CN112301429B - Tube furnace refitting device and method for preparing monocrystalline metal foil and two-dimensional material - Google Patents
Tube furnace refitting device and method for preparing monocrystalline metal foil and two-dimensional material Download PDFInfo
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- 239000002184 metal Substances 0.000 title claims abstract description 72
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 72
- 239000011888 foil Substances 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000000463 material Substances 0.000 title claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 57
- 239000013078 crystal Substances 0.000 claims description 49
- 239000011889 copper foil Substances 0.000 claims description 47
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 238000000137 annealing Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910021389 graphene Inorganic materials 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 230000005294 ferromagnetic effect Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000010949 copper Substances 0.000 description 12
- 238000005229 chemical vapour deposition Methods 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 229910052582 BN Inorganic materials 0.000 description 5
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 4
- 229910000570 Cupronickel Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/02—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/08—Reaction chambers; Selection of materials therefor
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/16—Controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
- C30B29/403—AIII-nitrides
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
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- Thermal Sciences (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a tube furnace refitting device and a tube furnace refitting method for preparing a monocrystalline metal foil and a two-dimensional material. The method can finely adjust the position and the moving speed of the sample piece and the condition of the temperature gradient field under the premise of not changing the tightness of the furnace body and other furnace body parameters. The refitting method is simple to operate and wide in applicability, can be compatible with horizontal tube furnaces of most models, and reduces the requirements on special equipment in the conversion process of monocrystalline metal foil and the growth process of two-dimensional materials.
Description
Technical field:
the invention relates to a refitting method of a tube furnace for rapidly preparing monocrystalline metal foil and two-dimensional materials through an automatic propelling device, and belongs to the field of film materials.
The background technology is as follows:
the metal is an indispensable part of modern society, and has very wide application in the aspects of electronics, electricity, communication and the like. Currently, commercial metallic materials are available in the market, mainly polycrystalline and amorphous metals. Various defects existing in the polycrystalline and amorphous metals seriously affect the electrical and thermal properties of the metals, and the monocrystalline metal can exert the electrical and thermal properties to the maximum extent, so that the monocrystalline metal has very good application prospects in the aspects of electronics, devices and the like.
The monocrystalline metal foil has a single crystal face and is widely applied to the growth of two-dimensional monocrystalline materials. In recent years, with the rising research on two-dimensional materials, single-crystal metal foils have attracted attention from the scientific community. The size of the two-dimensional monocrystalline material is limited by the monocrystalline metal foil, and meanwhile, the defects of the monocrystalline metal foil can seriously affect the quality of the prepared two-dimensional monocrystalline material. Therefore, the preparation of the metal foil with large size, few defects and single crystal face is particularly important.
Commercial metal foils in commercial production vary in grain orientation and have many crystal defects, annealing is an effective method of single crystallization of polycrystalline metal foils.
At present, a method for carrying out constant-temperature annealing on polycrystalline metal foil is commonly used in laboratories. Heating the metal foil to a certain temperature close to and slightly lower than the melting point of the metal through a chemical vapor deposition device, and keeping the temperature for a plurality of hours, so that the crystal boundaries of each crystal grain are consistent in orientation and then spliced into a large-area monocrystalline metal foil:
1. patent CN201810343286.1 "a method for preparing a surface single crystal copper substrate for industrial production of two-dimensional materials" is to heat and anneal the oxidized commercial polycrystalline copper foil step by step to prepare the single crystal copper foil with (111) crystal face.
2. In the patent cn201310470590.X, a method for preparing a single crystal copper strip, the grain boundary regions of a polycrystalline copper strip are concentrated together to form a region which cannot be converted into a single crystal by a gradual heating method, so that the size of the region is kept relatively small. Under the effect of ultrasonic vibration, the area which is not converted into single crystal shows isotropy, and under the heating condition of enough time, the polycrystalline copper strip is finally converted into a continuous single crystal copper strip.
