CN210710764U - Vertical furnace for preparing graphene - Google Patents

Abstract

One embodiment of the present utility model provides a vertical furnace for preparing graphene, including a furnace body, a crystal boat and a heat shield; the furnace body is a cylinder with one end open, and the cylinder includes a cylindrical body part and the top end and the bottom end respectively arranged on both ends of the cylinder body, the opening is arranged on the bottom end, the top end is provided with an air-distribution plate, and a plurality of air distribution plates are provided on the air-distribution plate. A vent hole is provided, an air duct is arranged in the furnace body, and the air outlet of the air duct is arranged at the top part and is located between the top of the cylinder and the air-distributing plate; the crystal boat is provided with On the heat shield, the wafer boat and the heat shield can enter and exit the furnace body through the opening. The vertical furnace for preparing graphene according to an embodiment of the present invention can prepare graphene films with high quality and good uniformity.

Description

A kind of vertical furnace for preparing graphene

technical field

The utility model relates to a vertical furnace, in particular to a vertical furnace for preparing graphene by chemical vapor deposition.

Background technique

Graphene has been widely studied due to its good physical and chemical properties, such as ultra-high carrier mobility, high light transmittance, and good mechanical properties, and has been widely used in transparent conductive films, photodetection, catalysis, biodetection, etc. and other fields have shown its potential practical value.

Among the many preparation methods of graphene, the chemical vapor deposition method on the copper surface has many advantages such as high quality of the grown graphene and suitability for macro-scale preparation. At present, the more common chemical vapor deposition method for preparing graphene is usually on a copper foil substrate. However, due to the defects of the copper foil itself, such as unevenness and polycrystalline, the graphene grown in this way has wrinkles and defects, which greatly affects its own properties and limits its application in the field of high-end electronic devices.

Utility model content

A main purpose of the present invention is to provide a vertical furnace for preparing graphene, including a furnace body, a crystal boat and a heat shield; the furnace body is a cylinder with one end open, and the cylinder includes a cylinder body the top end and the bottom end respectively provided on both ends of the cylindrical body part, the opening is provided on the bottom end, the top end is provided with an air-distribution plate, and the air-distribution plate is provided with a plurality of ventilation holes, an air guide pipe is arranged in the furnace body, and the air outlet of the air guide pipe is arranged at the top part and is located between the top of the cylinder and the air distribution plate; the crystal boat It is arranged on the heat shield, and the wafer boat and the heat shield can enter and exit the furnace body through the opening.

According to an embodiment of the present invention, 100 to 500 of the ventilation holes are opened on the air distribution plate.

According to an embodiment of the present invention, the diameter of the ventilation hole is 1-5 mm.

According to an embodiment of the present invention, the wafer boat includes a first horizontal frame, a second horizontal frame, a first support rod, a second support rod and a third support rod, the first support rod, the second support rod The rod and the third support rod are arranged between the first horizontal frame and the second horizontal frame.

According to an embodiment of the present invention, the first horizontal frame and the second horizontal frame are both circular rings, and the diameter of the central through hole of the first horizontal frame is equal to the diameter of the central through hole of the second horizontal frame , the axis of the central through hole of the first horizontal frame and the axis of the central through hole of the second horizontal frame are located on the same straight line.

According to an embodiment of the present invention, the diameter of the first horizontal frame is larger than that of the second horizontal frame, a plurality of through holes are formed on the first horizontal frame, and the wafer boat passes through the plurality of through holes installed on the heat shield.

According to an embodiment of the present invention, the first support rod, the second support rod and the third support rod are parallel to each other and perpendicular to the first horizontal frame and the second horizontal frame.

According to an embodiment of the present invention, one or more grooves are provided on the first support rod, the second support rod, and the third support rod.

According to an embodiment of the present invention, the heat shield includes a first support sheet, a second support sheet, and a plurality of heat insulation sheets disposed between the first support sheet and the second support sheet.

