CN114956062A - Transfer method of single crystal wafer graphene film - Google Patents
Transfer method of single crystal wafer graphene film Download PDFInfo
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- CN114956062A CN114956062A CN202110213872.6A CN202110213872A CN114956062A CN 114956062 A CN114956062 A CN 114956062A CN 202110213872 A CN202110213872 A CN 202110213872A CN 114956062 A CN114956062 A CN 114956062A
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Images
Classifications
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a transfer method of a single crystal wafer graphene film, which comprises the following steps: sequentially forming a terpenoid micromolecule layer and an auxiliary supporting layer on the surface of the single crystal wafer graphene film directly grown on a growth substrate, and attaching a heat release adhesive tape to obtain a composite layer; separating the growth substrate by a bubbling stripping method; after the composite layer is dried, attaching the composite layer to a target substrate; and removing the thermal release tape and the adhesive layers in the composite layer. According to the transfer method of the single crystal wafer graphene film, a layered structure of a heat release adhesive tape/an auxiliary supporting layer/a terpenoid micromolecule layer/the single crystal wafer graphene film/a growth substrate is constructed, the film can be peeled from the growth substrate within a few minutes based on a bubbling peeling method, and the damage to the wafer graphene film in the bubbling process can be avoided; and the bubbling stripping method can not damage the growth substrate, the growth substrate can be repeatedly used, and the production cost can be greatly reduced. The transfer method disclosed by the invention is compatible with layer-by-layer transfer of graphene.
Description
Technical Field
The invention belongs to the field of carbon materials, and particularly relates to a transfer method of a single crystal wafer graphene film.
Background
Graphene, an inch-scale single crystal wafer, prepared by Chemical Vapor Deposition (CVD) is an ideal electronic material and is compatible with semiconductor processing. However, the single crystal wafer graphene prepared by the CVD method often grows on a metal growth substrate and cannot be directly applied to an electronic device, and the single crystal wafer graphene film needs to be transferred to SiO 2 and/Si, sapphire and the like.
At present, a transfer method for graphene on a wafer is rarely reported. The commonly used polymethyl methacrylate (PMMA) -assisted support-based etching growth substrate transfer method has the cost of sacrificing a single crystal wafer growth substrate, and cannot be recycled; and the etching process is as long as 12 hours, and the efficiency is low.
The traditional copper foil graphene transfer method etching method and the bubbling method are not suitable for transferring the wafer graphene. The graphene structure of the wafer is that a layer of very thin single crystal copper or alloy is subjected to magnetron sputtering on sapphire, and a layer of graphene grows on the single crystal copper or alloy. The quality of the wafer graphene is higher than that of the copper foil graphene, and the wafer graphene has the advantages of single crystal, high single-layer rate and no folds, for example, the wafer graphene can be completely and cleanly transferred on a silicon growth substrate, and a semiconductor device can be processed on the wafer graphene, so that high mobility can be achieved. However, the wafer graphene is more expensive than the copper foil graphene, and if the wafer graphene is transferred by using an etching method, a single crystal copper growth substrate in the wafer graphene is etched, so that the expensive single crystal copper growth substrate cannot be recovered and used for regrowing the graphene. In the etching method, the copper foil in the copper foil graphene can float on the liquid level of the etching liquid to be etched, and the wafer graphene can sink in the etching liquid to be etched due to the self weight. Due to the influence of the surface tension of water, macroscopic folds of the graphene on the wafer are easily caused by an etching method, and the integrity, uniformity and cleanliness of the graphene are seriously influenced. The bubbling method can retain the copper growth substrate, but the traditional bubbling method is not suitable for the transfer of the graphene on the wafer. The reason for this is that the copper growth substrate and graphene have strong acting force, and graphene is easily damaged in the bubbling process under the action of the surface tension of water; and about 30 minutes is spent to transfer each 4-inch wafer of graphene, which results in low transfer efficiency.
It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may comprise information of the prior art that is known to a person of ordinary skill in the art.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for transferring a graphene film from a single crystal wafer.
