CN110983287A - Method for transferring large-area two-dimensional materials - Google Patents

Method for transferring large-area two-dimensional materials Download PDF

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CN110983287A
CN110983287A CN201910999420.8A CN201910999420A CN110983287A CN 110983287 A CN110983287 A CN 110983287A CN 201910999420 A CN201910999420 A CN 201910999420A CN 110983287 A CN110983287 A CN 110983287A
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area
temperature
dimensional
molten pool
transferring
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付磊
曾梦琪
丁煜
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Wuhan University WHU
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Wuhan University WHU
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/01—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes on temporary substrates, e.g. substrates subsequently removed by etching
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/186—Preparation by chemical vapour deposition [CVD]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/003—Coating on a liquid substrate
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/305—Sulfides, selenides, or tellurides

Abstract

The invention provides a method for transferring a large-area two-dimensional material, which comprises the following steps: step 1, adopting a high-melting-point material substrate as a growth substrate; step 2, adopting a low-melting-point material as a molten pool material, and placing the molten pool material on a growth substrate; step 3, raising the temperature of the high-temperature area to the growth temperature of the material to be transferred to enable the material of the molten pool to form a liquid molten pool, and then starting to grow the material to be transferred to enable the material to be transferred to grow on the surface of the molten pool in a large area to form a large-area two-dimensional material; step 4, moving the growth substrate with the large-area two-dimensional material to a low-temperature area, wherein the temperature of the low-temperature area is lower than the melting point of the target substrate and is near the initial melting temperature of the molten pool material, so that the molten pool material is kept in a liquid state; and 5, placing the target substrate near the molten pool, and transferring the large-area two-dimensional material onto the target substrate through rotation and movement of a roller shaft positioned above the molten pool. The method can realize large-scale preparation and transfer of large-area two-dimensional materials.

Description

Method for transferring large-area two-dimensional materials
Technical Field
The invention belongs to the technical field of material science, and particularly relates to a method for transferring a large-area two-dimensional material.
Technical Field
Two-dimensional layered materials, such as graphene and transition metal dichalcogenides, with atomically thin thicknesses and unique electronic properties have become powerful candidates for next-generation nanoelectronic applications. The two-dimensional material layers are connected by stronger covalent bonds or ionic bonds, and the layers are combined by weaker van der Waals force, so that the bulk material can be peeled into the two-dimensional material by using a mechanical peeling method. Although the two-dimensional material obtained by peeling has higher quality, the systematic control on the aspects of material thickness, size and uniformity is lacked, and the application of the two-dimensional material in the fields of field effect tubes, photoelectric devices, energy conversion and the like is hindered.
To address this problem, researchers have been working on exploring other methods of large-scale growth of atomically thin layers of two-dimensional materials, including liquid phase lift-off, atomic layer deposition, chemical vapor deposition, physical vapor deposition, and the like. Liquid phase stripping has the advantage of high yield, but the size and thickness of the prepared thin layer material cannot be controlled, and the material is easily doped by impurities and has reduced quality. The atomic layer deposition is easy to obtain a film with low crystallinity, and is not beneficial to subsequent application. The two-dimensional material obtained by the chemical vapor deposition method has the advantages of controllable layer number, large area, high quality and the like, so that the two-dimensional material becomes a main research means of researchers.
