such as the number of layers of graphene film).
  • the method for transferring graphene by the electrostatic protection film according to the present invention is: using the electrostatic adsorption principle of the electrostatic protection film 1 to make the electrostatic protection film 1 It is bonded to the graphene 2 containing the substrate 3 (the structure is as shown in FIG. 2, and FIG.
  • FIG. 2 is a schematic structural view of the combination of the electrostatic protective film/graphene/substrate of the step (1) of the present invention), and then the lining bottom 3 Etching, electrostatic protection film with graphene 2 adsorbed 1 Re-attaching the surface-grown graphene substrate, repeating the etching step, and finally bonding the electrostatic protective film of the single-layer, two-layer or more layers of graphene to the target substrate, and then baking, The electrostatic protection film is removed by a method such as low-temperature cooling, and the purpose of transferring the multilayer graphene by the electrostatic protection film is achieved.
  • Figure 1 is a schematic diagram of a process flow for transferring graphene to the electrostatic protective film shown in the present invention.
  • Another object of the present invention is to provide a graphene film which is prepared by the method of the present invention.
  • the number of layers of the graphene film prepared by the method of the invention is ⁇ 1, for example, 1, 2, 3, 4, 5 8, 8, 9, etc., preferably ⁇ 2, further preferably 2 to 5.
  • the sheet resistance of the graphene film is 301.7 to 498.1 ⁇ / ⁇ . .
  • a third object of the present invention is to provide a use of the graphene film of the present invention for energy storage of an active material, preferably for hydrogen storage, a lithium ion battery, a supercapacitor or a fuel cell, and Electronics, high frequency circuits, photon sensors, gene electronics sequencing and noise reduction.
  • an active material preferably for hydrogen storage, a lithium ion battery, a supercapacitor or a fuel cell, and Electronics, high frequency circuits, photon sensors, gene electronics sequencing and noise reduction.
  • the present invention has the following beneficial effects:
  • the invention overcomes the defects of easy to break, difficult to operate, residue, easy to be contaminated in the process of transferring the graphene by the organic glue, and has the advantages of convenient operation, simple process, low cost, no residual glue, and reusability.
  • the method provided by the invention can be used for the transfer of graphene by the roll-to-roll technology, and the process is simple, and is beneficial to the large-scale production of the graphene film.
  • FIG. 1 is a schematic view showing a process flow of transferring a multilayer graphene by the electrostatic protection film of the present invention
  • FIG. 2 is a schematic structural view of a combination of the electrostatic protection film/graphene/substrate of the step (1) of the present invention
  • 1- electrostatic protective film 2-graphene; 3- growth substrate; 4-target substrate.
  • a method for transferring multilayer graphene by using an electrostatic protective film comprising the following steps:
  • a graphene film is prepared by a vapor deposition method using a copper foil as a substrate, and a copper foil having graphene is sandwiched between two glasses, and a certain force is applied to make the surface of the copper foil film flat and wrinkles less;
  • PP The electrostatic protective film and the copper foil with graphene are completely adhered, the film speed is 10 mm/min, and the film temperature is room temperature;
  • Electrostatic protective film / The combination of the graphene-containing copper foil is etched in an ammonium persulfate solution, the side of the electrostatic protection film faces upward, and the side of the copper foil faces downward; 10 min After that, the surface of the copper foil is washed with deionized water and ethanol, and the same method is used for continuous cleaning twice; after etching for 3 hours, the copper foil is completely removed; then graphene / The electrostatic protective film is taken out from the ammonium persulfate solution, and the surface of the graphene/electrostatic protective film is rinsed with deionized water and ethanol, and dried at room temperature;
  • the sheet resistance of the obtained two-layer graphene film was 401.6 ⁇ / ⁇ .
  • a method for transferring multilayer graphene by using an electrostatic protective film comprising the following steps:
  • the graphene film with copper foil as the substrate is prepared by vapor deposition method, and the copper foil with graphene is rolled by a laminator to make the copper foil film very flat, and the film speed is 200 mm/min; PET The electrostatic protection film is attached to the long graphene copper foil; the film speed is 200 mm/min, and the film temperature is room temperature;
  • the sheet resistance of the obtained two-layer graphene film was 301.7 ⁇ / ⁇ .
  • a method for transferring multilayer graphene by using an electrostatic protective film comprising the following steps:
  • the sheet resistance of the obtained two-layer graphene film was 332.5 ⁇ / ⁇ .
  • a method for transferring multilayer graphene by using an electrostatic protective film comprising the following steps:
  • Steps (1) - (2') are identical to those in Embodiment 2;
  • the sheet resistance of the obtained two-layer graphene film was 498.1 ⁇ / ⁇ .
  • a method for transferring multilayer graphene by using an electrostatic protective film comprising the following steps:
  • Steps (1) - (2') are identical to those in Embodiment 2.
  • the sheet resistance of the obtained double-layer graphene was 442.9 ⁇ / ⁇ .
  • a method for transferring multilayer graphene by using an electrostatic protective film comprising the following steps:
  • Steps (1) - (2) are identical to those in Embodiment 2.
  • the sheet resistance of the obtained three-layer graphene film was 208.3 ⁇ / ⁇ .
  • a method for transferring multilayer graphene by using an electrostatic protective film comprising the following steps:
  • Steps (1) - (2) are identical to those in Embodiment 2.
  • the sheet resistance of the obtained six-layer graphene film was 60.5 ⁇ / ⁇ .
  • a method for transferring multilayer graphene by using an electrostatic protective film comprising the following steps:
  • Step (1) - (2) is the same as in Example 2, but the film speed of the step (1) is 1 mm/min.
  • the film temperature is 200 °C.
  • the six-layer graphene/electrostatic protective film is completely attached to the glass substrate at a film speed of 1 mm/min, and the film temperature is 200 ° C; under 200 ° C baking conditions, the electrostatic protective film was removed to obtain a three-layer graphene film.
  • the sheet resistance of the obtained three-layer graphene film was 130.5 ⁇ / ⁇ .
  • a method for transferring multilayer graphene by using an electrostatic protective film comprising the following steps:
  • Step (1) - (2) is the same as in Example 2, but the film speed of the step (1) is 2000 mm/min.
  • the film temperature is 0 °C.
  • the six-layer graphene/electrostatic protective film is completely attached to the glass substrate at a film speed of 2000 mm/min. , the film temperature is 0 °C; at -210 °C, the electrostatic protection film is removed. , a six-layer graphene film was obtained.
  • the sheet resistance of the obtained six-layer graphene film was 55.2 ⁇ / ⁇ .
  • the present invention illustrates the detailed process equipment and process flow of the present invention by the above embodiments, but the present invention is not limited to the above detailed process equipment and process flow, that is, does not mean that the present invention must rely on the above detailed process equipment and The process can only be implemented. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.

Abstract

The present invention relates to a method for transferring a graphene film using an electrostatic protection film as a medium. The method comprises: using the electrostatic adsorption of an electrostatic protection film to adhere a graphene comprising a growth substrate, then removing the growth substrate to obtain a graphene/electrostatic protection film combination, and finally, adhering the single-layer graphene/electrostatic protection film combination to a target substrate and releasing static electricity to remove the electrostatic protection film to obtain a single-layer graphene film; alternatively, after the single-layer graphene/electrostatic protection film combination is obtained, replacing the electrostatic protection film with the single-layer graphene/electrostatic protection film combination, and on a new graphene comprising a growth substrate, repeatedly adhering the graphene/electrostatic protection film and removing the growth substrate in sequence, so as finally to obtain a multilayer graphene film. The method has a simple and convenient operation, has no residue of glue and does not need an organic solvent to conduct subsequent cleaning, thereby reducing the process costs for transferring a graphene film.