The transfer method of the single crystal wafer graphene film comprises the following steps: forming a terpenoid micromolecule layer on the surface of a single crystal wafer graphene film directly grown on a growth substrate, forming an auxiliary supporting layer on the terpenoid micromolecule layer, and attaching a thermal release adhesive tape on the auxiliary supporting layer to obtain a thermal release adhesive tape/auxiliary supporting layer/terpenoid micromolecule layer/single crystal wafer graphene film/growth substrate composite layer; separating the growth substrate of the thermal release tape/auxiliary supporting layer/terpenoid micromolecule layer/single crystal wafer graphene film/growth substrate composite layer from the thermal release tape/auxiliary supporting layer/terpenoid micromolecule layer/single crystal wafer graphene film by adopting a bubbling stripping method; after the obtained thermal release tape/auxiliary supporting layer/terpenoid micromolecule layer/single crystal wafer graphene film composite layer is dried, attaching the thermal release tape/auxiliary supporting layer/terpenoid micromolecule layer/single crystal wafer graphene film composite layer to a target substrate; and removing the auxiliary supporting layer/terpenoid small molecular layer composite layer after the thermal release adhesive tape is heated and released.
According to an embodiment of the invention, the thickness of the terpene small molecular layer is 50nm to 50 μm; the preferred thickness is 100nm to 1 μm; preferably, the terpene micromolecule layer is made of terpene micromolecules with the number average molecular weight of less than 100000, and more preferably one or more of borneol and camphor.
According to another embodiment of the present invention, the thickness of the auxiliary support layer is 50nm to 10 μm; the thickness is preferably 100nm to 1 μm.
According to another embodiment of the present invention, the thermal release tape is roll-bonded or vacuum-bonded without air bubbles in the bonding gap.
According to another embodiment of the invention, the bubbling stripping method is to immerse the thermal release tape/auxiliary support layer/terpenoid small molecular layer/single crystal wafer graphene film/growth substrate composite layer in a sodium hydroxide solution, the concentration of the sodium hydroxide is 0.01-5mol/L, the growth substrate is used as a negative electrode, platinum or graphite is used as an anode, and 1-10V direct current is applied between the positive electrode and the negative electrode for 1-10 minutes.
According to another embodiment of the present invention, the bubbling stripping method further comprises mechanical stripping while bubbling, wherein the mechanical stripping is to mechanically strip the thermal release tape/auxiliary support layer/terpenoid small molecule layer/single crystal wafer graphene composite layer from the growth substrate, and the stripping speed is 0.1cm/s-1 cm/s.
According to another embodiment of the invention, the thermal release tape/auxiliary supporting layer/terpene small molecular layer/single crystal wafer graphene composite layer is bonded to the target substrate by rolling or vacuum bonding after being dried for 1-12 hours; preferably, the release temperature of the thermal release adhesive tape is 100-200 ℃, and the release time is 1-60 min.
According to another embodiment of the invention, the removing of the auxiliary supporting layer/terpenoid small molecular layer composite layer comprises heat treatment at 100-200 ℃ for 15min-3h, and then washing with acetone, acetone and isopropanol in sequence, wherein the washing time is 5 min-30 min, 5 min-30 min and 0.5 min-10 min in sequence; the acetone and isopropanol are preferably of CMOS grade, UP grade or HPLC grade purity.
According to another embodiment of the present invention, the size of the single crystal wafer graphene thin film is 2 inches, 4 inches or 6 inches.
According to another embodiment of the present invention, the number of graphene thin films on the single crystal wafer is 1 to 100.
