CN108342716B - System and method for preparing two-dimensional material by plasma enhanced chemical vapor deposition - Google Patents

System and method for preparing two-dimensional material by plasma enhanced chemical vapor deposition Download PDF

Info

Publication number
CN108342716B
CN108342716B CN201711461217.2A CN201711461217A CN108342716B CN 108342716 B CN108342716 B CN 108342716B CN 201711461217 A CN201711461217 A CN 201711461217A CN 108342716 B CN108342716 B CN 108342716B
Authority
CN
China
Prior art keywords
substrate
plasma
dimensional material
gas
chamber
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.)
Active
Application number
CN201711461217.2A
Other languages
Chinese (zh)
Other versions
CN108342716A (en
Inventor
朱宏伟
甄真
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tsinghua University
Original Assignee
Tsinghua University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tsinghua University filed Critical Tsinghua University
Priority to CN201711461217.2A priority Critical patent/CN108342716B/en
Publication of CN108342716A publication Critical patent/CN108342716A/en
Application granted granted Critical
Publication of CN108342716B publication Critical patent/CN108342716B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C23C16/50—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 using electric discharges
    • C23C16/513—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 using electric discharges using plasma jets
    • 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
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0227—Pretreatment of the material to be coated by cleaning or etching
    • 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
    • C23C16/02—Pretreatment of the material to be coated
    • C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • C23C16/0281—Deposition of sub-layers, e.g. to promote the adhesion of the main coating of metallic sub-layers
    • 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
    • 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
    • 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
    • C23C16/34—Nitrides
    • C23C16/342—Boron nitride
    • 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
    • C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber

Abstract

A system and a method for preparing a two-dimensional material by plasma enhanced chemical vapor deposition belong to the technical field of two-dimensional material preparation. The system comprises a vacuum system, a substrate heating system, a plasma enhancement system and an air inlet pipeline; the vacuum system comprises a coating chamber and a sample introduction chamber, wherein the coating chamber and the sample introduction chamber are respectively provided with an air inlet, an air outlet and a plurality of observation windows. The invention aims to utilize plasma to assist in promoting the precursor reaction cracking, clean the surface and the cavity of the substrate under ultrahigh vacuum, and perform the fixed-point precursor supply through a specially designed air inlet pipeline, thereby realizing the preparation of two-dimensional materials on the surfaces of various materials. The invention emphasizes the auxiliary effect of the ultra-high cleanness of the environment and the surface on the growth of the two-dimensional material, realizes the growth of the two-dimensional film material by the system and the method, and cancels the damage of the traditional transfer process to the material and the limitation of the high-temperature growth to the substrate.