Description

一种以静电保护膜为媒介转移石墨烯薄膜的方法 Method for transferring graphene film by using electrostatic protective film as medium 技术领域Technical field
本发明涉及一种转移石墨烯薄膜的方法，具体涉及一种以静电保护膜为媒介转移单层或多层石墨烯薄膜的方法，属于导电薄膜材料领域。 The invention relates to a method for transferring a graphene film, in particular to a method for transferring a single layer or a plurality of graphene films by using an electrostatic protective film as a medium, and belongs to the field of conductive film materials.
背景技术Background technique
石墨烯薄膜具有高透光性、极高的载流子迁移率，在电子器件、太阳能电池等方面有着巨大的应用前景。为了制备石墨烯电子器件，首要的问题是制备出大尺寸的石墨烯薄膜，并转移至合适的目标基底上。 Graphene film has high light transmittance and high carrier mobility, and has great application prospects in electronic devices and solar cells. In order to prepare graphene electronic devices, the primary problem is to prepare a large-sized graphene film and transfer it to a suitable target substrate.
石墨烯薄膜的转移技术是将石墨烯在不同基体之间转移的方法，通常是将石墨烯从生长衬体转移到目标基体上。石墨烯薄膜的转移技术是制约石墨烯薄膜发展的关键因素，理想的转移技术应具有如下特点：（ 1 ）在转移过程中能保持石墨烯完整、无破损；（ 2 ）对石墨烯无污染（包括掺杂）；（ 3 ）工艺稳定、可靠，具有较强的适用性和稳定性。 The transfer technique of graphene film is a method of transferring graphene between different substrates, usually by transferring graphene from the growth liner to the target substrate. The transfer technology of graphene film is a key factor restricting the development of graphene film. The ideal transfer technology should have the following characteristics: 1) It can keep graphene intact and no damage during the transfer process; (2) It has no pollution to graphene (including doping); (3) The process is stable and reliable, and has strong applicability and stability.
目前，'腐蚀基体法'是应用较广泛的转移石墨烯的方法，该方法是采用聚甲基丙烯酸甲酯（ PMMA ）、热释放胶带等转移介质，用化学试剂将金属生长衬底腐蚀掉后将石墨烯转移到目标基底上。 At present, the 'corrosive matrix method' is a widely used method for transferring graphene by using polymethyl methacrylate (PMMA). Transfer medium such as heat release tape, and the metal growth substrate is etched away with a chemical reagent to transfer the graphene to the target substrate.
聚甲基丙烯酸甲酯（ PMMA ）转移的石墨烯电阻低，稳定性好，是科学研究中常用的方法；但是 PMMA 转移石墨烯的工艺流程复杂，转移周期长，不易操作，易破损等缺点，使其在转移大面积石墨烯上具有一定的局限性。 Polymethyl methacrylate (PMMA) transferred graphene has low electrical resistance and good stability, which is a commonly used method in scientific research; but PMMA The process of transferring graphene is complicated, the transfer period is long, it is difficult to operate, and it is easy to be broken, which has certain limitations in transferring large-area graphene.
热释放胶带转移方法实现了大面积石墨烯向柔性基底的转移，该技术成本较高，且胶带上的粘结剂易残留在石墨烯表面，清洗困难，影响石墨烯的质量。 The heat release tape transfer method realizes the transfer of large-area graphene to the flexible substrate. The cost of the technology is high, and the adhesive on the tape is liable to remain on the surface of the graphene, which is difficult to clean and affects the quality of the graphene.
另外，无转移介质'腐蚀基体法'利用多层石墨烯强度比单层石墨烯高的特点，可采用该方法对多层石墨烯转移。这种方法工艺过程更简单，因此也得到了一定的发展。这种方法仅适合小面积转移，其转移的完整性和可靠性无法与有介质的'腐蚀基体法'相比，所以该法在应用上有很大的局限性。 In addition, the non-transfer medium 'corrosion matrix method' utilizes the characteristics that the multi-layer graphene has higher strength than the single-layer graphene, and the method can be used to transfer the multilayer graphene. This method is simpler in process and has therefore been developed. This method is only suitable for small-area transfer, and the integrity and reliability of the transfer cannot be compared with the 'corrosion matrix method' with medium, so the method has great limitations in application.
总的来说，现有石墨烯薄膜的转移技术，转移得到的石墨烯薄膜存在残留杂质多、方块电阻高、稳定性不好以及工艺复杂等问题，因此开发一种高效的石墨烯薄膜的转移方法，是一个亟待解决的问题。 In general, the transfer technology of the existing graphene film, the transferred graphene film has many problems such as residual impurities, high sheet resistance, poor stability and complicated process, so an efficient transfer of graphene film is developed. The method is an urgent problem to be solved.
技术问题technical problem
针对现有技术的不足，本发明的目的之一在于提供一种成本较低、操作简单，且能够得到高质量石墨烯薄膜的转移方法。 In view of the deficiencies of the prior art, one of the objects of the present invention is to provide a transfer method which is low in cost, simple in operation, and capable of obtaining a high quality graphene film.
本发明所述的石墨烯薄膜的转移方法为以静电保护膜为媒介，通过合理地释放静电，实现石墨烯在不同衬底之间的转移。The method for transferring the graphene film according to the present invention is to use a static protective film as a medium to realize the transfer of graphene between different substrates by reasonably releasing static electricity.
技术解决方案Technical solution
本发明是通过如下实验方案实现的： The present invention is achieved by the following experimental scheme:
一种以静电保护膜为媒介转移石墨烯薄膜的方法，所述方法是利用静电保护膜的静电吸附作用贴合包含生长衬底的石墨烯，然后将衬底去除，得到单层石墨烯 / 静电保护膜结合体，最后将单层石墨烯 / 静电保护膜结合体贴合于目标基底上，释放静电去除静电保护膜，得到单层石墨烯薄膜； A method for transferring a graphene film by using an electrostatic protective film as a medium, wherein the graphene containing the growth substrate is bonded by electrostatic adsorption of the electrostatic protection film, and then the substrate is removed to obtain a single layer graphene / The electrostatic protective film is combined, and finally the single-layer graphene/electrostatic protective film combination is attached to the target substrate, and the static electricity is removed to remove the electrostatic protective film to obtain a single-layer graphene film;
所述方法还可在得到单层石墨烯 / 静电保护膜结合体后，以单层石墨烯 / 静电保护膜结合体代替静电保护膜，在新的包含衬底的石墨烯上依次重复进行以下两步骤 n-1 次：贴合石墨烯 / 静电保护膜、去除衬底；从而制备得到 n 层石墨烯薄膜，所述 n 的取值为≥ 2 的整数，例如 2 、 3 、 4 、 5 、 6 等。 The method may also be a single layer of graphene / after obtaining a single layer graphene / electrostatic protective film combination The electrostatic protective film combination is used instead of the electrostatic protective film, and the following two steps are repeated n-1 times on the new graphene containing the substrate: laminating the graphene/electrostatic protective film, removing the substrate; thereby preparing n For a graphene film, the value of n is an integer of ≥ 2, such as 2, 3, 4, 5, 6, and the like.
例如制备 3 层石墨烯薄膜的方法为：利用静电保护膜的静电吸附作用贴合包含生长衬底的石墨烯，然后将衬底去除，得到石墨烯 / 静电保护膜结合体；然后将得到的石墨烯 / 静电保护膜结合体贴合另一个包含生长衬底的石墨烯，再次将衬底去除，得到 2 层石墨烯 / 静电保护膜结合体；然后将得到的 2 层石墨烯 / 静电保护膜结合体贴合再一个包含生长衬底的石墨烯，再次将衬底去除，得到 3 层石墨烯 / 静电保护膜结合体；最后将 3 层石墨烯 / 静电保护膜结合体贴合于目标基底上后，去除静电保护膜后，得到 3 层石墨烯薄膜。 For example, preparation 3 The method for layering the graphene film is: bonding the graphene containing the growth substrate by electrostatic adsorption of the electrostatic protection film, and then removing the substrate to obtain a graphene/electrostatic protective film combination; and then obtaining the graphene/ The electrostatic protective film assembly is bonded to another graphene containing the growth substrate, and the substrate is again removed to obtain a two-layer graphene/electrostatic protective film combination; then the obtained two-layer graphene / The electrostatic protective film combination is bonded to another graphene containing the growth substrate, and the substrate is removed again to obtain a three-layer graphene/electrostatic protective film combination; finally, three layers of graphene/ After the electrostatic protection film assembly is bonded to the target substrate, the electrostatic protection film is removed to obtain a three-layer graphene film.
静电保护膜具有静电吸附能力，可以粘贴到光滑的物体表面，化学性质稳定、机械强度高，因此可以作为'腐蚀基体法'转移石墨烯的转移介质。 The electrostatic protective film has electrostatic adsorption ability and can be attached to a smooth surface of the object. It has stable chemical properties and high mechanical strength, so it can be used as a transfer medium for transferring graphene by the 'corrosive matrix method'.
本发明利用静电保护膜的静电吸附能力，将静电保护膜与包含生长衬底的石墨烯表面牢固的粘贴在一起；而在去除所述的衬底后，吸附了石墨烯的静电保护膜的静电吸附能力未发生改变，可以继续与包含衬底的石墨烯表面完全贴合，从而得到多层石墨烯薄膜 / 静电保护膜的结合体。而本发明所述去除衬底的过程没有特殊限定，任何一种可以将生长衬底去除的方法均可用于本发明。 The invention utilizes the electrostatic adsorption capacity of the electrostatic protection film to firmly adhere the electrostatic protection film to the surface of the graphene containing the growth substrate; and after removing the substrate, the static electricity of the electrostatic protection film of the graphene is adsorbed The adsorption capacity is unchanged, and the surface of the graphene containing the substrate can be continuously adhered to obtain a multilayer graphene film. / A combination of electrostatic protective films. While the process of removing the substrate of the present invention is not particularly limited, any method which can remove the growth substrate can be used in the present invention.
