CN109809358B - Method for clean and lossless transfer of large-area two-dimensional material by adopting liquid phase interface layer - Google Patents
Method for clean and lossless transfer of large-area two-dimensional material by adopting liquid phase interface layer Download PDFInfo
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Abstract
本发明涉及二维材料的转移技术，具体为一种采用包含液相界面层的复合转移介质实现洁净、无损转移大面积二维材料的方法。首先在位于初始基体的大面积二维材料表面形成液相界面层，并在液相界面层表面形成转移介质层；然后将转移介质/液相界面层/二维材料复合膜与初始基体分离；将界面层转变为液相，再将转移介质/液相界面层/二维材料复合膜的二维材料表面与目标基体结合；在去除转移介质和界面层之后，实现二维材料到目标基体的转移。该方法通过在转移介质与二维材料之间引入液相界面层的方法，改善转移介质与初始基体表面的二维材料之间的结合、以及转移介质表面的二维材料与目标基体之间的结合，同时减少转移介质与二维材料的直接接触。
The invention relates to a transfer technology of two-dimensional materials, in particular to a method for realizing clean and non-destructive transfer of large-area two-dimensional materials by using a composite transfer medium containing a liquid interface layer. First, a liquid interface layer is formed on the surface of the large-area two-dimensional material located on the initial matrix, and a transfer medium layer is formed on the surface of the liquid interface layer; then the transfer medium/liquid interface layer/two-dimensional material composite film is separated from the initial matrix; The interface layer is converted into a liquid phase, and then the surface of the two-dimensional material of the transfer medium/liquid interface layer/two-dimensional material composite film is combined with the target matrix; after removing the transfer medium and the interface layer, the transfer medium and the interface layer are realized. transfer. The method improves the bonding between the transfer medium and the two-dimensional material on the surface of the initial substrate, and the bonding between the two-dimensional material on the surface of the transfer medium and the target substrate by introducing a liquid interface layer between the transfer medium and the two-dimensional material. bonding while reducing the direct contact of the transfer medium with the 2D material.
Description
The technical field is as follows:
the invention relates to a transfer technology of a two-dimensional material, in particular to a method for realizing clean and lossless transfer of a large-area two-dimensional material by adopting a composite transfer medium containing a liquid phase interface layer.
Background art:
after a research group of the university of manchester in the united kingdom in 2004 adopts a tape stripping method (or a micro-mechanical stripping method) to separate and obtain a stably existing graphene material for the first time, the research on the preparation of a two-dimensional material is widely concerned. Various fabrication methods have been developed in succession, including solution lift-off, epitaxial growth, and Chemical Vapor Deposition (CVD). The CVD method is the main method for controllably preparing large-area and high-quality two-dimensional materials at present, and can realize the growth of large-area and high-quality two-dimensional materials on the surfaces (metal and nonmetal) of various base materials by controlling the preparation conditions such as temperature, carbon source, pressure and the like. For characterization, physical property measurement, and application research of two-dimensional materials, it is generally necessary to place the two-dimensional material on a specific substrate other than the preparation substrate and to avoid contamination and damage to the two-dimensional material during the transfer process. Therefore, the development of a clean and nondestructive transfer method of a large-area and high-quality two-dimensional material has important function and significance for promoting the research and application of the two-dimensional material.
According to the difference of the structural support layers of the two-dimensional materials, the transfer methods of the large-area two-dimensional materials can be divided into two categories: transfer medium assisted methods and target matrix binding methods. Compared with the latter, the former is obviously superior to the latter in terms of transferring multilayer two-dimensional materials and obtaining low surface roughness, and has stronger applicability to substrates, thus being widely adopted. For the transfer medium assisted methods, solid materials are currently used as transfer media. However, since the initial substrate of the large-area two-dimensional material is usually a polycrystalline material with a rough surface, it is difficult to achieve sufficient contact and complete matching between the solid transfer medium and the surface of the two-dimensional material on the target substrate, thereby resulting in breakage of the two-dimensional material during separation from the initial substrate and bonding with the target substrate. And most solid transfer media are high molecular polymers, and residues formed on the surface of the two-dimensional material are difficult to completely remove by a solvent cleaning and heating method, so that the surface of the two-dimensional material is polluted, the research on the intrinsic structure and the performance of the two-dimensional material is greatly influenced, and the application range of the two-dimensional material is limited. Although the residual pollution can be reduced by adopting the metal nano film or the small molecular organic film which is easy to remove as the transfer medium, the problems of low mechanical strength and easy breakage of the large-area film exist, so that the method is not suitable for transferring large-area two-dimensional materials. In order to solve the problems existing in the process of transferring the large-area two-dimensional material by using the solid transfer medium, the invention provides a method for transferring the large-area two-dimensional material by using the composite transfer medium comprising the liquid phase interface layer, which can simultaneously improve the structural integrity of the transferred large-area two-dimensional material and reduce the residue of the transfer medium on the surface of the two-dimensional material.