In order to realize practical application of the prepared two-dimensional material, the two-dimensional material needs to be transferred from a metal substrate to a target substrate, such as an insulating substrate of silicon dioxide, quartz, etc. The common transfer method comprises an etching method, a bubbling method and a hot pressing method, wherein the etching method comprises the steps of spinning and coating a thin layer of polymethyl methacrylate on the prepared two-dimensional material, placing the material on an acidic or alkaline solution after curing, etching off a metal substrate, then transferring the polymethyl methacrylate containing the two-dimensional material onto a target substrate, and finally removing the polymethyl methacrylate film by using acetone steam. The bubble method is a method in which a metal substrate on which polymethyl methacrylate is spin-coated is used as a cathode for an electrochemical reaction to cause a hydrolysis reaction, and a two-dimensional material and a substrate glass are bonded by hydrogen bubbles generated. The hot pressing method is suitable for a system with weak bonding force between the two-dimensional material and the metal substrate, and has certain limitation. Therefore, how to transfer large areas of two-dimensional material is a key factor to achieve further applications.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for transferring a large-area two-dimensional material, which enables mass production and transfer of a large-area two-dimensional material. In order to achieve the purpose, the invention adopts the following scheme:
the invention provides a method for transferring a large-area two-dimensional material, which is characterized by comprising the following steps of: step 1, adopting a high-melting-point material substrate with the melting point higher than the growth temperature of a material to be transferred as a growth substrate; step 2, adopting a low-melting-point material with a melting point lower than the growth temperature of the material to be transferred as a molten pool material, and placing the molten pool material on a growth substrate; step 3, raising the temperature of the high-temperature area to the growth temperature of the material to be transferred to enable the material of the molten pool to form a liquid molten pool, and then starting to grow the material to be transferred to enable the material to be transferred to grow on the surface of the molten pool in a large area to form a large-area two-dimensional material; step 4, moving the growth substrate with the large-area two-dimensional material to a low-temperature area, wherein the temperature of the low-temperature area is lower than the melting point of the target substrate and is near the initial melting temperature of the molten pool material, so that the molten pool material is kept in a liquid state; and 5, placing the target substrate near the molten pool, and transferring the large-area two-dimensional material onto the target substrate through rotation and movement of a roller shaft positioned above the molten pool.
Further, the method for transferring the large-area two-dimensional material provided by the invention can also have the following characteristics: in the step 1, the high-melting-point material is a metal material or an insulating material with a higher melting point, and the metal material is at least one of iron, cobalt, nickel, gold, silver, copper, platinum, palladium, aluminum, molybdenum, zinc, tungsten, chromium, titanium, vanadium, rhodium, ruthenium and iridium, preferably any one or combination of gold, silver, copper, molybdenum and tungsten; the insulating material is any one of sapphire, quartz, mica, silicon, hafnium oxide and beryllium oxide.
Further, the method for transferring the large-area two-dimensional material provided by the invention can also have the following characteristics: in the step 2, the growth substrate is sequentially subjected to ultrasonic cleaning by using three liquids of acetone, ethanol and ultrapure water to remove residual organic matters and impurities on the surface, and then the molten pool material is placed on the growth substrate.
Further, the method for transferring the large-area two-dimensional material provided by the invention can also have the following characteristics: in step 2, the low melting point material is a metal material or an inorganic salt.
Further, the method for transferring the large-area two-dimensional material provided by the invention can also have the following characteristics: in step 2, the low melting point metal material generally means a low melting point metal having a melting point of 250 ℃ or less, and becomes liquid when the temperature is higher than the melting point thereof. The addition amount of the low-melting-point metal material is 10-30 mg; when the low melting point metal is heated above its melting point, a liquid metal bath, a medium for two-dimensional material growth and a substrate are formed.
Further, the method for transferring the large-area two-dimensional material provided by the invention can also have the following characteristics: in step 2, the low-melting-point metal material is at least one of gallium, rubidium, tin, cadmium, lead, cesium, bismuth, indium and the like, preferably any one or combination of multiple of gallium, tin, indium, rubidium, cesium and bismuth; the low-melting-point inorganic salt is any one or combination of more of potassium chloride, sodium chloride, lithium chloride, zinc chloride, aluminum potassium chloride, aluminum sodium chloride, potassium bromide, lithium bromide, sodium bromide, aluminum lithium bromide, potassium iodide, lithium iodide, sodium iodide, potassium nitrate, sodium nitrate, lithium nitrate, nitrous acid, sodium thiocyanate and potassium thiocyanate, and preferably at least one of potassium chloride, sodium chloride, lithium chloride, zinc chloride, aluminum potassium chloride and aluminum sodium chloride.