优选地，本发明采用溶剂腐蚀法将衬底腐蚀去除，衬底被腐蚀完后转移到目标基底上；最后利用能降低静电吸附力的方法，达到将石墨烯转移到多种基底上的目的。本发明所述的降低静电吸附力的的目的是释放静电去除静电膜，对于降低静电吸附力的方法没有特殊限定，只要能够达到释放静电去除静电膜的目的，本领域技术人员有能力获知的降低静电吸附的方法均可用于本发明，如烘烤、低温冷却等释放静电去除静电保护膜的方法。 Preferably, the present invention removes the substrate by solvent etching, and the substrate is transferred to the target substrate after being etched; finally, the method for reducing the electrostatic adsorption force is used to transfer the graphene to a plurality of substrates. The purpose of reducing the electrostatic adsorption force according to the present invention is to release the static electricity removing electrostatic film. The method for reducing the electrostatic adsorption force is not particularly limited as long as the purpose of releasing the static electricity removing electrostatic film can be achieved, and those skilled in the art have the ability to obtain a reduction. The method of electrostatic adsorption can be used in the present invention, such as baking, low-temperature cooling, etc., to discharge static electricity to remove the electrostatic protective film.
本发明提供的静电保护膜转移石墨烯的方法具有使用方便、操作简单、无残留、可以重复使用、节省成本等特点。同时，本发明所提供的静电保护膜转移石墨烯的方法可以用于卷对卷（ roll-to-roll ）技术转移石墨烯，有利于石墨烯薄膜的规模化生产。所述的卷对卷技术是本领域的现有技术，本领域技术人员有能力获得相关的知识。 The method for transferring graphene by the electrostatic protective film provided by the invention has the characteristics of convenient use, simple operation, no residue, reusable use, and cost saving. Meanwhile, the method for transferring graphene by the electrostatic protective film provided by the present invention can be used for roll-to-roll ( Roll-to-roll technology transfer of graphene is beneficial to the large-scale production of graphene films. The roll-to-roll technology described is prior art in the art, and those skilled in the art have the ability to obtain relevant knowledge.
具体地，本发明是通过如下技术方案实现的，一种以静电保护膜为媒介转移石墨烯薄膜的方法包括如下步骤： Specifically, the present invention is achieved by the following technical solution, a method for transferring a graphene film by using an electrostatic protective film as a medium comprises the following steps:
（ 1 ）将静电保护膜贴合在包含生长衬底的石墨烯表面； (1) attaching an electrostatic protection film to the surface of the graphene including the growth substrate;
（ 2 ）去除步骤（ 1 ）所述的衬底，得到单层石墨烯 / 静电保护膜结合体； (2) removing the substrate described in the step (1) to obtain a single-layer graphene/electrostatic protective film combination;
（ 3 ）将石墨烯 / 静电保护膜结合体贴合在目标基底上，释放静电去除静电保护膜，得到石墨烯薄膜； (3) Graphene / The electrostatic protection film combination body is attached to the target substrate, and the static electricity is removed to remove the electrostatic protection film to obtain a graphene film;
其中，步骤（ 3 ）所述石墨烯 / 静电保护膜为步骤（ 2 ）所述的单层石墨烯 / 静电保护膜。 Wherein the graphene/electrostatic protective film in step (3) is the single layer graphene according to step (2) / Electrostatic protective film.
本发明利用静电保护膜的静电吸附能力，将静电保护膜与包含生长衬底的石墨烯表面牢固的粘贴在一起。去除所述的衬底后，吸附了石墨烯的静电保护膜的静电吸附能力未发生改变，可以继续与包含生长衬底的石墨烯表面完全贴合。 The present invention utilizes the electrostatic adsorption capacity of the electrostatic protection film to firmly bond the electrostatic protection film to the surface of the graphene containing the growth substrate. After the substrate is removed, the electrostatic adsorption property of the graphene-adsorbing electrostatic protective film is not changed, and the surface of the graphene containing the growth substrate can be continuously adhered.
优选地，在步骤（ 2 ）后任选进行步骤（ 2' ）： Preferably, step (2') is optionally carried out after step (2):
（ 2' ）将步骤（ 2 ）得到的单层石墨烯 / 静电保护膜结合体代替步骤（ 1 ）所述的静电保护膜，重复步骤（ 1 ） ~ 步骤（ 2 ） n-1 次，制备得到 n 层石墨烯 / 静电保护膜结合体；所述 n 的取值为≥ 2 的整数； (2') replacing the single-layer graphene/electrostatic protective film combination obtained in the step (2) (1) The electrostatic protective film is repeated steps (1) to (2) n-1 times to prepare an n-layer graphene/electrostatic protective film combination; the value of n is ≥ 2 Integer
其中，当步骤（ 2 ）后进行步骤（ 2' ）时，步骤（ 3 ）所述石墨烯 / 静电保护膜为步骤（ 2' ）所述的多层石墨烯 / 静电保护膜；所述石墨烯薄膜为多层石墨烯薄膜。 Wherein, when the step (2') is performed after the step (2), the graphene/electrostatic protective film of the step (3) is a step ( 2') The multilayer graphene/electrostatic protective film; the graphene film is a multilayer graphene film.
静电保护膜是本领域技术人员有能力获知的一种自粘性膜，根据静电保护膜的材质不同，其包括但不限于 OPP 静电保护膜、 PE （聚乙烯）静电保护膜、 PET （聚对苯二甲酸乙二醇酯）静电保护膜、 PVC （聚氯乙烯）静电保护膜和 PP （聚丙烯）静电保护膜等，本发明对于静电保护膜的材质不做特别的限定，任何一种能够通过现有技术或新技术获得的静电保护膜均可用于本发明。 The electrostatic protection film is a self-adhesive film which is known to those skilled in the art, and includes, but is not limited to, the material of the electrostatic protection film. OPP electrostatic protective film, PE (polyethylene) electrostatic protective film, PET (polyethylene terephthalate) electrostatic protective film, PVC (polyvinyl chloride) electrostatic protective film and PP (Polypropylene) Electrostatic protective film, etc. The material of the electrostatic protective film is not particularly limited in the present invention, and any electrostatic protective film which can be obtained by the prior art or new technology can be used in the present invention.
优选地，本发明所述静电保护膜选自 PE （聚乙烯）静电保护膜、 PET （聚对苯二甲酸乙二醇酯）静电保护膜、 PVC （聚氯乙烯）静电保护膜和 PP （聚丙烯）静电保护膜中的任意一种，优选 PET 静电保护膜、 PVC 静电保护膜中的任意一种。 Preferably, the electrostatic protection film of the present invention is selected from the group consisting of PE (polyethylene) electrostatic protection film, PET (polyethylene terephthalate) electrostatic protective film, PVC (polyvinyl chloride) electrostatic protective film and PP (polypropylene) electrostatic protective film, preferably PET electrostatic protective film, PVC Any of the electrostatic protective films.
本发明对石墨烯薄膜转移的目标基底没有限定，本领域技术任意可以根据自己的需要和实际情况进行选择。优选地，本发明所述目标基底选自玻璃、 PET 、硅片、 PI （聚酰亚胺）、 PVC 、 PE 、 PP 、 PS （聚苯乙烯）中的任意一种，优选 PP 、 PE 、硅片中的任意一种。 The target substrate of the graphene film transfer in the present invention is not limited, and any technology in the art can be selected according to its own needs and actual conditions. Preferably, the target substrate of the present invention is selected from the group consisting of glass, PET, silicon wafer, PI Any one of (polyimide), PVC, PE, PP, and PS (polystyrene) is preferably any of PP, PE, and silicon wafer.
本发明步骤（ 1 ）所述的包含衬底的石墨烯是现有技术可以制备的，制备方法为本领域技术人员所熟知的，典型但非限制性的实例有气相沉积法等。步骤（ 1 ）所述的将静电保护膜贴合在包含衬底的石墨烯表面意指静电保护膜贴合在石墨烯薄膜非衬底的一面，贴合完成后得到静电保护膜 / 石墨烯 / 衬底的结合体，其结构自下而上依次为衬底、石墨烯、静电保护膜。 Steps of the invention (1) The graphene-containing graphene is prepared by the prior art, and the preparation methods are well known to those skilled in the art, and typical but non-limiting examples are vapor deposition methods and the like. step 1 The adhesion of the electrostatic protection film to the graphene surface including the substrate means that the electrostatic protection film is adhered to the non-substrate side of the graphene film, and the electrostatic protection film / graphene is obtained after the bonding is completed. The combination of the substrates has a structure of a substrate, a graphene, and an electrostatic protection film from bottom to top.
本发明步骤（ 2 ）中去除生长衬底的方法可以采用但不仅限于湿法刻蚀法。所述湿法刻蚀法采用刻蚀液将步骤（ 1 ）得到的静电保护膜 / 石墨烯 / 衬底中的生长衬底去除，刻蚀液的选择也应该与衬底的材质有关。而刻蚀应该是本领域技术人员熟练掌握的技巧，包括何种材质选择何种刻蚀液，典型但非限制性的刻蚀液例子有氯化铜、氯化铁、硝酸铁、硝酸、过氧化氢 - 硫酸、氨碱、过硫酸盐等。具体的刻蚀液的选择和刻蚀步骤的选择，本领域技术人员可以根据实际情况进行选择。 Steps of the invention (2 The method of removing the growth substrate may be performed by, but not limited to, wet etching. The wet etching method uses the etching solution to obtain the electrostatic protective film / graphene obtained in the step (1) / The growth substrate in the substrate is removed, and the selection of the etching solution should also be related to the material of the substrate. Etching should be a skill skilled by those skilled in the art, including which material to choose which etching solution. Typical but non-limiting examples of etching liquids are copper chloride, ferric chloride, ferric nitrate, nitric acid, and Hydrogen peroxide - Sulfuric acid, ammonia base, persulfate, etc. The selection of the specific etching liquid and the selection of the etching step can be selected by those skilled in the art according to actual conditions.
