CN108048816B - Apparatus and method for proximity catalytic chemical vapor deposition - Google Patents
Apparatus and method for proximity catalytic chemical vapor deposition Download PDFInfo
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- CN108048816B CN108048816B CN201711296987.6A CN201711296987A CN108048816B CN 108048816 B CN108048816 B CN 108048816B CN 201711296987 A CN201711296987 A CN 201711296987A CN 108048816 B CN108048816 B CN 108048816B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/305—Sulfides, selenides, or tellurides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
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Abstract
The present application provides an apparatus and method for close proximity catalytic chemical vapor deposition, the apparatus comprising: an upper heater and a lower heater disposed in a vertical direction; motors for controlling their lifting; a sample stage on the lower heater surface for receiving a substrate; a horizontal rail between the sample stage and the upper heater; the support plate is used for placing a catalyst, and a reaction area used for approaching to catalytic chemical vapor deposition is arranged between the support plate and the sample table; wherein the upper and lower heaters are used to provide the reaction zone with the temperature required for growth of the two-dimensional material. By using the device and the method of the application, the active substances of the two-dimensional material obtained by catalysis on the surface of the catalyst can be diffused to the substrate, so that a required film is deposited on the substrate; while thin films or heterojunctions of two-dimensional materials that strongly depend on the catalyst can be grown on substrates that do not have catalytic functions.
Description
Technical Field
The application relates to the field of nano materials, in particular to a device and a method for growing a two-dimensional material on a substrate without catalysis.
Background
Currently, two-dimensional materials are grown over large areas, typically using Chemical Vapor Deposition (CVD) techniques, and have been moved from the laboratory stage into the industrial production stage. The development and progress of the technology can be said to be the basis for the popularization and application of two-dimensional materials.
Currently, two-dimensional materials are mainly in two families: graphene-based materials and transition metal disulfide materials, and the most important one of the graphene-based materials is graphene. Graphene has excellent electrical, thermal, optical and mechanical properties, but its zero band gap severely hinders its application as an electronic device and also reduces its electrical properties due to scattering of substrate impurities. However, if graphene can be grown directly on a silicon wafer or other target substrate, the transfer process is omitted, and the quality of the deposited graphene is improved greatly.
At present, a good substrate for the growth of a two-dimensional material, such as a silicon wafer, or a substrate with hexagonal boron nitride deposited on the surface, and the like, does not have a catalytic function, and graphene is catalyst-dependent, so that the common CVD technology cannot meet the requirement of the substrate without the catalytic function, and therefore, a catalyst is required to be introduced near the substrate to catalyze a precursor of the two-dimensional material, active substances of the two-dimensional material are obtained to be diffused to the substrate material for nucleation and growth, and therefore, the adjacent catalytic chemical vapor deposition technology needs to be developed.
Disclosure of Invention
In view of the above, it is an object of the present application to provide an apparatus and method for proximity-catalyzed chemical vapor deposition.
In one aspect, the present application provides an apparatus for proximity-catalyzed chemical vapor deposition, the apparatus comprising:
an upper heater and a lower heater disposed opposite to each other in a vertical direction;
a motor electrically connected to the upper and lower heaters for controlling their elevation in the vertical direction;
a sample stage disposed on the lower heater surface for placement on a substrate on which a two-dimensional material is grown during the adjacent catalytic chemical vapor deposition;
a horizontal rail disposed between and spaced apart from the sample stage and the upper heater; and
the carrier plate is arranged on the horizontal guide rail and provided with one or more through holes for placing catalysts, and a reaction area for adjacent catalytic chemical vapor deposition is arranged between the carrier plate and the sample table;
wherein the upper heater and the lower heater are configured to provide the reaction zone with a temperature suitable for growth of the two-dimensional material.
Preferably, the device further comprises a grating scale arranged between the sample stage and the carrier plate for measuring the distance between the substrate and the catalyst.
Preferably, the perforations of the carrier plate are circular holes for placing circular cap-shaped catalysts.