The inorganic salt used in the invention is molten salt which can form a molten mass after being melted, such as halide, nitrate and sulfate of alkali metal and alkaline earth metal, and the inorganic salt is solid at standard temperature and atmospheric pressure and forms liquid after the temperature is increased. The fused salt is a fused mass composed of metal cations and non-metal anions, wherein more than 80 kinds of cations are contained, more than 30 kinds of anions are contained, and the fused salt can reach more than 2400 kinds. Selecting any one or more inorganic salts with low melting point as a reaction medium, heating to raise the temperature, melting the salt body to form a liquid molten pool, and using the liquid molten pool as a medium and a substrate for two-dimensional material growth. The addition amount of the inorganic salt is 10-50 mg.
The metal or molten salt liquid bath provides a liquid phase environment for the reaction, so that the reaction system has higher fluidity and reaction activity, compared with a solid phase, the diffusion and migration rates of reactants in the liquid phase are higher, the reaction time can be shortened, the temperature required by the reaction is reduced, and a two-dimensional material with good uniformity, larger area and higher quality can be obtained.
Further, the method for transferring the large-area two-dimensional material provided by the invention can also have the following characteristics: in step 3, the material to be transferred is grown by chemical vapor deposition.
Further, the method for transferring the large-area two-dimensional material provided by the invention can also have the following characteristics: in the step 3, the temperature of a high-temperature area is raised to the growth temperature of the material to be transferred in the atmosphere of hydrogen and inert gas, so that the molten pool material forms a liquid molten pool, the temperature in the step is 300-1200 ℃, the temperature raising time is 10-50 min, then the large-area two-dimensional material is grown, the gas of elements required for growing the two-dimensional material is introduced, the flow rate of the hydrogen is set to be 10-500 sccm, the flow rate of the inert gas is set to be 50-1000 sccm, and the growth time is 5-120 min. The inert gas is selected from at least one of nitrogen and argon, preferably argon.
Further, the method for transferring the large-area two-dimensional material provided by the invention can also have the following characteristics: in step 3, the flow rate of the hydrogen gas is set to 10-200 sccm, and the flow rate of the inert gas is set to 100-600 sccm.
Further, the method for transferring the large-area two-dimensional material provided by the invention can also have the following characteristics: the large-area two-dimensional material is graphene, hexagonal boron nitride, transition metal dichalcogenide and the like; the transition metal dichalcogenide comprises three major classes of sulfide, telluride and selenide; when the large-area two-dimensional material is graphene, the carbon source is selected from at least one of carbon monoxide, methane, ethane, propane, butane, pentane, hexane, cyclohexane, ethylene, propylene, butadiene, pentene, cyclopentadiene, acetylene, methanol, ethanol, benzene, toluene, and phthalocyanine; when the large-area two-dimensional material is molybdenum sulfide, sulfur powder is used as a sulfur source, and the molybdenum source is selected from molybdenum trioxide and ammonium molybdate, preferably molybdenum trioxide.
Further, the method for transferring the large-area two-dimensional material provided by the invention can also have the following characteristics: in the step 3, when the large-area two-dimensional material is graphene, the flow rate of the carbon source is 3-200 sccm, preferably 20-100 sccm; the ratio of the carbon source gas to the hydrogen gas is 1: 50-1: 2, preferably 1: 10-1: 2; the carbon source is preferably one or more of methane, ethylene, ethanol and cyclohexane.
Further, the method for transferring the large-area two-dimensional material provided by the invention can also have the following characteristics: in the step 3, when the large-area two-dimensional material is graphene, the addition amount of the sulfur source is 5-100 mg, and the addition amount of the molybdenum source is 1-10 mg.
