CN112938945A - CVD graphene preparation device and preparation method of graphene film - Google Patents
CVD graphene preparation device and preparation method of graphene film Download PDFInfo
- Publication number
- CN112938945A CN112938945A CN202110130327.0A CN202110130327A CN112938945A CN 112938945 A CN112938945 A CN 112938945A CN 202110130327 A CN202110130327 A CN 202110130327A CN 112938945 A CN112938945 A CN 112938945A
- Authority
- CN
- China
- Prior art keywords
- graphene
- growth substrate
- graphene growth
- fixing
- hole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/186—Preparation by chemical vapour deposition [CVD]
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- C30B30/00—Production of single crystals or homogeneous polycrystalline material with defined structure characterised by the action of electric or magnetic fields, wave energy or other specific physical conditions
Abstract
The invention relates to a device for preparing graphene by CVD and a preparation method of a graphene film. The invention provides a CVD graphene preparation device which comprises a support base, a graphene growth substrate and a top cover. The support base is cyclic annular enclosed construction, and the top is equipped with through-penetration hole, is equipped with the fixed column on a through-penetration hole inside wall. The fixed end of the graphene growth substrate is bent and provided with an opening matched with the fixed column. Be equipped with the fixed plate on the top cap inside wall, be equipped with the trompil with fixed column looks adaptation on the fixed plate. When the device is used, the graphene growth substrate is inserted into the through hole, the opening of the fixing column is sleeved with the opening of the fixing end through the bending structure of the fixing end, the fixing column is adjacent to the through hole, the fixing plate of the top cover is inserted into the through hole and sleeved with the opening of the fixing column, and the fixing end is clamped tightly. The graphene film prepared by the device has no folds, and the space utilization rate of the graphene growing device is improved. Also provides a method for preparing the graphene film by using the device.
Description
Technical Field
The invention relates to the technical field of graphene, in particular to a device for preparing graphene by CVD and a preparation method of a graphene film.
Background
Graphene is a polymer made of carbon atoms in sp2The hybrid tracks form a hexagonal honeycomb lattice two-dimensional carbon nanomaterial. The graphene has excellent optical, electrical and mechanical properties, has important application prospects in the aspects of materials science, micro-nano processing, energy, biomedicine, drug delivery and the like, and is considered to be a revolutionary material in the future.
At present, a large-area and high-quality graphene film is mainly prepared by a Chemical Vapor Deposition (CVD) method, but the quality of the graphene film prepared by the CVD method is greatly influenced by a substrate, however, most of common commercial copper foils are polycrystalline, impurities exist, the roughness is high, and the graphene and the substrate have thermal expansion mismatch in a cooling process. The existence of the problems causes a large amount of grain boundaries, defects and wrinkles in the graphene film, and the application of the graphene is greatly limited.
In addition, in the traditional process of preparing the graphene film, the graphene growth substrate is generally directly placed in the quartz tube. Due to the fact that the temperature of the growing graphene is extremely high, the graphene growing substrate is extremely easy to deform in the process of heating and cooling and is easy to adhere to the wall of the quartz tube, and therefore the graphene is folded or damaged, and the yield is low. Furthermore, since the heating space of the graphene growing device is limited, the size and the number of the graphene films grown at a single time are limited, and the space utilization rate of the device is not high, so that the waste of resources is caused. Even though the conventional apparatus for manufacturing a graphene thin film may vertically place a substrate, there is a problem in that the manufactured thin film is not flat.
The existing method for improving the production efficiency of the graphene film is a roll-to-roll growth technology or increasing the diameter and the length of a furnace tube. However, the quality of the graphene film prepared by the roll-to-roll growth technology is difficult to achieve when the substrate is kept in a static state; increasing the diameter and length of the furnace tube will bring about the increase of the manufacturing difficulty, volume and cost of the device and the uneven gas introduction in the preparation process. Therefore, the mass preparation of graphene films by using static substrates is still a problem which needs to be solved urgently in the industry.