According to the transfer method of the single crystal wafer graphene film, a layered structure of a thermal release tape/an auxiliary supporting layer/a terpenoid micromolecule layer/the single crystal wafer graphene film/a growth substrate is constructed, the film can be peeled from the growth substrate within a few minutes based on a bubbling peeling method, and the damage to the wafer graphene film in the bubbling process can be avoided; and the bubbling stripping method can not damage the growth substrate, the growth substrate can be repeatedly used, and the production cost can be greatly reduced. According to the transfer method, the wafer graphene film is transferred to the target substrate such as a silicon wafer or sapphire by a dry method, so that water-oxygen doping between the wafer graphene and the target substrate can be avoided, and the transfer method can ensure that the mobility of the transferred wafer graphene film is not reduced. Moreover, because the interaction force between the terpene micromolecules and the single crystal wafer graphene film is weak, and the terpene micromolecules are easily dissolved in various organic solvents, the auxiliary supporting layer/terpene micromolecule layer can be easily removed from the surface of the wafer graphene film, meanwhile, the auxiliary supporting layer can be prevented from remaining on the surface of the wafer graphene film, and the cleanness and the integrity of the transferred wafer graphene film can be ensured. The transfer method can realize large-scale transfer of large-area wafer graphene and is compatible with batch transfer of 2-inch, 4-inch and 6-inch wafer graphene. The transfer method can realize the lossless transfer of the graphene on the wafer, the integrity is more than 90% ("integrity" refers to a result of dividing the area of a damaged part by the total area observed through an optical microscope photo), and compared with a traditional electrochemical bubbling method, the integrity of the transferred graphene is obviously improved. The transfer method disclosed by the invention is compatible with layer-by-layer transfer of graphene, and can realize transfer of 1-100 layers of uniform wafer graphene.
Drawings
Fig. 1 is a schematic flow chart of a graphene wafer transfer process in embodiment 1.
Fig. 2 is a photograph and an optical microscope image of a graphene thin film of a wafer transferred onto a silicon wafer substrate in example 1.
Fig. 3 is a raman spectrum and atomic force microscope characterization of the graphene thin film wafer in example 1.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples.
The transfer method of the single crystal wafer graphene film comprises the following steps: forming a terpenoid micromolecule layer on the surface of the single crystal wafer graphene film directly grown on a growth substrate, forming an auxiliary supporting layer on the terpenoid micromolecule layer, and attaching a heat release adhesive tape on the auxiliary supporting layer to obtain a heat release adhesive tape/auxiliary supporting layer/terpenoid micromolecule layer/single crystal wafer graphene film/growth substrate composite layer; separating a growth substrate of the thermal release tape/auxiliary supporting layer/terpenoid micromolecule layer/single crystal wafer graphene film/growth substrate composite layer from the thermal release tape/auxiliary supporting layer/terpenoid micromolecule layer/single crystal wafer graphene film composite layer by adopting a bubbling stripping method; after the obtained thermal release tape/auxiliary supporting layer/terpenoid micromolecule layer/single crystal wafer graphene film composite layer is dried, attaching the thermal release tape/auxiliary supporting layer/terpenoid micromolecule layer/single crystal wafer graphene film composite layer to a target substrate; and removing the auxiliary supporting layer/terpenoid small molecular layer composite layer after heating to remove the heat release adhesive tape.
Specifically, the method for transferring the single crystal wafer graphene film firstly forms a terpenoid micromolecule layer on the surface of the single crystal wafer graphene film directly grown on a growth substrate. The growth substrate may be any growth substrate suitable for growing single crystal wafer graphene, such as, but not limited to, single crystal copper or copper alloys. The direct growth may be, but is not limited to, chemical vapor deposition. The terpene small molecules may be dissolved in an organic solvent to form a solution, and then the terpene small molecule layer is formed on the graphene wafer film by any suitable coating method. The solvent for dissolving the small organic molecules can be ethyl acetate and ethyl lactate, and the mass concentration of the small terpene molecules in the solution can be any concentration convenient for coating and is preferably 10-30 wt%. The coating method can be, but is not limited to, spin coating, and the spin coating speed can be 500-3000rpm, preferably 5000-2000 rpm. Generally, the spin coating can be performed 1-3 times according to the film forming condition, and the time of each spin coating can be 30s-5 min. The skilled person can select the appropriate solvent, coating means and various parameters of the coating process according to the actual needs. The terpene micromolecule layer is prepared from terpene micromolecules with the number average molecular weight of less than 100000. Preferably, the terpene small molecules are selected from one or more of borneol and camphor. The thickness of the terpenoid micromolecule layer is 100 nm-50 mu m. When the thickness of the terpene small molecular layer is less than 100nm, the isolation effect between the terpene small molecular layer and the auxiliary support layer is not optimal, and the degree of influence on reducing the pollution of the polymer in the auxiliary support layer on the graphene wafer film when the auxiliary support layer is subsequently removed is small, but a person skilled in the art should understand that the pollution of the auxiliary support layer on the graphene wafer film can be reduced as long as the terpene small molecular layer is arranged between the auxiliary support layer and the graphene wafer film, and the limitation of the thickness of not less than 100nm is only to achieve the purpose of reducing the pollution to an ideal standard, and is not to limit the invention. When the thickness of the terpene micromolecule layer is more than 50 μm, residues are easily left when the terpene micromolecule layer is removed, and the cleanliness of the graphene thin film on the wafer is affected. Preferably, the thickness of the terpene micromolecule layer is 500 nm-10 μm.