Preferably, the apparatus further comprises a photodiode disposed in the vertical direction for defining a position of the upper heater during lifting.
Preferably, the apparatus further comprises a transmission for controlling the movement of the horizontal rail in a horizontal direction.
In another aspect, the present application provides a method for proximity catalytic chemical vapor deposition using the apparatus described above, the method comprising:
1) Placing a catalyst in the perforations of the support plate and placing the substrate on the sample stage;
2) The positions of the upper heater and the lower heater are adjusted through a motor, and a two-dimensional material precursor is placed in the reaction zone; and
3) The upper and lower heaters are turned on to bring the reaction zone to a temperature required for growth of the two-dimensional material for adjacent catalytic chemical vapor deposition, thereby obtaining a film of the two-dimensional material on the substrate.
Preferably, the method is performed by placing the device in a vacuum environment.
Preferably, the motor is a stepper motor, and the positions of the upper and lower heaters are adjusted by the stepper motor in cooperation with the grating scale and the photodiode, preferably after the adjustment, the distance between the catalyst and the substrate is 20-100 microns.
Preferably, the substrate is a catalytically inactive substrate such as a silicon wafer or hexagonal boron nitride and the two-dimensional material is a graphene-based material or a transition metal disulfide material.
Preferably, the material of the carrier plate comprises tungsten, and the catalyst is metallic copper, platinum or rhodium.
With the device and the method of the application, the active substances obtained by catalysis on the surface of the catalyst can be diffused to the substrate, so that the wanted film is deposited on the substrate. By using the device and the method, the film which is strongly dependent on the catalyst can be grown on the substrate without the catalytic function, and further the heterojunction of the two-dimensional material can be grown.
Drawings
FIG. 1 is a schematic diagram of an apparatus for proximity-catalyzed chemical vapor deposition in accordance with one embodiment of the present application.
Fig. 2 is a schematic illustration of a specific round cap catalyst used in accordance with one embodiment of the present application.
Detailed Description
In this context, adjacent catalytic chemical vapor deposition is defined as: the high temperature deposition zone or reaction zone has a substrate and a catalyst suspended above the substrate in a very close spacing (e.g., less than about 100 microns) from the substrate, and the suspended catalyst is used to catalytically decompose the two-dimensional material precursor to active groups which deposit a film by thermal movement onto the underlying substrate. The process technology can grow graphene and other two-dimensional materials depending on the catalyst on a substrate without catalysis.
In order to achieve close-up catalytic chemical vapor deposition, in particular on a substrate that is not catalytic, the application provides an apparatus comprising:
an upper heater and a lower heater disposed opposite to each other in a vertical direction;
a motor electrically connected to the upper and lower heaters for controlling their elevation in the vertical direction;
a sample stage disposed on the lower heater surface for placement on a substrate on which a two-dimensional material is grown during the adjacent catalytic chemical vapor deposition;
a horizontal rail disposed between and spaced apart from the sample stage and the upper heater; and
the carrier plate is arranged on the horizontal guide rail and provided with one or more through holes for placing catalysts, and a reaction area for adjacent catalytic chemical vapor deposition is arranged between the carrier plate and the sample table;
wherein the upper heater and the lower heater are configured to provide the reaction zone with a temperature suitable for growth of the two-dimensional material.
In the device of the application, the heaters arranged opposite to each other in the vertical direction (for example by means of a motor shaft or other fixing means) are upper and lower two heaters spaced apart from each other by a certain distance (for example but not limited to a heater with tantalum heating wire as heating wire, tungsten as heating wire also being possible), the lower heater being for example used for directly heating the substrate, the upper heater being used for directly heating the catalyst suspended on the carrier plate, thereby providing a temperature (for example in the range of 900-1200 ℃) suitable for the growth of two-dimensional materials such as graphene on the substrate in the reaction zone. The surface of the lower heater is provided with a sample stage for placing a substrate such as a silicon wafer, or a substrate coated with hexagonal boron nitride on the surface, or the like. Preferably, the sample stage is quartz with embedded wires, and the sample stage is made of quartz, because the sample stage can bear high temperature of up to 1000 ℃ and can be used as a blocking material to block dust pollution possibly brought by a heater.