Description

System and method for preparing two-dimensional material by plasma enhanced chemical vapor deposition
Technical Field
The invention relates to a system and a method for preparing a two-dimensional material by plasma enhanced chemical vapor deposition, belonging to the field of two-dimensional material preparation systems and methods.
Background
The research of two-dimensional materials has gained much attention since 2004 when a single atomic layer of graphene was separated by a small composition mechanical exfoliation method of Geim, university of manchester, england and the nobel prize was obtained thereby. The application of the two-dimensional materials is greatly limited by the preparation mode, and most of the two-dimensional materials prepared at present have low quality, extremely low yield and extremely high cost and cannot be compatible with the current chip preparation technology. Taking graphene as an example, under the current preparation technical conditions, the graphene is low in quality, and the characteristics such as electron migration deviate from the intrinsic characteristics, so that the graphene cannot be applied to the related applications of high-performance electronic and optoelectronic devices. The main reason is that no industrial synthesis method for large-area high-quality single crystal or polycrystalline graphene is found, so that the performance of the graphene material can not reach the theoretical level, and the cost of the graphene material can not be any advantage.
Among graphene preparation methods facing new applications and lower industrial costs, the chemical vapor deposition method (x.li, w.cai, J et al.science 2009,324,1312) published in Science in 2009 has obtained the affirmation of scientific research and industry with the highest cost performance and stability, and is the most effective method for preparing large-area high-quality graphene films at present. Based on the method, many researches are optimized aiming at different angles, but the quality of the graphene cannot be fundamentally improved, and the application bottleneck of the graphene is solved. This is largely due to the high energy consumption of the process which increases its cost greatly due to the high temperature requirements, while greatly limiting the use of functionalized semiconductor substrates, thus mandatorily introducing an etch transfer process. The graphene is degraded by defects, crystal boundaries, folds and the like generated in the cooling process due to the larger expansion coefficient difference between the graphene and the substrate in the process, and the graphene is further and more seriously degraded by the defects, damages, folds, pollution and other factors generated in the transfer operation process, so that the performance of the graphene is finally deviated from the intrinsic property. Meanwhile, other two-dimensional materials such as elementary substance two-dimensional nanocrystals of phospholene, stannylene and the like and many other two-dimensional materials are limited by the preparation method, and high-quality thin film materials cannot be directly prepared on the functionalized substrate.
Disclosure of Invention
Based on the difficulty of the preparation of the current two-dimensional material, the invention aims to provide a system and a method for preparing the two-dimensional material by Plasma Enhanced Chemical Vapor Deposition (PECVD); the method realizes the cleaning of the surface of the substrate and the decomposition of the precursor at lower temperature (30-600 ℃) under the ultrahigh vacuum by methods such as ultrahigh vacuum, plasma enhancement, substrate heating and the like, and finally grows high-quality elementary substance two-dimensional nanocrystals, layered transition metal chalcogenide compounds, layered metal halide compounds, layered metal oxides and transition metal carbon/nitrogen compounds on the surfaces of various metal materials, inorganic nonmetal materials and high polymer materials.
The technical scheme of the invention is as follows:
a system for preparing two-dimensional material by plasma enhanced chemical vapor deposition is characterized in that: the system comprises a vacuum system, a substrate heating system, a plasma enhancement system and an air inlet pipeline; the vacuum system comprises a vacuum pump, a coating chamber and a sample introduction chamber, and the two vacuum chambers are connected with a valve through a pipeline; an air inlet, an air outlet and a plurality of observation windows are respectively arranged on the film coating chamber and the sample injection chamber; a substrate pushing frame is arranged in the sample injection cavity and connected with the magnetic force transmission rod; a substrate heating system is arranged in the coating chamber, and comprises a sample table, an upper heater and a lower heater which are respectively arranged above and below the sample table; the plasma enhancement system comprises a plasma generator; the upper polar plate and the lower polar plate are respectively arranged on the upper surface and the lower surface of the sample table and are respectively connected with a plasma generator arranged outside the film coating chamber through leads.