优选地，本发明步骤（ 2 ）所述刻蚀液选自氯化铁（ FeCl3 ）、硝酸铁（ Fe(NO3)3 ）、硝酸（ HNO3 ）、过硫酸铵（ (NH4)2S2O8 ）和过硫酸钾（ K2S2O8 ）中的任意 1 种或至少 2 种以上的组合，所述组合例如 FeCl3/(NH4)2S2O 8 、 K2S2O8/HNO3 、 K2S2O8/(NH4) 2S2O8 、 HNO3/FeCl3/HNO3 等。Preferably, the etching liquid of the step (2) of the present invention is selected from the group consisting of ferric chloride (FeCl 3 ), ferric nitrate (Fe(NO 3 ) 3 ), nitric acid (HNO 3 ), ammonium persulfate ((NH 4 ) 2 Any one or a combination of at least two of S 2 O 8 ) and potassium persulfate (K 2 S 2 O 8 ), such as FeCl 3 /(NH 4 ) 2 S 2 O 8 , K 2 S 2 O 8 /HNO 3 , K 2 S 2 O 8 /(NH 4 ) 2 S 2 O 8 , HNO 3 /FeCl 3 /HNO 3 and the like.
步骤（ 3 ）所述石墨烯 / 静电保护膜贴合在目标基底上是本领域技术人员所熟知的技术，典型但非限制性的实例有将石墨烯 / 静电保护膜结合体转移至目标基底上，烘烤。本领域技术人员应该明了，石墨烯 / 静电保护膜贴合在目标基底上的步骤中，石墨烯 / 静电保护膜的石墨烯层与目标基底贴合，即贴合后的结构从下向上依次是目标基底、多层（或单层）石墨烯薄膜和静电保护膜。 Step (3) of the graphene / The attachment of an electrostatic protection film to a target substrate is well known to those skilled in the art, and typical but non-limiting examples are graphene/ The electrostatic protective film combination is transferred to the target substrate and baked. It should be apparent to those skilled in the art that the graphene/electrostatic protective film is attached to the target substrate, and the graphene / The graphene layer of the electrostatic protection film is bonded to the target substrate, that is, the bonded structure is a target substrate, a multilayer (or single layer) graphene film, and an electrostatic protection film in this order from bottom to top.
石墨烯 / 静电保护膜与目标基底贴合后需要释放静电保护膜界面处的静电，降低保护膜与石墨烯之间的静电力，才能将保护膜去除，然后得到需要的石墨烯薄膜。优选地，步骤（ 3 ）所述释放静电的方法为烘烤、低温冷却中的任意一种。 Graphene / After the electrostatic protective film is bonded to the target substrate, the static electricity at the interface of the electrostatic protective film needs to be released, and the electrostatic force between the protective film and the graphene is lowered to remove the protective film, and then the desired graphene film is obtained. Preferably, step (3) The method of releasing static electricity is any one of baking and cryogenic cooling.
优选地，所述烘烤的温度为 40~200 ℃，例如 42~188 ℃、 51~173 ℃、 66~141 ℃、 48 ℃、 89 ℃、 129 ℃、 145 ℃、 160 ℃、 183 ℃、 195 ℃等，优选 50~180 ℃，进一步优选 70~150 ℃，特别优选 100~120 ℃。 Preferably, the baking temperature is 40 to 200 ° C, for example, 42 to 188 ° C, 51 to 173 ° C, 66~141 °C, 48 °C, 89 °C, 129 °C, 145 °C, 160 °C, 183 °C, 195 °C, etc., preferably 50~180 °C, further preferred 70 to 150 ° C, particularly preferably 100 to 120 ° C.
优选地，所述冷却的温度为 -210~0 ℃，例如 -210~-5 ℃、 -200~-10 ℃、 -164~-23 ℃、 -2 ℃、 -22 ℃、 -50 ℃、 -80 ℃、 -111 ℃、 -135 ℃、 -160 ℃、 -193 ℃等，优选 -200~-5 ℃，进一步优选 -160~-20 ℃，特别优选 -100~-50 ℃。 Preferably, the cooling temperature is -210 to 0 °C, for example -210 to -5 °C, -200 to -10 °C, -164~-23 °C, -2 °C, -22 °C, -50 °C, -80 °C, -111 °C, -135 °C, -160 °C, -193 °C, etc., preferably -200 to -5 ° C, further preferably -160 to -20 ° C, particularly preferably -100 to -50 ° C.
本发明所提供的静电保护膜转移石墨烯的方法中，步骤（ 1 ）和步骤（ 3 ）均涉及到'贴合'工艺。由于静电保护膜本身具有自粘性，贴合工艺的要求即不产生气泡，如有气泡，石墨烯薄膜的理化性质尤其是电学性能会受到很大的影响。因此，能够将石墨烯薄膜良好贴合在静电保护膜、将石墨烯薄膜良好贴合在目标基底上的贴合工艺方法均可用于本发明。优选地，步骤（ 1 ）和步骤（ 3 ）所述的贴合方法为人工粘贴，机器覆膜粘贴中的任意一种，优选机器覆膜粘贴。机器贴覆膜所述的机器同样是本领域技术人员熟知的设备，典型但非限制性的实例有静电保护膜贴合机、覆膜机等。 In the method for transferring graphene by electrostatic protection film provided by the present invention, step (1) and step (3) ) are related to the 'fit' process. Since the electrostatic protection film itself has self-adhesiveness, the bonding process requires no bubbles, and if there are bubbles, the physical and chemical properties of the graphene film, especially the electrical properties, are greatly affected. Therefore, a bonding process capable of adhering a graphene film to an electrostatic protection film and bonding a graphene film to a target substrate well can be used in the present invention. Preferably, the step ( 1) and steps (3) The bonding method described above is any one of manual bonding and machine film bonding, and is preferably applied by a machine film. Machines described as machine-coated films are also well known to those skilled in the art, and typical, but non-limiting examples are electrostatic protective film laminators, laminators, and the like.
优选地，本发明步骤（ 3 ）所述机器覆膜粘贴的覆膜速度为 0~2000mm/min ，例如 1~2000 mm/min 、 5~1980 mm/min 、 150~2000 mm/min 、 11 mm/min 、 80 mm/min 、 280 mm/min 、 778 mm/min 、 1635 mm/min 、 1880 mm/min 、 1973 mm/min 等，优选 10~180mm/min ，进一步优选 20~150mm/min ，特别优选 30~140mm/min 。 Preferably, in the step (3) of the present invention, the film speed of the machine film is 0 to 2000 mm/min, for example, 1~2000 mm/min, 5~1980 mm/min, 150~2000 mm/min, 11 mm/min, 80 mm/min, 280 Mm/min, 778 mm/min, 1635 mm/min, 1880 mm/min, 1973 mm/min, etc., preferably 10~180 mm/min Further, it is preferably 20 to 150 mm/min, particularly preferably 30 to 140 mm/min.
优选地，本发明步骤（ 3 ）所述机器覆膜粘贴的覆膜温度为 0~200 ℃，例如 1-199 ℃、 18-187 ℃、 50-150 ℃、 2 ℃、 13 ℃、 45 ℃、 89 ℃、 110 ℃、 165 ℃、 189 ℃、 197 ℃等，优选 3~198 ℃，进一步优选 20~80 ℃，特别优选 40~70 ℃。 Preferably, the film temperature of the machine film adhered in the step (3) of the present invention is 0 to 200 ° C, for example, 1-199 ° C, 18-187 °C, 50-150 °C, 2 °C, 13 °C, 45 °C, 89 °C, 110 °C, 165 °C, 189 °C, 197 °C, etc., preferably 3~198 °C, further preferably 20 to 80 °C, particularly preferably 40 to 70 °C.
作为优选技术方案，本发明所述以静电保护膜为媒介转移石墨烯薄膜的方法包括如下步骤： As a preferred technical solution, the method for transferring a graphene film by using an electrostatic protection film as described in the present invention includes the following steps:
（ 1 ）将静电保护膜贴合在包含生长衬底的石墨烯薄膜表面； (1) attaching an electrostatic protection film to the surface of the graphene film including the growth substrate;
（ 2 ）去除步骤（ 1 ）所述的生长衬底，得到单层石墨烯 / 静电保护膜结合体； (2) removing the growth substrate described in the step (1) to obtain a single-layer graphene/electrostatic protective film combination;
（ 2' ）将步骤（ 2 ）得到的单层石墨烯 / 静电保护膜结合体代替步骤（ 1 ）所述的静电保护膜，重复步骤（ 1 ） ~ 步骤（ 2 ），制备得到双层石墨烯 / 静电保护膜结合体； (2') replacing the single-layer graphene/electrostatic protective film combination obtained in the step (2) (1) The electrostatic protective film is repeated, steps (1) to (2) are repeated to prepare a bilayer graphene/electrostatic protective film combination;
（ 3 ）将石墨烯 / 静电保护膜结合体贴合在目标基底上，释放静电去除静电保护膜，得到石墨烯薄膜； (3) Graphene / The electrostatic protection film combination body is attached to the target substrate, and the static electricity is removed to remove the electrostatic protection film to obtain a graphene film;
其中，步骤（ 3 ）所述石墨烯 / 静电保护膜为步骤（ 2 ）所述的单层石墨烯 / 静电保护膜；所述石墨烯薄膜为双层石墨烯薄膜。 Wherein the graphene/electrostatic protective film in step (3) is the single layer graphene according to step (2) / An electrostatic protective film; the graphene film is a two-layer graphene film.
本领域技术人员应该明了，制备单层石墨烯薄膜的步骤是步骤（ 1 ）、（ 2 ）、（ 3 ），即仅进行一次静电保护膜和包含生长衬底的石墨烯薄膜的贴合；而制备多层石墨烯薄膜的步骤是进行步骤（ 1 ）、（ 2 ）、（ 2' ）、（ 3 ），即进行多次静电保护膜（或静电保护膜 / 石墨烯结合体）和包含生长衬底的石墨烯薄膜的贴合。而所述的'多次'为本领域技术人员可根据实际情况（如石墨烯薄膜的层数）进行自行选择。 It should be apparent to those skilled in the art that the steps of preparing a single-layer graphene film are steps (1), (2), (3). ), that is, the bonding of the electrostatic protection film and the graphene film including the growth substrate is performed only once; and the step of preparing the multilayer graphene film is to perform steps (1), (2), (2'), (3) ), that is, multiple electrostatic protection films (or electrostatic protection film / A combination of a graphene bond and a graphene film comprising a growth substrate. The 'multiple times' can be selected by a person skilled in the art according to actual conditions (such as the number of layers of graphene film).