An auxiliary support layer is then formed on the terpene small molecule layer. The auxiliary supporting layer plays a role in improving supporting strength so as to facilitate transfer of the wafer graphene film. Meanwhile, when the subsequent heat release adhesive tape is removed, the auxiliary supporting layer can ensure the integrity of the wafer graphene film, so that the transferred wafer graphene film has a complete structure and excellent performance. The thickness of the auxiliary supporting layer is 100 nm-10 μm. The auxiliary supporting layer is too thin (less than 100nm) to play a supporting role, and too thick (more than 10 μm) is easy to leave residues on the graphene film of the wafer during subsequent removal, so that the graphene film of the wafer does not meet the requirement of cleanliness, and the supporting effect is not obviously improved when the auxiliary supporting layer is too thick. Therefore, the thickness is preferably 500nm to 5 μm. The auxiliary support layer may be formed of polymethyl methacrylate. The PMMA can be dissolved in an organic solvent to form a solution and then coated on the surface of the terpene small molecular layer. The coating method can be any suitable method, such as but not limited to spin coating, and the spin coating speed can be 500-. The spin coating of PMMA may be performed 1-3 times according to the film forming condition, and the spin coating time may be 30s-5 min. After coating, the coating can be formed into a film by baking and the like, wherein the baking temperature can be 100-200 ℃, and the baking time can be 1-5 min.
After that, a Thermal Release Tape (TRT) was attached to the auxiliary support layer. The attachment means may be any suitable means such as, but not limited to, press attachment, roll attachment, vacuum attachment, and the like. The thermal release tape/auxiliary support layer/terpenoid micromolecule layer/single crystal wafer graphene film/growth substrate composite layer is obtained after the step. To ensure the transferred effect, it is preferable that the fit gap has no air bubbles.
And then, separating the growth substrate of the thermal release tape/auxiliary support layer/terpenoid micromolecule layer/single crystal wafer graphene film/growth substrate composite layer from the thermal release tape/auxiliary support layer/terpenoid micromolecule layer/single crystal wafer graphene film composite layer by adopting a bubbling stripping method. The bubbling stripping method comprises the steps of immersing the composite layer of the thermal release tape/the auxiliary supporting layer/the terpenoid micromolecule layer/the single crystal wafer graphene film/the growth substrate in a sodium hydroxide solution, wherein the growth substrate is a negative electrode, platinum or graphite is an anode, and 1-10V direct current is applied between the positive electrode and the negative electrode for 1-10 minutes, preferably 3-5V. The concentration of sodium hydroxide is 0.01 to 5mol/L, preferably 0.05 to 5mol/L, and more preferably 0.1 to 2 mol/L. During the bubbling process, the metal film in the growth substrate connected with the anode generates hydrogen bubbles, which can reduce the acting force of the graphene wafer film and the growth substrate, so that the thermal release tape/the auxiliary support layer/the terpenoid micromolecule layer/the single crystal graphene wafer film is easy to separate from the growth substrate. Meanwhile, the growth substrate is not damaged in the bubbling stripping process, and can be reused, so that the growth cost is reduced. The parameters used in the bubbling stripping process can be selected according to actual conditions, considering factors such as the strength, size and density of generated bubbles, and the corrosion of the electrolyte on the graphene film of the wafer, and the like, and the appropriate voltage, time and electrolyte concentration are selected, and the above parameters are only preferred parameters, and do not mean that other parameters cannot achieve the purpose of the invention.