Disclosure of Invention
Based on the method, the invention provides a CVD graphene preparation device and a preparation method of a graphene film. Through the device with graphite alkene growth substrate interval suspension, avoided the contact of substrate with the pipe wall, reduced graphite alkene film and produced crystal boundary, fold and damage, and improved the space utilization of growth graphite alkene device.
In one aspect of the invention, a CVD graphene preparation device is provided, which comprises a movably connected bracket base, a plurality of graphene growth substrates and a top cover;
the bracket base is of an annular closed structure, a plurality of through holes arranged in parallel are arranged at the top of the bracket base at intervals, and a fixing column is arranged on one inner side wall of each through hole;
the graphene growth substrate is provided with a bent fixed end which is provided with an opening matched with the fixed column;
a fixed plate is arranged on the inner side wall of the top cover, wherein an opening matched with the fixed column is formed in the fixed plate; the number of the fixing plates is less than or equal to that of the through holes;
when the device is used, the graphene growth substrate is inserted into the through hole, the opening of the graphene growth substrate is sleeved on the fixing column of the hole adjacent to the through hole through the bending structure of the fixing end, the fixing plate of the top cover is inserted into the through hole and sleeved on the fixing column through the opening of the fixing plate, and the fixing end is clamped tightly.
In some embodiments, the distance between the edges of adjacent through-holes is greater than or equal to 2 mm; the fixed end of the graphene growth substrate is bent twice in the same direction, and the distance between the two bent creases is equal to the distance between the edges of the adjacent through holes.
In some embodiments, a baffle is installed on the inner side wall of the bottom of the bracket base, and when the graphene growth substrate is inserted into the through-penetration hole, the baffle can be inserted between two adjacent graphene growth substrates.
In some embodiments, the material of the graphene growth substrate is one or more of copper, nickel, iron, tungsten, molybdenum, cobalt, platinum and ruthenium.
In some embodiments, the stent base is circular in cross-section.
In some embodiments, the top cover conforms to the top of the holder base.
In one aspect of the present invention, a method for preparing a graphene film is also provided, which includes the following steps:
assembling the device in a reaction chamber, heating, and annealing the graphene growth substrate; and
and introducing a gaseous carbon source, and carrying out chemical reaction on the graphene growth substrate to deposit the graphene film.
In some embodiments, a gas is also introduced during the annealing process of the graphene growth substrate, and the gas is selected from one or more of argon, hydrogen and oxygen.
In some embodiments, the carbon source is selected from at least one of methane, ethylene, acetylene, and n-hexane.
In some embodiments, prior to assembly, the graphene growth substrate is previously subjected to:
sequentially washing in an acid solution, water and a first organic solvent;
carrying out electrochemical polishing; and
and sequentially washing in water and a second organic solvent.
In some embodiments, the acidic solution is at least one of phosphoric acid, acetic acid, dilute hydrochloric acid, and dilute nitric acid.
In some embodiments, the first organic solvent and the second organic solvent are each independently selected from at least one of ethanol, acetone, and isopropanol.
Has the advantages that:
the device provided by the invention is used for parallelly suspending the graphene growth substrates side by side, so that the graphene growth substrates are not in contact with pipe walls and the like in the heating process, and the graphene growth substrates are not in contact with each other, and the adhesion between the substrates and other structures is avoided, thereby preventing the graphene film from wrinkling and breaking and improving the yield of the graphene film. And moreover, the interval area between the through holes in the top of the support base is attached to the bending structure of the graphene growth substrate, so that the substrate is prevented from generating stress and wrinkles, and the prepared graphene film is more smooth.
In addition, compare the mode that the graphite alkene growth base was hung in parallel side by side in traditional single monolithic mode of transversely putting, improved production efficiency greatly, also the maximize has improved the space utilization of growth graphite alkene film device.