本发明所述的静电保护膜转移石墨烯的方法为：利用静电保护膜 1 的静电吸附原理，使静电保护膜 1 与包含衬底 3 的石墨烯 2 贴合（结构如图 2 所示，图 2 为本发明步骤（ 1 ）所述静电保护膜 / 石墨烯 / 衬底的结合体的结构示意图），此后对衬底 3 进行刻蚀，将吸附了石墨烯 2 的静电保护膜 1 重新与表面生长有石墨烯的衬底贴合，重复刻蚀步骤，最后将吸附了单层、两层或更多层的石墨烯的静电保护膜与目标基底进行贴合，然后通过烘烤、低温冷却等方法去除静电保护膜，实现了利用静电保护膜转移多层石墨烯的目的。图 1 为本发明所示的静电保护膜转移石墨烯的工艺流程示意图。 The method for transferring graphene by the electrostatic protection film according to the present invention is: using the electrostatic adsorption principle of the electrostatic protection film 1 to make the electrostatic protection film 1 It is bonded to the graphene 2 containing the substrate 3 (the structure is as shown in FIG. 2, and FIG. 2 is a schematic structural view of the combination of the electrostatic protective film/graphene/substrate of the step (1) of the present invention), and then the lining bottom 3 Etching, electrostatic protection film with graphene 2 adsorbed 1 Re-attaching the surface-grown graphene substrate, repeating the etching step, and finally bonding the electrostatic protective film of the single-layer, two-layer or more layers of graphene to the target substrate, and then baking, The electrostatic protection film is removed by a method such as low-temperature cooling, and the purpose of transferring the multilayer graphene by the electrostatic protection film is achieved. Figure 1 is a schematic diagram of a process flow for transferring graphene to the electrostatic protective film shown in the present invention.
本发明的目的之二是提供一种石墨烯薄膜，所述石墨烯薄膜由本发明所述的方法制备得到。 Another object of the present invention is to provide a graphene film which is prepared by the method of the present invention.
优选地，本发明所述方法制备得到的石墨烯薄膜的层数≥ 1 ，例如 1 、 2 、 3 、 4 、 5 、 8 、 9 等，优选≥ 2 ，进一步优选 2~5 。 Preferably, the number of layers of the graphene film prepared by the method of the invention is ≥ 1, for example, 1, 2, 3, 4, 5 8, 8, 9, etc., preferably ≥ 2, further preferably 2 to 5.
优选地，当石墨烯薄膜的层数为 2 时，所述石墨烯薄膜的方块电阻为 301.7~498.1 Ω/□ 。 Preferably, when the number of layers of the graphene film is 2, the sheet resistance of the graphene film is 301.7 to 498.1 Ω/□. .
本发明的目的之三是提供一种本发明所述石墨烯薄膜的用途，所述石墨烯薄膜用于能量储存活性材料，优选用于储氢、锂离子电池、超级电容器或者燃料电池，以及纳电子器件、高频电路、光子传感器、基因电子测序和减少噪音。 A third object of the present invention is to provide a use of the graphene film of the present invention for energy storage of an active material, preferably for hydrogen storage, a lithium ion battery, a supercapacitor or a fuel cell, and Electronics, high frequency circuits, photon sensors, gene electronics sequencing and noise reduction.
有益效果Beneficial effect
与现有技术相比，本发明具有如下有益效果： Compared with the prior art, the present invention has the following beneficial effects:
（ 1 ）本发明克服了采用有机胶转移石墨烯过程中容易破损、不易操作、有残留物、易污染等缺点，具有操作方便、工艺简单、成本低、无残胶、可以重复使用等特点。 ( 1 The invention overcomes the defects of easy to break, difficult to operate, residue, easy to be contaminated in the process of transferring the graphene by the organic glue, and has the advantages of convenient operation, simple process, low cost, no residual glue, and reusability.
（ 2 ）本发明提供的方法可用于卷对卷技术转移石墨烯，工艺简单，有利于石墨烯薄膜的规模化生产。 ( 2 The method provided by the invention can be used for the transfer of graphene by the roll-to-roll technology, and the process is simple, and is beneficial to the large-scale production of the graphene film.
（ 3 ）去除静电保护膜后无残留物，对石墨烯无任何污染，不会影响载流子的运输性能。 (3) After removing the electrostatic protective film, there is no residue, no pollution to the graphene, and no influence on the transportability of the carrier.
附图说明DRAWINGS
附图用来提供对该专利的进一步理解说明，构成说明书的一部分，并不构成对本发明的限制。 The drawings are intended to provide a further understanding of the invention and are not a limitation of the invention.
图 1 本发明所述静电保护膜转移多层石墨烯的工艺流程示意图； 1 is a schematic view showing a process flow of transferring a multilayer graphene by the electrostatic protection film of the present invention;
图 2 本发明步骤（ 1 ）所述静电保护膜 / 石墨烯 / 衬底的结合体的结构示意图； 2 is a schematic structural view of a combination of the electrostatic protection film/graphene/substrate of the step (1) of the present invention;
其中， 1- 静电保护膜； 2- 石墨烯； 3- 生长衬底； 4- 目标基底。 Among them, 1- electrostatic protective film; 2-graphene; 3- growth substrate; 4-target substrate.
本发明的实施方式Embodiments of the invention
为便于理解本发明，本发明列举实施例如下。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。 To facilitate an understanding of the invention, the invention is set forth below. It should be understood by those skilled in the art that the present invention is not to be construed as limited.
实施例 1 ： Example 1
一种采用静电保护膜转移多层石墨烯的方法，包括以下步骤： A method for transferring multilayer graphene by using an electrostatic protective film, comprising the following steps:
（ 1 ）利用铜箔作为衬底通过气相沉积法制备石墨烯薄膜，将长有石墨烯的铜箔夹在两块玻璃之间，施加一定的力使铜箔薄膜表面平整、褶皱少；通过覆膜机将 PP 静电保护膜和长有石墨烯的铜箔完全贴合，覆膜速度 10mm/min ，覆膜温度为室温； ( 1 A graphene film is prepared by a vapor deposition method using a copper foil as a substrate, and a copper foil having graphene is sandwiched between two glasses, and a certain force is applied to make the surface of the copper foil film flat and wrinkles less; PP The electrostatic protective film and the copper foil with graphene are completely adhered, the film speed is 10 mm/min, and the film temperature is room temperature;
（ 2 ）将静电保护膜 / 长有石墨烯的铜箔的结合体放入过硫酸铵溶液中刻蚀，静电保护膜的一面朝上，铜箔的一面朝下； 10min 后，采用去离子水和乙醇清洗铜箔的表面，同样的方法，连续清洗两次；刻蚀 3h ，铜箔完全去除；然后将石墨烯 / 静电保护膜从过硫酸铵溶液中取出，用去离子水和乙醇冲洗石墨烯 / 静电保护膜的表面，室温下晾干； (2) Electrostatic protective film / The combination of the graphene-containing copper foil is etched in an ammonium persulfate solution, the side of the electrostatic protection film faces upward, and the side of the copper foil faces downward; 10 min After that, the surface of the copper foil is washed with deionized water and ethanol, and the same method is used for continuous cleaning twice; after etching for 3 hours, the copper foil is completely removed; then graphene / The electrostatic protective film is taken out from the ammonium persulfate solution, and the surface of the graphene/electrostatic protective film is rinsed with deionized water and ethanol, and dried at room temperature;
（ 2' ）将石墨烯 / 静电保护膜结合体取代步骤（ 1 ）中所述的静电保护膜，重复步骤（ 1 ） ~ （ 2 ）的操作，形成双层石墨烯 / 静电保护膜结合体； (2') replacing the electrostatic protective film described in the step (1) with the graphene/electrostatic protective film combination, and repeating the step (1) ~ (2) operation to form a double layer graphene / electrostatic protection film combination;
（ 3 ）利用覆膜机将双层石墨烯 / 静电保护膜结合体与 PET 完全贴合，覆膜转速为 10mm/min ，覆膜温度为 30 ℃，然后 40 ℃烘烤去除静电保护膜，得到双层石墨烯薄膜。 (3) Using a laminator to completely bond the double-layer graphene/electrostatic protective film combination to PET, and the film rotation speed is 10mm/min. The film temperature was 30 ° C, and then the electrostatic protection film was baked at 40 ° C to obtain a double-layer graphene film.
性能测试： Performance Testing:
所得到双层石墨烯薄膜的方块电阻为 401.6 Ω/□ 。 The sheet resistance of the obtained two-layer graphene film was 401.6 Ω/□.
实施例 2 ： Example 2:
一种采用静电保护膜转移多层石墨烯的方法，包括以下步骤： A method for transferring multilayer graphene by using an electrostatic protective film, comprising the following steps:
（ 1 ）通过气相沉积法制备铜箔为衬底的石墨烯薄膜，将长有石墨烯的铜箔通过覆膜机滚压使铜箔薄膜非常平整，覆膜速度为 200mm/min ；采用覆膜技术，将 PET 静电保护膜贴合到长有石墨烯铜箔上；覆膜速度为 200mm/min ，覆膜温度为室温； ( 1 The graphene film with copper foil as the substrate is prepared by vapor deposition method, and the copper foil with graphene is rolled by a laminator to make the copper foil film very flat, and the film speed is 200 mm/min; PET The electrostatic protection film is attached to the long graphene copper foil; the film speed is 200 mm/min, and the film temperature is room temperature;
（ 2 ）将静电保护膜与长有石墨烯的铜箔的结合体放入氯化铁溶液中刻蚀， 10min 后，采用去离子水和甲醇清洗铜箔的表面，同样的方法，连续清洗两次；刻蚀 3h ，铜箔完全去除；然后将石墨烯 / 静电保护膜从氯化铁溶液中取出，用去离子水和甲醇冲洗石墨烯 / 静电保护膜的表面， 40 ℃ 烘干； (2) The combination of the electrostatic protective film and the copper foil with graphene is etched in a ferric chloride solution for 10 minutes. After that, the surface of the copper foil is cleaned with deionized water and methanol, and the same method is used for continuous cleaning twice; after 3 hours of etching, the copper foil is completely removed; then graphene / The electrostatic protective film is taken out from the ferric chloride solution, and the surface of the graphene/electrostatic protective film is rinsed with deionized water and methanol, and dried at 40 ° C;
（ 2' ）将石墨烯 / 静电保护膜结合体取代步骤（ 1 ）中所述的静电保护膜，重复步骤（ 1 ） ~ （ 2 ）的操作，形成双层石墨烯 / 静电保护膜结合体； (2') replacing the electrostatic protective film described in the step (1) with the graphene/electrostatic protective film combination, and repeating the step (1) ~ (2) operation to form a double layer graphene / electrostatic protection film combination;