Preferably, mechanical stripping can be performed while bubbling stripping, the acting force between the thermal release tape/auxiliary supporting layer/terpenoid small molecular layer/single crystal wafer graphene film composite layer and the growth substrate is greatly reduced in the bubbling stripping process, the wafer graphene film is not damaged by mechanical stripping, and the stripping process can be greatly shortened. Preferably, the mechanical peeling speed is 0.1cm/s to 1cm/s, and any suitable peeling speed can be selected by those skilled in the art on the principle that the peeling process does not damage the graphene film on the wafer, such as, but not limited to, 0.1cm/s, 0.2cm/s, 0.3cm/s, 0.4cm/s, 0.5cm/s, 0.6cm/s, 0.7cm/s, 0.8cm/s, 0.9cm/s, 1cm/s, etc.
And cleaning the stripped heat release adhesive tape/auxiliary supporting layer/terpenoid micromolecule layer/single crystal wafer graphene film composite layer, and removing the electrolyte in the composite layer. The composite layer can be cleaned according to actual conditions. After that, the composite layer is dried, preferably dried naturally.
And then, transferring the dried thermal release tape/auxiliary support layer/terpenoid micromolecule layer/single crystal wafer graphene film composite layer onto a target substrate. The target substrate may be any substrate suitable for a semiconductor device substrate, such as a silicon wafer, sapphire, or the like. The dry heat release tape/auxiliary supporting layer/terpenoid micromolecule layer/single crystal wafer graphene film composite layer can avoid introducing water and oxygen in the transfer process, so that the reduction of the carrier mobility of the wafer graphene after transfer is avoided. The bonding of the composite layer to the target substrate may be by any suitable means, such as, but not limited to, roll bonding, vacuum bonding, and the like.
And removing the thermal release adhesive tape after the composite layer is attached to the target substrate. The thermal release tape can be removed by common means, such as but not limited to, the release temperature is 100 ℃ to 200 ℃, and the release time is 1-60 min. The skilled person can select the appropriate temperature and time according to the actual situation of the heat release adhesive tape.
Finally, the auxiliary support layer/terpenoid small molecular layer composite layer is removed. The organic solvent can be used for dissolving and removing, and the high-temperature annealing can also be used for removing. The organic solvent can be acetone, ethanol, isopropanol, N-methylpyrrolidone, etc. For example, the organic solvent glue removing mode can be that the single crystal wafer graphene film is washed by the organic solvent after being thermally treated at 100-200 ℃ for 15min-3h, the binding force between the single crystal wafer graphene film and the target substrate can be increased in the thermal treatment process, and the phenomenon that the wafer graphene film is folded when the subsequent organic solvent is washed is avoided. The organic solvent washing comprises washing with acetone, acetone and isopropanol sequentially for 5-30 min, 5-30 min and 0.5-10 min, wherein the acetone and the isopropanol preferably have CMOS grade, UP grade purity or HPLC grade purity. For example, the high temperature annealing process can be performed by introducing hydrogen gas with a flow rate of 100-1000sccm and argon gas with a flow rate of 100-1000sccm at a temperature of 300-400 ℃ for 1-24 h. The above two methods are only examples, and other methods or other parameters may be adopted in the above two methods as long as the process does not damage the graphene film and the target substrate of the wafer, and does not introduce impurities.
The transfer method of the invention is suitable for the diameter of the graphene film of the single crystal wafer, which is 2 inches, 4 inches or 6 inches. The transfer method disclosed by the invention can be compatible with layer-by-layer transfer of graphene, and can realize transfer of 1-100 layers of uniform wafer graphene. The layer-by-layer transfer is to repeat the transfer step for multiple times to form the wafer graphene overlapped with the single crystal wafer graphene film which is transferred for multiple times. The skilled person can select the appropriate number of transfer layers according to the actual requirement, such as but not limited to 1 layer, 5 layers, 10 layers, 15 layers, 20 layers, 25 layers, 30 layers, 40 layers, 50 layers, 60 layers, 70 layers, 80 layers, 90 layers or 100 layers, etc.