According to an embodiment of the present invention, the heat shield includes a plurality of uprights, and a plurality of through holes are provided on the first support sheet, the second support sheet, and the plurality of heat insulation sheets. A plurality of uprights pass through the first support sheet, the second support sheet and the plurality of heat insulation sheets through the plurality of through holes.

The vertical furnace for preparing graphene according to an embodiment of the present invention can prepare graphene films with high quality and good uniformity.

Description of drawings

Various objects, features and advantages of the present invention will become more apparent from consideration of the following detailed description of the preferred embodiments of the present invention in conjunction with the accompanying drawings. The accompanying drawings are merely exemplary illustrations of the present invention and are not necessarily drawn to scale. Throughout the drawings, the same reference numbers refer to the same or like parts. in:

Fig. 1 is the position schematic diagram of the heating element, furnace body, crystal boat, heat shield of the vertical furnace for preparing graphene according to one embodiment of the present utility model;

2A is a schematic structural diagram of a furnace body according to an embodiment of the present invention;

2B is a schematic structural diagram of an air-distribution plate according to an embodiment of the present invention;

3A is a schematic structural diagram of a wafer boat according to an embodiment of the present invention;

3B is a top view of the wafer boat shown in FIG. 3A;

4 is a schematic structural diagram of a heat shield according to an embodiment of the present invention;

5 is a simulation analysis diagram of airflow and heat of a furnace body according to an embodiment of the present invention;

6A is a schematic diagram of a graphene single crystal wafer prepared in Example 1 of the present invention;

6B is a Raman spectrum of the graphene single crystal wafer obtained in Example 1 of the present invention along the arrow direction of FIG. 6A;

7A is a schematic diagram of a graphene single crystal wafer prepared in Example 2 of the present invention;

FIG. 7B is a Raman spectrum diagram of the graphene single crystal wafer obtained in Example 2 of the present invention along the arrow direction of FIG. 7A .

Detailed ways

Typical embodiments embodying the features and advantages of the present invention will be described in detail in the following description. It should be understood that the present utility model can have various changes in different embodiments without departing from the scope of the present utility model, and the descriptions and illustrations therein are essentially for the purpose of illustration rather than use to limit the utility model.

One embodiment of the present utility model adopts the method of "magnetron sputtering + high temperature annealing" to prepare a single crystal copper (111) or single crystal copper-nickel alloy substrate on a single crystal sapphire substrate, and adopts the method of "consistent orientation, seamless splicing" ” method to prepare graphene single crystal wafers.

One embodiment of the present utility model provides a vertical furnace, which can be used to prepare single-crystal graphene wafers by atmospheric pressure chemical vapor deposition, especially for epitaxial growth preparation on copper/sapphire wafers or copper-nickel/sapphire wafer substrates Single crystal graphene wafers.

The device of one embodiment of the present invention is suitable for the normal pressure static growth of graphene films, and can realize the batch preparation of graphene single crystal wafers, which provides a basis for the large-scale production of graphene films.

1 to 4 , a vertical furnace for preparing graphene according to an embodiment of the present invention includes a furnace body 10, a crystal boat 20, a heat shield 30 and a heating component 40; the crystal boat 20 is arranged on the heat shield 30 , the wafer boat 20 and the heat shield 30 can move in and out of the furnace body 10 .

In one embodiment, the furnace body 10 adopts a vertical structure, and gas is supplied at the top.

In one embodiment, the material of the furnace body 10 may be quartz, silicon carbide, etc., preferably quartz.

In one embodiment, the furnace body 10 is a cylinder with one end open. The cylinder is composed of a cylindrical body portion 11 , a top end portion 12 and a bottom end portion 13 respectively located at both ends of the cylindrical body portion 11 . The cylindrical body portion 11 and the top end portion 12 It communicates with the bottom end 13 .

In one embodiment, the opening of the cylinder is provided with an outer edge which is perpendicular to the side wall and extends out of the cylinder.

