CN115744886A - Graphene growth support and graphene growth method - Google Patents
Graphene growth support and graphene growth method Download PDFInfo
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- CN115744886A CN115744886A CN202211482483.4A CN202211482483A CN115744886A CN 115744886 A CN115744886 A CN 115744886A CN 202211482483 A CN202211482483 A CN 202211482483A CN 115744886 A CN115744886 A CN 115744886A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000011889 copper foil Substances 0.000 claims abstract description 67
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 23
- 239000010439 graphite Substances 0.000 claims abstract description 23
- 239000010453 quartz Substances 0.000 claims abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
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- -1 graphite alkene Chemical class 0.000 abstract description 8
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- 239000010939 rose gold Substances 0.000 description 10
- 229910001112 rose gold Inorganic materials 0.000 description 10
- 208000035388 Ring chromosome 22 syndrome Diseases 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
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- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
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- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
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Abstract
The invention relates to the technical field of graphene growth by a CVD (chemical vapor deposition) method, and mainly aims to provide a graphene growth support which comprises a carrier for loading a growth substrate, wherein the carrier is arranged into a hollow pipeline, the outer surface and the inner wall of the carrier are used for loading the growth substrate, two ends of the carrier are provided with fixing pieces which are used for fixing the growth substrate and are detachably connected with the carrier, and the fixing pieces are provided with first through holes for gas to pass through. Through the structure that changes the graphite rod, set up to hollow pipeline, the pipeline surface all can place the copper foil and fix through the mounting with inside, and the copper foil loads the increase of size and avoids caving in and the adhesion phenomenon takes place, and its load capacity is 6 times of same planar dimension graphite plate. The introduction of sieve pore structure, pressure ring gas homogenizing ring can accelerate growth rate, homogeneity and the domain size of graphite alkene, and 5min can realize that high quality graphite alkene continuous film's preparation obtains, compares ordinary quartz boat sample frame, and growth rate promotes 5 times.
Description
Technical Field
The invention relates to the technical field of graphene preparation by a CVD (chemical vapor deposition) method, in particular to a graphene growth support and a method for growing graphene.
Background
As a typical hot-wall CVD production system, the quartz tube furnace becomes a universal device for researching and preparing two-dimensional materials in various scientific research institutions and colleges due to the advantages of simple structure, simple and convenient operation, simple maintenance and the like. In general, quartz tube furnaces undertake both rapid proof development of small experiments and small-scale preparative growth of high-quality two-dimensional materials, in which the sample holder serves as a direct load with the indispensable components for the reactants and products, whose proper selection and design are crucial for the preparative process and the end result. Specifically, the properties of the raw materials, the properties of the target product, the types of materials, the reactivity, the gas dynamics, and the like are factors to be specifically considered in selection and design, and according to the above, some popular sample holders, such as quartz boats, corundum crucibles, and graphite rods having different sizes and shapes, have been popularized.
However, these sample holders are often single-function, crude and do not adequately meet the needs of a particular experiment. For example, in the growth process of the copper-based graphene film, if a quartz boat is used as a sample loading container, the following problems occur: (1) copper foil loading size limitation; (2) The copper foil is easy to collapse and fold and is adhered to the quartz boat; (3) does not withstand molten copper; and (4) the gas flow in the boat is blocked and the concentration distribution is not uniform. Corundum crucibles, in addition to being resistant to high temperatures, also suffer from the above-mentioned problems. The graphite plate can solve most of the problems, can ensure the size and the smoothness, can resist high temperature, does not influence airflow flow and generate concentration difference, and has the unique defects that the copper foil is easy to slide off the graphite plate, and the loading and later-stage unloading are not convenient. Therefore, a sample holder capable of solving the above problems is designed according to actual requirements.
Disclosure of Invention
Aiming at the problems, the invention provides a graphene growth support, which solves the problem of inconvenience in loading and unloading of copper foil by improving the traditional graphite plate structure, improves the copper foil loading capacity, and improves the quantity of graphene produced on graphite rods with the same volume.
The purpose of the invention is realized by the following technical scheme:
the utility model provides a graphite alkene growth support, including the carrier that is used for loading the growth substrate, the carrier sets up to hollow pipeline, the surface and the inner wall of carrier are used for loading the growth substrate, the both ends of carrier be equipped with be used for fixing the growth substrate and with carrier detachable connections's mounting, be equipped with the first through-hole that supplies gas to pass through on the mounting.