3. Patent CN201710028076.9, "preparation method of oversized multilayer single crystal graphene and oversized single crystal copper-nickel alloy", uses nickel plated single crystal copper foil as raw material, prepares oversized single crystal copper-nickel alloy (1-5 cm) by constant temperature annealing method, and then uses single crystal copper-nickel alloy as substrate to obtain oversized high quality multilayer single crystal graphene by normal pressure chemical vapor deposition method.
The method has high annealing temperature and long period, and the prepared metal foil monocrystal has small size and limits the size and performance of the two-dimensional material grown on the monocrystal metal foil.
In the constant temperature annealing process, the atmosphere conditions in the heating and annealing processes are strictly regulated, so that the large-area polycrystalline metal foil can be quickly and efficiently directly converted into the monocrystalline metal foil.
4. Patent CN201610147553.9, "a method for converting a polycrystalline copper foil into single crystal Cu (100)" and paper Surface monocrystallization of copper foil for fast growth of large single-crystal graphene under free molecular flow (adv. Mater.2016,28,8968-8974) describe a method for converting a polycrystalline copper foil surface into a single crystal copper foil rapidly and efficiently using oxygen adsorption-induced reconstruction. The crystal face of the single crystal copper foil is a (100) crystal face, and the size reaches 6cm multiplied by 6cm.
Subsequent studies of Seeded growth of large single-crystal copper foils with high-index facets (Nature, 2020,581.406-410) in 5.2020 have also found that the pre-oxidation treatment has an important role in producing single crystal metal foil in the high index crystal plane.
Hyung-Joon Shin and Rodney S.Ruoff et al, in Colossal grain growth yields single-crystal metal foils by contact-free annealing (science.2018, 362 (6418): 1021-1025) from Korean basic science research Institute (IBS) 6.2018 obtained inexpensive and readily available single crystal metal foils including large area Cu (111), ni (111), co (0001), pt (111) and Pd (111) single crystal metal foils by a contactless annealing method. The area of the single-crystal copper foil is up to 32cm 2 。
The preparation of single crystal copper foil with unique Cu <211> step is realized in the manner of seed crystal induction and high temperature annealing in the paper Epitaxial growth of a-square-centimetre single crystal hexagonal boron nitride monolayer on copper published in J.Nature by the university of Beijing Wang Enge, dapeng, liu Kaihui researchers and cooperators in 7.2019, and large-area boron nitride single crystal is synthesized by utilizing the coupling property of the single crystal copper foil and hexagonal boron nitride.
The method adopts annealing at a fixed temperature, and combines other auxiliary means to promote the transformation from the polycrystalline copper foil to the monocrystalline copper foil. However, the period required is generally 2-12 hours, and the range of transformation of the single crystal metal foil is limited to the sample at the center of the furnace temperature, which is very disadvantageous for enlarging the transformation efficiency and scale.
8.2017, published in Science Bulletin journal Ultrafast epitaxial growth of metre-simplified single-crystal graphene on industrial Cu foil (Science Bulletin 62 (2017) 1074-1080), shows a method for rapidly obtaining large-area single-crystal copper and growing graphene on single-crystal copper by using a temperature gradient as a driving force;
9. in the patent CN201610191702.1, a rotating device is arranged in a first low-temperature area and a second low-temperature area at two ends of a chemical vapor deposition system, and a metal substrate can continuously pass through a furnace temperature center through the rotating device, so that the transformation of a monocrystalline copper foil and the growth of monocrystalline graphene are realized.
The method provides a good method for preparing large-area monocrystalline copper and graphene, namely a temperature gradient driven monocrystalline conversion method. This method requires pushing the polycrystalline metal foil at a constant speed in a closed CVD furnace. So far, the purpose of pushing the metal foil at a constant speed and creating a temperature gradient is achieved by adopting a mode of arranging a rotating wheel in a tube furnace. This approach is demanding for conventional tube furnace equipment and requires additional sealing means. Obviously not compatible with most tube furnace equipment on the market, and therefore also limits the large-scale conversion of single crystal metal foils.