Further, the method for transferring the large-area two-dimensional material provided by the invention can also have the following characteristics: the target substrate is any one of a silicon wafer, a mica sheet, a polymer film (PET film) and a quartz sheet.
Further, the method for transferring the large-area two-dimensional material provided by the invention can also have the following characteristics: in step 5, the height of the roller is set to just contact with the large-area two-dimensional material, and the roller moves from one side of the liquid pool to the target substrate positioned at the other side, and simultaneously rotates.
Action and Effect of the invention
The invention combines the growth and the transfer of the large-area two-dimensional material, the growth of the two-dimensional material is realized in the high-temperature area, the transfer of the two-dimensional material is realized in the low-temperature area, the obtained large-area two-dimensional material is transferred to the target substrate by utilizing the rotation of the roller, the operation is simple and convenient, no polymer residue exists, no damage is caused in the transfer process, the crystallinity and the quality of the obtained two-dimensional material are high, the large-scale preparation and transfer of the large-area two-dimensional material can be realized, and the invention is suitable for industrial large-scale. The invention realizes the transfer of any substrate, has universality and is beneficial to exploring the properties and application of two-dimensional materials in various aspects.
Drawings
FIG. 1 is a schematic diagram of a process for growing and transferring a two-dimensional material according to a first embodiment of the present invention;
FIG. 2 is a pictorial view of a liquid metal bath in accordance with an embodiment of the present invention;
FIG. 3 is a photo of graphene prepared by transferring to a silicon wafer substrate according to a first embodiment of the present invention;
fig. 4 is a raman spectrum measured after the prepared graphene is transferred onto a silicon wafer substrate according to the first embodiment of the present invention;
fig. 5 is a photograph of graphene prepared by transferring to a quartz substrate according to a fourth embodiment of the present invention;
fig. 6 is a raman spectrum measured after the prepared graphene is transferred to a quartz substrate in the fourth embodiment of the present invention;
FIG. 7 is a Raman spectrum of molybdenum disulfide prepared by transferring it to a silicon wafer substrate according to example seven of the present invention.
Detailed Description
The following describes in detail a specific embodiment of the method for transferring a large-area two-dimensional material according to the present invention with reference to the accompanying drawings.
As shown in FIG. 1, the apparatus used for carrying out the following examples is an apparatus in which the top of the reaction furnace is an oblong structure, and has a high temperature zone and a low temperature zone, and in the low temperature zone, a plurality of rows of rolls are provided, and the rolls are integrally movable back and forth, and the rolls are rotatable individually, and the rotational speed (angular speed) of the rolls is set to 190 DEG/s, and the movement speed is set to 1 mm/s.
< example one > transfer of Large area graphene
(1) Cutting to size of 1 x 1cm2The tungsten sheet is taken as a high-melting-point metal substrate, ultrasonic cleaning is carried out in acetone, ethanol and ultrapure water for 20min, and the cleaned tungsten sheet is dried by high-purity nitrogen.
(2) 40mg of gallium metal was weighed out and placed on a tungsten plate, and the weighed metal gallium metal was placed together in a graphite boat.
(3) As shown in FIG. 1, the graphite boat is placed in the high temperature region of the quartz tube in the chemical vapor deposition device, so that the metal is fused into the liquid molten pool shown in FIG. 2, high-purity argon gas is introduced as a shielding gas, the flow rate is 200sccm, hydrogen gas is introduced, the flow rate is 20sccm, the temperature of the high temperature region is programmed from room temperature to 1020 ℃ for 40min, and meanwhile, the temperature of the low temperature region is programmed to 250 ℃ and is kept unchanged. When the temperature of the high-temperature zone reaches 1020 ℃, introducing a carbon source methane, wherein the flow rate is 10sccm, the growth time is 15min, then stopping introducing the methane, and ending the reaction.
(4) And moving the metal substrate with the large-area graphene to a low-temperature area, wherein the temperature is 250 ℃, and the liquid metal gallium still keeps liquid at the temperature.