In a further technical scheme, the fixing piece comprises an end cover used for fixing the growth substrate positioned on the outer surface of the carrier and a pressing ring used for fixing the growth substrate positioned on the inner wall of the carrier; the end cover comprises an end plate and an outer ring, the surface of the end plate is provided with the first through hole, the parts of the outer ring arranged at the two ends of the carrier are in transition fit with the outer surface of the carrier, and a first gap for accommodating a growth substrate is reserved between the parts of the outer ring and the carrier; and part of the pressure ring is in transition fit with the inner wall of the carrier, and a second gap for accommodating a growth substrate is reserved between the part of the pressure ring and the carrier.
In a further technical scheme, the compression ring is fixedly connected with one side, facing the carrier pipeline, of the end cover, and extends into the carrier pipeline.
In another technical scheme, the pressing ring and the end cover are arranged into two parts which are independent from each other.
In a further technical scheme, the part of the carrier, which is in contact with the end panel, is arranged as an end surface, and the end surface is provided with an air uniform channel which is used for communicating the first through hole with the interior of the carrier pipeline.
In a further technical scheme, the gas distributing channel comprises a first channel and a second channel which are perpendicular to each other and are communicated, the first channel is communicated with the first through hole and is arranged along the axial direction of the carrier, and the second channel is communicated with the interior of the carrier pipeline and is arranged along the radial direction of the carrier.
In a further technical scheme, the pressure ring is further provided with a second through hole communicated with the air homogenizing channel.
In a further technical scheme, the fixing piece and the carrier are made of graphite.
In a further technical scheme, the aperture of the first through hole is set to be 1.5mm, the aperture of the second through hole is set to be 0.8mm, the pipe diameter of the uniform air channel is set to be 0.8mm, and the pipe diameter of the carrier is set to be 24mm in outer diameter and 20mm in inner diameter.
In a further technical scheme, a bolt hole is formed in the fixing piece, a positioning hole matched with the bolt hole is formed in the carrier, and the positioning hole is a blind hole; the bolt hole is internally provided with a bolt in transition fit with the bolt hole, and the bottom of the bolt extends into the positioning hole.
The other purpose of the invention is to provide a graphene growth method, cutting two 30um copper foils with the sizes of 13.5 × 13.5cm and 13.5 × 12.5cm respectively, cleaning the two copper foils sequentially with acetone and absolute ethyl alcohol, loading the two copper foils on the outer surface and the inner wall of the carrier respectively, pressing and fixing the copper foils on the inner wall by a pressing ring, and pressing and fixing the copper foils on the outer surface by an outer ring; when the growth substrate is loaded, the growth substrate is not overlapped with the gas homogenizing through hole, so that smooth gas circulation in the gas homogenizing channel is ensured.
And then, pushing the whole sample rack fixed with the copper foil into a quartz tube furnace, and setting a growth program to prepare the continuous graphene film, wherein the specific growth parameters and steps are as follows: (1) Pushing the sample rack loaded with the copper foil into the middle part of a tube furnace, closing a furnace cover and a quartz tube sealing flange, and opening a mechanical pump to vacuumize to about 0 Pa; (2) Opening control software, setting a program, and totally comprising four processes of gas washing, temperature rising, heat preservation and temperature reduction; (3) gas washing: the temperature is set to 25 ℃ at room temperature, and CH of 5sccm is introduced 4 20sccm H 2 And Ar of 200sccm is kept introduced for 2min; (4) temperature rise: the heating rate is set to 15 ℃/min, the temperature is increased to 1040 ℃, and 20sccmH is introduced during the heating period 2 And (5) annealing at a constant temperature of 200 sccmAr: annealing at 1040 deg.C for 30min while continuously introducing 20sccmH 2 And (6) growth with 200 sccmAr: introducing 30sccmCH 4 、20sccmH 2 And 200sccmAr, growing for 20min; (7) cooling: close CH 4 And H 2 And cooling to room temperature by 400 sccmAr to obtain the graphene film. The mechanical pump is kept normally open throughout the process to provide the low pressure required for graphene growth. System for makingIn the preparation process, raw material gas flows through the copper foil on the outer surface of the carrier and the copper foil on the inner wall of the carrier through the first through hole and/or sequentially flows along the first through hole, the gas homogenizing channel and the second through hole, and graphene grows on the copper foil substrate to prepare the continuous graphene film.