Further, in the device for suspending the graphene growth substrates in parallel side by side, when the graphene growth substrates are annealed, the parts of the substrates for growing the graphene belong to non-contact annealing. Compared with the traditional annealing mode, the non-contact annealing mode can change the crystal orientation of the substrate material from polycrystal to monocrystal through one-time short-time annealing, so that the crystal orientation is changed more smoothly, the single crystal graphene can be easily prepared, and the crystal boundary and the defects of the graphene are greatly reduced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic structural diagram of a CVD graphene manufacturing apparatus used in an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a top cover of the CVD graphene manufacturing apparatus in fig. 1;
fig. 3 is a schematic structural diagram of a graphene growth substrate in the CVD graphene manufacturing apparatus in fig. 1;
fig. 4 is a schematic structural view of a CVD graphene manufacturing apparatus used in another embodiment of the present invention.
Detailed Description
Reference will now be made in detail to embodiments of the invention, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment, can be used on another embodiment to yield a still further embodiment.
It is therefore intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention are disclosed in or are apparent from the following detailed description. It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. In the description of the invention, "a plurality" means at least two, e.g., two, three, etc., unless explicitly specified otherwise.
With reference to fig. 1 to 3 as schematic diagrams, in one aspect of the present invention, an apparatus for manufacturing graphene by CVD is provided, which includes a support base 1, a plurality of graphene growth substrates 2, and a top cover 3, which are movably connected;
the bracket base 1 is of an annular closed structure, a plurality of through holes 11 which are arranged in parallel are arranged at the top of the bracket base at intervals, and a fixing column 111 is arranged on one inner side wall of each through hole 11;
the graphene growth substrate 2 is provided with a bent fixed end which is provided with an opening 21 matched with the fixed column 111;
a fixing plate 31 is arranged on the inner side wall of the top cover 3, wherein an opening 311 matched with the fixing column 111 is formed in the fixing plate 31; the number of the fixing plates 31 is less than or equal to the number of the through holes 11;
when the device is used, the graphene growth substrate 2 is inserted into the through hole 11, the opening 21 of the fixing end is sleeved on the fixing column 111 of the hole adjacent to the through hole 11 through the bending structure of the fixing end, and the fixing plate 31 of the top cover 3 is inserted into the through hole 11 and sleeved on the fixing column 111 through the opening 311 of the fixing end, so that the fixing end is clamped.
The device provided by the invention is used for parallelly suspending the graphene growth substrates 2 side by side, so that the graphene growth substrates 2 are ensured not to be contacted with the pipe wall and the like in the heating process, and the graphene growth substrates 2 are also prevented from being contacted with each other, thereby avoiding the adhesion between the graphene growth substrates 2 and other structures, preventing the graphene film from wrinkling and breaking and improving the yield of the graphene film.
And compare in the mode that traditional single monolithic is violently put with the mode that graphite alkene growth substrate 2 parallel suspension side by side, improved production efficiency greatly, also the maximize has improved the space utilization of growth graphite alkene film device.
Further, the installation mode of the graphene growth substrate 2 also ensures that the graphene growth substrate does not generate stress, and the substrate does not deform after being heated and softened, so that the prepared graphene film is more flat.
In some embodiments, the shape of the through-penetration 11 may be rectangular, oval, circular, or trapezoidal. Preferably, the shape of the through-penetration 11 is rectangular. Furthermore, the number of the through holes 11 is 1-20.
In some embodiments, the number of the fixing posts 111 on an inner sidewall of the through-penetration 11 is greater than or equal to 3, and may be determined according to the length of the inner sidewall of the through-penetration 11, and may be, for example, 4, 5, or 6.
In some embodiments, the distance between the edges of adjacent through-holes 11 is greater than or equal to 2mm, and may be, for example, 5mm, 10mm, 15mm, or 20 mm. In a preferred embodiment, the interval between the edges of adjacent through-holes 11 is 10 mm.
The distance between the edges of the adjacent through holes 11 is controlled within the range, so that the adhesion between the adjacent graphene growth substrates 2 can be avoided.