(5) Under the rotation of the roller shaft, graphene is transferred to the silicon wafer, part of liquid gallium metal is remained on the silicon wafer, the liquid gallium metal is quickly washed away by hydrochloric acid, and the graphene on the silicon wafer after being washed is shown in figure 3.
(6) FIG. 4 is a Raman spectrum of graphene transferred to a silicon wafer, from which it can be seen that the transfer method is feasible and that the distance from graphene is 2700cm-1The characteristic peak shows that the half-peak width is narrow, and the obtained graphene has high crystallinity. The method integrates growth and transfer, and can quickly obtain a large-area two-dimensional material on a target substrate.
< example two > transfer of Large area graphene
(1) Cutting to size of 1 x 2cm2The tungsten sheet is taken as a high-melting-point metal substrate, ultrasonic cleaning is carried out in acetone, ethanol and ultrapure water for 20min, and the cleaned tungsten sheet is dried by high-purity nitrogen.
(2) 40mg of gallium metal was weighed out and placed on a tungsten plate, and the weighed metal gallium metal was placed together in a graphite boat.
(3) Placing the graphite boat in a high-temperature area of a quartz tube in a chemical vapor deposition device, introducing high-purity argon gas serving as protective gas at a flow rate of 200sccm, introducing hydrogen gas at a flow rate of 20sccm, and programming the high-temperature area from room temperature to 1020 ℃ for 40min, and simultaneously programming the low-temperature area to 250 ℃ and keeping the temperature unchanged. When the temperature of the high-temperature zone reaches 1020 ℃, introducing a carbon source methane, wherein the flow rate is 10sccm, the growth time is 30min, then stopping introducing the methane, and ending the reaction.
(4) And moving the metal substrate with the large-area graphene to a low-temperature area, wherein the temperature is 250 ℃, and the liquid metal gallium still keeps liquid at the temperature.
(5) Under the rotation of the roller shaft, the graphene is transferred to a silicon wafer, and part of liquid gallium metal remained on the silicon wafer is quickly washed away by hydrochloric acid.
< example III > transfer of Large area graphene
(1) Cutting to size of 1 x 1cm2The copper sheet is taken as a high-melting-point metal substrate, ultrasonic cleaning is carried out in acetone, ethanol and ultrapure water for 20min, and then the cleaned copper sheet is dried by high-purity nitrogen.
(2) 40mg of gallium metal was weighed out and placed on a copper plate, and the metal gallium was placed together in a graphite boat.
(3) Placing the graphite boat in a high-temperature area of a quartz tube in a chemical vapor deposition device, introducing high-purity argon gas serving as protective gas at a flow rate of 200sccm, introducing hydrogen gas at a flow rate of 20sccm, and programming the high-temperature area from room temperature to 1060 ℃ for 45min, and simultaneously programming the low-temperature area to 250 ℃ and keeping the temperature unchanged. When the temperature of the high-temperature zone reaches 1060 ℃, introducing a carbon source methane, wherein the flow rate is 10sccm, the growth time is 15min, then stopping introducing the methane, and ending the reaction.
(4) And moving the metal substrate with the large-area graphene to a low-temperature area, wherein the temperature is 250 ℃, and the liquid metal gallium still keeps liquid at the temperature.
(5) Under the rotation of the roller shaft, the graphene is transferred to a silicon wafer, and part of liquid gallium metal remained on the silicon wafer is quickly washed away by hydrochloric acid.
< example four > transfer of Large area graphene
(1) Cutting to size of 1 x 1cm2The tungsten sheet is taken as a high-melting-point metal substrate, ultrasonic cleaning is carried out in acetone, ethanol and ultrapure water for 20min, and the cleaned tungsten sheet is dried by high-purity nitrogen.
(2) 40mg of gallium metal was weighed out and placed on a tungsten plate, and the weighed metal gallium metal was placed together in a graphite boat.