The invention content is as follows:
the invention aims to provide a method for cleanly and nondestructively transferring a large-area two-dimensional material by adopting a liquid phase interface layer, which improves the combination between a transfer medium and the two-dimensional material on the surface of an initial substrate and the combination between the two-dimensional material on the surface of the transfer medium and a target substrate by introducing the liquid phase interface layer between the transfer medium and the two-dimensional material, reduces the direct contact between the transfer medium and the two-dimensional material, and can simultaneously improve the structural integrity of the transferred large-area two-dimensional material and reduce the residue of the transfer medium on the surface of the two-dimensional material. Therefore, the method can be used as an effective method for cleanly and nondestructively transferring large-area two-dimensional materials.
The technical scheme of the invention is as follows:
a method for clean and lossless transfer of large-area two-dimensional materials by adopting a liquid phase interface layer improves the combination between a transfer medium and the two-dimensional materials on the surface of an initial substrate and the combination between the two-dimensional materials on the surface of the transfer medium and a target substrate by introducing the liquid phase interface layer between the transfer medium and the two-dimensional materials, and simultaneously reduces the direct contact between the transfer medium and the two-dimensional materials; firstly, forming a liquid phase interface layer on the surface of a large-area two-dimensional material positioned on an initial substrate, and forming a transfer medium layer on the surface of the interface layer; then separating the transfer medium/liquid phase interface layer/two-dimensional material composite membrane from the initial matrix; then combining the two-dimensional material surface of the transfer medium/liquid phase interface layer/two-dimensional material composite film with a target matrix; after removing the transfer medium and the interface layer, realizing the transfer of the two-dimensional material to the target substrate; the method of introducing a liquid phase interface layer between the transfer medium and the two-dimensional material improves the combination among the transfer medium, the two-dimensional material and the target substrate, thereby improving the structural integrity of the large-area two-dimensional material to be transferred; because the barrier effect of the interface layer and the liquefied interface layer are easier to remove than the solid-phase material, the residue of the transfer medium on the surface of the two-dimensional material is obviously reduced, and the method is used as an effective method for cleanly and nondestructively transferring the large-area two-dimensional material; the method comprises the following specific steps:
(1) forming a liquid phase interface layer on the surface of the two-dimensional material positioned on the initial substrate, and then forming a transfer medium layer on the surface of the liquid phase interface layer;
(2) separating the transfer medium/liquid phase interface layer/two-dimensional material composite membrane from the initial matrix;
(3) combining the two-dimensional material surface of the transfer medium/liquid phase interface layer/two-dimensional material composite film with a target matrix;
(4) the transfer medium and the liquid phase interface layer are removed.
The method for clean and lossless transfer of the large-area two-dimensional material by adopting the liquid phase interface layer has the advantages that the average number of layers of the two-dimensional material on the surface of the initial matrix is single-layer, double-layer, few-layer or multi-layer, and the number of layers is less than 50.
The method for cleanly and nondestructively transferring the large-area two-dimensional material by adopting the liquid phase interface layer is characterized in that the two-dimensional material is grown by adopting a deposition method, or is grown by adopting a precipitation method, or is grown by an epitaxial method.
The method for clean and lossless transfer of the large-area two-dimensional material by adopting the liquid phase interface layer is characterized in that the adopted liquid phase interface layer material is liquid under the operation condition of transferring the two-dimensional material, is liquid at least in the process of combining the two-dimensional material and a target matrix, and is solid, liquid or gaseous under the conditions of normal temperature and normal pressure.
The method for clean and lossless transfer of large-area two-dimensional material by adopting the liquid phase interface layer includes, but is not limited to: printing, roll coating, slot coating, wire bar coating, blade coating, spray coating, spin coating, pulling, dropping, physical deposition or chemical vapor deposition; methods of forming a transfer medium at the surface of a two-dimensional material/liquid phase interface layer include, but are not limited to: attaching or electrostatic adsorption; the method for combining the two-dimensional material surface of the transfer medium/liquid phase interface layer/two-dimensional material composite film with the target substrate includes but is not limited to: fitting, pressing, adsorbing or bonding; methods of removing the transfer medium and the liquid phase interface layer include stripping, dissolution, heating, chemical reaction, light irradiation, or irradiation.
The method for cleanly and nondestructively transferring the large-area two-dimensional material by adopting the liquid phase interface layer does not generate chemical reaction or dissolution with the transfer medium, the two-dimensional material and the initial matrix.
The method for clean and lossless transfer of the large-area two-dimensional material by adopting the liquid phase interface layer comprises one or two of an etching matrix method and a stripping method; the stripping method comprises a direct stripping method, a gas intercalation stripping method and a gas bubbling method; the gas bubbling method is referred to Chinese invention patent: a method for transferring two-dimensional materials in a low-cost and nondestructive way, and the patent number is ZL 201110154465.9.
The method for clean and lossless transfer of large-area two-dimensional materials by adopting the liquid phase interface layer is characterized in that the transfer medium material comprises one or the combination of more than two of organic matters, metals, non-metals, metal compounds and non-metal compounds;
the initial matrix of the two-dimensional material is a composite material of one or more than two of metals or alloys thereof, such as Pt, Ni, Cu, Co, Ir, Ru, Au, Ag, Fe, Mo, W, Ti, Zr, V, Nb, Ta and Cr; or the initial matrix is one or more of composite materials of titanium carbide, molybdenum carbide, zirconium carbide, vanadium carbide, niobium carbide, tantalum carbide, chromium carbide and tungsten carbide; or the initial matrix is Si or SiO2、Al2O3Compounding one or more than two semiconductors; or the initial matrix is a composite material of a conductor and a semiconductor;
the target matrix adopted is a high molecular polymer: polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polysiloxane, polycarbonate, polyethylene, polyvinyl chloride, polystyrene, polypropylene, or the target substrate is a semiconductor: silicon, silicon oxide, silicon nitride, aluminum oxide, or glass, or the target substrate is a conductor: pt, Ni, Cu, Co, Ir, Ru, Au, Ag, Fe, Mo and alloys thereof, and the shape of the target substrate is a plane, a curved surface or a mesh surface.
The method for clean and lossless transfer of large-area two-dimensional materials by adopting the liquid phase interface layer is characterized in that the alloy is copper alloy, nickel alloy or stainless steel.
The method for cleanly and nondestructively transferring the large-area two-dimensional material by adopting the liquid phase interface layer realizes the transfer of the multi-layer two-dimensional material by adopting a mode of laminating transfer on the surface of the two-dimensional material positioned on an initial matrix or the surface of a target matrix.
The invention has the characteristics and beneficial effects that:
1. the invention utilizes the characteristic that the liquid phase material has better fluidity and surface filling property compared with the solid material, adopts the mode of introducing the liquid phase interface layer between the transfer medium and the two-dimensional material, improves the surface matching and combination among the transfer medium, the two-dimensional material and the target matrix, and can fully play the structural supporting and protecting functions of the transfer medium on the large-area two-dimensional material, thereby improving the structural integrity of the transferred large-area two-dimensional material.
2. According to the invention, the liquid phase interface layer is introduced between the solid transfer medium and the two-dimensional material, and the two-dimensional material is prevented from being in direct contact with the transfer medium by using the barrier effect of the liquid phase material, so that the residue of the transfer medium on the surface of the two-dimensional material can be obviously reduced; meanwhile, compared with a solid phase material, the liquid phase material on the surface of the object is easier to clean and remove, and the residue of a liquid phase interface layer on the surface of the two-dimensional material can be avoided. The transfer medium can be reused, so that the transfer cost is reduced.
3. The method for introducing the liquid phase interface layer between the transfer medium and the two-dimensional material has the characteristics of simplicity and easiness in operation, is easy to realize large-scale amplification, and can improve the operability and stability of the original process.
4. The method reduces the residue of the transfer medium on the surface of the two-dimensional material, thereby being beneficial to reusing the transfer medium and reducing the transfer cost.
Description of the drawings:
FIG. 1 is a schematic diagram of a process for transferring a large area of two-dimensional material.
The specific implementation mode is as follows:
in the specific implementation process, as shown in fig. 1, a liquid-phase interface layer is formed on the surface of a large-area two-dimensional material located on an initial substrate, and a transfer medium layer is formed on the surface of the liquid-phase interface layer; then separating the transfer medium/liquid phase interface layer/two-dimensional material composite membrane from the initial matrix; converting the interface layer into a liquid phase, and combining the two-dimensional material surface of the transfer medium/liquid phase interface layer/two-dimensional material composite film with a target substrate; after the transfer medium and the interface layer are removed, the transfer of the two-dimensional material to the target substrate is achieved. The method of introducing a liquid phase interface layer between the transfer medium and the two-dimensional material improves the combination among the transfer medium, the two-dimensional material and the target substrate, thereby improving the structural integrity of the large-area two-dimensional material to be transferred; because the barrier effect of the interface layer and the liquefied two-dimensional material are easier to remove than the solid-phase material, the residual of the transfer medium on the surface of the two-dimensional material can be obviously reduced, and the method can be used as an effective method for cleanly and nondestructively transferring the large-area two-dimensional material.
The present invention will be explained in further detail below by way of examples and figures.
Example 1
As shown in fig. 1, a metal copper foil was used as a starting substrate, Polydimethylsiloxane (PDMS) was used as a transfer medium, polyethylene terephthalate (PET) was used as a target substrate, and a liquid epoxy resin was used as a liquid phase interface layer. Growing a single-layer graphene film on a metal copper foil by using a CVD (chemical vapor deposition) method, and printing an epoxy resin layer with the thickness of 2 microns on the surface of the copper foil on which the graphene is grown after the copper foil is cooled. And pressing the PDMS film (with the thickness of 100 microns) on the surface of the PDMS film (with the pressure of less than 0.2MPa) by adopting a rolling method, so that the epoxy resin forms a liquid phase interface layer between the two-dimensional material and the PDMS. And connecting the PDMS/epoxy resin/graphene/copper foil to the negative electrode of a constant current power supply, and using a platinum sheet as the positive electrode. In this example, the electrolyte was 0.8mol/L NaSO4In the water solution, PDMS/epoxy resin/graphene/copper foil is immersed in electrolyte, 0.5 ampere of current is applied, the voltage used in the electrolysis process is 3-6 volts, the operation temperature in the electrolysis process is 15-30 ℃, and the gas generated by electrolysis is hydrogen (H)2). And after the PDMS/epoxy resin/graphene is completely separated from the copper foil, taking the PDMS/epoxy resin/graphene out of the NaOH solution, washing with water and completely drying. And (3) laminating the graphene surface of PDMS/epoxy resin/graphene on the PET substrate by a rolling method under the pressure of 0.2 MPa. And (2) soaking PDMS/epoxy resin/graphene/PET in an acetone solution, and directly stripping the PDMS film from the surface of the graphene after the epoxy resin is completely dissolved in the acetone solution to complete the transfer of the large-area graphene.
Example 2
The difference from the embodiment 1 is that:
as shown in fig. 1, a few or more layers of other two-dimensional materials (in this embodiment, graphene may be replaced with a transition metal chalcogenide such as boron nitride or molybdenum disulfide, or a boron alkene, or a silicon alkene) are grown on the surface of a starting substrate by a CVD method using different materials (in this embodiment, a metal copper foil may be replaced with a foil of a metal such as nickel or platinum or an alloy thereof (such as a copper-nickel alloy), a metal thin film stably bonded to a silicon wafer, and a metal carbide such as molybdenum carbide or tungsten carbide, or another semiconductor such as silicon or germanium). Different materials (in this embodiment, PET may be replaced with a polymer such as PEN, polycarbonate, or the like, or silicon oxide, glass, or the like) are used as the target substrate. Different materials (in this embodiment, PDMS may be replaced by polymers such as PET, or semiconductors such as silicon oxide and glass) are used as the transfer medium. Other materials that are liquid at room temperature and pressure are used as the liquid interface layer, including small molecule organic substances (e.g., xylene), high molecular polymers (e.g., polyisobutylene), non-metals (e.g., bromine), and the like. The two-dimensional material and the initial substrate were separated by etching the substrate, in this example, a 1M molar ferric chloride aqueous solution was used to etch the copper foil, and then the surface of the two-dimensional material was rinsed with water and completely dried.
Example 3
The difference from the embodiment 1 is that:
as shown in fig. 1, a material that is solid at normal temperature and pressure, such as triacontane, is used as the liquid interface layer. And pressing a triacontane layer (with the thickness of 10 micrometers) and a PDMS film (with the thickness of 100 micrometers) on the surface of the graphene by adopting a hot rolling method, pressing the triacontane layer and the PDMS film on the surface of the graphene at the temperature of 100 ℃ and under the pressure of 0.2MPa, and liquefying the triacontane so as to form a liquid phase interface layer between the two-dimensional material and the PDMS. After the triacontane is cooled and solidified, connecting the PDMS/triacontane/graphene/copper foil to the negative electrode of a constant current power supply, and using a platinum sheet as the positive electrode. In this example, the electrolyte was 0.8mol/L NaSO4Soaking PDMS/triacontane/graphene/copper foil into electrolyte, applying 0.5 ampere of current, controlling the voltage of 3-6V, the operation temperature of 15-30 deg.C, and generating hydrogen (H) as the gas2). And after the PDMS/triacontane/graphene is completely separated from the copper foil, taking the PDMS/triacontane/graphene out of the NaOH solution, washing with water and completely drying. Adhering the graphene surface of PDMS/graphene/two-dimensional material on the PET substrate by hot rolling (temperature 100 deg.C, pressure 0.2MPa), and bondingAn interfacial layer of liquid triacontane was formed between graphene and PDMS to promote adequate contact of graphene with the PET matrix. After the triacontane is cooled and solidified, the PDMS film is directly peeled off from the surface of the triacontane. Finally, immersing the triacontane/graphene/PET in ether, and completing the transfer of the large-area two-dimensional material after the triacontane is completely dissolved in the ether.
Example 4
The difference from the embodiment 1 is that:
in this embodiment, a large-area four-layer two-dimensional material is obtained by lamination transfer. After the PDMS/acetone/two-dimensional material composite film is obtained, the two-dimensional material surface of the composite film is attached to the surface of the two-dimensional material on the copper foil through a rolling method, the steps of etching the copper foil, cleaning and drying are repeated, and the PDMS/acetone/double-layer two-dimensional material composite film is obtained. Repeating the steps until the PDMS/acetone/four-layer two-dimensional material composite membrane is obtained. And then the two-dimensional material surface of the composite film is attached to the PET substrate by a hot rolling method, the hot pressing temperature is 110 ℃, and the pressure is 0.1 MPa. Directly stripping the PDMS film from the surface of the two-dimensional material by adopting a mode of stripping immediately after hot pressing. Because the hot pressing temperature is higher than the boiling point of acetone, the acetone is completely volatilized from the surface of the two-dimensional material in the process of peeling the PDMS film, and thus the clean and lossless transfer of the large-area four-layer two-dimensional material is completed. The peeled PDMS film can be reused.
The results of the examples show that the method of the present invention improves the bonding between the transfer medium and the two-dimensional material of the surface of the initial substrate, and between the two-dimensional material of the surface of the transfer medium and the target substrate, while reducing direct contact between the transfer medium and the two-dimensional material, by introducing a liquid-phase interface layer between the transfer medium and the two-dimensional material.
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