In some embodiments, the fixed end of the graphene growth substrate 2 is bent twice in the same direction, and the distance between the two bent creases is equal to the distance between the edges of the adjacent through holes 11. Further, the spacing area between the two bent creases of the fixed end is attached to the spacing area between the adjacent through holes 11.
In some embodiments, the material of the graphene growth substrate 2 is copper, nickel, iron, tungsten, molybdenum, cobalt, platinum or ruthenium, or an alloy of the metals. In a preferred embodiment, the graphene growth substrate 2 is made of copper foil. In a more preferred embodiment, the material of the graphene growth substrate 2 is a single crystal copper foil, such as Cu (111). This is because the single crystal copper foil (111) and graphene have a small lattice mismatch and thermal expansion mismatch, and are very suitable as a base material for graphene growth.
In the present invention, as a further illustration, the thickness of the graphene growth substrate 2 is not limited. In some embodiments, the graphene growth substrate 2 has a thickness of 8 μm to 100 μm, and may also have a thickness of 15 μm, 40 μm, 60 μm, 70 μm, or 80 μm. The thickness of the graphene growth substrate 2 is controlled within the range, so that the graphene growth substrate is not too thin and easy to deform, and the waste of production cost is avoided.
In a preferred embodiment, the graphene growth substrate 2 has a thickness of 25 μm.
As illustrated in fig. 4 as a schematic view, in some embodiments, a baffle 12 may be further installed on an inner side wall of the bottom of the support base 1, and when the graphene growth substrates 2 are inserted into the through-holes 11, the baffle 12 may be inserted between two adjacent graphene growth substrates 2.
The introduction of the baffle 12 can further prevent the adhesion between two adjacent graphene growth substrates 2, thereby ensuring that the prepared graphene film is free from wrinkles and damages.
In some embodiments, the shape of the baffle 12 is not limiting, and may be, for example, a circle, a regular or irregular polygon. Preferably, the regular polygon is selected from any one of a rectangle, a square, a trapezoid, a triangle, a pentagon, a hexagon, or a parallelogram. More preferably, the baffle 12 is rectangular, square, regular pentagonal or regular hexagonal.
In some embodiments, the baffle 12 has a height of 2mm to 50mm, a thickness of 1mm to 5mm, and a length of 20mm to 200 mm.
In some embodiments, the material of the support base 1, the fixing posts 111, the baffle 12, the top cover 3 and the fixing plate 31 is a high temperature resistant hard material or a hard material coated with a high temperature resistant layer, for example, the material of the support base 1, the fixing posts 111, the baffle 12, the top cover 3 and the fixing plate 31 may be at least one selected from quartz, carbon fiber, corundum, high temperature ceramic, silicon carbide and silicon nitride.
In some embodiments, the stent base 1 is annular in cross-section, and a "ring" in this application is a closed hollow structure formed by a strip itself after joining around the head and the tail. The "ring" may be of any shape, for example circular, triangular, trapezoidal, parallelogram, irregular polygonal, preferably circular and regular polygonal, such as square, regular pentagon, regular hexagon, etc., in cross-section. In a preferred embodiment, the cross-section of the holder base 1 is circular. This is because the deposition of graphene by the CVD method is usually performed in a pipeline, and the space utilization of the pipeline can be improved to the greatest extent by arranging the device in a circular ring structure.
In some embodiments, the top cover 3 is attached to the top of the rack base 1.
In one aspect of the present invention, a method for preparing a graphene film is also provided, which includes the following steps:
assembling the device in a reaction chamber, heating, and annealing the graphene growth substrate 2; and
and introducing a gaseous carbon source, and performing chemical reaction on the graphene growth substrate 2 to deposit the graphene film.