(3) Placing the graphite boat in a high-temperature area of a quartz tube in a chemical vapor deposition device, introducing high-purity argon gas serving as protective gas at a flow rate of 200sccm, introducing hydrogen gas at a flow rate of 20sccm, and programming the high-temperature area from room temperature to 1020 ℃ for 40min, and simultaneously programming the low-temperature area to 250 ℃ and keeping the temperature unchanged. When the temperature of the high-temperature zone reaches 1020 ℃, introducing a carbon source methane, wherein the flow rate is 10sccm, the growth time is 15min, then stopping introducing the methane, and ending the reaction.
(4) And moving the metal substrate with the large-area graphene to a low-temperature area, wherein the temperature is 250 ℃, and the liquid metal gallium still keeps liquid at the temperature.
(5) Under the rotation of the roller shaft, the graphene is transferred to the quartz plate, part of liquid metal gallium remained on the quartz plate is quickly washed away by hydrochloric acid, the graphene on the quartz plate after being washed is shown in figure 5, obvious gallium residue is avoided, no wrinkles are generated, and the obtained graphene is relatively flat.
(6) FIG. 6 is a Raman spectrum of graphene transferred onto a quartz plate, from which it can be seen that the transfer method is feasible and from graphene at 2670cm-1The characteristic peak shows that the half-peak width is narrow, and the obtained graphene has high crystallinity. The method integrates growth and transfer, and can quickly obtain a large-area two-dimensional material on a target substrate.
< example five > transfer of large-area graphene
(1) Cutting to size of 1 x 1cm2The tungsten sheet is used as a high-melting-point metal substrate, and is subjected to ultrasonic cleaning in acetone, ethanol and ultrapure waterThe sound time is 20min, and the cleaned tungsten plate is dried by high-purity nitrogen.
(2) 40mg of gallium indium tin alloy is weighed and placed on a tungsten sheet, and the gallium indium tin alloy and the tungsten sheet are placed in a graphite boat together.
(3) Placing the graphite boat in a high-temperature area of a quartz tube in a chemical vapor deposition device, introducing high-purity argon gas serving as protective gas at a flow rate of 200sccm, introducing hydrogen gas at a flow rate of 20sccm, and programming the high-temperature area from room temperature to 1020 ℃ for 40min, and simultaneously programming the low-temperature area to 100 ℃ and keeping the temperature unchanged. When the temperature of the high-temperature zone reaches 1020 ℃, introducing a carbon source methane, wherein the flow rate is 10sccm, the growth time is 60min, then stopping introducing the methane, and ending the reaction.
(4) And moving the metal substrate with the large-area graphene to a low-temperature area, wherein the temperature is 100 ℃, and the gallium indium tin alloy still keeps a liquid state.
(5) Under the rotation of the roller shaft, the graphene is transferred to the silicon chip, and part of gallium-indium-tin alloy is remained on the silicon chip and is quickly washed away by hydrochloric acid.
< example six > transfer of Large area graphene
(1) Cutting to size of 1 x 1cm2The copper sheet is taken as a high-melting-point metal substrate, ultrasonic cleaning is carried out in acetone, ethanol and ultrapure water for 20min, and then the cleaned copper sheet is dried by high-purity nitrogen.
(2) 40mg of gallium indium tin alloy is weighed and placed on a copper sheet, and the gallium indium tin alloy and the copper sheet are placed in a graphite boat together.
(3) Placing the graphite boat in a high-temperature area of a quartz tube in a chemical vapor deposition device, introducing high-purity argon gas serving as protective gas at a flow rate of 200sccm, introducing hydrogen gas at a flow rate of 20sccm, and programming the high-temperature area from room temperature to 1060 ℃ for 40min, wherein the programming temperature of the low-temperature area is increased to 100 ℃ and the temperature is kept unchanged. When the temperature of the high-temperature zone reaches 1060 ℃, introducing a carbon source methane, wherein the flow rate is 10sccm, the growth time is 15min, then stopping introducing the methane, and ending the reaction.