In the apparatus of the present application, the motor used is preferably a stepper motor (e.g., available from Infrax Inc.) for controlling the movement of the upper and lower heaters in the vertical direction. In the device, the upper heater and the lower heater can move freely in the vertical direction, so that the support plate and the catalyst are convenient to detach, and the distance between the substrate and the catalyst can be accurately controlled. The carrier plate and the catalyst are mounted on a horizontal rail so as to be movable in the horizontal direction.
In the device of the application, the horizontal rail is placed in a horizontal direction (i.e. parallel to the upper surface of the sample stage), for example it may be mounted directly on a support or rack of the device of the application by means of a mount or be arranged between the sample stage and the upper heater by other means known in the art. Preferably, the horizontal guide rail is connected with a transmission device (such as a roller) so that the carrier plate arranged thereon can move in the horizontal direction.
In the device according to the application, the carrier plate for the catalyst is arranged on a horizontal rail, for example, can be fastened to the horizontal rail by means of fastening means such as bolts or can be placed directly on the horizontal rail. Preferably, the carrier plate has perforations, preferably circular apertures, for suspending, for example, a circular cap shaped catalyst. The carrier plate can be made of a material with high rigidity, high heat resistance and low thermal expansion rate, and is preferably made of tungsten metal. In the present application, the carrier plate may be a metal plate having a size of about 40mm by about 2 mm.
Preferably, the apparatus of the present application further includes a photodiode (e.g., LXD-BPW 28) for defining the elevation position of the upper heater, which is coupled to a stepper motor to stop the descent of the upper heater after it has been lowered to a specific position.
Preferably, the apparatus of the application further comprises a grating scale (e.g. a Raney 1 micron resolution grating scale) for measuring the separation distance between the sample stage and the lower surface of the horizontal rail or carrier plate, more particularly the grating scale can also be used for measuring the distance between the catalyst suspended by the carrier plate and the substrate on the sample stage. Preferably, the grating ruler measurement accuracy is 1 micrometer. Preferably, the grating ruler is matched with the stepping motor, so that the lifting displacement of the lower heater can be accurately controlled.
The application also provides a method for performing close-proximity catalytic chemical vapor deposition by using the device, which comprises the following steps:
1) Placing a catalyst in the perforations of the support plate and placing the substrate on the sample stage;
2) The positions of the upper heater and the lower heater are adjusted through a motor, and a two-dimensional material precursor is placed in a reaction zone; and
3) The upper and lower heaters are turned on to bring the reaction zone to a temperature required for growth of the two-dimensional material for adjacent catalytic chemical vapor deposition, thereby obtaining a film of the two-dimensional material on the substrate.
In the method of the present application, preferably, the positions of the upper heater and the lower heater are adjusted by the stepping motor in cooperation with the grating scale and the photodiode. For example, it is preferable that the distance between the catalyst and the substrate is 20 micrometers to 100 micrometers after the adjustment.
In the method of the present application, preferably, the substrate is a catalytically inactive substrate such as a silicon wafer or hexagonal boron nitride, and the two-dimensional material is a graphene-based material or a transition metal disulfide material.
In the process of the present application, the catalyst is preferably metallic copper, platinum or rhodium, more preferably copper. More preferably, these metal catalysts are round-cap shaped catalysts, which are made round-cap shaped in order to increase the rigidity thereof. Such a circular cap-shaped catalyst can be easily placed or suspended in the circular holes of the carrier plate. During the close proximity of the catalytic chemical vapor deposition, the catalyst softens at the high temperature of the reaction zone provided by the upper and lower heaters, while the rounded cap-shaped nature can increase the internal rigidity of these catalysts, reducing the deformation of their entire structure in the vertical direction. The distance between the catalyst and the substrate is substantially close, e.g., below about 100 microns, due to the close proximity of the catalyst, thereby preventing the catalyst from deforming too severely to contact the substrate under prolonged elevated temperatures. In close catalysis, it is important to prevent the catalyst from severely deforming to contact the substrate, and the use of such a catalyst of specific nature can be further effective in reducing deformation, producing a particular effect.