In the above technical solution, the gas inlet pipeline comprises a precursor gas pipeline, an auxiliary gas pipeline, a protective gas pipeline and a mixing chamber; the precursor gas inlet pipeline is divided into two paths, wherein one path is independently controlled to be introduced above the sample table in the vacuum cavity, and the gas pipeline is provided with a telescopic adjusting mechanism; the other path is mixed with an auxiliary gas pipeline and a protective gas pipeline through a gas mixing chamber and then is introduced into the film coating chamber.
Preferably, the plasma enhancement system adopts a low-temperature plasma energy source and utilizes radio-frequency discharge or microwave discharge to carry out plasma enhancement.
Preferably, the upper heater and the lower heater adopt resistance wires or infrared heating devices.
The invention provides a method for preparing a two-dimensional material by plasma enhanced chemical vapor deposition, which is characterized by comprising the following steps of:
1) cleaning the substrate before placing the substrate into a sample injection chamber;
2) after the substrate is placed in the sample injection chamber, air suction is started again to ensure that the vacuum degree reaches at least 5.0 × 10-3Pa；
3) The substrate is sent to a coating chamber sample table by using a magnetic force transmission rod and a substrate push frame, and when the background pressure is at least 8×10-7When Pa is needed, starting a plasma enhancement system to carry out plasma cleaning on the substrate until the vacuum degree of the system is stable; shutting down the plasma enhancement system while heating the substrate to 30 ℃ to 600 ℃;
4) when cleaning is finished and the substrate is heated to a specified temperature, mixed gas of protective gas and auxiliary gas is controlled by a mass flow meter to be introduced into the coating chamber, and precursor gas is controlled by a mass flow meter to be introduced above the sample stage or introduced into the coating chamber through a gas mixing chamber;
5) starting the plasma enhancement system again to perform auxiliary enhancement on the two-dimensional material in the substrate growth process;
6) and closing the precursor gas and the auxiliary gas after the growth of the substrate of the two-dimensional material is finished, and cooling the two-dimensional material in the protective gas atmosphere.
The two-dimensional material comprises: elemental two-dimensional nanocrystals, layered transition metal chalcogenides, layered metal halide compounds, layered metal oxides, and transition metal carbides and nitrides; the substrate is made of metal materials, inorganic non-metal materials or high polymer materials.
The invention has the following advantages and prominent technical effects: the invention aims at the environment required by the growth of the two-dimensional material, and meets the requirement of preparing the high-quality two-dimensional material on the surfaces of various functional substrates by building plasma-assisted chemical vapor deposition equipment and matching with a preparation method. Unlike the deterioration of the quality of the two-dimensional material and the limitation of the substrate type caused by the preparation conditions in the conventional chemical vapor deposition method, the invention emphasizes that the ultra-clean substrate surface provides the substrate surface and energy required for the growth of the two-dimensional material at a lower temperature under the assistance of ultra-high vacuum and plasma enhancement. The ultra-cleaning of the substrate surface by the preparation method can improve the catalytic activity, reduce the energy required by the cracking of the precursor on the surface and improve the quality of the grown two-dimensional material. The invention greatly improves the quality of the prepared two-dimensional material, breaks the limitation of the traditional preparation of the two-dimensional material, can directly grow the two-dimensional material on an ultra-clean functional substrate, cancels the transfer process of the traditional process, meets the requirements of high-end application on the quality of the two-dimensional material and the like, and finally solves the fundamental problem of the application of the two-dimensional material in the aspects of electronic and optoelectronic devices.
Drawings
FIG. 1 is a schematic structural diagram of a system for preparing a two-dimensional material by plasma enhanced chemical vapor deposition according to the present invention.
FIG. 2 is a schematic top view of a sample chamber and a coating chamber according to the present invention.
FIG. 3 is a schematic structural diagram of a coating chamber according to the present invention.
FIG. 4 is a schematic diagram of a method for preparing a two-dimensional material according to the present invention.
In the figure: 1-a vacuum pump; 11-a coating chamber; 12-a sample introduction chamber; 13-a magnetic force transfer rod; 14-a substrate pusher; 15-observation window; 2-a sample stage; 21-an upper heater; 22-a lower heater; 3-a plasma generating device; 31-a lower pole plate; 32-an upper pole plate; 4-air mixing chamber; 41-precursor gas line; 41 a-a pipeline for introducing a precursor of the coating cavity; 41 b-a precursor gas pipeline which is introduced into the gas mixing chamber; 42-auxiliary gas line; 43-protective gas line; 44-gas line heating zones; 45-a telescopic adjusting mechanism; 5-a precursor; 6-a substrate; 7-two-dimensional material.