In one embodiment, the height of the cylindrical portion 11 accounts for 80-84% of the total height of the cylinder, the height of the top end portion 12 accounts for 8-10% of the total height of the cylinder, and the height of the bottom end portion 13 accounts for the total height of the cylinder. 8 to 10%.

In one embodiment, the opening of the cylinder is provided at the bottom end portion 13 , and the top end portion 12 of the cylinder is provided with an arc-shaped top portion (cylinder top). An air duct 14 is arranged in the cylinder, and the air outlet of the air duct 14 is arranged on the top end portion 12 to realize air supply at the top end.

In one embodiment, the top portion 12 is provided with a homogeneous air plate 121 , and a plurality of ventilation holes 121 a are opened on the air homogeneous plate 121 .

In one embodiment, the air duct 14 is substantially Z-shaped, and includes a first horizontal portion 141 , a vertical portion 142 , a second horizontal portion 143 and an air outlet portion 144 that are connected in sequence, and the first horizontal portion 141 is perpendicular to the vertical portion 142 . The air outlet part 144 is parallel to the second horizontal part 143; the air guide pipe 14 enters the cylinder from the bottom end 13, the first horizontal part 141 is located outside the cylinder, and the vertical part 142 is located in the cylinder and is adjacent to the side of the cylinder The vertical part 142 of the air guide pipe 14 penetrates the cylindrical part 11, the second horizontal part 143 is located below the air homogeneous plate 121, the air outlet 144 enters the top part 12 through the air homogeneous plate 121, and the air outlet of the air guide pipe 14 is located at the air outlet The second horizontal portion 143 is arranged so that the air outlet of the air duct 14 is adjacent to the center of the air distribution plate 121 or located just above the center of the air distribution plate 121 .

In one embodiment, a through hole is formed in the air distribution plate 121 for the air outlet 144 to pass through, and the through hole can be located at the center of the air distribution plate 121 .

In one embodiment, the disposition of the gas-sparing pan 121 , especially the arrangement of the air outlet at or near the center of the gas-sparing pan 121 , can evenly disperse the process gas entering the furnace body 10 from the top, so that it can be distributed along the inner edge of the furnace body 10 . The diameter direction of the cross section is evenly distributed.

In one embodiment, the air distribution plate 121 is a circular sheet, and its diameter is equal to or slightly smaller than the inner diameter of the cylinder, so that the air distribution plate 121 can be arranged in the cylinder.

In one embodiment, 100-500 ventilation holes 121a, such as 150, 200, 250, 300, 350, 400, etc., are opened on the air distribution plate 121 .

In one embodiment, the diameter of the ventilation hole 121a may be 1˜5 mm, for example, 2 mm, 3 mm, 4 mm, or the like.

In one embodiment, the height of the cylinder of the furnace body 10 may be 833-837 mm, such as 835 mm and 836 mm; the inner diameter of the cylinder may be 299-301 mm, such as 300 mm; the outer diameter of the cylinder including the outer edge may be 378-378 mm 382mm, for example, 380mm; the distance from the air distribution plate 121 to the top of the cylinder can be 80mm; the distance from the position where the gas guide 14 enters the furnace body 10 to the opening of the cylinder can be 80mm.

In one embodiment, the wafer boat 20 is used to carry the growth substrate, and the growth substrate can be horizontally disposed on the wafer boat 20 .

In one embodiment, the wafer boat 20 is a frame structure including a first horizontal frame 21 , a second horizontal frame 22 , a first support rod 23 , a second support rod 24 and a third support rod 25 , wherein the first The support rod 23 , the second support rod 24 and the third support rod 25 are arranged between the first horizontal frame 21 and the second horizontal frame 22 .

In one embodiment, the first horizontal frame 21 and the second horizontal frame 22 are respectively circular rings, the diameter of the first horizontal frame 21 is larger than that of the second horizontal frame 22 , and the diameter of the central through hole of the first horizontal frame 21 is the same as the diameter of the second horizontal frame 21 . The diameters of the central through holes of the frame 22 are equal.

In one embodiment, the axis of the central through hole of the first horizontal frame 21 and the axis of the central through hole of the second horizontal frame 22 are located on the same straight line.