（ 3 ）将双层石墨烯 / 静电保护膜完全贴在玻璃基底上，在 100 ℃ 的烘烤条件下，去除静电保护膜，得到双层石墨烯薄膜。 (3) The double-layer graphene/electrostatic protective film is completely attached to the glass substrate at 100 °C Under the baking condition, the electrostatic protection film is removed to obtain a double-layer graphene film.
性能测试： Performance Testing:
所得到双层石墨烯薄膜的方块电阻为 301.7 Ω/□ 。 The sheet resistance of the obtained two-layer graphene film was 301.7 Ω/□.
实施例 3 ： Example 3:
一种采用静电保护膜转移多层石墨烯的方法，包括以下步骤： A method for transferring multilayer graphene by using an electrostatic protective film, comprising the following steps:
（ 1 ）通过气相沉积法制备镍箔为衬底的石墨烯薄膜，将长有石墨烯的铜箔通过覆膜机滚压使镍箔薄膜非常平整，覆膜速度为 1000mm/min ；采用覆膜技术，将 PVC 静电保护膜贴合到长有石墨烯镍箔上；其中，覆膜速度为 1000mm/min ； ( 1 The graphene film with nickel foil as the substrate is prepared by vapor deposition method, and the copper foil with graphene is rolled by a laminator to make the nickel foil film very flat, and the film speed is 1000 mm/min; Will PVC The electrostatic protection film is attached to the long graphene nickel foil; wherein the film speed is 1000 mm/min;
（ 2 ）将静电保护膜与长有石墨烯的镍箔的结合体放入的硝酸铁溶液中刻蚀； 10min 后，采用去离子水和甲醇清洗镍箔的表面，同样的方法，连续清洗两次；刻蚀 3h ，镍箔完全去除；然后将石墨烯 / 静电保护膜从氯化铁溶液中取出，用去离子水和甲醇冲洗石墨烯 / 静电保护膜的表面， 60 ℃烘干； (2) etching the iron nitrate solution in which the combination of the electrostatic protection film and the nickel foil having graphene is placed; 10 min After that, the surface of the nickel foil is cleaned with deionized water and methanol, and the same method is used for continuous cleaning twice; after 3 hours of etching, the nickel foil is completely removed; then graphene / The electrostatic protection film is taken out from the ferric chloride solution, and the surface of the graphene/electrostatic protective film is rinsed with deionized water and methanol, and dried at 60 ° C;
（ 2' ）将石墨烯 / 静电保护膜结合体取代步骤（ 1 ）中所述的静电保护膜，重复步骤（ 1 ） ~ （ 2 ）的操作，形成双层石墨烯 / 静电保护膜结合体； (2') replacing the electrostatic protective film described in the step (1) with the graphene/electrostatic protective film combination, and repeating the step (1) ~ (2) operation to form a double layer graphene / electrostatic protection film combination;
（ 3 ）最后将双层石墨烯 / 静电保护膜完全贴在硅片基底上，在 150 ℃的烘烤条件下，去除静电保护膜，得到双层石墨烯薄膜。 (3) Finally, the double-layer graphene/electrostatic protective film is completely attached to the silicon substrate, at 150 Under the baking condition of °C, the electrostatic protective film was removed to obtain a two-layer graphene film.
性能测试： Performance Testing:
所得到双层石墨烯薄膜的方块电阻为 332.5 Ω/□ 。 The sheet resistance of the obtained two-layer graphene film was 332.5 Ω/□.
实施例 4 ： Example 4:
一种采用静电保护膜转移多层石墨烯的方法，包括以下步骤： A method for transferring multilayer graphene by using an electrostatic protective film, comprising the following steps:
步骤（ 1 ） - （ 2' ）同实施例 2 中完全相同； Steps (1) - (2') are identical to those in Embodiment 2;
（ 3 ）利用覆膜机将双层石墨烯 / 静电保护膜与 PI 完全贴合，在 -210 ℃ 的条件下，去除静电保护膜，得到双层石墨烯薄膜。 (3) Using a laminator to completely bond the double-layer graphene/electrostatic protective film to PI at -210 °C Under the conditions, the electrostatic protection film was removed to obtain a double-layer graphene film.
性能测试： Performance Testing:
所得到双层石墨烯薄膜的方块电阻为 498.1 Ω/□ 。 The sheet resistance of the obtained two-layer graphene film was 498.1 Ω/□.
实施例 5 ： Example 5:
一种采用静电保护膜转移多层石墨烯的方法，包括以下步骤： A method for transferring multilayer graphene by using an electrostatic protective film, comprising the following steps:
步骤（ 1 ） - （ 2' ）同实施例 2 中完全相同。 Steps (1) - (2') are identical to those in Embodiment 2.
（ 3 ）利用覆膜机将双层石墨烯 / 静电保护膜与 PI 完全贴合，在 0 ℃ 的条件下，去除静电保护膜。 (3) Using a laminator to completely bond the double-layer graphene/electrostatic protective film to PI at 0 °C Under the conditions, remove the electrostatic protective film.
所得到双层石墨烯的方块电阻为 442.9 Ω/□ 。 The sheet resistance of the obtained double-layer graphene was 442.9 Ω/□.
实施例 6 ： Example 6:
一种采用静电保护膜转移多层石墨烯的方法，包括以下步骤： A method for transferring multilayer graphene by using an electrostatic protective film, comprising the following steps:
步骤（ 1 ） - （ 2 ）同实施例 2 中完全相同。 Steps (1) - (2) are identical to those in Embodiment 2.
（ 2' ）重复步骤（ 1 ）和（ 2 ）的操作 2 次，形成三层石墨烯 / 静电保护膜结合体； ( 2 ' ) Repeat steps ( 1 ) and ( 2 ) twice to form three layers of graphene / Electrostatic protective film combination;
（ 3 ）将三层石墨烯 / 静电保护膜完全贴在玻璃基底上，在 -196 ℃的条件下，去除静电保护膜。 (3) The three-layer graphene/electrostatic protective film is completely attached to the glass substrate at -196 The electrostatic protective film was removed under the conditions of °C.
性能测试： Performance Testing:
所得到三层石墨烯薄膜的方块电阻为 208.3Ω/□ 。 The sheet resistance of the obtained three-layer graphene film was 208.3 Ω/□.
实施例 7 ： Example 7:
一种采用静电保护膜转移多层石墨烯的方法，包括以下步骤： A method for transferring multilayer graphene by using an electrostatic protective film, comprising the following steps:
步骤（ 1 ） - （ 2 ）同实施例 2 中完全相同。 Steps (1) - (2) are identical to those in Embodiment 2.
（ 2' ）重复步骤（ 1 ）和（ 2 ）的操作 5 次，形成六层石墨烯 / 静电保护膜结合体； ( 2 ' ) Repeat steps ( 1 ) and ( 2 ) for 5 times to form six layers of graphene / Electrostatic protective film combination;
（ 3 ）将六层石墨烯 / 静电保护膜完全贴在玻璃基底上，在 -123 ℃的条件下，去除静电保护膜。 (3) The six-layer graphene/electrostatic protective film is completely attached to the glass substrate at -123 The electrostatic protective film was removed under the conditions of °C.
性能测试： Performance Testing:
所得到六层石墨烯薄膜的方块电阻为 60.5 Ω/□ 。 The sheet resistance of the obtained six-layer graphene film was 60.5 Ω/□.
实施例 8 Example 8
一种采用静电保护膜转移多层石墨烯的方法，包括以下步骤： A method for transferring multilayer graphene by using an electrostatic protective film, comprising the following steps:
步骤（ 1 ） - （ 2 ）同实施例 2 中相同，但步骤（ 1 ）的覆膜速度为 1mm/min ，覆膜温度为 200 ℃。 Step (1) - (2) is the same as in Example 2, but the film speed of the step (1) is 1 mm/min. The film temperature is 200 °C.
（ 2' ）重复步骤（ 1 ）和（ 2 ）的操作 2 次，形成三层石墨烯 / 静电保护膜结合体； (2') repeating the operations of steps (1) and (2) twice to form a three-layer graphene/electrostatic protective film combination;
（ 3 ）将六层石墨烯 / 静电保护膜完全贴在玻璃基底上，覆膜速度为 1mm/min ，覆膜温度为 200 ℃；在 200 ℃的烘烤条件下，去除静电保护膜，得到三层石墨烯薄膜。 (3) The six-layer graphene/electrostatic protective film is completely attached to the glass substrate at a film speed of 1 mm/min, and the film temperature is 200 ° C; under 200 ° C baking conditions, the electrostatic protective film was removed to obtain a three-layer graphene film.
性能测试： Performance Testing:
所得到三层石墨烯薄膜的方块电阻为 130.5 Ω/□ 。 The sheet resistance of the obtained three-layer graphene film was 130.5 Ω/□.
实施例 9 Example 9
一种采用静电保护膜转移多层石墨烯的方法，包括以下步骤： A method for transferring multilayer graphene by using an electrostatic protective film, comprising the following steps:
步骤（ 1 ） - （ 2 ）同实施例 2 中相同，但步骤（ 1 ）的覆膜速度为 2000mm/min ，覆膜温度为 0 ℃。 Step (1) - (2) is the same as in Example 2, but the film speed of the step (1) is 2000 mm/min. The film temperature is 0 °C.
（ 2' ）重复步骤（ 1 ）和（ 2 ）的操作 5 次，形成六层石墨烯 / 静电保护膜结合体； (2') repeating the operations of steps (1) and (2) five times to form a six-layer graphene/electrostatic protective film combination;
（ 3 ）将六层石墨烯 / 静电保护膜完全贴在玻璃基底上，覆膜速度为 2000mm/min ，，覆膜温度为 0 ℃；在 -210 ℃的条件下，去除静电保护膜。，得到六层石墨烯薄膜。 (3) The six-layer graphene/electrostatic protective film is completely attached to the glass substrate at a film speed of 2000 mm/min. , the film temperature is 0 °C; at -210 °C, the electrostatic protection film is removed. , a six-layer graphene film was obtained.
性能测试： Performance Testing:
所得到六层石墨烯薄膜的方块电阻为 55.2 Ω/□ 。 The sheet resistance of the obtained six-layer graphene film was 55.2 Ω/□.
申请人声明，本发明通过上述实施例来说明本发明的详细工艺设备和工艺流程，但本发明并不局限于上述详细工艺设备和工艺流程，即不意味着本发明必须依赖上述详细工艺设备和工艺流程才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。 The Applicant declares that the present invention illustrates the detailed process equipment and process flow of the present invention by the above embodiments, but the present invention is not limited to the above detailed process equipment and process flow, that is, does not mean that the present invention must rely on the above detailed process equipment and The process can only be implemented. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.