The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
Example 1
As shown in the process flow chart of fig. 1, a common commercially available Borneol (-) -borneeol (97%) is dissolved in ethyl lactate with a mass concentration of 25 wt%, and the Borneol solution is uniformly covered on the surface of a 4-inch wafer graphene film/copper/sapphire wafer by a spin coater at a rotation speed of 1000rpm and spin-coated for 2 times. Then, a PMMA solution (with a molecular weight of 950K, PMMA dissolved in ethyl lactate and a mass fraction of 4 wt%) is spin-coated, the rotation speed is 1000rpm, and the PMMA solution is baked on a heating platform for 3min at a temperature of 130 ℃. The thickness of the borneol is 400nm, and the total thickness of the borneol and the PMMA layer is 640 nm. And then adhering a Thermal Release Tape (TRT) to the PMMA in a rolling manner to obtain a 'TRT/PMMA/borneol layer/wafer graphene film/copper/sapphire' composite structure. Fixing the composite structure on a carrier, completely immersing the composite structure in 1mol/L sodium hydroxide solution, connecting copper in the composite structure by using a negative electrode of a direct current power supply, connecting a positive electrode of the direct current power supply with a graphite plate serving as another electrode, applying 4V voltage on the direct current power supply for 3min, weakening the interaction between the 'TRT/PMMA/ice sheet layer/wafer graphene film' and the 'copper/sapphire' growth substrate by using hydrogen bubbles continuously generated on the surface of copper, and then slowly stripping the 'TRT/PMMA/ice sheet layer/wafer graphene film' composite structure from the 'copper/sapphire' growth substrate by using a wafer clamp. And (3) washing the composite structure of the TRT/PMMA/ice sheet layer/wafer graphene film in deionized water for 15min, and repeating for 2 times. The copper/sapphire growth substrate is washed clean by a small amount of deionized water, dried by high-purity nitrogen and used for subsequent regeneration of high-quality wafer graphene films. And after the obtained 'TRT/PMMA/borneol layer/wafer graphene film' composite layer is naturally dried, rolling and attaching the composite layer to a silicon wafer containing an oxide layer with the thickness of 300nm, and heating and releasing on a 120 ℃ hot bench to remove TRT. Baking the obtained PMMA/borneol layer/wafer graphene film/silicon wafer at 180 ℃ for 1h, and then washing, wherein the washing mode is that acetone, acetone and isopropanol are used for washing for 10min, 10min and 0.5min in sequence, and nitrogen is used for drying to obtain the 4-inch wafer graphene film on the transferred silicon wafer.
A photograph and micrograph of the wafer graphene film of this example transferred to a four inch silicon wafer is shown in fig. 2. In fig. 2, a photo shows a photo of a 4-inch wafer graphene on a silicon wafer substrate after TRT is released, b photo shows an optical micrograph, c photo shows a wafer graphene film with PMMA/ice sheets removed, and d photo shows an optical micrograph of the wafer graphene film with PMMA/ice sheets removed. As can be seen from the drawings in fig. 2, the graphene thin film transferred in example 1 is not damaged.
Fig. 3 shows raman characterization (shown in photograph a) and atomic force microscopy characterization (shown in photograph b) of 4 inch wafer graphene transferred to a silicon wafer for this example. From the Raman spectrum, the graphene is successfully transferred to the silicon target substrate, and the D peak is small, so that the damage is less and the integrity is higher. The atomic force microscope characterization picture shows that the transferred graphene has a cleaner surface and less particle pollutant residue.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (10)
1. A method for transferring a graphene film of a single crystal wafer is characterized by comprising the following steps:
forming a terpenoid micromolecule layer on the surface of a single crystal wafer graphene film directly grown on a growth substrate, forming an auxiliary supporting layer on the terpenoid micromolecule layer, and attaching a thermal release adhesive tape on the auxiliary supporting layer to obtain a thermal release adhesive tape/auxiliary supporting layer/terpenoid micromolecule layer/single crystal wafer graphene film/growth substrate composite layer;
separating the growth substrate of the thermal release tape/auxiliary supporting layer/terpenoid micromolecule layer/single crystal wafer graphene film/growth substrate composite layer from the thermal release tape/auxiliary supporting layer/terpenoid micromolecule layer/single crystal wafer graphene film by adopting a bubbling stripping method;
after the obtained thermal release tape/auxiliary supporting layer/terpenoid micromolecule layer/single crystal wafer graphene film composite layer is dried, attaching the thermal release tape/auxiliary supporting layer/terpenoid micromolecule layer/single crystal wafer graphene film composite layer to a target substrate; and
and after the thermal release adhesive tape is heated and released, removing the auxiliary supporting layer/terpenoid small molecular layer composite layer.