(4) And moving the metal substrate with the large-area graphene to a low-temperature region, wherein the temperature is 100 ℃, and the gallium indium tin alloy still keeps a liquid state at the temperature.
(5) Under the rotation of the roller shaft, the graphene is transferred to the quartz plate, and part of liquid metal gallium remained on the quartz plate is quickly washed away by hydrochloric acid.
< EXAMPLE VII > transfer of Large area molybdenum disulfide
(1) Taking the size of 1 x 1cm2The mica sheet is used as a substrate and is placed in the groove of the graphite boat;
(2) weighing 40mg of mixed salt (NaCl: KCl ═ 1:1) and placing the mixed salt on a mica sheet, placing a graphite boat in a high-temperature zone of a quartz tube in a chemical vapor deposition device, weighing 25mg of molybdenum trioxide and placing the molybdenum trioxide in a small quartz boat, weighing 100mg of sulfur powder and placing the sulfur powder in another small quartz boat, and placing the two small quartz boats in an outer area of the quartz tube in the chemical vapor deposition device, wherein the quartz tube is in contact with air;
(3) introducing high-purity argon as a protective gas with the flow rate of 200sccm, and programming the temperature of the high-temperature region from room temperature to 700 ℃ for 30min, and simultaneously programming the temperature of the low-temperature region to 300 ℃ and keeping the temperature unchanged. When the temperature of the high-temperature zone reaches 700 ℃, pushing the molybdenum trioxide and the sulfur powder into the low-temperature zone, introducing hydrogen, wherein the flow rate is 20sccm, the growth time is 5min, then pulling out the sulfur powder, and finishing the reaction.
(4) And (3) solidifying the molten salt at low temperature, spin-coating PMMA on the solidified salt body, drying, putting into a beaker filled with ultrapure water, dissolving the salt in the ultrapure water, transferring PMMA onto a silicon wafer, and removing the PMMA by using acetone vapor to obtain the molybdenum disulfide on the substrate of the silicon wafer.
(5) FIG. 7 is a Raman spectrum of molybdenum disulfide on a silicon wafer substrate, as seen at 385cm–1And 406cm–1The characteristic peak of molybdenum disulfide single crystal appears nearby, which proves that the transfer method is feasible and can simply, conveniently and quickly obtain large-area two-dimensional material on a target substrate.
The above embodiments are merely illustrative of the technical solutions of the present invention. The method for transferring large-area two-dimensional materials according to the present invention is not limited to the embodiments described above, but is subject to the scope defined by the claims. Any modification or supplement or equivalent replacement made by a person skilled in the art on the basis of this embodiment is within the scope of the invention as claimed in the claims.
In addition, in the present invention, the size of the obtained two-dimensional material is corresponding to the size of the substrate, and a larger two-dimensional material can be obtained with a larger substrate, and is not limited to the size described in the embodiments.

Claims (10)

1. A method of transferring large areas of two-dimensional material, comprising the steps of:
step 1, adopting a high-melting-point material substrate with the melting point higher than the growth temperature of a material to be transferred as a growth substrate;
step 2, adopting a low-melting-point material with a melting point lower than the growth temperature of the material to be transferred as a molten pool material, and placing the molten pool material on the growth substrate;
step 3, raising the temperature of the high-temperature area to the growth temperature of the material to be transferred, so that the molten pool material forms a liquid molten pool, and then starting to grow the material to be transferred, so that the material to be transferred grows on the surface of the molten pool in a large area, and a large-area two-dimensional material is formed;
step 4, moving the growth substrate on which the large-area two-dimensional material grows to a low-temperature region, wherein the temperature of the low-temperature region is lower than the melting point of a target substrate and is near the initial melting temperature of the molten pool material, so that the molten pool material is kept in a liquid state;
and 5, placing the target substrate near the molten pool, and transferring the large-area two-dimensional material to the target substrate through rotation and movement of a roller shaft positioned above the molten pool.