In one embodiment, through holes 211 , through holes 212 , through holes 213 , and through holes 214 are formed on the first horizontal frame 21 , and the wafer boat 20 passes through the through holes 211 , 212 , through holes 213 , and through holes 214 . Installed on the heat shield 30 .

In one embodiment, the through hole 211 , the through hole 212 , the through hole 213 , and the through hole 214 are circular through holes with the same diameter, and their distance from the center of the first horizontal frame 21 is equal. The connection lines of the connection line, the through hole 212 and the through hole 214 all pass through the center of the circle 21 of the first horizontal frame, and the two connection lines are perpendicular to each other, so that the through hole 211, the through hole 212, the through hole 213, and the through hole 214 can be evenly distributed. arranged on the first horizontal frame 21 .

In one embodiment, one end of the first support rod 23 is connected to the first horizontal frame 21 and the other end is connected to the second horizontal frame 22 . Specifically, the two ends of the first support rod 23 and the first horizontal frame can be respectively connected 21. The second horizontal frame 22 is provided with a connecting hole, and the first support rod 23 is connected with the first horizontal frame 21 and the second horizontal frame 22 through rivets. The arrangement of the second support rod 24 and the third support rod 25 may be the same as that of the first support rod 23 .

In one embodiment, the first support rod 23 , the second support rod 24 and the third support rod 25 are arranged in parallel and perpendicular to the first horizontal frame 21 and the second horizontal frame 22 .

In one embodiment, the first support rod 23 , the second support rod 24 and the third support rod 25 are all parallel to the axis of the central through hole of the first horizontal frame 21 and the axis of the central through hole of the second horizontal frame 22 , and the third A support rod 23 , a second support rod 24 and a third support rod 25 are located on the concentric circles of the central through hole of the first horizontal frame 21 and the central through hole of the second horizontal frame 22 . The first support rod 23 and the second support rod 24 The degree of the arc between them is 90°, and the degree of the arc between the first support rod 23 and the third support rod 25 is 180°.

In one embodiment, the first support rod 23 , the second support rod 24 , and the third support rod 25 have the same structure, are all rod-shaped, and are provided with one or more structures for supporting the growth substrate, such as grooves 231 , so that a plurality of growth substrates can be placed on the wafer boat 20 at the same time.

In one embodiment, the plurality of grooves on the first support rod 23 , the second support rod 24 , and the third support rod 25 correspond to each other, so that the growth substrate can be horizontally disposed on the wafer boat 20 .

In one embodiment, on the three support rods, one or more grooves 231 are opened along the length direction thereof, for example, 2 to 50 grooves, specifically 5, 10, 15, 20, and 25 grooves. , 30, 35, 40, 45, etc.

In one embodiment, simulation software is used to simulate the airflow and heat distribution for different substrate sizes and chip spacings, and with the debugging of the growth process, it is concluded that when the spacing of the plurality of grooves 231 is greater than 2 mm, it is preferable to It is 8-10mm, which can realize the growth of high-quality graphene films.

In one embodiment, the wafer boat 20 can be modified according to the size and quantity of the growth substrates, for example, to meet the growth of 1-50 graphene single crystal wafers with a size of 2-6 inches.

In one embodiment, the structure of the wafer boat 20 can meet the growth requirement of 25 4-inch or 6-inch single crystal wafers/batch.

In one embodiment, the material of the boat 20 may be alumina, quartz, etc., preferably quartz.

In one embodiment, the heat shield 30 is used to insulate the inner cavity of the furnace body 10 from the outside.

In one embodiment, the heat shield 30 includes a first support sheet 31 , a second support sheet 32 , and a plurality of heat insulation sheets 33 disposed between the first support sheet 31 and the second support sheet 32 .

In one embodiment, the first support sheet 31 , the second support sheet 32 , and the plurality of heat insulating sheets 33 are fixed together by a plurality of uprights 34 .