Claims (10)

  1. 一种以静电保护膜为媒介转移石墨烯薄膜的方法，其特征在于，所述方法是利用静电保护膜的静电吸附作用贴合包含生长衬底的石墨烯，然后将生长衬底去除，得到单层石墨烯 / 静电保护膜结合体，最后将单层石墨烯 / 静电保护膜结合体贴合于目标基底上，释放静电去除静电保护膜，得到单层石墨烯薄膜；A method for transferring a graphene film by using an electrostatic protection film as a medium, wherein the method comprises: bonding a graphene containing a growth substrate by electrostatic adsorption of an electrostatic protection film, and then removing the growth substrate to obtain a single Graphene / electrostatic protective film combination, finally a single layer of graphene / electrostatic protective film combination attached to the target substrate, releasing static electricity to remove the electrostatic protective film to obtain a single layer of graphene film;
    所述方法还可在得到单层石墨烯 / 静电保护膜结合体后，以单层石墨烯 / 静电保护膜结合体代替静电保护膜，在新的包含生长衬底的石墨烯上依次重复进行以下两步骤 n-1 次：贴合石墨烯 / 静电保护膜、去除衬底；从而制备得到 n 层石墨烯薄膜，所述 n 的取值为≥ 2 的整数。The method may also be a single layer of graphene / after obtaining a single layer graphene / electrostatic protective film combination The electrostatic protective film combination is used instead of the electrostatic protective film, and the following two steps are repeated n-1 times on the new graphene containing the growth substrate: laminating the graphene/electrostatic protective film, removing the substrate; thereby preparing n For a graphene film, the value of n is an integer of ≥ 2.
  2. 如权利要求 1 所述的方法，其特征在于，所述方法包括如下步骤：The method of claim 1 wherein said method comprises the steps of:
    （ 1 ）将静电保护膜贴合在包含生长衬底的石墨烯薄膜表面；(1) attaching an electrostatic protection film to the surface of the graphene film including the growth substrate;
    （ 2 ）去除步骤（ 1 ）所述的生长衬底，得到单层石墨烯 / 静电保护膜结合体；(2) removing the growth substrate described in the step (1) to obtain a single-layer graphene/electrostatic protective film combination;
    （ 3 ）将石墨烯 / 静电保护膜结合体贴合在目标基底上，释放静电去除静电保护膜，得到石墨烯薄膜；(3) Graphene / The electrostatic protection film combination body is attached to the target substrate, and the static electricity is removed to remove the electrostatic protection film to obtain a graphene film;
    其中，步骤（ 3 ）所述石墨烯 / 静电保护膜为步骤（ 2 ）所述的单层石墨烯 / 静电保护膜；所述石墨烯薄膜为单层石墨烯薄膜。Wherein the graphene/electrostatic protective film in step (3) is the single layer graphene according to step (2) / An electrostatic protective film; the graphene film is a single-layer graphene film.
  3. 如权利要求 2 所述的方法，其特征在于，所述方法在步骤（ 2 ）后任选进行步骤（ 2' ）：The method of claim 2 wherein said method optionally performs step (2') after step (2):
    （ 2' ）将步骤（ 2 ）得到的单层石墨烯 / 静电保护膜结合体代替步骤（ 1 ）所述的静电保护膜，重复步骤（ 1 ） ~ 步骤（ 2 ） n-1 次，制备得到 n 层石墨烯 / 静电保护膜结合体；所述 n 的取值为≥ 2 的整数；(2') replacing the electrostatic protective film described in the step (1) with the single-layer graphene/electrostatic protective film combination obtained in the step (2), repeating the step (1) ~ Step (2) n-1 times, to prepare an n-layer graphene / electrostatic protective film combination; the value of n is an integer of ≥ 2;
    其中，当步骤（ 2 ）后进行步骤（ 2' ）时，步骤（ 3 ）所述石墨烯 / 静电保护膜为步骤（ 2' ）所述的多层石墨烯 / 静电保护膜；所述石墨烯薄膜为 n 层石墨烯薄膜。Wherein, when the step (2') is performed after the step (2), the graphene/electrostatic protective film of the step (3) is the multilayer graphene described in the step (2') / electrostatic protective film; the graphene film is an n-layer graphene film.
  4. 如权利要求 1~3 之一所述的方法，其特征在于，所述静电保护膜选自 PE 静电保护膜、 PET 静电保护膜、 PVC 静电保护膜、 PP 静电保护膜中的任意一种，优选 PET 静电保护膜、 PVC 静电保护膜中的任意一种；The method according to any one of claims 1 to 3, wherein the electrostatic protection film is selected from the group consisting of a PE electrostatic protective film, a PET electrostatic protective film, and a PVC. Any one of an electrostatic protective film and a PP electrostatic protective film, preferably any one of a PET electrostatic protective film and a PVC electrostatic protective film;
    优选地，所述目标基底选自玻璃、 PET 、硅片、 PI 、 PVC 、 PE 、 PP 、 PS 、中的任意 1 种，优选 PP 、 PE 、硅片、玻璃中的任意一种。 Preferably, the target substrate is selected from any one of glass, PET, silicon wafer, PI, PVC, PE, PP, PS, preferably Any of PP, PE, silicon, and glass.
  5. 如权利要求 2~4 之一所述的方法，其特征在于，步骤（ 2 ）所述去除生长衬底的方法是湿法刻蚀，所述刻蚀液选自氯化铁、硝酸铁、硝酸、过硫酸铵和过硫酸钾中的任意一种或至少两种的组合，优选过硫酸铵和 / 或过硫酸钾。 The method according to any one of claims 2 to 4, characterized in that the step (2) The method of removing the growth substrate is a wet etching, and the etching liquid is selected from any one or a combination of at least two of ferric chloride, iron nitrate, nitric acid, ammonium persulfate, and potassium persulfate. Ammonium persulfate and/or potassium persulfate are preferred.
  6. 如权利要求 2~5 之一所述的方法，其特征在于，步骤（ 3 ）所述释放静电去除静电保护膜的方法为烘烤、低温冷却中的任意一种； The method according to any one of claims 2 to 5, characterized in that the step (3) The method for releasing the static electricity to remove the electrostatic protection film is any one of baking and low temperature cooling;
    优选地，所述烘烤的温度为 40~200 ℃，优选 50~180 ℃，进一步优选 70~150 ℃，特别优选 100~120 ℃；Preferably, the baking temperature is 40 to 200 ° C, preferably 50 to 180 ° C, further preferably 70 to 150 ° C, particularly preferably 100 to 120 °C;
    优选地，所述冷却的温度为 -210~0 ℃，优选 -200~-5 ℃，进一步优选 -160~-20 ℃，特别优选 -100~-50 ℃。Preferably, the cooling temperature is -210 to 0 ° C, preferably -200 to -5 ° C, further preferably -160 to -20 ° C, particularly preferably -100~-50 °C.
  7. 如权利要求 2~6 之一所述的方法，其特征在于，步骤（ 1 ）和步骤（ 3 ）所述的贴合方法为人工粘贴，机器覆膜粘贴中的任意 1 种，优选机器覆膜粘贴；Method according to one of claims 2 to 6, characterized in that step (1) and step (3) The bonding method described above is any one of manual bonding and machine film bonding, and is preferably a machine film bonding;
    优选地，所述机器覆膜粘贴的覆膜速度为 1~2000mm/min ，优选 10~1800 mm/min ，进一步优选 20~1500 mm/min ，特别优选 30~1400 mm/min ；Preferably, the film speed of the machine film is 1 to 2000 mm/min, preferably 10 to 1800 mm/min, and further preferably 20~1500 mm/min, especially preferably 30~1400 mm/min;
    优选地，所述机器覆膜粘贴的覆膜温度为 0~200 ℃，优选 3~198 ℃，进一步优选 20~80 ℃，特别优选 40~70 ℃。Preferably, the temperature of the film coated by the machine film is 0 to 200 ° C, preferably 3 to 198 ° C, further preferably 20 to 80 ° C, particularly preferably 40~70 °C.
  8. 如权利要求 1~7 之一所述的方法，其特征在于，所述方法包括如下步骤：The method according to any one of claims 1 to 7, wherein the method comprises the following steps:
    （ 1 ）将静电保护膜贴合在包含生长衬底的石墨烯薄膜表面；(1) attaching an electrostatic protection film to the surface of the graphene film including the growth substrate;
    （ 2 ）去除步骤（ 1 ）所述的生长衬底，得到单层石墨烯 / 静电保护膜结合体；(2) removing the growth substrate described in the step (1) to obtain a single-layer graphene/electrostatic protective film combination;
    （ 2' ）将步骤（ 2 ）得到的单层石墨烯 / 静电保护膜结合体代替步骤（ 1 ）所述的静电保护膜，重复步骤（ 1 ） ~ 步骤（ 2 ），制备得到双层石墨烯 / 静电保护膜结合体；(2') replacing the electrostatic protective film described in the step (1) with the single-layer graphene/electrostatic protective film combination obtained in the step (2), repeating the step (1) ~ Step (2), preparing a bilayer graphene / electrostatic protective film combination;
    （ 3 ）将石墨烯 / 静电保护膜结合体贴合在目标基底上，释放静电去除静电保护膜，得到石墨烯薄膜；(3) Graphene / The electrostatic protection film combination body is attached to the target substrate, and the static electricity is removed to remove the electrostatic protection film to obtain a graphene film;
    其中，步骤（ 3 ）所述石墨烯 / 静电保护膜为步骤（ 2 ）所述的单层石墨烯 / 静电保护膜；所述石墨烯薄膜为双层石墨烯薄膜。 Wherein the graphene/electrostatic protective film in step (3) is the single layer graphene according to step (2) / An electrostatic protective film; the graphene film is a two-layer graphene film.
  9. 一种如权利要求1~8之一所述的石墨烯薄膜，其特征在于，所述石墨烯薄膜的层数≥1，优选≥ 2，进一步优选2~5。 A graphene film according to any one of claims 1 to 8, characterized in that the number of layers of the graphene film is ≥ 1, preferably ≥ 2, more preferably 2 to 5.
  10. 一种如权利要求9所述的石墨烯薄膜的用途，其特征在于，所述石墨烯薄膜用于能量储存活性材料，优选用于储氢、锂离子电池、超级电容器或者燃料电池，以及纳电子器件、高频电路、光子传感器、基因电子测序和减少噪音。 Use of the graphene film according to claim 9, wherein the graphene film is used for energy storage active materials, preferably for hydrogen storage, lithium ion batteries, supercapacitors or fuel cells, and nanoelectronics Devices, high frequency circuits, photon sensors, gene electronics sequencing and noise reduction.
PCT/CN2013/074835 2012-07-31 2013-04-26 Method for transferring graphene film using electrostatic protection film as medium WO2014019387A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201210269206.5 2012-07-31
CN201210269206.5A CN102774118B (en) 2012-07-31 2012-07-31 Method for transferring graphene film with static protective film as medium