Compared with the prior art, the invention has the following beneficial effects:
(1) The copper foil has an increased loading capacity 6 times that of a graphite plate with the same plane size, and the collapse and adhesion phenomena are avoided.
(2) Integrative difunctional, the structure is excellent and neat, and the sample frame outside can provide the function the same with ordinary graphite board sample frame, and inboard because the structure in confinement space to and the introduction of sieve mesh structure, the even gas ring of clamping ring, can accelerate growth rate, homogeneity and the domain size of graphite alkene, 5min can realize that the preparation of high quality graphite alkene continuous film obtains, compares ordinary quartz boat sample frame, and growth rate has promoted 5 times.
Drawings
Fig. 1 is a schematic view of the overall structure of a graphene film growth apparatus according to the present invention;
fig. 2 is a schematic structural diagram of a carrier part of a graphene film growth apparatus according to the present invention;
FIG. 3 is a schematic structural diagram of an end cap portion of a graphene film growth apparatus according to the present invention;
FIG. 4 is a schematic structural diagram of a pressure ring portion of the graphene film growth apparatus according to the present invention;
FIG. 5 is a schematic structural view of the fitting between the carrier and the pressure ring according to the present invention;
FIG. 6 is a schematic structural view of another embodiment of the fastening member of the present invention;
FIG. 7 is a schematic partial cross-sectional view of a fastener of the present invention engaging a carrier;
FIG. 8 is an SEM image of a copper foil after CVD growth of the inner wall of the carrier in example 1;
FIG. 9 is an SEM image of the copper foil after CVD growth of the inner wall of the carrier of example 2.
The device comprises a carrier-1, an outer surface-11, an inner wall-12, a fixing piece-2, an end cover-21, an end panel-211, an outer ring-212, a pressing ring-22, a first through hole-23, a second through hole-24, a bolt hole-25, a first gap-3, a second gap-4, an air homogenizing channel-5, a first channel-51 and a second channel-52.
Detailed Description
The following examples are presented to further illustrate the invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. The reagents, methods and apparatus employed in the present invention are conventional in the art, except as otherwise indicated.
The following are specific examples:
example 1
The utility model provides a graphite alkene growth support, as shown in fig. 1-5, includes carrier 1 that is used for loading the growth substrate, carrier 1 sets up to hollow pipeline, the pipe diameter of carrier 1 sets up to external diameter 24mm, internal diameter 20mm, and the length of carrier sets up to 15cm, the surface 11 and the inner wall 12 of carrier 1 are used for loading the growth substrate, the both ends of carrier 1 are equipped with and are used for fixing the growth substrate and with carrier 1 detachable connections's mounting 2, be equipped with on mounting 2 and supply the aperture that gas passes through to set up to 1.5 mm's first through-hole 23. The specific detachable connection mode is that a bolt hole 25 is arranged on the fixing piece 2, a positioning hole matched with the bolt hole 25 is arranged on the carrier 1, and the positioning hole is a blind hole; a bolt in transition fit with the bolt hole 25 is arranged in the bolt hole, and the bottom of the bolt extends into the positioning hole.
The fixing piece 2 and the carrier 1 are made of graphite. As shown in fig. 1 and 2, the fixing member 2 includes an end cap 21 for fixing a growth substrate on the outer surface 11 of the carrier 1 and a pressing ring 22 for fixing a growth substrate on the inner wall 12 of the carrier 1; in this embodiment, the end cap 21 and the pressure ring 22 are provided as two separate parts. The pressing ring 22 is fixedly connected with one side, facing the carrier 1 pipeline, of the end cover 21, and extends into the carrier 1 pipeline.