In one embodiment, the first support sheet 31 , the second support sheet 32 and the heat insulating sheet 33 are all provided with a plurality of through holes, and the plurality of uprights 34 pass through the first support sheet 31 , the second support sheet 31 and the second support sheet 34 through the corresponding through holes. Support sheet 32 and heat insulation sheet 33 .

In one embodiment, the first supporting sheet 31 and the second supporting sheet 32 are annular, the heat insulating sheet 33 is a circular sheet with a gap, the first supporting sheet 31 , the second supporting sheet 32 , a plurality of spacers. The thermal fins 33 are connected by four uprights 34 , and the tops of the four uprights 34 protrude from the second support sheet 32 and are respectively connected through the through holes 211 , 212 , 213 and 214 on the first horizontal frame 21 . Yu Jingzhou 20.

In one embodiment, the bottom ends of the four uprights 34 protrude from the first support piece 31 and are connected with the lifting component (not shown in the figure), so that the wafer boat 20 and the heat shield 30 can pass through under the action of the lifting component. The bottom end 13 enters the furnace body 10, wherein the lifting component can be an existing lifting device.

During operation, the heat shield 30 is located at the furnace mouth (the opening of the bottom end 13 ) of the furnace body 10 , which can prevent the heat in the furnace body 10 from diffusing through the furnace mouth, and play a role of heat insulation.

In one embodiment, the number of heat insulating sheets 33 may be one or more, for example, 1 to 10, and specifically, may be 3, 5, 8, and the like.

In one embodiment, the material of the heat shield 30 may be quartz, alumina, stainless steel, or the like.

In the vertical furnace for preparing graphene according to an embodiment of the present invention, when in use, a plurality of pre-fabricated growth substrates (substrates) are placed on the support rods of the crystal boat 20, and the crystal boat is moved by lifting parts. 20. The heat shield 30 is sent into the furnace body 10, and the gas duct 14 is controlled to introduce the required gas into the furnace body 10, and the furnace body 10 is heated by the heating component 40. After rising to the required temperature, the gas is introduced into the furnace body 10 through the duct 14. The carbon source, after a period of time, forms a graphene single crystal film on the surface of the substrate.

In one embodiment, the growth substrate used is a copper/sapphire wafer or a copper-nickel/sapphire wafer.

The simulation analysis of airflow and heat is carried out on the furnace body 10 according to an embodiment of the present invention, and it is concluded that the direct gas flow of each layer of growth substrate is uniform. As shown in FIG. 5 , the heat distribution from the edge to the center of the furnace body is relatively uniform.

According to the device of one embodiment of the present invention, the obtained graphene single crystal has high quality and uniform quality.

Hereinafter, the vertical furnace for preparing graphene according to an embodiment of the present invention will be further described with reference to specific examples. Among them, the experimental methods involved are conventional methods unless otherwise specified; the reagents and materials used can be obtained from commercial sources unless otherwise specified.

Example 1

According to the method disclosed in the patent application CN 107354506A, a Cu(111) single crystal with a thickness of 500 nm is obtained on a 4-inch sapphire single crystal substrate, and the obtained copper (111) single crystal thin film/sapphire is placed on the wafer boat 20 as a growth substrate, The crystal boat 20 and the heat shield 30 are sent into the furnace body 10 through the lifting part, and the gas guide 14 is controlled to introduce 2000 sccm Ar and 40 sccm H ₂ into the furnace body 10; the heating part 40 is used for heating, and the furnace body is heated after 1 hour. The temperature in 10 was raised from room temperature to 1000°C; 40 sccm of diluted methane was introduced, and the volume percentage of methane in the diluted carbon source gas was 0.1%. After 120 minutes of growth, the entire wafer surface is covered with graphene, and the obtained product is shown in Figure 6A. The graphene film is of high quality and has good uniformity, and the Raman data is shown in Figure 6B.