In the method, the upper heater and the lower heater are started to raise the temperature of the reaction zone, and after the temperature reaches the growth temperature, the precursor is introduced into the chamber and is catalytically decomposed into active substances after reaching the surface of the catalyst, part of the active substances are adsorbed on the surface of the catalyst, part of the active substances are desorbed, a free diffusion distance exists before the active substances and other substances are combined into gas molecules, and if the active substances reach the substrate within the free diffusion distance, the active substances are adsorbed and nucleated on the substrate, and the active substances can slowly grow into films on the substrate. The diffusion distance here, i.e. the distance between the carrier plate or horizontal rail and the sample, more precisely the specific distance between the substrate and the catalyst surface, is usually in the order of micrometers. In the method, according to actual requirements, the movement of the sample stage can be automatically controlled through the cooperation of the motor and the grating ruler, so that a proper distance is formed between the substrate and the catalyst.
In the method of the application, the device is preferably placed under high vacuum (e.g., up to 10 vacuum degrees) such as a stainless steel chamber -6 Pa), i.e. the process of the application is also carried out in a high vacuum environment.
The following description of the embodiments of the present application will be made more apparent and fully by reference to the accompanying drawings, in which it is shown, however, only some, but not all embodiments of the application. All other embodiments, which can be made by a person skilled in the art based on embodiments of the application without any inventive effort, fall within the scope of the application.
FIG. 1 is a schematic diagram of an apparatus for proximity-catalyzed chemical vapor deposition in accordance with one embodiment of the present application. As shown in fig. 1, the apparatus of the present application mainly comprises: the device of the application mainly comprises: an upper heater and a lower heater disposed in a vertical direction; motors for controlling their lifting; a sample stage disposed on the lower heater surface for receiving a substrate; a horizontal guide rail between the sample stage and the upper heater; the carrier plate is arranged on the horizontal guide rail and used for suspending the circular cap-shaped catalyst, and a reaction area used for approaching to the catalytic chemical vapor deposition is arranged between the carrier plate and the sample table; control means for controlling the elevation of the sample stage, optionally a grating scale for measuring the distance between the sample stage and the horizontal rail, etc.
More specifically, for example, the horizontal rail, which may be, but is not limited to, stainless steel, is mounted on the wall of the vacuum chamber, for example, by fasteners such as bolts. Preferably, there are two horizontal rails, each fixed to two side walls of the vacuum chamber, with a gap between them, for example about 3-5 cm, for the mounting of a carrier plate, for example about 4-6 cm in width, for mounting on both rails. Preferably, the carrier plate can be made of a metal tungsten material, and has the advantage that the tungsten material has a high melting point, so that the deformation amount of the tungsten material at the growth temperature is small. One or more perforations or round holes, for example of about 1-3 cm diameter, are drilled in the carrier plate, for example by means of a drill, for receiving, for example, a round-cap-shaped catalyst, wherein the round-cap-shaped catalyst is placed directly in the round holes of the carrier plate. A substrate for growing a two-dimensional material, such as graphene, is placed directly on the sample stage. The sample stage is connected to the lower heater by fasteners such as bolts, preferably quartz. Preferably, the lower heater is composed of two parts, namely an inner heating wire (which is preferably tantalum) and an outer cylindrical ceramic body as a hollow structure. More preferably, tantalum wire as the heating wire is wound around the inside of the ceramic body, both of which constitute the lower heater. Preferably, there is a recess (e.g., a recess with internal threads) below the lower heater for connecting it to the motor shaft. The motor shaft may be stainless steel. As with the lower heater, the upper heater of the apparatus of the present application may preferably be comprised of two parts, an inner heater wire (which is preferably tantalum) and an outer cylindrical ceramic body which is a hollow structure. More preferably, tantalum wire as the heating wire is wound around the inside of the ceramic body, both of which constitute the lower heater. Preferably, there is a recess (e.g., a recess with internal threads) below the upper heater for connecting it to the motor shaft. Optionally, the apparatus of the present application comprises a grating scale. The grating ruler can be composed of two parts, namely a scale grating and a grating reading head. The grating reading head is connected to the movable part of the device (in the illustrated device, the sample stage), and the scale grating is connected to the lower surface of the guide rail. Preferably, the device of the present application comprises a photodiode or other limiting means for defining the position of the upper heater, in particular the lowered lowest position. Preferably, the photodiode is mounted on the vacuum chamber wall by a threaded connection, and preferably sealed by a vacuum flange.