As shown in fig. 2 and 7, the end cap 21 includes an end plate 211 and an outer ring 212, the surface of the end plate 211 is provided with the first through hole 23, and portions of the outer ring 212 arranged at two ends of the carrier 1 are in transition fit with the outer surface 11 of the carrier 1, and a first gap 3 for accommodating a growth substrate is left between the portions and the carrier 1; and part of the pressing ring 22 is in transition fit with the inner wall 12 of the carrier 1, and a second gap 4 for accommodating a growth substrate is reserved between the part of the pressing ring and the carrier 1. Carrier 1 with the part of end panel 211 contact sets up to the terminal surface, the terminal surface is equipped with and is used for the intercommunication first through-hole 23 with the even gas passageway 5 of carrier 1 pipeline inside, even gas passageway 5 includes that mutually perpendicular and the pipe diameter of intercommunication set up to 0.8 mm's first passageway 51 and second passageway 52, first passageway 51 with first through-hole 23 intercommunication just follows the axial direction of carrier 1 sets up, second passageway 52 with communicate and follow in the carrier 1 pipeline carrier 1 radial direction sets up. The pressing ring 22 is further provided with a second through hole 24 which is communicated with the air homogenizing channel 5, wherein the aperture of the second through hole 24 is set to be 0.8mm, and specifically, the second through hole 24 is communicated with the second channel 52.
Examples 1 to 1
Two copper foils with the thickness of 30um and the sizes of 13.5 × 13.5cm and 13.5 × 12.5cm are cut, washed by acetone and absolute ethyl alcohol in sequence and then loaded on the outer side and the inner side of the central circular tube carrier 1 respectively, wherein the copper foil on the inner side is fixed by a pressing ring 22, and the copper foil on the outer side is fixed by end covers 21 on two sides. And then, pushing the whole sample rack fixed with the copper foil into a quartz tube furnace, and setting a growth program to prepare the continuous graphene film, wherein the specific growth parameters and steps are as follows: (1) Pushing the sample rack loaded with the copper foil into the middle part of a tube furnace, closing a furnace cover and a quartz tube sealing flange, and opening a mechanical pump to vacuumize to about 0 Pa; (2) Opening control software, setting a program, and totally comprising four processes of gas washing, temperature rising, heat preservation and temperature reduction; (3) gas washing: the temperature is set to 25 ℃ at room temperature, and CH of 5sccm is introduced 4 20sccm of H 2 Keeping Ar of 200sccm introduced for 2min; (4) temperature rise: the heating rate is set to 15 ℃/min, the temperature is increased to 1040 ℃, and 20sccmH is introduced during the heating period 2 And (5) annealing at the temperature of 200 sccmAr: annealing at 1040 deg.C for 30min while continuously introducing 20sccmH 2 And (6) growth: introducing 30sccmCH 4 、20sccmH 2 And 200sccmAr, growing for 20min; (7) cooling: close CH 4 And H 2 And cooling to room temperature by 400 sccmAr to obtain the graphene film.
After the growth process is finished and the sample is cooled to room temperature, introducing Ar gas to break the vacuum of the tube furnace, opening the sealing flange when the normal pressure is recovered, pulling out the whole sample frame with the sample by using the sample push hook, taking down the positioning pin and the end covers at two sides of the sample frame, and pulling one side of the copper foil outwards to take out the film at the outer side of the sample frame; similarly, the film on the inner side of the sample rack can be taken down by taking off the uniform air pressure rings at the two ends of the inner side and then drawing out the copper foil. In the production process, the flowing direction of gas mainly has three directions, gas firstly flows through the outer surface of the carrier 1, the gas is catalytically grown into a graphene film when passing through the copper foil of the outer surface 11, meanwhile, the gas enters the carrier 1 pipeline through the first through holes 23 on the end plate 211, the gas flows through the copper foil surface on the inner wall 12 and is catalytically grown into the graphene film, in addition, part of gas also passes through the first through holes 23, meanwhile, the gas homogenizing channel 5 on the end surface and enters the pipeline from the second through holes 24 on the inner wall 12 of the carrier 1.
Example 2
Unlike embodiment 1, the end surface of the carrier 1 of this embodiment is not provided with the gas uniforming passage 5. Therefore, during the process of growing graphene, gas can only enter the carrier 1 pipeline through the first through holes 23 on the end plate 211.
