A method for preparing patterned graphene film

Abstract

The present invention discloses a method for preparing a patterned graphene film, comprising: method 1: first preparing a patterned inorganic layer on a copper plate substrate, exposing the area where the graphene film is needed, covering the area where the graphene film is not needed with the inorganic layer, and growing the graphene film in the area not covered by the inorganic layer; depositing or coating other substrates on the obtained graphene layer; using a chemical solution to dissolve the copper plate substrate, thereby transferring the patterned graphene layer to other substrates; or method 2: first preparing a patterned copper layer on any substrate, and growing the graphene film only in the area with the copper layer. The present invention uses the copper layer as a catalyst for growing the graphene film, directly patterns the copper layer through a yellow light process, or covers the surface with a patterned inorganic layer, so that the grown graphene film itself is patterned, and the operation is simple and easy to implement.

Description

Technical Field

[0001] The invention relates to the technical field of graphyne manufacturing, and in particular to a method for preparing a patterned graphyne film. Background Art

[0002] GDYNE is composed of sp 2 A new type of two-dimensional planar carbon material composed of two forms of carbon hybridization: sp and sp. Figure 1 As shown in Figure 2, graphyne has a large π-conjugated structure and an intrinsic band gap. In addition, theoretical calculations show that it has excellent charge transport capabilities. Therefore, graphyne has broad application prospects in energy conversion and photo / electrocatalysis. At present, the method for preparing graphyne thin films is usually to use hexaethynylbenzene as a monomer, copper sheet as a substrate and catalyst, and grow a large-area, continuous graphyne film on a copper sheet through a Glaser-Hay coupling reaction.

[0003] Since photoelectric conversion devices such as organic solar cells and organic light-emitting diodes are very sensitive to water and oxygen, the entire device needs to be completely covered by the encapsulation layer to obtain a longer service life. When using graphyne film as a carrier transport layer, the continuous graphyne film will cause water and oxygen to enter the device along the graphyne layer, shortening the service life of the photoelectric conversion device. In addition, the continuous graphyne film may also cause the occurrence of lateral current, thereby reducing the photoelectric conversion efficiency. Therefore, in the actual use of graphyne film, it is necessary to pattern it, that is, to obtain a graphyne film with controllable area and shape. The patterning of graphyne film can be obtained by etching or transfer, but the former is likely to cause the residue of the graphyne layer, and the latter is likely to cause the rupture of the graphyne film. In order to expand the commercial application prospects of graphyne film, it is necessary to develop a method for obtaining a patterned graphyne film. Summary of the invention

[0004] In order to solve the problems existing in the prior art, the purpose of the present invention is to provide a method for preparing a patterned Graphyne film, using a copper layer as a catalyst for growing a Graphyne film, directly patterning the copper layer through a yellow light process, or covering a patterned inorganic layer on its surface, so that the grown Graphyne film itself is patterned, and the operation is simple and easy to implement. In addition, the patterned Graphyne film is further transferred to a non-copper target substrate in combination with a transfer technology, expanding the application scenarios of the patterned Graphyne film.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0006] A method for preparing a patterned graphene film, comprising:

[0007] Method 1: first prepare a patterned inorganic layer on a copper substrate, expose the area where the gypsum film is needed, cover the area where the gypsum film is not needed with the inorganic layer, and grow the gypsum film in the area not covered by the inorganic layer; or

[0008] Method 2: On any substrate, a patterned copper layer is first prepared, and then a graphyne film is grown only in the area with the copper layer.

[0009] Optionally, the step of first preparing a patterned inorganic layer on the copper substrate, exposing the area where the gypsum film is required, covering the area where the gypsum film is not required with the inorganic layer, and growing the gypsum film in the area not covered by the inorganic layer specifically includes:

[0010] Step 1: Deposit an inorganic layer on a copper substrate;

[0011] Step 2: coating a positive photoresist on the inorganic layer, using a photomask 1 to expose the area where the graphyne film needs to be grown, then developing and removing the part of the photoresist, further etching the inorganic layer in the area, thereby exposing the metal copper layer in the area; dissolving and removing the photoresist on the obtained patterned inorganic layer;

[0012] Step 3: Using hexaethynylbenzene as a monomer, a graphyne film is grown on the exposed copper layer area through a Glaser-Hay coupling reaction, thereby obtaining a patterned graphyne layer;

[0013] Step 4: coating the inorganic layer and the gypsum layer with a positive photoresist, exposing the patterned inorganic layer region using a photomask 2, developing and removing the photoresist in the exposed region, further etching the inorganic layer in the region, thereby leaving only the patterned gypsum layer on the copper substrate, and finally dissolving and removing the photoresist on the patterned gypsum layer; or

[0014] Negative photoresist is coated on the inorganic layer and the graphyne layer, and the patterned graphyne layer area is still exposed using mask 1, so that the photoresist of this part is retained during development, and the remaining inorganic layer is further etched, so that only the patterned graphyne layer is retained on the copper plate substrate.

[0015] Furthermore, the inorganic layer is silicon nitride or silicon oxide.

[0016] Furthermore, it also includes:

[0017] Depositing or coating other substrates on the obtained Graphene layer;

[0018] The copper substrate is dissolved using a chemical solution, thereby transferring the patterned Graphene layer to other substrates.

[0019] Furthermore, the other substrate is transparent conductive glass or a flexible polymer film.

[0020] Furthermore, the chemical solution is ferric chloride.

[0021] Optionally, the step of first preparing a patterned copper layer on any substrate and growing the graphyne film only in the region with the copper layer specifically includes:

[0022] Step 1: deposit a copper metal layer on any substrate;

[0023] Step 2: coating the metal copper layer with a positive photoresist, using a photomask to expose the area where the graphyne film is not required to be grown, then developing and removing the photoresist, and further etching the metal copper layer in the area, thereby obtaining a patterned metal copper layer;

[0024] Step 3: Using hexaethynylbenzene as a monomer, a graphyne film is grown on the exposed copper layer area through a Glaser-Hay coupling reaction to obtain a patterned graphyne layer.

[0025] Principle of the invention: The goal of the invention is to obtain a patterned gyrene layer. To this end, different types of patterned copper substrates are first prepared (one is to grow a patterned inorganic layer on a copper substrate, and the other is to directly prepare a patterned copper layer), and then copper is used as a catalyst for the synthesis of gyrene, so that the grown gyrene layer has a corresponding pattern.

[0026] Compared with the prior art, the present invention has at least the following advantages:

[0027] 1. In the prior art, the carbon material (graphene layer) is directly etched. If the etching time is too long, the substrate will be damaged, and if it is too short, residues will be left. In the present invention, the etching process acts on the supporting material (such as copper plate) or the inorganic layer (such as SiN, SiO, etc.), thus avoiding these problems.

[0028] 2. In the prior art, a whole surface of Graphyne film is transferred to a target substrate with a pattern. The pattern on the target substrate can be defined by a photoresist, and then the Graphyne layer on the photoresist is stripped off by dissolving the photoresist, while the Graphyne layer in direct contact with the target substrate is retained. Since the Graphyne layer is usually only tens of nanometers thick, and the adsorption of the Graphyne layer to the substrate is only physical adsorption, when the Graphyne on it is stripped off due to the dissolution of the photoresist, it is easy to strip off the Graphyne around the photoresist at the same time, resulting in an incomplete Graphyne pattern finally left on the target substrate. In the present invention, the pre-grown Graphyne layer is patterned, so in the process of transfer, there is no step of dissolving the photoresist, and the resulting pattern will be more complete.

[0029] 3. The present invention first prepares a patterned inorganic layer on the copper substrate, exposes the area where the gypsum film is needed, and covers the area where the gypsum film is not needed with the inorganic layer. Since the copper plate is not only a substrate but also a catalyst, the gypsum film will only grow in the area not covered by the inorganic layer. The patterned inorganic layer or copper layer is prepared in advance, and the yellow light process can be used, so the area and shape of the gypsum film to be finally obtained can be accurately controlled by the mask.

[0030] 4. The present invention deposits or coats other substrates on the patterned gypsum layer, and then etches the copper substrate with a chemical solution, thereby achieving the transfer of the gypsum film, which can keep the gypsum film pattern intact and not prone to cracking.

[0031] 5. The present invention uses a copper layer as a catalyst for growing a gypsum film, directly patterns the copper layer through a yellow light process, or covers a patterned inorganic layer on its surface, so that the grown gypsum film itself is patterned, which is relatively easy to implement in terms of process. In addition, the patterned gypsum film is further transferred to a non-copper target substrate by combining transfer technology, expanding the application scenarios of patterned gypsum films. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for use in the description of the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0033] Figure 1 Schematic diagram of the structure of graphyne;

[0034] Figure 2 This is a flow chart of preparing a patterned graphene film in Example 1;

[0035] Figure 3 This is a flow chart of preparing a patterned graphene film in Example 3;

[0036] Figure 4 Flowchart for transferring patterned Graphyne films to other substrates. DETAILED DESCRIPTION

[0037] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0038] A method for preparing a patterned graphene film, comprising:

[0039] Method 1: first prepare a patterned inorganic layer on a copper substrate, expose the area where the gypsum film is needed, cover the area where the gypsum film is not needed with the inorganic layer, and grow the gypsum film in the area not covered by the inorganic layer; or

[0040] Method 2: On any substrate, a patterned copper layer is first prepared, and then a graphyne film is grown only in the area with the copper layer.

[0041] Embodiment 1:

[0042] A method for preparing a patterned graphene film, such as Figure 2 As shown, including:

[0043] Step 1: depositing an inorganic layer 110 on the copper substrate 100, such as silicon nitride, silicon oxide, etc.;

[0044] Step 2: Coat a positive photoresist on the inorganic layer 110, use mask 1 (Mask 1) to expose the area where the graphyne film needs to be grown, then develop and remove the photoresist, further etch the inorganic layer in the area, thereby exposing the metal copper layer in the area; dissolve and remove the photoresist on the patterned inorganic layer 110.

[0045] Step 3: Using hexaethynylbenzene as a monomer, a graphyne film is grown on the exposed copper layer region through a Glaser-Hay coupling reaction, thereby obtaining a patterned graphyne layer 120 .

[0046] Step 4: Coat positive photoresist on the inorganic layer 110 and the graphyne layer 120, use mask 2 (Mask 2) to expose the patterned inorganic layer area, then develop and remove the photoresist in the exposed area, and further etch the inorganic layer in this area, so that only the patterned graphyne layer 120 is retained on the copper plate substrate 100, and finally dissolve and remove the photoresist on the patterned graphyne layer 120.

[0047] Embodiment 2:

[0048] In Example 1, two different masks are used. To reduce the types of masks used, Example 1 is adjusted as follows:

[0049] In the fourth step of Example 1, a negative photoresist is coated on the inorganic layer 110 and the graphyne layer 120, and the patterned graphyne layer area is still exposed using mask 1 (Mask 1), so that the photoresist of this part is retained during development, and the remaining inorganic layer 110 is further etched, so that only the patterned graphyne layer 120 is retained on the copper plate substrate 100.

[0050] Embodiment 3:

[0051] In Examples 1 and 2, the yellow light process is used twice. To reduce the number of times the yellow light process is used, Example 1 is adjusted as follows: Figure 3 As shown:

[0052] Step 1: depositing a metal copper layer 210 on an arbitrary substrate 200;

[0053] Step 2: Coat positive photoresist on the metal copper layer 210 , use a mask to expose the area where the graphyne film is not required to grow, then develop and remove the photoresist, and further etch the metal copper layer in the area, thereby obtaining a patterned metal copper layer 210 .

[0054] Step 3: Using hexaethynylbenzene as a monomer, a graphyne film is grown on the exposed copper layer region through a Glaser-Hay coupling reaction, thereby obtaining a patterned graphyne layer 220 .

[0055] Compared with Embodiment 1 and 3, the number of yellow light processes is reduced, which helps to reduce production costs.

[0056] Example 4: Figure 4 shown.

[0057] Step 1: The Graphene layer 120 obtained in Examples 1 and 2 is deposited or coated on other substrates 300, such as transparent conductive glass (indium tin oxide, ITO) or a flexible polymer film (polyimide, PI);

[0058] Step 2: using a chemical solution, such as ferric chloride, to dissolve the copper plate substrate 100, thereby transferring the patterned Graphene layer to another substrate 300.

[0059] The above description is only for the purpose of facilitating those skilled in the art to understand the technical solution of the present invention and is not intended to limit the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing a patterned graphene film, characterized in that: include: Method 1: First prepare a patterned inorganic layer on a copper substrate, expose the area where the gypsum film is needed, cover the area where the gypsum film is not needed with the inorganic layer, and grow the gypsum film in the area not covered by the inorganic layer, specifically including: Step 1: Deposit an inorganic layer on a copper substrate; Step 2: coating a positive photoresist on the inorganic layer, using a photomask 1 to expose the area where the graphyne film needs to be grown, then developing and removing the part of the photoresist, further etching the inorganic layer in the area, thereby exposing the metal copper layer in the area; dissolving and removing the photoresist on the obtained patterned inorganic layer; Step 3: Using hexaethynylbenzene as a monomer, a graphyne film is grown on the exposed copper layer area through a Glaser-Hay coupling reaction, thereby obtaining a patterned graphyne layer; Step 4: coating the inorganic layer and the gypsum layer with a positive photoresist, exposing the patterned inorganic layer region using a photomask 2, developing and removing the photoresist in the exposed region, further etching the inorganic layer in the region, thereby leaving only the patterned gypsum layer on the copper substrate, and finally dissolving and removing the photoresist on the patterned gypsum layer; or A negative photoresist is coated on the inorganic layer and the gypsum layer, and the patterned gypsum layer area is still exposed using the photomask 1, so that the photoresist of this part is retained during the development, and the remaining inorganic layer is further etched, so that only the patterned gypsum layer is retained on the copper plate substrate; or Method 2: On any substrate, a patterned copper layer is first prepared, and a graphyne film is grown only in the area with the copper layer, specifically comprising: Step 1: deposit a copper metal layer on any substrate; Step 2: coating the metal copper layer with a positive photoresist, using a photomask to expose the area where the graphyne film is not required to be grown, then developing and removing the photoresist, and further etching the metal copper layer in the area, thereby obtaining a patterned metal copper layer; Step 3: Using hexaethynylbenzene as a monomer, a graphyne film is grown on the exposed copper layer area through a Glaser-Hay coupling reaction to obtain a patterned graphyne layer.

2. The method according to claim 1, characterized in that The inorganic layer is silicon nitride or silicon oxide.

3. The method according to claim 1, characterized in that Also includes: Depositing or coating other substrates on the obtained Graphene layer; The copper substrate is dissolved using a chemical solution, thereby transferring the patterned Graphene layer to other substrates.

4. The method according to claim 3, characterized in that The other substrate is transparent conductive glass or a flexible polymer film.

5. The method according to claim 3, characterized in that: The chemical solution is ferric chloride.

6. A patterned graphene film prepared by the method according to any one of claims 1-5.

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