2. The method of transferring large area two-dimensional materials as claimed in claim 1, wherein:
wherein, in the step 1, the high-melting-point material is a metal material or an insulating material with a higher melting point,
the metal material is at least one of iron, cobalt, nickel, gold, silver, copper, platinum, palladium, aluminum, molybdenum, zinc, tungsten, chromium, titanium, vanadium, rhodium, ruthenium and iridium;
the insulating material is any one of sapphire, quartz, mica, silicon, hafnium oxide and beryllium oxide.
3. The method of transferring large area two-dimensional materials as claimed in claim 1, wherein:
wherein, in the step 2, the low-melting-point material is a metal material or an inorganic salt, the metal material is at least one of gallium, rubidium, tin, cadmium, lead, cesium, bismuth, indium and the like,
the inorganic salt is any one or combination of more of potassium chloride, sodium chloride, lithium chloride, zinc chloride, aluminum potassium chloride, aluminum sodium chloride, potassium bromide, lithium bromide, sodium bromide, aluminum lithium bromide, potassium iodide, lithium iodide, sodium iodide, potassium nitrate, sodium nitrate, lithium nitrate, nitrous acid, sodium thiocyanate and potassium thiocyanate, and preferably at least one of potassium chloride, sodium chloride, lithium chloride, zinc chloride, aluminum potassium chloride and aluminum sodium chloride.
4. The method of transferring large area two-dimensional materials as claimed in claim 1, wherein:
in step 3, growing the material to be transferred by using a chemical vapor deposition method.
5. The method of transferring large area two-dimensional materials as claimed in claim 4, wherein:
in the step 3, in the atmosphere of hydrogen and inert gas, the temperature of a high-temperature region is raised to the growth temperature of the material to be transferred, so that the molten pool material forms a liquid molten pool, then the large-area two-dimensional material is grown, gas of elements required for growing the two-dimensional material is introduced, the flow rate of the hydrogen is set to be 10-500 sccm, and the flow rate of the inert gas is set to be 50-1000 sccm.
6. The method of transferring large area two-dimensional materials as claimed in claim 5, wherein:
in step 3, the flow rate of the hydrogen gas is set to be 10-200 sccm, and the flow rate of the inert gas is set to be 100-600 sccm.
7. The method of transferring large area two-dimensional materials as claimed in claim 5, wherein:
wherein the large-area two-dimensional material is graphene, hexagonal boron nitride and a transition metal dichalcogenide;
transition metal dichalcogenides include sulfides, tellurides, selenides;
when the large area two-dimensional material is graphene, the carbon source is selected from at least one of carbon monoxide, methane, ethane, propane, butane, pentane, hexane, cyclohexane, ethylene, propylene, butadiene, pentene, cyclopentadiene, acetylene, methanol, ethanol, benzene, toluene, and phthalocyanine;
when the large-area two-dimensional material is molybdenum sulfide, sulfur powder is used as a sulfur source, and the molybdenum source is selected from molybdenum trioxide and ammonium molybdate.
8. The method of transferring large area two-dimensional materials as claimed in claim 5, wherein:
in step 3, when the large-area two-dimensional material is graphene, the flow rate of a carbon source is 3-200 sccm, and the ratio of the carbon source gas to hydrogen is 1: 50-1: 2.
9. The method of transferring large area two-dimensional materials as claimed in claim 1, wherein:
the target substrate is any one of a silicon wafer, a mica sheet, a polymer film and a quartz sheet.
10. The method of transferring large area two-dimensional materials as claimed in claim 1, wherein:
in step 5, the height of the roller is set to be just contacted with the large-area two-dimensional material, the roller moves from one side of the liquid pool to the target substrate positioned at the other side, and the roller also rotates.
CN201910999420.8A 2019-10-21 2019-10-21 Method for transferring large-area two-dimensional materials Pending CN110983287A (en)

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Application publication date: 20200410