Example 2

According to the method disclosed in the patent application CN 108447773A, a CuNi(111) single crystal with a thickness of 500 nm was obtained on a 4-inch sapphire single crystal substrate, and the obtained CuNi(111) single crystal thin film/sapphire was placed on the wafer boat 20 as a growth substrate, The boat 20 and the heat shield 30 are sent into the furnace body 10 through the lifting part, and the gas guide 14 is controlled to introduce 2000 sccmAr and 40 sccm H ₂ into the furnace body 10; the heating part 40 is used for heating, and the furnace body 10 The internal temperature was raised from room temperature to 1000°C; 40 sccm of diluted methane was introduced, and the volume percentage of methane in the diluted carbon source gas was 0.1%. After 10 minutes of growth, the entire wafer surface is covered with graphene, and the obtained product is shown in Figure 7A. The graphene film is of high quality and has good uniformity, and the Raman data is shown in Figure 7B.

Unless otherwise specified, the terms used in the present invention are the meanings commonly understood by those skilled in the art.

The embodiments described in the present utility model are only for exemplary purposes, and are not intended to limit the protection scope of the present utility model. Those skilled in the art can make various other substitutions, changes and improvements within the scope of the present utility model. Therefore, The present invention is not limited to the above-mentioned embodiments, but only limited by the claims.

Claims (10)

1. a vertical furnace for preparing Graphene, is characterized in that, comprises: A furnace body, the furnace body is a cylinder with an opening at one end, the cylinder includes a cylinder body part and a top end part and a bottom end part respectively arranged at both ends of the cylinder body part, and the opening is arranged at the bottom end part , the top part is provided with a gas-distribution plate, a plurality of ventilation holes are opened on the gas-distribution plate, a gas guide pipe is arranged in the furnace body, and the air outlet of the gas guide pipe is arranged on the top part and is located between the top of the cylinder and the air distribution plate; crystal boat; and A heat shield, the wafer boat is arranged on the heat shield, and the wafer boat and the heat shield can enter and exit the furnace body through the opening. 2 . The vertical furnace for preparing graphene according to claim 1 , wherein 100 to 500 ventilation holes are opened on the gas-distributing plate. 3 . 3 . The vertical furnace for preparing graphene according to claim 2 , wherein the diameter of the ventilation hole is 1-5 mm. 4 . 4. The vertical furnace for preparing graphene according to claim 1, wherein the crystal boat comprises a first horizontal frame, a second horizontal frame, a first support rod, a second support rod and a third A support rod, the first support rod, the second support rod and the third support rod are arranged between the first horizontal frame and the second horizontal frame. 5. The vertical furnace for preparing graphene according to claim 4, wherein the first horizontal frame and the second horizontal frame are rings, and the first horizontal frame has a central through hole. The diameter of the center through hole of the second horizontal frame is equal to the diameter of the central through hole of the second horizontal frame, and the axis of the central through hole of the first horizontal frame and the axis of the central through hole of the second horizontal frame are located on the same straight line. 6. The vertical furnace for preparing graphene according to claim 5, wherein the diameter of the first horizontal frame is larger than that of the second horizontal frame, and there are many openings on the first horizontal frame. through holes, and the wafer boat is disposed on the heat shield through the plurality of through holes. 7. The vertical furnace for preparing graphene according to claim 4, wherein the first support rod, the second support rod and the third support rod are parallel to each other and perpendicular to the The first horizontal frame and the second horizontal frame. 8. The vertical furnace for preparing graphene according to any one of claims 4 to 7, characterized in that, in the first support rod, the second support rod, the third support rod are provided with one or more grooves. 9 . The vertical furnace for preparing graphene according to claim 1 , wherein the heat shield comprises a first support sheet, a second support sheet, and a A plurality of thermal insulation sheets between the second support sheets. 10 . The vertical furnace for preparing graphene according to claim 9 , wherein the heat shield comprises a plurality of uprights, and the first support sheet, the second support sheet, the A plurality of through holes are provided on each of the plurality of heat insulation sheets, and the plurality of uprights pass through the first support sheet, the second support sheet and the plurality of heat insulation sheets through the plurality of through holes.

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