Example 2-1
The procedure for preparing and loading the sample was the same as in example 1. The sample holder fixed with the copper foil is pushed into a quartz tube furnace, a growth program is set to prepare a continuous graphene film, specific production parameters and steps are consistent with those of example 1, however, in the production process, the flow direction of gas mainly has two directions, as shown in a diagram X, the gas firstly flows through the outer surface of the carrier 1, and is catalyzed to grow into the graphene film when passing through the copper foil on the outer surface 11, and simultaneously enters the pipeline of the carrier 1 through the first through holes 23 on the end panel 211 and is catalyzed to grow into the graphene film when passing through the surface of the copper foil on the inner wall 12. After the growth procedure is finished and the sample is cooled to room temperature, introducing Ar gas to break the vacuum of the tube furnace, opening the sealing flange when the normal pressure is recovered, pulling out the whole sample rack with the sample by using the sample push hook, taking down the positioning pin and the end covers at two sides of the sample rack, and pulling one side of the copper foil to outwards pull out, namely taking down the film at the outer side of the sample rack; similarly, the film on the inner side of the sample holder can be taken down by taking off the uniform air pressure rings at the two ends of the inner side and then drawing out the copper foil.
Example 3
Unlike embodiment 1, in this embodiment, as shown in fig. 6, the pressing ring 22 and the end cap 21 are fixedly connected to each other as an integral component.
Example 3-1
The procedure for preparing and loading the sample was the same as in example 1.
Two copper foils with the thickness of 30um and the sizes of 13.5 × 13.5cm and 13.5 × 12.5cm are cut, washed by acetone and absolute ethyl alcohol in sequence and then loaded on the outer side and the inner side of the central circular tube carrier 1 respectively, wherein the copper foil on the inner side is fixed by a pressing ring 22, and the copper foil on the outer side is fixed by end covers 21 on two sides. And then pushing the sample frame fixed with the copper foil into a quartz tube furnace, setting a growth program to prepare a continuous graphene film, wherein the specific growth parameters and steps are as follows: (1) Pushing the sample rack loaded with the copper foil into the middle part of the tube furnace, closing the furnace cover and the quartz tube sealing flange, and opening a mechanical pump to vacuumize to about 0 Pa; (2) Opening control software, setting a program, and totally comprising four processes of gas washing, temperature rising, heat preservation and temperature lowering; (3) gas washing: the temperature is set to 25 ℃ at room temperature, and CH of 5sccm is introduced 4 20sccm H 2 And Ar of 200sccm is kept introduced for 2min; (4) temperature rise: the heating rate is set to 15 ℃/min, the temperature is increased to 1040 ℃, and 20sccmH is introduced during the heating period 2 And (5) annealing at the temperature of 200 sccmAr: annealing at 1040 deg.C for 30min while continuously introducing 20sccmH 2 And (6) growth with 200 sccmAr: introducing 30sccmCH 4 、20sccmH 2 And 200sccmAr, growth for 20min; (7) cooling: close CH 4 And H 2 And cooling to room temperature by 400 sccmAr to obtain the graphene film. After the growth procedure is finished and the sample is cooled to room temperature, introducing Ar gas to break the vacuum of the tube furnace, opening the sealing flange when the normal pressure is recovered, pulling out the whole sample rack with the sample by using the sample push hook, taking down the positioning pin and the end covers at two sides of the sample rack, and pulling one side of the copper foil to outwards pull out, namely taking down the film at the outer side of the sample rack; similarly, the film on the inner side of the sample rack can be taken down by taking off the uniform air pressure rings at the two ends of the inner side and then drawing out the copper foil.
In the production process, the flowing direction of gas mainly has three directions, gas firstly flows through the outer surface of the carrier 1, the gas is catalytically grown into a graphene film when passing through the copper foil of the outer surface 11, meanwhile, the gas enters the carrier 1 pipeline through the first through holes 23 on the end plate 211, the gas flows through the copper foil surface on the inner wall 12 and is catalytically grown into the graphene film, in addition, part of gas also passes through the first through holes 23, meanwhile, the gas homogenizing channel 5 on the end surface and enters the pipeline from the second through holes 24 on the inner wall 12 of the carrier 1.
Comparative example
The common graphite plate with the same plane size is used as a carrier 1, copper foil with the same size is attached to the surface of a graphite rod, and the graphite rod is pushed into a quartz tube furnace to grow graphene. The growth procedure was set the same as in example 1. And after the growth is finished, taking down the copper foil loaded on the outer surface of the graphite rod.
The copper foils obtained according to examples 1 to 3 and comparative example methods were removed and tested for the successful growth of a continuous graphene film on the copper foil. The principle of the method is that if the graphene film is grown on the surface of the copper foil, the protective oxygen of the graphene film cannot penetrate through the film to react with the copper foil, so that the color cannot be changed before and after heating and annealing, and the original rose gold is kept; if the color is largely changed after annealing, the graphene is not grown if the color is changed to black (copper oxide), red (cuprous oxide), bluish (basic copper carbonate), or the like, and the range of the color change is larger.