Detailed Description
The invention is further elucidated with reference to the figures and embodiments.
As shown in FIG. 1, the PECVD system provided by the invention comprises a vacuum system, a substrate heating system, a plasma enhancement system and an air inlet pipeline. The vacuum system comprises a vacuum pump 1, a coating chamber 11 and a sample introduction chamber 12, and the two vacuum chambers are connected through a pipeline and a valve. An air inlet, an air outlet and a plurality of observation windows are respectively arranged on the coating chamber 11 and the sample injection chamber 12. The sample chamber 12 is internally provided with a substrate pushing frame 14 and a magnetic force transmission rod 13, and the substrate pushing frame 14 is connected with the magnetic force transmission rod 13.
As shown in fig. 2, a substrate heating system is provided within the coating chamber 11 to maximize the catalytic activity of the substrate and provide some energy for two-dimensional material growth. The substrate heating system comprises a sample table 2, an upper heater 21 and a lower heater 22 which are respectively arranged above and below the sample table; the heater adopts resistance wire or infrared heating device, and the double-layer heater ensures the uniformity of heating the substrate on the sample stage and the temperature maintenance
As shown in FIG. 3, in order to achieve and maintain the ultra-high vacuum during the operation of the coating chamber 11, the system is designed with a sample introduction chamber 12 for substrate exchange exposed to the atmosphere, and then the substrate is transferred by the magnetic force transmission rod 13 and the substrate pusher 14.
The plasma enhancement system comprises a plasma generating device 3, an upper polar plate 32 and a lower polar plate 31; the upper polar plate 32 and the lower polar plate 31 are respectively arranged on the upper surface and the lower surface of the sample stage and are respectively connected with the plasma generating device 3 arranged outside the coating chamber 11 through leads. The plasma generating device adopts a low-temperature plasma energy source, can provide radio frequency discharge or microwave discharge, is enhanced by an upper polar plate and a lower polar plate through a lead wire, and ensures that the plasma concentration on the surface of the substrate on the sample table is maximized.
The gas inlet line comprises a precursor gas line 41, an auxiliary gas line 42 and a shielding gas line 43; the precursor inlet line 41 is divided into two paths. One of the paths 41a is introduced into the vacuum cavity through an independent valve control, and above the sample table 2, the gas pipeline 41a is provided with a telescopic adjusting mechanism and can move above the substrate. The design can realize the single crystal controllable growth of the two-dimensional material through the fixed-point precursor gas supply; and the other path 41b is connected with the gas mixing chamber 4 and is introduced into the coating chamber 12, so that the rapid growth of the polycrystalline two-dimensional material can be realized.
As shown in fig. 4, the present invention provides a method for preparing a two-dimensional material by plasma enhanced chemical vapor deposition:
1) cleaning the substrate before placing the substrate into a sample injection chamber; this step serves to remove contaminants from the surface of the substrate.
2) After the substrate is placed into the sample injection chamber, air extraction is started, and the vacuum degree reaches at least 5.0 × 10-3Pa; the step ensures that the sample introduction chamber reaches a certain vacuum degree and the connection between the sample introduction chamber and the coating chamber is openedThe cleanness and the vacuum degree of the coating chamber are ensured during the valve operation.
3) After the valve is opened, the substrate is sent to a sample stage of the coating chamber by using a magnetic transmission rod and a substrate push frame, and the background pressure is at least 8 × 10-7When Pa is needed, starting a plasma enhancement system to carry out plasma cleaning on the substrate until the vacuum degree of the system is stable; the step removes the residual oxide layer on the surface of the substrate and other pollutants which are difficult to remove, improves the surface appearance and greatly reduces the surface roughness. Then shutting down the plasma system and heating the substrate to 30-600 ℃; to increase the catalytic activity of the substrate and to provide the energy required for a certain two-dimensional material growth.
4) When cleaning is finished and the substrate is heated to a specified temperature, mixed gas of protective gas and auxiliary gas is controlled by a mass flow meter to be introduced into the coating chamber, and precursor gas is controlled by a mass flow meter to be introduced above the sample stage or introduced into the coating chamber through a gas mixing chamber; in the step, reaction precursors, auxiliary gas and protective gas are introduced to carry out growth reaction of the two-dimensional material.
5) Starting the plasma enhancement system again in the growth process of the substrate of the two-dimensional material to assist in enhancing the growth of the two-dimensional material; the plasma enhanced system is beneficial to cracking of precursor gas and nucleation growth of two-dimensional materials.
6) Closing the precursor gas and the auxiliary gas after the growth of the substrate of the two-dimensional material is finished, and cooling in a protective gas atmosphere;
based on the PECVD system, the invention emphasizes the cleanliness of the system under ultrahigh vacuum, and replaces the high temperature requirement of the traditional CVD with the assistance of plasma, thereby achieving extremely high cleanliness in the system, atomic-level cleaning of the surface of a substrate 6, cracking 5 of a precursor and high activity of the surface of the substrate, and growing a high-quality two-dimensional material 7. Based on this technology, several specific examples are given below to further understand the practice of the present invention.
Example 1:
the invention provides a specific preparation method of high-quality graphene, which specifically comprises the following steps:
1) before putting a copper foil, a nickel foil, a silicon wafer or glass and other substrates into a sample introduction chamber, carrying out ultrasonic cleaning on the substrates by using dilute hydrochloric acid, acetone, alcohol and deionized water;
2) after the substrate is placed in the sample injection chamber, the system is exposed to the atmosphere for a short time and is filled with dry nitrogen, and the vacuum degree reaches at least 5.0 × 10 within 20 minutes-3Pa；
3) The substrate is sent to a sample stage of the coating chamber by using a magnetic transmission rod and a substrate push frame, and when the background pressure is in ultrahigh vacuum (better than 8 × 10)-7Pa), starting a plasma enhancement system to carry out plasma cleaning on the substrate until the vacuum degree of the system is stable; shutting down the plasma system while heating the running substrate to 450 ℃;
4) when cleaning is finished and the substrate is heated to a specified temperature, controlling the mixed atmosphere of argon and hydrogen introduced through a mass flow meter, and introducing methane gas through a single gas path;
5) and starting the plasma enhanced auxiliary carbon source for cracking again and beginning to deposit graphene, and closing methane and rapidly cooling under a protective atmosphere after the deposition is finished.
Example 2:
the invention provides a specific preparation method of high-quality molybdenum disulfide, which comprises the following steps:
1) before a silicon chip, glass or gallium nitride and other substrates are placed in a sample injection chamber, carrying out ultrasonic cleaning on the substrates by using dilute hydrochloric acid, acetone, alcohol and deionized water;
2) plating Mo with the thickness of 1nm on a substrate by utilizing magnetron sputtering or evaporation;
3) after the substrate is placed in the sample injection chamber, the system is exposed to the atmosphere for a short time and is filled with dry nitrogen, and the vacuum degree reaches at least 5.0 × 10 within 20 minutes-3Pa。
4) The substrate is sent to a sample stage of the coating chamber by using a magnetic transmission rod and a substrate push frame, and when the background pressure is in ultrahigh vacuum (better than 8 × 10)-7Pa), starting a plasma enhancement system to carry out plasma cleaning on the substrate until the vacuum degree of the system is stable; the plasma system was turned off while the substrate was heated to 300 deg.C；
5) When cleaning is finished and the substrate is heated to a specified temperature, hydrogen sulfide is introduced into the coating cavity by utilizing the gas path independently introduced into the coating cavity under the control of the mass flow meter;
6) starting plasma enhanced auxiliary vulcanization again and starting to prepare molybdenum disulfide, closing hydrogen sulfide after deposition is finished, and reducing temperature in ultrahigh vacuum
Example 3:
the invention provides a specific high-quality hexagonal boron nitride preparation method, which specifically comprises the following steps:
1) before putting a Si (100) substrate into a sample injection chamber, carrying out ultrasonic cleaning on the substrate by using dilute hydrochloric acid, acetone, alcohol and deionized water;
2) after the substrate is placed in the sample injection chamber, the system is exposed to the atmosphere for a short time and is filled with dry nitrogen, and the vacuum degree reaches at least 5.0 × 10 within 20 minutes-3Pa；
3) The substrate is sent to a sample stage of the coating chamber by using a magnetic transmission rod and a substrate push frame, and when the background pressure is in ultrahigh vacuum (better than 8 × 10)-7Pa), starting a plasma enhancement system to carry out plasma cleaning on the substrate until the vacuum degree of the system is stable; shutting down the plasma system while heating the running substrate to 550 ℃;
4) when the cleaning is completed and the substrate is heated to the specified temperature, the introduction of N is controlled by the mass flow meter2/B(OCH3)3Or N2/B2H3Mixing precursor gas;
5) and starting the plasma enhanced auxiliary precursor for cracking again and beginning to deposit the hexagonal boron nitride, and closing the precursor gas and rapidly cooling after the deposition is finished.

Claims (5)

1. A system for preparing two-dimensional material by plasma enhanced chemical vapor deposition is characterized in that: the system comprises a vacuum system, a substrate heating system, a plasma enhancement system and an air inlet pipeline; the vacuum system comprises a vacuum pump (1), a coating chamber (11) and a sample introduction chamber (12), and the two vacuum chambers are connected with a valve through a pipeline; an air inlet, an air outlet and a plurality of observation windows are respectively arranged on the film coating chamber (11) and the sample injection chamber (12); a substrate pushing frame (14) is arranged in the sample feeding cavity (12), and the substrate pushing frame (14) is connected with the magnetic force transmission rod (13); a substrate heating system is arranged in the coating chamber (11), and comprises a sample table (2), and an upper heater (21) and a lower heater (22) which are respectively arranged above and below the sample table; the plasma-enhanced system comprises a plasma generator (3); the upper polar plate (32) and the lower polar plate (31) are respectively arranged on the upper surface and the lower surface of the sample table and are respectively connected with a plasma generator (3) arranged outside the coating cavity (11) through leads;
the gas inlet pipeline comprises a precursor gas pipeline (41), an auxiliary gas pipeline (42), a protective gas pipeline (43) and a gas mixing chamber (4); the precursor gas inlet pipeline (41) is divided into two paths, wherein one path of gas pipeline (41a) is independently controlled to be introduced above the sample stage (2) in the vacuum cavity, and the gas pipeline (41a) is provided with a telescopic adjusting mechanism; the other path of gas pipeline (41b) is mixed with the auxiliary gas pipeline (42) and the protective gas pipeline (43) through the gas mixing chamber (4) and then is introduced into the film coating chamber (11).
2. The system of claim 1, wherein the plasma enhanced chemical vapor deposition system comprises: the plasma enhancement system adopts a low-temperature plasma energy source and utilizes radio frequency discharge or microwave discharge to enhance the plasma.
3. The system of claim 1, wherein the plasma enhanced chemical vapor deposition system comprises: the upper heater (21) and the lower heater (22) adopt resistance wires or infrared heating devices.
4. A method of producing a two-dimensional material by plasma-enhanced chemical vapor deposition using the system of claim 1 or 2, the two-dimensional material comprising: elementary two-dimensional nanocrystals, layered transition metal chalcogenides, layered metal halide compounds, layered metal oxides, and transition metal carbides and nitrides, characterized in that the method comprises the steps of:
1) cleaning the substrate before placing the substrate into a sample injection chamber;
2) after the substrate is placed in the sample injection chamber, air suction is started again to ensure that the vacuum degree reaches at least 5.0 × 10-3Pa；
3) The substrate is fed to a sample stage of the coating chamber by using a magnetic transmission rod and a substrate push frame, and the background pressure is at least 8 × 10-7When Pa is needed, starting a plasma enhancement system to carry out plasma cleaning on the substrate until the vacuum degree of the system is stable; shutting down the plasma enhancement system while heating the substrate to 30 ℃ to 600 ℃;
4) when cleaning is finished and the substrate is heated to a specified temperature, mixed gas of protective gas and auxiliary gas is controlled by a mass flow meter to be introduced into the coating chamber, and precursor gas is controlled by a mass flow meter to be introduced above the sample stage or introduced into the coating chamber through a gas mixing chamber;
5) starting the plasma enhancement system again to perform auxiliary enhancement on the two-dimensional material in the substrate growth process;
6) and closing the precursor gas and the auxiliary gas after the growth of the substrate of the two-dimensional material is finished, and cooling the two-dimensional material in the protective gas atmosphere.
5. The method of claim 4, wherein the two-dimensional material is prepared by plasma enhanced chemical vapor deposition, the method comprising: the substrate is made of metal materials, inorganic non-metal materials or high polymer materials.
CN201711461217.2A 2017-12-28 2017-12-28 System and method for preparing two-dimensional material by plasma enhanced chemical vapor deposition Active CN108342716B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711461217.2A CN108342716B (en) 2017-12-28 2017-12-28 System and method for preparing two-dimensional material by plasma enhanced chemical vapor deposition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711461217.2A CN108342716B (en) 2017-12-28 2017-12-28 System and method for preparing two-dimensional material by plasma enhanced chemical vapor deposition

Publications (2)

Publication Number Publication Date
CN108342716A CN108342716A (en) 2018-07-31
CN108342716B true CN108342716B (en) 2020-08-18

Family

ID=62962549

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711461217.2A Active CN108342716B (en) 2017-12-28 2017-12-28 System and method for preparing two-dimensional material by plasma enhanced chemical vapor deposition

Country Status (1)

Country Link
CN (1) CN108342716B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107675141B (en) * 2017-10-25 2023-08-04 南昌大学 Device for preparing nitride material
CN109580325B (en) * 2018-11-17 2023-08-29 金华职业技术学院 Method for preparing film sample by deposition
CN109267037A (en) * 2018-11-21 2019-01-25 新疆大学 Atmospheric plasma enhances chemical vapor deposition method and the equipment using this method
CN111218667A (en) * 2018-11-23 2020-06-02 北京北方华创微电子装备有限公司 Surface treatment method of gas distribution device and deposition equipment
CN109536930B (en) * 2018-12-27 2023-07-18 安徽贝意克设备技术有限公司 Plasma enhanced multi-source two-dimensional material preparation equipment and working method thereof
CN111809165A (en) * 2020-07-16 2020-10-23 上海华力微电子有限公司 Cleaning method of deposition equipment
CN111876752A (en) * 2020-08-03 2020-11-03 中国科学院长春光学精密机械与物理研究所 MOCVD device and semiconductor material production equipment

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106609392A (en) * 2015-10-23 2017-05-03 中国科学院苏州纳米技术与纳米仿生研究所 Two-dimension nano-film preparation device and method

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170190582A1 (en) * 2016-01-06 2017-07-06 Wenjie Fu Novel Methods To Grow Two Dimensional Nano-Materials By Using Solid-State Materials as Feedstock

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106609392A (en) * 2015-10-23 2017-05-03 中国科学院苏州纳米技术与纳米仿生研究所 Two-dimension nano-film preparation device and method

Also Published As

Publication number Publication date
CN108342716A (en) 2018-07-31

Similar Documents

Publication Publication Date Title
CN108342716B (en) System and method for preparing two-dimensional material by plasma enhanced chemical vapor deposition
CN109371381B (en) Method for preparing single-layer molybdenum sulfide/tungsten sulfide in-plane heterojunction by low-temperature one-step method
CN103981507B (en) A kind of graphene preparation method
CN109809372B (en) Method for preparing single-layer tungsten diselenide nanobelt based on space confinement strategy
CN110790313A (en) Preparation method of 3R phase transition metal chalcogenide two-dimensional nanosheet
CN112853290B (en) Preparation method of large-area molybdenum disulfide film
CN105568253B (en) A kind of method of apparatus for plasma chemical vapor deposition growth hexagonal boron nitride
CN105177705A (en) Method For Producing Diamond Film
CN102102220A (en) Preparation method of graphene on diamond (111) surface
CN108658065B (en) Graphene doping preparation and repair method
CN106609392A (en) Two-dimension nano-film preparation device and method
CN103606514B (en) Based on the chemical corrosion transfer method of GaN substrate CVD extending and growing graphene
CN107083540A (en) A kind of gallium nitride base film on flexible polyimide substrate and preparation method thereof
CN104313684A (en) Method for preparing hexagonal boron nitride (h-BN) two-dimensional atomic crystal
US20130168229A1 (en) Method of preparing graphene layer
CN106756870A (en) A kind of method that plasma enhanced chemical vapor deposition grows Graphene
JP2016519843A (en) Ge quantum dot growth method, Ge quantum dot composite material and application thereof
CN113832432B (en) Preparation method of two-dimensional compound semiconductor film
CN108314019B (en) Preparation method of large-area high-quality graphene film with uniform layer number
CN110055589B (en) Large-size single-layer hexagonal boron nitride single crystal or film and preparation method thereof
CN101928933A (en) Method for preparing silicon carbide film
CN110512194A (en) Star-like microwave plasma CVD device and the method for preparing large-area two-dimensional material
CN111139526A (en) Method for obtaining single crystal boron nitride film by ion beam sputtering deposition
CN103915319A (en) Method for manufacturing graphene device through moved CVD graphene
CN103388130B (en) The preparation method of ECR-PEMOCVD low temperature depositing InN film on ZnO buffer/diamond thin/Si multi-layer film structure substrate

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