The invention comprises the following steps:
aiming at the problems, the invention adopts a refitting method of a horizontal tube furnace for rapidly preparing monocrystalline metal foil and two-dimensional materials by an automatic propulsion device. The internal push rod is connected with the external connecting rod by a non-contact connection method, so that the atmosphere condition and the structural composition of an internal system of the furnace body are not affected, and the internal push rod is directly compatible with most tubular furnaces on the market without other sealing devices or accessories. The sample piece moves at a constant speed or a variable speed according to a set program, so that the control of the temperature gradient is realized, and the transformation of the monocrystalline metal foil and the growth of the two-dimensional material are realized. The invention comprises the following steps:
the invention aims to provide an automatic propelling device capable of propelling materials in a CVD furnace at a constant speed, and aims to solve the technical problem that a conventional CVD furnace cannot propel sample materials in the conventional CVD furnace during closed heating.
The technical scheme of the invention is as follows: the automatic propelling device for propelling the materials in the closed CVD furnace comprises a driving system, a T-shaped connecting rod, a magnet and an L-shaped push rod. The stepping motor of the driving system drives the connecting rod to move, and when the connecting rod moves, the push rod is driven to move due to the mutual attraction effect of the magnet at the top end of the connecting rod and the push rod in the CVD furnace, so that the synchronous movement of the stepping motor, the connecting rod and the push rod is realized, the annealing of metal foil in the CVD furnace is pushed, and the growth of the two-dimensional material is realized.
Specifically, the driving system comprises a power supply, a controller, a driver and a stepping motor. By setting the parameters of the controller, the stepping motor can move within the required speed and distance.
Specifically, the connecting rod comprises an upper connecting rod and a lower connecting rod, the lower connecting rod is fixed on the stepping motor, and the upper connecting rod and the lower connecting rod are matched, so that the height can be adjusted. Meanwhile, the top end of the upper connecting rod can fix the magnet.
Specifically, the push rod is a ferromagnetic substance and can generate an interaction attraction effect with the magnet at the upper end of the connecting rod. The length of the push rod is not limited, but the metal foil can be pushed to pass through the furnace temperature center completely.
Drawings
FIG. 1 is a schematic view of the overall structure of a self-propelled device of the present invention retrofitted to a horizontal CVD furnace.
Reference numeral 1: 1-stepper motor, 2-lower connecting rod, 3-upper connecting rod, 4-L-shaped push rod, 5-oxide and metal foil and 6-magnet
FIG. 2 is XRD pattern of single crystal copper foil
FIG. 3 is a SEM image of single crystal graphene
FIG. 4 is a SEM image of single crystal hexagonal boron nitride
Detailed Description
The operation of the present invention will be described in detail with reference to examples, which are conventional in the art unless specifically described otherwise, and materials which are commercially available unless specifically described otherwise.
The invention uses a chemical vapor deposition system to anneal the metal foil and perform two-dimensional single crystal material growth. The device comprises a driving system consisting of a controller, a driver and a stepping motor, a connecting rod, a magnet and a push rod. Under the action of the controller and the driver, the stepping motor can move a certain distance along a certain direction at a certain speed. The stepping motor drives the connecting rod to move, and the magnet at the upper end of the connecting rod interacts with the ferromagnetic push rod in the closed CVD furnace to drive the push rod to move together, so that the metal foil is pushed to pass through the furnace temperature center at a specific speed.
The device anneals the metal foil and grows the graphene film as follows:
placing commercial polycrystalline metal foil carried by a quartz plate in a chemical vapor deposition furnace, wherein one end of the metal foil is connected with a push rod, and the other end of the metal foil is just at the center of the furnace temperature. Introducing mixed gas composed of argon with flow of more than 250sccm and hydrogen with flow of 25-50sccm into the system, rapidly heating to 1030 ℃ or higher, and annealing the metal foil for 20-60 minutes.
Setting required parameters in the controller, wherein the running distance of the stepping motor is the same as that of the metal foil, and the running speed is 0.5-2cm/min. After the metal foil is annealed, a stepping motor is started, and the metal foil is pushed to pass through the furnace temperature center at a uniform speed in a straight line in sequence at the temperature. And after the annealing is finished, cooling the temperature in the furnace to room temperature to obtain the large-area monocrystalline metal foil.
And thirdly, placing the monocrystalline metal foil carried by the quartz plate in a chemical vapor deposition furnace, wherein one end of the metal foil is connected with the push rod, and the other end of the metal foil is positioned at the center of the furnace temperature. Introducing mixed gas composed of argon with the flow rate of more than 150sccm and hydrogen with the flow rate of 5-20sccm into the system, rapidly heating to the temperature of more than 1030 ℃, introducing methane with the flow rate of 1-5sccm into the furnace at the moment, starting a stepping motor, and pushing the metal foil to sequentially pass through the center of the furnace at a constant speed of 1-5 cm/min.
And (IV) cooling the copper foil after passing through the furnace temperature center, and cooling to room temperature after the growth is finished to obtain the high-quality large-area monocrystalline graphene film.
The invention has the advantages that:
1. the operation is simple, and the monocrystalline copper foil and the graphene film can be rapidly and efficiently prepared;
2. the monocrystal metal foil and the graphene film prepared by the chemical vapor deposition method have large size, high quality and few defects, and have good application prospects;
3. the commercial polycrystalline metal foil is used as a raw material, so that the cost is low, the compatibility is good, and no special requirement is imposed on equipment.
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention is described below by means of specific embodiments shown in the accompanying drawings. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention.
Example 1:
a commercial polycrystalline copper foil with the size of 20cm multiplied by 2cm multiplied by 25 mu m is placed in a quartz tube of a vapor deposition furnace by using a quartz plate, one end of the copper foil is connected with a push rod, and the other end of the copper foil is just at the center of the furnace temperature. And (3) introducing mixed gas consisting of argon with the flow of 500sccm and hydrogen with the flow of 25sccm into the system, rapidly heating to 1030 ℃, and annealing the copper foil for 20 minutes.
After annealing the copper foil, starting a stepping motor, and pushing the copper foil to sequentially pass through the furnace temperature center at a constant speed of 1cm/min at 1030 ℃. And after the copper foil passes through the furnace temperature center, cooling the temperature in the furnace to room temperature to obtain the large-area monocrystalline copper foil.
And thirdly, placing the monocrystalline copper foil carried by the quartz plate in a chemical vapor deposition furnace, wherein one end of the copper foil is connected with the push rod, and the other end of the copper foil is positioned at the center of the furnace temperature. And (3) introducing mixed gas consisting of argon with the flow of 500sccm and hydrogen with the flow of 10sccm into the system, rapidly heating to 1030 ℃, introducing methane with the flow of 1sccm into the furnace, starting a stepping motor, and pushing the copper foil to sequentially pass through the furnace temperature center at a constant speed of 2.5 cm/min.
And (IV) the copper foil passes through the furnace temperature center completely, and the growth is finished, at the moment, the heating and the methane supply can be stopped, and the copper foil is cooled to room temperature under the protection of argon and hydrogen, so that the high-quality large-area monocrystalline graphene film can be obtained.
Example 2:
a commercial polycrystalline copper foil with the size of 20cm multiplied by 2cm multiplied by 25 mu m is placed in a quartz tube of a vapor deposition furnace by using a quartz plate, one end of the copper foil is connected with a push rod, and the other end of the copper foil is just at the center of the furnace temperature. And (3) introducing mixed gas consisting of argon with the flow of 250sccm and hydrogen with the flow of 50sccm into the system, rapidly heating to 1065 ℃, and annealing the copper foil for 20 minutes.
After annealing the copper foil, starting a stepping motor, and pushing the copper foil to sequentially pass through the furnace temperature center at a constant speed of 1cm/min at a temperature of 1065 ℃. And after the copper foil passes through the furnace temperature center, cooling the temperature in the furnace to room temperature to obtain the large-area monocrystalline copper foil.
And thirdly, placing the monocrystalline copper foil carried by the quartz plate in a chemical vapor deposition furnace, wherein one end of the copper foil is connected with the push rod, and the other end of the copper foil is positioned at the center of the furnace temperature. And (3) introducing mixed gas consisting of argon with the flow of 150sccm and hydrogen with the flow of 10sccm into the system, rapidly heating to 1065 ℃, introducing thermally decomposed borane ammonia complex into the furnace at the moment, starting a stepping motor, and pushing the copper foil to sequentially pass through the furnace temperature center at a constant speed of 2.5 cm/min.
And (IV) the copper foil passes through the furnace temperature center completely, and the growth is finished, at the moment, the heating and the supply of borane ammonia can be stopped, and the copper foil is cooled to room temperature under the protection of argon and hydrogen, so that the high-quality large-area monocrystal hexagonal boron nitride film can be obtained.
The scope of the invention is indicated by the appended claims rather than by the foregoing description, and all changes that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (4)
1. A tube furnace refitting device for preparing monocrystalline metal foil and two-dimensional material is characterized by comprising a driving system, a T-shaped connecting rod, an L-shaped push rod and a magnet;
the driving system comprises a power supply, a controller, a driver and a stepping motor; the T-shaped connecting rod comprises an upper connecting rod and a lower connecting rod, the upper connecting rod and the lower connecting rod are matched, the height is adjusted, the lower connecting rod is fixedly connected with the stepping motor, and the top end of the upper connecting rod is fixedly provided with the magnet; the L-shaped push rod is arranged in the tube furnace; the L-shaped push rod is made of ferromagnetic substances, and the L-shaped push rod and the upper magnet of the upper connecting rod are attracted mutually;
the L-shaped push rod is close to the heat treatment area and is made of high-temperature resistant materials; the height of the T-shaped connecting rod is adjustable, and the length of the L-shaped push rod is adjustable.
2. A tube furnace retrofit apparatus for producing single crystal metal foil and two-dimensional material according to claim 1, wherein the T-bar drive is belt drive, chain drive or gear drive.
3. A tube furnace retrofit apparatus for producing single crystal metal foil and two-dimensional material according to claim 1, wherein the T-shaped link is a rail, a travelling car or a robotic arm.
4. A method of using a tube furnace retrofit device for producing single crystal metal foil and two-dimensional material according to any one of claims 1-3, comprising the steps of:
placing commercial polycrystalline metal foil carried by quartz plates in a tubular furnace, connecting one end of the metal foil with an L-shaped push rod, and introducing mixed gas consisting of argon with the flow of more than 250sccm and hydrogen with the flow of 25-50sccm into the system at the position of the center of the furnace temperature, rapidly heating the tubular furnace to the temperature of more than 1030 ℃, and annealing the metal foil for 20-60 minutes;
setting required parameters in a controller, setting the running distance of a stepping motor to be the same as that of the metal foil, setting the running speed to be 0.5-2cm/min, starting the stepping motor after annealing the metal foil, pushing the metal foil to pass through the furnace temperature center at a constant speed in a straight line in sequence at the speed, finishing annealing, and cooling the temperature in the furnace to the room temperature to obtain the large-area monocrystalline metal foil;
placing a monocrystalline metal foil carried by a quartz plate in a tube furnace, connecting one end of the metal foil with a push rod, and placing the other end of the metal foil at the center of the furnace temperature, introducing mixed gas comprising argon with the flow rate of more than 150sccm and hydrogen with the flow rate of 5-20sccm into the tube furnace, rapidly heating the tube furnace to the temperature of more than 1030 ℃, introducing methane with the flow rate of 1-5sccm into the furnace at the moment, starting a stepping motor, and pushing the metal foil to sequentially pass through the center of the furnace temperature at the constant speed of 1-5 cm/min;
and (IV) cooling the copper foil after passing through the furnace temperature center, and cooling to room temperature after the growth is finished to obtain the high-quality large-area monocrystalline graphene film.
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