The copper-based graphene thin films grown according to the methods of examples 1 to 3 and comparative example were placed in a heating table or a tube furnace and heated without any protective gas in the atmospheric environment, and the test results are shown in the following table, the copper foils after graphene growth on the outer surface and the inner side wall of the carriers of examples 1 to 3 did not change in color before and after heating and annealing, the original rose gold color was maintained, and the copper foils on the outer surface of the graphite rod still maintained the rose gold color after the same annealing treatment, which proves that the continuous graphene thin films were grown on the copper foils on the inner wall and the outer surface of examples 1 to 3.
| Experimental groups | Outer surface copper foil size | Inner wall copper foil size | Color of outer surface copper foil | Color of inner wall copper foil |
| Example 1 | 13.5*13.5cm | 13.5*12.5cm | Rose gold | Rose gold |
| Example 2 | 13.5*13.5cm | 13.5*12.5cm | Rose gold | Rose gold, partial red or black |
| Example 3 | 13.5*13.5cm | 13.5*12.5cm | Rose gold | Rose gold |
| Comparative example | 13.5cm*4cm | Is composed of | Rose gold | Is composed of |
And in addition, the copper-based graphene film is observed through a scanning electron microscope so as to judge whether the graphene is generated or not, the appearance after growth, the substrate coverage degree, the single-layer rate and the like. Fig. 8 is a scanning electron microscope picture of the copper-based graphene film on the inner wall in example 1, from which it can be visually seen that the graphene film successfully grows on the surface of the copper foil, and a few wrinkle appearances of the graphene film can be seen, as indicated by white arrows, macro origin of the wrinkle appearances comes from a difference in thermal expansion coefficients of the graphene and the copper foil, more wrinkles are generated in a cooling process after the graphene grows, particularly in a rapid cooling process, and micro origin is an intrinsic appearance of the graphene. The wrinkles observed here are mainly the result of the difference in thermal expansion coefficient, and are a basis for observing and determining whether the graphene film is successfully grown.
The design of the L-shaped gas homogenizing channel can effectively reduce the influence of gas flow blockage caused by the introduction of the internal pressure ring, and the occurrence of gas flow blockage can easily cause copper vapor and the aggregation and stay of the growth atmosphere on the inner growth surface, thereby influencing the growth dynamics behavior of graphene, comparing the characterization results of a graphene film scanning electron microscope with fig. 8 and fig. 9 (fig. 9 is a copper foil SEM image after the growth of the inner wall of the carrier without the gas homogenizing channel in embodiment 2), it can be seen that after the L-shaped circular pore channel and the porous gas homogenizing internal pressure ring are introduced, the graphene film in fig. 8 is uniformly covered on the surface of the substrate, and impurities such as amorphous carbon, black spots (multilayer graphene) and white spot particles (copper particles) are not seen on the surface; instead of introducing the L-shaped circular pore channel and the porous uniform gas internal pressure ring, only the non-porous internal pressure ring is used, as shown in fig. 9, a large number of white copper particles exist on the surface of the graphene film, as indicated by a rectangular frame, and in addition, due to a gas phase catalysis phenomenon generated by diffuse aggregation of copper vapor and an adhesion phenomenon of copper particles on the graphene film, a large range of multi-layer graphene is formed, as indicated by a color weight region indicated by an arrow in fig. 9.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A graphene growth support comprising a support for supporting a growth substrate, characterized in that: the carrier sets up to hollow pipeline, the surface and the inner wall of carrier are used for loading the growth substrate, the both ends of carrier are equipped with and are used for fixing growth substrate and with carrier detachable connections's mounting, be equipped with the first through-hole that supplies gas to pass through on the mounting.
2. The graphene growth scaffold according to claim 1, wherein: the fixing piece comprises an end cover used for fixing the growth substrate positioned on the outer surface of the carrier and a pressing ring used for fixing the growth substrate positioned on the inner wall of the carrier; the end cover comprises an end plate and an outer ring, the surface of the end plate is provided with the first through hole, the outer rings are arranged at two ends of the carrier, the parts of the outer rings are in transition fit with the outer surface of the carrier, and a first gap for accommodating a growth substrate is reserved between the parts of the outer rings and the carrier; and part of the pressure ring is in transition fit with the inner wall of the carrier, and a second gap for accommodating a growth substrate is reserved between the part of the pressure ring and the carrier.