2. The method for transferring the graphene film from the single crystal wafer according to claim 1, wherein the thickness of the terpene small molecular layer is 50nm to 50 μm; preferably, the thickness is 100nm to 1 μm; preferably, the terpene micromolecule layer is made of terpene micromolecules with the number average molecular weight of less than 100000, and more preferably one or more of borneol and camphor.
3. The method for transferring the graphene film on the single crystal wafer according to claim 1, wherein the thickness of the auxiliary supporting layer is 50nm to 10 μm; preferably, the thickness is 100nm to 1 μm; preferably, the auxiliary support layer comprises polymethyl methacrylate.
4. The method for transferring graphene according to claim 1, wherein the thermal release tape is applied by rolling or vacuum-applying without bubbles in the application gap.
5. The method for transferring the graphene film on the single crystal wafer according to claim 1, wherein the bubbling peeling method is to immerse the thermal release tape/auxiliary support layer/terpene small molecular layer/graphene film on the single crystal wafer/growth substrate composite layer into a sodium hydroxide solution, the concentration of the sodium hydroxide is 0.01-5mol/L, the growth substrate is a negative electrode, platinum or graphite is an anode, and a direct current of 1-10V is applied between the positive electrode and the negative electrode for 1-10 minutes.
6. The method for transferring the graphene film on the single crystal wafer according to claim 5, wherein the bubbling stripping method further comprises mechanical stripping while bubbling, the mechanical stripping is to mechanically strip the thermal release tape/auxiliary support layer/terpene small molecular layer/graphene composite layer from the growth substrate, and the stripping speed is 0.1cm/s to 1 cm/s.
7. The method for transferring the graphene film on the single crystal wafer according to claim 6, wherein the thermal release tape/auxiliary support layer/terpenoid small molecular layer/graphene composite layer on the single crystal wafer is dried for 1-12h and then is attached to the target substrate by rolling or vacuum bonding; preferably, the release temperature of the thermal release adhesive tape is 100-200 ℃, and the release time is 1-60 min.
8. The method for transferring the graphene film on the single crystal wafer as claimed in claim 1, wherein the step of removing the auxiliary supporting layer/terpenoid small molecular layer composite layer comprises the steps of performing heat treatment at 100-200 ℃ for 15min-3h, and then sequentially washing with acetone, acetone and isopropanol for 5-30 min, 5-30 min and 0.5-10 min; the acetone and isopropanol are preferably of CMOS grade, UP grade or HPLC grade purity.
9. The method for transferring the graphene film as claimed in claim 1, wherein the graphene film is 2 inches, 4 inches or 6 inches in size.
10. The transfer method of the single crystal wafer graphene film according to claim 1, wherein the transfer step is repeated for a plurality of times to obtain the graphene wafer with 1-100 layers.
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| CN104192833A (en) * | 2014-08-20 | 2014-12-10 | 中国科学院上海高等研究院 | Transfer method of graphene film |
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| CN110581063A (en) * | 2019-10-22 | 2019-12-17 | 北京石墨烯研究院 | Transfer method of graphene wafer |
| CN111362258A (en) * | 2020-02-12 | 2020-07-03 | 浙江大学 | Graphene film transfer method using beeswax as supporting layer |
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| CN104192833A (en) * | 2014-08-20 | 2014-12-10 | 中国科学院上海高等研究院 | Transfer method of graphene film |
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