When the graphene growth substrate 2 is annealed by using a conventional annealing method, the conversion of the polycrystalline single crystal cannot be smoothly realized by a single annealing, and multiple times of annealing for a long time are generally required. In the annealing process, the part for growing the graphene on the graphene growth substrate 2 is not in contact with other structures, so that the method belongs to non-contact annealing. By using a non-contact annealing mode, the crystal orientation of the graphene growth substrate 2 can be changed into single crystal from polycrystal through one-time short-time annealing, so that the crystal orientation is changed more smoothly.
In some embodiments, a gas selected from one or more of argon, hydrogen and oxygen is also introduced into the graphene growth substrate 2 during the annealing process. The introduction of the gas may further substantially remove impurities that may be present on the substrate.
In one embodiment, during the annealing treatment of the graphene growth substrate 2, the introduced gas is a mixed gas of argon and hydrogen; in another embodiment, during the annealing treatment of the graphene growth substrate 2, firstly introducing argon, and then introducing a mixed gas of argon and hydrogen; in yet another embodiment, a mixture of argon and oxygen is introduced first, followed by a mixture of argon and hydrogen.
In some embodiments, the annealing temperature is 1000 ℃ to 1080 ℃ and the annealing time is 1h to 12 h. In a preferred embodiment, the annealing temperature is 1050 ℃ and the annealing time is 12 h.
In some embodiments, the carbon source is selected from at least one of methane, ethylene, acetylene, and n-hexane. In a preferred embodiment, the carbon source is methane.
In some embodiments, prior to assembly, the graphene growth substrate 2 is previously subjected to the following treatments:
sequentially washing in an acid solution, water and a first organic solvent;
carrying out electrochemical polishing; and
and sequentially washing in water and a second organic solvent.
The defects of impurities, gullies and the like on the surface of the graphene growth substrate 2 are removed through a treatment mode of combining cleaning of an acid solution, water and an organic solvent and electrochemical polishing. And the interference of impurities on the crystal orientation transformation in the post annealing treatment process is eliminated.
In some embodiments, the acidic solution is at least one of phosphoric acid, acetic acid, dilute hydrochloric acid, and dilute nitric acid. In a preferred embodiment, the acidic solution is acetic acid.
In some embodiments, the first organic solvent and the second organic solvent are both volatile solvents. In some embodiments, the first organic solvent and the second organic solvent are each independently selected from at least one of ethanol, acetone, and isopropanol. In a preferred embodiment, the first organic solvent is acetone and ethanol and the second organic solvent is ethanol.
In some embodiments, the electrochemical polishing is performed using a polishing solution.
In some embodiments, the polishing solution is a phosphoric acid system polishing solution, for example, a 10 (v/v)% -90 (v/v)% phosphoric acid aqueous solution or a polishing solution of phosphoric acid and other additives, wherein the other additives may be selected from one or more of viscosity modifiers, brighteners, and corrosion inhibitors.
In some embodiments, the electrochemical polishing has a current density of 20A/m2～200A/m2The polishing time is 2min to 30 min. The electrochemical polishing current density can also be 50A/m2、80A/m2、100A/m2、109A/m2、120A/m2、140A/m2、170A/m2、180A/m2. In a preferred embodiment, the electrochemical polishing has a current density of 40A/m2The polishing time was 30 min.
In some embodiments, the deposition time for performing the chemical reaction on the graphene growth substrate 2 to deposit the graphene thin film is 10min to 120 min. In a preferred embodiment, the deposition time for performing the chemical reaction on the graphene growth substrate 2 to deposit the graphene thin film is 20 min.
The following describes the CVD graphene production apparatus and the method for producing a graphene thin film according to the present invention in further detail with reference to specific examples.
Unless otherwise specified, reagents, materials and the like used in examples of the present invention are commercially available.
Example 1 preparation of graphene thin films
Fig. 1 is a schematic structural view of a CVD graphene production apparatus used in this embodiment.