Publications (1)

Publication Number Publication Date
WO2014019387A1 true WO2014019387A1 (en) 2014-02-06

Family

ID=47119322

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2013/074835 WO2014019387A1 (en) 2012-07-31 2013-04-26 Method for transferring graphene film using electrostatic protection film as medium

Country Status (2)

Country Link
CN (1) CN102774118B (en)
WO (1) WO2014019387A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109130162A (en) * 2018-08-31 2019-01-04 合肥泰沃达智能装备有限公司 A kind of manual laminating machine of light guide plate processing
CN113873738A (en) * 2021-09-26 2021-12-31 中国工程物理研究院激光聚变研究中心 Self-supporting carbon-based capacitor target and preparation method thereof

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102774118B (en) * 2012-07-31 2015-05-13 无锡格菲电子薄膜科技有限公司 Method for transferring graphene film with static protective film as medium
CN103332680A (en) * 2013-06-28 2013-10-02 重庆墨希科技有限公司 Transferable graphene film and transfer method thereof
CN103332682B (en) * 2013-07-10 2015-08-19 合肥微晶材料科技有限公司 A kind of method of membrane screen and laminating machine superposition transfer large-area graphene
CN103332683B (en) * 2013-07-10 2014-12-03 合肥微晶材料科技有限公司 Graphene storage method
WO2015015386A1 (en) * 2013-08-01 2015-02-05 Basf Se Two-dimensional graphene-based porous polymer and the preparation thereof
CN104339748A (en) * 2013-08-07 2015-02-11 苏州沛德导热材料有限公司 Graphite protective film
CN104192832B (en) * 2014-08-14 2017-04-05 常州二维碳素科技股份有限公司 A kind of method and the graphene film obtained by the method for transfer Graphene
CN104477894B (en) * 2014-12-12 2017-06-09 中国科学院宁波材料技术与工程研究所 A kind of method for shifting Graphene
CN104445176B (en) * 2014-12-12 2017-04-12 中国科学院宁波材料技术与工程研究所 Graphene protector
CN104451592B (en) * 2014-12-15 2017-02-22 中国科学院微电子研究所 Method for nondestructively transferring graphene from metal surface to surface of target substrate
CN104817073B (en) * 2015-03-27 2017-01-11 中国科学技术大学 Method for transferring graphene film to TEM copper net
CN104890312B (en) * 2015-06-24 2018-02-23 中国科学院宁波材料技术与工程研究所 The method and graphene composite material of graphene layer on a kind of protection group bottom
CN105563919A (en) * 2015-12-24 2016-05-11 无锡格菲电子薄膜科技有限公司 Storable graphene membrane and preparation method thereof
CN106129797A (en) * 2016-08-09 2016-11-16 广东工业大学 Based on WS2the ultrashort pulse fiber laser of/Graphene hetero-junctions
CN106775146A (en) * 2016-11-25 2017-05-31 重庆墨希科技有限公司 The preparation method of OCA substrate Graphene touch-screens
CN106626556A (en) * 2016-12-28 2017-05-10 镇江博昊科技有限公司 Copper-based graphene composite film coil
CN107065303A (en) * 2017-05-05 2017-08-18 武汉华星光电技术有限公司 Mouth word glue and backlight assembly
CN112590354B (en) * 2020-12-08 2022-07-05 宁波华丰包装有限公司 Antistatic membrane of graphite alkene and calendering device thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101764051A (en) * 2010-01-15 2010-06-30 电子科技大学 Method for transferring graphene film
CN101913598A (en) * 2010-08-06 2010-12-15 浙江大学 Method for preparing graphene membrane
US20110048625A1 (en) * 2009-08-27 2011-03-03 Caldwell Joshua D METHOD FOR THE REDUCTION OF GRAPHENE FILM THICKNESS AND THE REMOVAL AND TRANSFER OF EPITAXIAL GRAPHENE FILMS FROM SiC SUBSTRATES
CN102173412A (en) * 2011-01-17 2011-09-07 南昌大学 Method for transferring graphene by using polymethylmethacrylate
CN102774118A (en) * 2012-07-31 2012-11-14 无锡格菲电子薄膜科技有限公司 Method for transferring graphene film with static protective film as medium

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101019029B1 (en) * 2007-08-14 2011-03-04 한국과학기술연구원 Graphene hybrid material and method for preparing the same using chemical vapor deposition
US8535553B2 (en) * 2008-04-14 2013-09-17 Massachusetts Institute Of Technology Large-area single- and few-layer graphene on arbitrary substrates
US10164135B2 (en) * 2009-08-07 2018-12-25 Guardian Glass, LLC Electronic device including graphene-based layer(s), and/or method or making the same
US10167572B2 (en) * 2009-08-07 2019-01-01 Guardian Glass, LLC Large area deposition of graphene via hetero-epitaxial growth, and products including the same
WO2012031238A2 (en) * 2010-09-03 2012-03-08 The Regents Of The University Of Michigan Uniform multilayer graphene by chemical vapor deposition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110048625A1 (en) * 2009-08-27 2011-03-03 Caldwell Joshua D METHOD FOR THE REDUCTION OF GRAPHENE FILM THICKNESS AND THE REMOVAL AND TRANSFER OF EPITAXIAL GRAPHENE FILMS FROM SiC SUBSTRATES
CN101764051A (en) * 2010-01-15 2010-06-30 电子科技大学 Method for transferring graphene film
CN101913598A (en) * 2010-08-06 2010-12-15 浙江大学 Method for preparing graphene membrane
CN102173412A (en) * 2011-01-17 2011-09-07 南昌大学 Method for transferring graphene by using polymethylmethacrylate
CN102774118A (en) * 2012-07-31 2012-11-14 无锡格菲电子薄膜科技有限公司 Method for transferring graphene film with static protective film as medium

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109130162A (en) * 2018-08-31 2019-01-04 合肥泰沃达智能装备有限公司 A kind of manual laminating machine of light guide plate processing
CN113873738A (en) * 2021-09-26 2021-12-31 中国工程物理研究院激光聚变研究中心 Self-supporting carbon-based capacitor target and preparation method thereof
CN113873738B (en) * 2021-09-26 2024-01-12 中国工程物理研究院激光聚变研究中心 Self-supporting carbon-based capacitor target and preparation method thereof

Also Published As

Publication number Publication date
CN102774118B (en) 2015-05-13
CN102774118A (en) 2012-11-14

Similar Documents

Publication Publication Date Title
WO2014019387A1 (en) Method for transferring graphene film using electrostatic protection film as medium
TWI653765B (en) Electronic device including graphene bottom layer and manufacturing method thereof
EP2462263B1 (en) Debonding and transfer techniques for hetero-epitaxially grown graphene
KR102513763B1 (en) Method for the fabrication and transfer of graphene
EP2584075B1 (en) Large area deposition and doping of graphene, and products including the same
CN102795619B (en) Graphene thin film transferring method based on physical adsorption
US10167572B2 (en) Large area deposition of graphene via hetero-epitaxial growth, and products including the same
JP2013513544A (en) Extensive precipitation of graphene on a substrate and products containing it
CN104944417A (en) Preparation method of graphene-boron nitride heterojunction
Kim et al. A review on transfer process of two-dimensional materials
CN109321893A (en) Preparation method, graphene protective film and its application method of graphene protective film
WO2013002564A2 (en) Anti-releasing composition, graphene laminate including the composition, and preparation method thereof
WO2018201952A1 (en) Graphene production method and device for realizing same
CN110517809A (en) A kind of transparent graphene conductive film, preparation method and application
CN114920239B (en) Two-dimensional material transferring or stacking method based on water vapor
CN116281890A (en) Method for transferring boron nitride
CN104925800A (en) Method for transferring fluorinated graphene
CN115589756A (en) Process method for preparing patterned graphene in large area in situ

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13824924

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13824924

Country of ref document: EP

Kind code of ref document: A1