3. The graphene growth scaffold according to claim 2, wherein: the pressing ring is fixedly connected with one side, facing the carrier pipeline, of the end cover, and extends towards the inside of the carrier pipeline.
4. The graphene growth scaffold according to claim 2, wherein: the pressing ring and the end cover are arranged into two mutually independent parts.
5. The graphene growth scaffold according to claim 2, wherein: the carrier with the part of end panel contact sets up to the terminal surface, the terminal surface is equipped with and is used for the intercommunication first through-hole with the even gas channel of carrier pipeline inside.
6. The graphene growth scaffold according to claim 5, wherein: the gas distributing channel comprises a first channel and a second channel which are perpendicular to each other and communicated with each other, the first channel is communicated with the first through hole and arranged along the axial direction of the carrier, and the second channel is communicated with the interior of the carrier pipeline and arranged along the radial direction of the carrier.
7. A graphene growth scaffold according to claim 5 or 6, wherein: the clamping ring is further provided with a second through hole communicated with the gas homogenizing channel.
8. The graphene growth scaffold of claim 1, wherein: the aperture of the first through hole is set to be 1.5mm, the aperture of the second through hole is set to be 0.8mm, the pipe diameter of the gas homogenizing channel is set to be 0.8mm, and the pipe diameter of the carrier is set to be 24mm in outer diameter and 20mm in inner diameter; the fixing piece and the carrier are made of graphite; a bolt hole is formed in the fixing piece, a positioning hole matched with the bolt hole is formed in the carrier, and the positioning hole is a blind hole; the bolt hole is internally provided with a bolt in transition fit with the bolt hole, and the bottom of the bolt extends into the positioning hole.
9. A method for graphene growth, comprising the steps of 1) cutting a copper foil as a substrate for graphene growth to prepare a graphene growth scaffold according to claims 1 to 8; 2) After being cleaned, the copper foils are respectively loaded on the outer surface and the inner wall of the carrier, the copper foils on the inner wall are pressed and fixed by the pressing ring, and the copper foils on the outer surface are pressed and fixed by the outer ring; 3) And then pushing the sample frame fixed with the copper foil into a quartz tube furnace, wherein in the preparation process, raw material gas flows through the copper foil on the outer surface of the carrier and/or flows through the copper foil on the inner wall of the carrier along the first through hole, the gas homogenizing channel and the second through hole in sequence, and graphene grows on the copper foil substrate to prepare the continuous graphene film.
10. The graphene growing method according to claim 9, wherein in step 2), the growth substrate does not coincide with the gas distribution holes.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN203360006U (en) * | 2013-07-10 | 2013-12-25 | 合肥微晶材料科技有限公司 | Quartz carrier for improving smoothness of graphene |
| CN111591980A (en) * | 2020-05-12 | 2020-08-28 | 洛阳彤润信息科技有限公司 | Preparation method of multilayer graphene |
| KR102408821B1 (en) * | 2016-07-21 | 2022-06-14 | 우니베르시대드 테크니카 페데리코 산타 마리아 | Method and system for producing graphene on copper substrates by modified chemical vapor deposition (AP-CVD) |
| CN115215331A (en) * | 2022-08-06 | 2022-10-21 | 深圳市冠凌电子智能科技有限公司 | Graphene film preparation device with large domain size |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN203360006U (en) * | 2013-07-10 | 2013-12-25 | 合肥微晶材料科技有限公司 | Quartz carrier for improving smoothness of graphene |
| KR102408821B1 (en) * | 2016-07-21 | 2022-06-14 | 우니베르시대드 테크니카 페데리코 산타 마리아 | Method and system for producing graphene on copper substrates by modified chemical vapor deposition (AP-CVD) |
| CN111591980A (en) * | 2020-05-12 | 2020-08-28 | 洛阳彤润信息科技有限公司 | Preparation method of multilayer graphene |
| CN115215331A (en) * | 2022-08-06 | 2022-10-21 | 深圳市冠凌电子智能科技有限公司 | Graphene film preparation device with large domain size |
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