(1) Selecting a copper foil with the thickness of 25 micrometers, cutting the copper foil into a plurality of rectangular foils with certain sizes to serve as a graphene growth substrate 2, blowing off pollutants such as dust possibly existing on the graphene growth substrate 2 by using nitrogen, and punching a plurality of equally spaced open holes 21 at one end of the graphene growth substrate 2 side by using a punching machine;
(2) placing the graphene growth substrate 2 in an acetic acid solution, carrying out ultrasonic cleaning for 5min, and then sequentially carrying out ultrasonic cleaning for 5min in deionized water, acetone and ethanol solutions;
(3) preparing a polishing solution from 100mL of deionized water, 50mL of phosphoric acid, 50mL of ethanol, 10mL of isopropanol and 1g of urea, then placing the graphene growth substrate 2 cleaned in the step (2) into the polishing solution, and placing the graphene growth substrate in the polishing solution at a current density of 40A/m2Performing electrochemical polishing for 30min under the condition of (1);
(4) ultrasonically cleaning the polished graphene growth substrate 2 in the step (3) in deionized water and ethanol solution for 5min, and then drying by using nitrogen;
(5) and (4) assembling the graphene growth substrate 2 treated in the step (4), the support base 1 and the top cover 3, and placing the assembly in a reaction chamber. Introducing argon gas with the flow rate of 500sccm and hydrogen gas with the flow rate of 50sccm under atmospheric pressure, then raising the temperature to 1050 ℃, and carrying out annealing treatment on the graphene growth substrate 2 for 12 hours; then, a mixed gas of methane and argon gas with a flow rate of 5sccm (the volume concentration of methane is 0.5%) is introduced for chemical deposition, and the deposition time is 20 min. And then rapidly cooling, finishing the growth of the graphene, and taking down the graphene growth substrate 2, thereby completing the preparation of the graphene film.
Example 2 preparation of graphene thin films
Fig. 4 is a schematic structural view of a CVD graphene manufacturing apparatus used in this embodiment.
This example 2 was prepared substantially identically to example 1, except that: and (5) thermal annealing parameters and graphene deposition parameters.
(1) Selecting a copper foil with the thickness of 25 micrometers, cutting the copper foil into a plurality of rectangular foils with certain sizes to serve as a graphene growth substrate 2, blowing off pollutants such as dust possibly existing on the graphene growth substrate 2 by using nitrogen, and punching a plurality of equally spaced open holes 21 at one end of the graphene growth substrate 2 side by using a punching machine;
(2) placing the graphene growth substrate 2 in an acetic acid solution, carrying out ultrasonic cleaning for 5min, and then sequentially carrying out ultrasonic cleaning for 5min in deionized water, acetone and ethanol solutions;
(3) preparing a polishing solution from 100mL of deionized water, 50mL of phosphoric acid, 50mL of ethanol, 10mL of isopropanol and 1g of urea, then placing the graphene growth substrate 2 cleaned in the step (2) into the polishing solution, and placing the graphene growth substrate in the polishing solution at a current density of 40A/m2Performing electrochemical polishing for 30min under the condition of (1);
(4) ultrasonically cleaning the polished graphene growth substrate 2 in the step (3) in deionized water and ethanol solution for 5min, and then drying by using nitrogen;
(5) and (4) assembling the graphene growth substrate 2 treated in the step (4), the support base 1 and the top cover 3, and placing the assembly in a reaction chamber. Introducing argon gas with the flow rate of 500sccm under atmospheric pressure, then raising the temperature to 1060 ℃, and then simultaneously introducing the argon gas with the flow rate of 500sccm and the hydrogen gas with the flow rate of 50sccm to perform annealing treatment on the graphene growth substrate 2 for 4 hours; then, a mixed gas of ethylene and argon (ethylene volume concentration: 5%) was introduced at a flow rate of 4sccm to perform chemical deposition for 20 min. And then rapidly cooling, finishing the growth of the graphene, and taking down the graphene growth substrate 2, thereby completing the preparation of the graphene film.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (12)
1. A CVD graphene preparation device is characterized by comprising a bracket base, a plurality of graphene growth substrates and a top cover which are movably connected;
the bracket base is of an annular closed structure, a plurality of through holes arranged in parallel are formed in the top of the bracket base at intervals, and a fixing column is arranged on one inner side wall of each through hole;
the graphene growth substrate is provided with a bent fixed end which is provided with an opening matched with the fixed column;
a fixed plate is arranged on the inner side wall of the top cover, and an opening matched with the fixed column is formed in the fixed plate; the number of the fixing plates is less than or equal to that of the through holes;
when the device is used, the graphene growth substrate is inserted into the through hole, the opening of the graphene growth substrate is sleeved on the fixing column of the hole adjacent to the through hole through the bending structure of the fixing end, the fixing plate of the top cover is inserted into the through hole and sleeved on the fixing column through the opening of the fixing plate, and the fixing end is clamped tightly.