Fig. 2 is a schematic illustration of a specific round cap catalyst used in accordance with one embodiment of the present application. As shown in FIG. 2, the catalyst preferably used in the present application is a round-cap-shaped catalyst obtained by press forming, wherein the thickness of the cap rim portion of the round-cap-shaped catalyst is about 0.1mm (left view) and the diameter thereof is about 30mm (right view), and the height of the lower portion of the cap rim is about 2mm and the diameter thereof is about 20mm.
Example 1
In the embodiment, graphene serving as a two-dimensional material is grown on a silicon wafer serving as a substrate and without catalysis by using a method of adjacent catalysis chemical vapor deposition.
Since the growth of graphene is highly dependent on the catalyst, it is difficult to grow graphene on a silicon wafer without catalysis by conventional existing methods. However, with the method of the present application of close proximity catalytic chemical vapor deposition, due to the close proximity of the catalyst to the substrate, typically within about 100 microns, it is possible for the active species decomposed on the catalyst to nucleate and grow on the substrate by diffusion before recombining and becoming precursor gases, thereby obtaining complete graphene.
The upper heater is first moved up and the lower heater is moved down so that sufficient space is left for operation. The cleaned silicon wafer (micro-nano technology, inc. of St. Job) with 300 nm oxide layer was then placed on the sample stage of the lower heater. The carrier plate is placed on the horizontal guide rail, and the circular-cap-shaped catalyst copper is placed in the round holes of the carrier plate. The upper heater was lowered and stopped when reaching the limit of the photodiode, where the position was 1mm from the upper surface of the carrier plate. The lower heater is lifted, and the distance between the upper surface of the silicon wafer and the lower surface of the circular cap-shaped catalyst copper is set to be 50 microns through the reading of the grating ruler and the thickness of the silicon wafer.
Sealing the system, starting to vacuumize the whole system until the whole system is vacuumized to 1 multiplied by 10 -5 Pa or below. The power to the upper and lower heaters was turned on to heat the system to about 1000 c. After reaching about 1000 ℃, 5sccm of methane gas as a graphene precursor, and 1sccm of hydrogen gas were introduced. After about 50 minutes of reactive deposition, the wafer surface would be covered with graphene. At this time, the power supply to the upper and lower heaters is turned off, and methane and hydrogen are turned off, after which the lower heater is lowered, and the reaction is completed.
Experimental results prove that by utilizing the adjacent catalytic chemical vapor deposition method, graphene can be grown on a substrate without a catalytic effect, so that the graphene obtained by the traditional vapor deposition method omits a transfer step, and the transfer step is exactly the key of poor quality of the graphene at present. In other words, by using the method of the application, not only can graphene be directly deposited on the target substrate, but also a two-dimensional material film with better performance can be obtained.
Example 2
In the embodiment, graphene is grown on a copper sheet substrate on which a hexagonal boron nitride film is grown by utilizing a method of adjacent catalytic chemical vapor deposition.
The copper sheet on which the hexagonal boron nitride film is grown is covered with hexagonal boron nitride, so that the catalysis effect of the copper sheet is lost, and the graphene is almost impossible to deposit directly on the copper sheet by a conventional method. However, by using the method of the present application, graphene can be nucleated on hexagonal boron nitride, specifically as follows:
the upper heater is first moved up and the lower heater is moved down so that sufficient space is left for operation. The copper sheet with the hexagonal boron nitride film grown thereon was then placed on the sample stage of the lower heater. The carrier plate is placed on the horizontal guide rail, and the circular-cap-shaped catalyst copper is placed in the round holes of the carrier plate. The upper heater is lowered to stop at the limit position of the photodiode, and the distance between the position and the upper surface of the carrier plate is 1mm. The lower heater was raised and the distance between the copper sheet and the lower surface of the circular cap-shaped catalyst copper was set to 30 μm by the reading of the grating ruler and the thickness of the copper sheet.
Sealing the system, starting to vacuumize the whole system until the whole system is vacuumized to 1 multiplied by 10 -5 Pa or below. The power to the upper and lower heaters was turned on to heat the reaction zone to about 1000 ℃. After reaching 1000 ℃, the copper sheet was annealed by holding for 30 minutes. After that, 10sccm of methane gas was introduced. After the reaction was deposited for about 30 minutes, the power to the upper and lower heaters was turned off, the methane gas source was turned off, and the lower heater was lowered, and the reaction was completed.
Experimental results prove that graphene can be deposited on hexagonal boron nitride by utilizing the adjacent catalytic chemical vapor deposition method disclosed by the application, so that the heterojunction of hexagonal boron nitride-graphene is obtained.
The application has been described in detail above but is not limited to the specific embodiments described herein. Those skilled in the art will appreciate that other modifications and variations may be made without departing from the scope of the application. The scope of the application is defined by the appended claims.
Claims (13)
1. An apparatus for close proximity catalytic chemical vapor deposition, the apparatus comprising:
an upper heater and a lower heater disposed opposite to each other in a vertical direction;
a motor electrically connected to the upper and lower heaters for controlling the upper and lower heaters to be lifted in the vertical direction;
a sample stage disposed on the lower heater surface for placement on a substrate on which a two-dimensional material is grown during the adjacent catalytic chemical vapor deposition;
a horizontal rail disposed between and spaced apart from the sample stage and the upper heater; and
the carrier plate is arranged on the horizontal guide rail and provided with one or more through holes for placing catalysts, and a reaction area for adjacent catalytic chemical vapor deposition is arranged between the carrier plate and the sample table;
wherein the upper heater and the lower heater are configured to provide the reaction zone with a temperature suitable for growth of the two-dimensional material.
2. The apparatus of claim 1, further comprising a grating disposed between the sample stage and the carrier plate for measuring a distance between a substrate and a catalyst.
3. The apparatus of claim 1, wherein the perforations of the carrier plate are circular holes for receiving a circular cap shaped catalyst.
4. The apparatus of claim 1, further comprising a photodiode disposed in the vertical direction for defining a position of the upper heater during lifting.
5. The apparatus of claim 1, further comprising a transmission for controlling movement of the horizontal rail in a horizontal direction.
6. A method of performing proximity-catalyzed chemical vapor deposition using the apparatus of claim 1, the method comprising:
1) Placing a catalyst in the perforations of the support plate and placing the substrate on the sample stage;
2) The positions of the upper heater and the lower heater are adjusted through a motor, and a two-dimensional material precursor is placed in the reaction zone; and
3) The upper and lower heaters are turned on to bring the reaction zone to a temperature required for growth of the two-dimensional material for adjacent catalytic chemical vapor deposition, thereby obtaining a film of the two-dimensional material on the substrate.
7. The method of claim 6, wherein the placing of the device in a vacuum environment is performed.
8. The method of claim 6, wherein the motor is a stepper motor, the apparatus further comprises a grating scale disposed between the sample stage and the carrier plate for measuring a distance between a substrate and a catalyst, and a photodiode disposed in the vertical direction for defining a position of the upper heater during lifting, and positions of the upper and lower heaters are adjusted by the stepper motor in cooperation with the grating scale and the photodiode.
9. The method of claim 8, wherein the catalyst is spaced from the substrate by a distance of 20 microns to 100 microns.
10. The method of claim 6, wherein the substrate is a catalytically inactive substrate and the two-dimensional material is a graphene-based material or a transition metal disulfide material.
11. The method of claim 10, wherein the catalytically inactive substrate is a silicon wafer.
12. The method of claim 10, wherein the catalytically inactive substrate is hexagonal boron nitride.
13. The method of claim 6, wherein the material of the carrier plate is metallic tungsten and the catalyst is metallic copper, platinum or rhodium.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000073172A (en) * | 1998-08-27 | 2000-03-07 | Hideki Matsumura | Catalytic chemical vapor deposition apparatus |
| JP2003049271A (en) * | 2001-08-03 | 2003-02-21 | Japan Advanced Inst Of Science & Technology Hokuriku | Catalytic chemical vapor growth method and catalytic chemical vapor growth apparatus |
| JP2004107766A (en) * | 2002-09-20 | 2004-04-08 | Japan Advanced Inst Of Science & Technology Hokuriku | Catalytic chemical vapor deposition method and catalytic chemical vapor deposition device |
| JP2006278459A (en) * | 2005-03-28 | 2006-10-12 | Ulvac Japan Ltd | Thin film formation method and film deposition apparatus for field assisted catalytic chemical vapor growth |
| CN101323947A (en) * | 2008-08-05 | 2008-12-17 | 东南大学 | Localized heating chemical vapor deposition apparatus and method |
| KR20110115869A (en) * | 2010-04-16 | 2011-10-24 | 경희대학교 산학협력단 | The method and apparatus for fabricating thin film of superhydrophobic material using catalytic chemical vapor deposition |
| CN105568253A (en) * | 2016-01-06 | 2016-05-11 | 复旦大学 | Method for growing hexagonal boron nitride by plasma chemical vapor deposition equipment |
| CN207727143U (en) * | 2017-12-08 | 2018-08-14 | 中国科学技术大学 | Device for closing on catalytic chemical gaseous phase deposition |
Family Cites Families (2)
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| TW455912B (en) * | 1999-01-22 | 2001-09-21 | Sony Corp | Method and apparatus for film deposition |
| JP4948021B2 (en) * | 2006-04-13 | 2012-06-06 | 株式会社アルバック | Catalytic chemical vapor deposition system |
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000073172A (en) * | 1998-08-27 | 2000-03-07 | Hideki Matsumura | Catalytic chemical vapor deposition apparatus |
| JP2003049271A (en) * | 2001-08-03 | 2003-02-21 | Japan Advanced Inst Of Science & Technology Hokuriku | Catalytic chemical vapor growth method and catalytic chemical vapor growth apparatus |
| JP2004107766A (en) * | 2002-09-20 | 2004-04-08 | Japan Advanced Inst Of Science & Technology Hokuriku | Catalytic chemical vapor deposition method and catalytic chemical vapor deposition device |
| JP2006278459A (en) * | 2005-03-28 | 2006-10-12 | Ulvac Japan Ltd | Thin film formation method and film deposition apparatus for field assisted catalytic chemical vapor growth |
| CN101323947A (en) * | 2008-08-05 | 2008-12-17 | 东南大学 | Localized heating chemical vapor deposition apparatus and method |
| KR20110115869A (en) * | 2010-04-16 | 2011-10-24 | 경희대학교 산학협력단 | The method and apparatus for fabricating thin film of superhydrophobic material using catalytic chemical vapor deposition |
| CN105568253A (en) * | 2016-01-06 | 2016-05-11 | 复旦大学 | Method for growing hexagonal boron nitride by plasma chemical vapor deposition equipment |
| CN207727143U (en) * | 2017-12-08 | 2018-08-14 | 中国科学技术大学 | Device for closing on catalytic chemical gaseous phase deposition |
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