2. The CVD graphene manufacturing apparatus according to claim 1, wherein the distance between the edges of the adjacent through holes is not less than 2 mm; the fixed end of the graphene growth substrate is bent twice in the same direction, and the distance between two bent creases is equal to the distance between the edges of adjacent through holes.
3. The graphene manufacturing apparatus according to claim 1 or 2, wherein a baffle is mounted on an inner side wall of a bottom of the support base, and when the graphene growth substrates are inserted into the through-holes, the baffle can be inserted between two adjacent graphene growth substrates.
4. The apparatus of claim 3, wherein the graphene growth substrate is made of one or more of copper, nickel, iron, tungsten, molybdenum, cobalt, platinum, and ruthenium.
5. The CVD graphene manufacturing apparatus of claim 1, wherein a cross section of the holder base is a circular ring.
6. The CVD graphene manufacturing apparatus of claim 1, wherein the top cover is attached to a top of the holder base.
7. The preparation method of the graphene film is characterized by comprising the following steps:
placing the device assembly of any one of claims 1 to 6 in a reaction chamber, heating, and annealing the graphene growth substrate; and
and introducing a gaseous carbon source, and carrying out chemical reaction on the graphene growth substrate to deposit the graphene film.
8. The method for preparing the graphene film according to claim 7, wherein a gas is further introduced during the annealing treatment of the graphene growth substrate, and the gas is selected from one or more of argon, hydrogen and oxygen.
9. The method for preparing a graphene film according to claim 7, wherein the carbon source is at least one selected from methane, ethylene, acetylene, and n-hexane.
10. The method for preparing the graphene film according to any one of claims 7 to 9, wherein the graphene growth substrate is subjected to the following treatment in advance before assembly:
sequentially washing in an acid solution, water and a first organic solvent;
carrying out electrochemical polishing; and
and sequentially washing in water and a second organic solvent.
11. The method according to claim 10, wherein the acidic solution is at least one of phosphoric acid, acetic acid, diluted hydrochloric acid, and diluted nitric acid.
12. The method for preparing a graphene thin film according to claim 10, wherein the first organic solvent and the second organic solvent are each independently selected from at least one of ethanol, acetone, and isopropanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110130327.0A CN112938945B (en) | 2021-01-29 | 2021-01-29 | CVD graphene preparation device and preparation method of graphene film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110130327.0A CN112938945B (en) | 2021-01-29 | 2021-01-29 | CVD graphene preparation device and preparation method of graphene film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112938945A true CN112938945A (en) | 2021-06-11 |
| CN112938945B CN112938945B (en) | 2023-03-07 |
Family
ID=76240171
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110130327.0A Active CN112938945B (en) | 2021-01-29 | 2021-01-29 | CVD graphene preparation device and preparation method of graphene film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112938945B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012105777A2 (en) * | 2011-01-31 | 2012-08-09 | Samsung Techwin Co., Ltd. | Method and apparatus for manufacturing graphene |
| CN104477893A (en) * | 2014-12-12 | 2015-04-01 | 中国科学院重庆绿色智能技术研究院 | Clamp for preparing graphene in double type manner and method for preparing graphene |
| CN104649259A (en) * | 2015-02-06 | 2015-05-27 | 北京大学 | Large monocrystal graphene and preparation method thereof |
| CN204778848U (en) * | 2015-06-09 | 2015-11-18 | 常州二维碳素科技股份有限公司 | Mould of growth graphite alkene |
| CN109518158A (en) * | 2019-01-04 | 2019-03-26 | 无锡第六元素电子薄膜科技有限公司 | A kind of graphene film magnanimity preparation method |
| CN110937594A (en) * | 2019-12-24 | 2020-03-31 | 云南大学 | Hanging and inserting sheet type quartz boat and method for growing graphene |
-
2021
- 2021-01-29 CN CN202110130327.0A patent/CN112938945B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012105777A2 (en) * | 2011-01-31 | 2012-08-09 | Samsung Techwin Co., Ltd. | Method and apparatus for manufacturing graphene |
| CN104477893A (en) * | 2014-12-12 | 2015-04-01 | 中国科学院重庆绿色智能技术研究院 | Clamp for preparing graphene in double type manner and method for preparing graphene |
| CN104649259A (en) * | 2015-02-06 | 2015-05-27 | 北京大学 | Large monocrystal graphene and preparation method thereof |
| CN204778848U (en) * | 2015-06-09 | 2015-11-18 | 常州二维碳素科技股份有限公司 | Mould of growth graphite alkene |
| CN109518158A (en) * | 2019-01-04 | 2019-03-26 | 无锡第六元素电子薄膜科技有限公司 | A kind of graphene film magnanimity preparation method |
| CN110937594A (en) * | 2019-12-24 | 2020-03-31 | 云南大学 | Hanging and inserting sheet type quartz boat and method for growing graphene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112938945B (en) | 2023-03-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104159736B (en) | The extensive monolayer of high-quality and multi-layer graphene by means of chemical gaseous phase deposition produce | |
| JP5428420B2 (en) | Polycrystalline silicon reactor | |
| CN102229426B (en) | Preparation method of equiangular hexagonal graphene arranged in single layer sequentially | |
| KR102538805B1 (en) | graphene synthesis | |
| US9048092B2 (en) | Process for preparing graphene based on metal film-assisted annealing and the reaction with Cl2 | |
| CN109518158B (en) | Macroscopic quantity preparation method of graphene film | |
| CN102105620A (en) | Susceptor with support bosses | |
| CN103643288A (en) | Preparation method of high-quality large-size monocrystal graphene | |
| TWI748147B (en) | Method for making graphene adhesive film and method for transferring graphene | |
| CN112522775B (en) | Preparation method of wafer-level single crystal copper foil and preparation method of regular graphene | |
| CN102092670B (en) | Carbon nano-tube composite structure and preparation method thereof | |
| CN106756870A (en) | A kind of method that plasma enhanced chemical vapor deposition grows Graphene | |
| JP2003286017A (en) | Method for transferring aligned carbon nanotube film | |
| JPS61201607A (en) | Product consisting of pyrolytically prepared boron nitride and its preparation | |
| CN107188161A (en) | Graphene and preparation method thereof | |
| CN112938945B (en) | CVD graphene preparation device and preparation method of graphene film | |
| CN112760612B (en) | Preparation method of self-supporting nano-needle porous diamond | |
| CN108364860B (en) | Graphene-catalyzed substrate corrosion solution and substrate corrosion method | |
| US20180354803A1 (en) | Method for making carbon nanotube array | |
| CN112779517A (en) | Preparation method of self-supporting nanocone diamond | |
| CN101775592A (en) | Direct-current plasma CVD apparatus and method for producing diamond using the same | |
| CN102910614A (en) | Method for heterogeneous epitaxial growth of graphene | |
| TW483053B (en) | Chemical vapor deposition apparatus and chemical vapor deposition process | |
| US10450191B2 (en) | Device for making carbon nanotube array | |
| CN107244666B (en) | Method for growing large-domain graphene by taking hexagonal boron nitride as point seed crystal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |