CN108342716A - Plasma enhanced chemical vapor deposition prepares the system and method for two-dimensional material - Google Patents
Plasma enhanced chemical vapor deposition prepares the system and method for two-dimensional material Download PDFInfo
- Publication number
- CN108342716A CN108342716A CN201711461217.2A CN201711461217A CN108342716A CN 108342716 A CN108342716 A CN 108342716A CN 201711461217 A CN201711461217 A CN 201711461217A CN 108342716 A CN108342716 A CN 108342716A
- Authority
- CN
- China
- Prior art keywords
- substrate
- dimensional material
- plasma
- 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.)
- Granted
Links
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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Plasma enhanced chemical vapor deposition prepares the system and method for two-dimensional material, belongs to two-dimensional material preparing technical field.The system comprises vacuum system, substrate heating system, plasma enhancing system and air inlet pipelines；Vacuum system contains coating chamber and sample introduction chamber, and air inlet, gas outlet and multiple observation windows are respectively equipped in coating chamber and sample introduction chamber.The present invention is directed to facilitate forerunner's precursor reactant to crack using plasmaassisted, and cleaning of the realization to substrate surface and cavity under ultrahigh vacuum, presoma fixed point supply is being carried out by special designing air inlet pipeline, two-dimensional material is prepared in surfaces of various materials to realize.The present invention emphasizes that the superelevation on environment and surface cleans booster action grow for two-dimensional material, and with the growth of this System and method for realization two-dimensional film material, cancels limitation of traditional transfer process to the destruction of material and high growth temperature to substrate.
Description
Technical field
The present invention relates to the system and methods that plasma enhanced chemical vapor deposition prepares two-dimensional material, belong to two-dimentional material
Expect preparation system and method field.
Background technology
As graceful Geim groups of Chester university of Britain in 2004 successfully isolate the stone of monoatomic layer with mechanical stripping method
Black alkene and since obtaining the Nobel Prize with this, the research of two-dimensional material just obtains extensive concern.The application of two-dimensional material at present
Be severely limited to its preparation method, the most poor quality of two-dimensional material prepared at present, yield is extremely low, cost is high and with
Current chip technology of preparing can not be compatible with.By taking graphene as an example, under the conditions of current technology of preparing, graphene poor quality,
The characteristics such as electron transfer deviate its intrinsic property so that it is relevant that graphene can not be applied to high-performance electronic, opto-electronic device
In.Its is main the reason is that not yet find the industrial preparative method of large-area high-quality monocrystalline or polycrystalline graphite alkene at present,
So that grapheme material one side performance far can not reach its theoretical rank, on the other hand can not also occupy in cost any
Advantage.
In the graphene preparation method that facing new opplication and lower industrialization cost, sent out on Science in 2009
The chemical vapour deposition technique (X.Li, W.Cai, J et al.Science 2009,324,1312) of table with highest cost performance with
Stability obtains the affirmative of scientific research and industrial quarters, is to prepare the maximally efficient side of large-area high-quality graphene film at present
Method.Based on such method, many researchs have all carried out method optimization for different angles, but all can not fundamentally improve stone
The quality of black alkene, solve graphene applies bottleneck.This is mostly attributed to demand of the method to high temperature and high energy consumption is increased
Its cost is added, while having significantly limited the use of functionalization semiconductor substrate again, therefore has forcibly introduced etching and turn
The process of shifting.Graphene makes to generate defect, crystal boundary, fold in temperature-fall period with the larger expansion coefficient difference of substrate in the process
Deng the deterioration to graphene, along with the factors such as defect, breakage, fold, pollution caused by transfer operation in the process are to graphite
Alkene can cause further even more serious deterioration, finally so that the deviation of graphene performance is intrinsic.At the same time, other two-dimensional materials
Such as phosphorus alkene, tin alkene simple substance two-dimensional nano crystal and other many two-dimensional materials are all limited by the limitation of its preparation method, nothing
Method directly prepares high-quality thin film material on functionalization substrate.
Invention content
Based on difficulty prepared by current two-dimensional material, the purpose of the present invention is to propose to a kind of plasma enhanced chemical vapor
Deposit the system and method that (PECVD) prepares two-dimensional material；Pass through the side such as ultrahigh vacuum, plasma enhancing and silicon
Method realizes under ultrahigh vacuum, the decomposition of the cleaning and presoma of substrate surface under lower temperature (30 DEG C to 600 DEG C), finally
Various metals material, inorganic non-metallic material, high molecular material surface on growth high quality simple substance two-dimensional nano crystal,
Stratiform transient metal chalcogenide compound, laminated metal halogen compound, layered metal oxide and transition metal carbon/nitrification
Object.
Technical scheme is as follows：
A kind of system that plasma enhanced chemical vapor deposition prepares two-dimensional material, it is characterised in that：The system packet
Include vacuum system, substrate heating system, plasma enhancing system and air inlet pipeline；The vacuum system includes vacuum pump, plating
Membrane cavity room and sample introduction chamber are connected by pipeline with valve between two vacuum chambers；In coating chamber and sample introduction chamber
It is respectively equipped with air inlet, gas outlet and multiple observation windows；Sample introduction chamber interior is equipped with substrate push bracket, substrate push bracket and magnetic force
Transmission lever connects；Substrate heating system is set in coating chamber, and substrate heating system includes sample stage, and is separately mounted to
Upper heater above and below sample stage and lower heater；The plasma enhancing system contains plasma generator；
Top crown and bottom crown are separately positioned on the upper and lower surface of sample stage, and by lead and are arranged respectively in coating chamber
External plasma generator connection.
In above-mentioned technical proposal, the air inlet pipeline includes precursor gas pipeline, auxiliary gas piping, protective gas
Pipeline and mixing chamber；The presoma air inlet pipeline is divided into two-way, wherein independent control is passed through inside vacuum cavity all the way
Above sample stage, this gas piping is equipped with expansion regulating mechanism；Another way is passed through with auxiliary gas piping and protective gas pipeline
It is passed through coating chamber after mixing chamber mixing.
Preferably, the plasma enhancing system uses low-temperature plasma energy source, utilizes radio frequency discharge or microwave
Electric discharge carries out plasma enhancing.
Preferably, the upper heater and lower heater use resistance wire or infrared heating device.
The method that a kind of plasma enhanced chemical vapor deposition provided by the invention prepares two-dimensional material, it is characterised in that
This method comprises the following steps：
1) it places the substrate into before sample introduction chamber, is cleaned；
2) after placing the substrate into sample introduction chamber, then start to be evacuated, vacuum degree is made to be at least up to 5.0 × 10-3Pa；
3) utilize magnetic force transmission lever and substrate push bracket that substrate is sent on coating chamber sample stage, when background pressure is in extremely
Few 8 × 10-7When Pa, opens plasma enhancing system and plasma cleaning is carried out to substrate until system vacuum is stablized；It closes
Plasma enhancing system, while to silicon to 30 DEG C to 600 DEG C；
4) when cleaning is completed and silicon is to assigned temperature, the mixed gas of protective gas and auxiliary gas is passed through
Mass flowmenter control is passed through coating chamber, and precursor gas controls independent gas circuit by mass flowmenter and is passed through above sample stage
Or coating chamber is passed through by mixing chamber；
5) it is again turned on plasma enhancing system, auxiliary enhancing is carried out during substrate growth to two-dimensional material；
6) two-dimensional material closes precursor gas and auxiliary gas after substrate growth, and under protective gas atmosphere
Cool down.
Two-dimensional material of the present invention includes：Simple substance two-dimensional nano crystal, stratiform transient metal chalcogenide compound, stratiform gold
Belong to halogen compound, layered metal oxide and transition metal carbide and nitride；The substrate is using metal material, inorganic
Nonmetallic materials or high molecular material.
The present invention has the following advantages and the technique effect of high-lighting：The present invention grows required environment for two-dimensional material,
By building plasma auxiliary chemical gas into depositing device, and it is equipped with preparation method, to reach high quality two-dimensional material more
Requirement prepared by kind functional substrate surface.Different from the two-dimentional material caused by the preparation condition in traditional chemical vapour deposition technique
Expect that the deterioration of quality and the restriction of substrate type, the present invention emphasize the substrate surface of ultra-clean in ultrahigh vacuum and plasma
Under the auxiliary of body enhancing, the substrate surface and energy needed for two-dimensional material growth are provided at a lower temperature.Preparation method
Its catalytic activity will be improved to the ultra-clean of substrate surface, reduce energy of the presoma needed for the cracking of surface, and improve and give birth to
The quality of long two-dimensional material.Substrate heating system auxiliary is recycled to further increase the activity of substrate surface, the present invention is to made
Standby two-dimensional material increased quality is big, breaks the previous limitation for preparing two-dimensional material, can be directly directly raw by two-dimensional material
It is longer than in the functional substrate of ultra-clean, cancels the transfer process of traditional handicraft, reaches high-end applications to the side such as two-dimensional material quality
The requirement in face, the root problem of application of the final solution two-dimensional material in terms of electronics, opto-electronic device.
Description of the drawings
Fig. 1 is the structural representation for the system that plasma enhanced chemical vapor deposition provided by the invention prepares two-dimensional material
Figure.
Fig. 2 is the overlooking structure diagram of sample introduction chamber and coating chamber of the present invention.
Fig. 3 is the structural schematic diagram of the coating chamber of the present invention.
Fig. 4 provides two-dimensional material preparation method schematic diagram for the present invention.
In figure：1- vacuum pumps；11- coating chambers；12- sample introduction chambers；13- magnetic force transmission levers；14- substrate push bracket；15- is seen
Survey window；2- sample stages；21- upper heaters；22- lower heaters；3- plasma producing apparatus；31- bottom crowns；32- top crowns；
4- mixing chambers；41- precursor gas pipelines；41a- is passed through plated film cavity precursor gas pipeline；41b- is passed through mixing chamber forerunner
Body gas piping；42- assists gas piping；43- protective gas pipelines；44- gas pipings heating tape；45- expansion regulating mechanisms；
5- presomas；6- substrates；7- two-dimensional materials.
Specific implementation mode
The present invention is further elaborated with reference to the accompanying drawings and examples.
As shown in Figure 1, PECVD system provided by the present invention includes vacuum system, substrate heating system, plasma increasing
Strong system and air inlet pipeline.Wherein vacuum system includes vacuum pump 1, coating chamber 11 and sample introduction chamber 12, two vacuum chambers
Between connected with valve by pipeline.In coating chamber 11 and sample introduction chamber 12 respectively be equipped with air inlet, gas outlet and
Multiple observation windows.Sample introduction chamber 12 is internally provided with substrate push bracket 14 and magnetic force transmission lever 13, and substrate push bracket 14 is transmitted with magnetic force
Bar 13 connects.
As shown in Fig. 2, substrate heating system is set in coating chamber 11, the catalytic activity for maximizing substrate, and
The energy of certain two-dimensional material growth is provided.Substrate heating system includes sample stage 2, and is separately mounted to the upper of sample stage
The upper heater 21 and lower heater 22 of side and lower section；Heater uses resistance wire or infrared heating device, double boiler to protect
The holding of the uniformity and temperature of silicon on sample stage is demonstrate,proved
As shown in figure 3, can reach and keep ultrahigh vacuum at work for coating chamber 11, thus system design have into
The substrate that sample chamber 12 is used to expose air is replaced, then carries out substrate transmission by magnetic force transmission lever 13 and substrate push bracket 14.
Plasma enhancing system contains plasma producing apparatus 3, top crown 32 and bottom crown 31；Top crown 32 is under
Pole plate 31 is separately positioned on the upper and lower surface of sample stage, and by lead and is arranged outside coating chamber 11 respectively
Plasma producing apparatus 3 connects.Plasma producing apparatus use low-temperature plasma energy source, can provide radio frequency discharge or
Microwave discharge is enhanced by lead by upper bottom crown, it is ensured that substrate surface maximizes plasma density on sample stage.
Air inlet pipeline includes precursor gas pipeline 41, auxiliary gas piping 42 and protective gas pipeline 43；Described
Presoma air inlet pipeline 41 divides for two-way.Wherein all the way 41a is passed through by independent valve control inside vacuum cavity, 2 top of sample stage,
This gas piping 41a has expansion regulating mechanism, can just be moved on substrate.Such design can pass through fixed point
Precursor gas supplies, and the monocrystalline controllable growth of two-dimensional material may be implemented；In addition 41b connect with mixing chamber 4 and is passed through plating all the way
The fast-growth of polycrystalline two-dimensional material may be implemented in membrane cavity room 12.
As shown in figure 4, the present invention provides the method that plasma enhanced chemical vapor deposition prepares two-dimensional material：
1) it places the substrate into before sample introduction chamber, is cleaned；This step is for removing the pollutant of substrate surface
It removes.
2) after placing the substrate into sample introduction chamber, then start to be evacuated, vacuum degree is at least up to 5.0 × 10-3Pa；This step makes
Sample introduction chamber reaches certain vacuum degree, it is ensured that open connect with coating chamber valve when ensure coating chamber cleaning and very
Reciprocal of duty cycle.
3) after opening valve, substrate is sent on coating chamber sample stage using magnetic force transmission lever and substrate push bracket, works as the back of the body
Scape pressure is at least 8 × 10-7When Pa, opens plasma enhancing system and plasma cleaning is carried out to substrate until system vacuum
Degree is stablized；This step eliminates the remaining oxide layer of substrate surface and the pollutant of other more difficult removals, and improves surface
Pattern greatly reduces surface roughness.Plasma system is closed later simultaneously to carrying out silicon to 30 DEG C to 600
℃；To improve the catalytic activity of substrate, and provide the energy needed for certain two-dimensional material growth.
4) when cleaning is completed and silicon is to assigned temperature, the mixed gas of protective gas and auxiliary gas is passed through
Mass flowmenter control is passed through coating chamber, and precursor gas controls independent gas circuit by mass flowmenter and is passed through above sample stage
Or coating chamber is passed through by mixing chamber；This step has been passed through precursors and auxiliary gas and protective gas, carries out two
Tie up the growth response of material.
5) two-dimensional material is again turned on plasma enhancing system during substrate growth, grows and carries out to two-dimensional material
Auxiliary enhancing；Plasma enhancing system is conducive to the cracking of precursor gas and the nucleating growth of two-dimensional material.
6) two-dimensional material closes precursor gas and auxiliary gas after substrate growth, and under protective gas atmosphere
Cooling；
The present invention emphasizes the cleannes of system under ultrahigh vacuum, and to utilize plasma based on this PECVD system
Auxiliary replaces tradition CVD for the demand of high temperature, reaches cleannes high in system, and the atomic level on 6 surface of substrate cleans,
The cracking 5 of presoma and the high activity of substrate surface, to grow high quality two-dimensional material 7.Based on this technology, name
Go out several specific embodiments to further understand the specific implementation of the present invention.
Embodiment 1：
Specific high-quality graphene preparation method provided by the invention, specifically comprises the following steps：
1) before the substrates such as copper foil, nickel foil, silicon chip or glass being put into sample introduction chamber, to substrate dilute hydrochloric acid, acetone, wine
Essence and deionized water are cleaned by ultrasonic；
2) after substrate is put into sample introduction chamber, after the system short time exposes air and fills drying nitrogen, vacuum degree reaches within 20 minutes
To at least 5.0 × 10-3Pa；
3) utilize magnetic force transmission lever and substrate push bracket that substrate is sent on coating chamber sample stage, when background pressure is in super
(it is better than 8 × 10 under high vacuum-7When Pa), opens plasma enhancing system and plasma cleaning is carried out to substrate until system vacuum
Degree is stablized；Plasma system is closed simultaneously to carrying out silicon to 450 DEG C；
4) it when cleaning is completed and silicon is to assigned temperature, begins through mass flowmenter control and is passed through argon gas hydrogen
Mixed atmosphere, and methane gas is passed through by independent gas circuit；
5) it is again turned on plasma enhancing auxiliary carbon source and cracks and start to deposit graphene, methane is closed simultaneously after deposition
The fast cooling under protective atmosphere.
Embodiment 2：
Specific high quality method for preparing molybdenum disulfide provided by the invention, specifically comprises the following steps：
1) before the substrates such as silicon chip, glass or gallium nitride being put into sample introduction chamber, to substrate dilute hydrochloric acid, acetone, alcohol
And deionized water is cleaned by ultrasonic；
2) Mo of 1nm thickness is plated on substrate using magnetron sputtering or vapor deposition；
3) after substrate is put into sample introduction chamber, after the system short time exposes air and fills drying nitrogen, vacuum degree reaches within 20 minutes
To at least 5.0 × 10-3Pa。
4) utilize magnetic force transmission lever and substrate push bracket that substrate is sent on coating chamber sample stage, when background pressure is in super
(it is better than 8 × 10 under high vacuum-7When Pa), opens plasma enhancing system and plasma cleaning is carried out to substrate until system vacuum
Degree is stablized；Plasma system is closed simultaneously to carrying out silicon to 300 DEG C；
5) when cleaning is completed and silicon is to assigned temperature, mass flowmenter control is begun through, is led to using independent
Enter gas circuit in plated film cavity and is passed through hydrogen sulfide；
6) it is again turned on plasma enhancing auxiliary and vulcanizes and start to prepare molybdenum disulfide, hydrogen sulfide is closed simultaneously after deposition
Cool down under ultrahigh vacuum
Embodiment 3：
Specific high quality hexagonal boron nitride preparation method provided by the invention, specifically comprises the following steps：
1) before Si (100) substrate being put into sample introduction chamber, to substrate dilute hydrochloric acid, acetone, alcohol and deionized water
It is cleaned by ultrasonic；
2) after substrate is put into sample introduction chamber, after the system short time exposes air and fills drying nitrogen, vacuum degree reaches within 20 minutes
To at least 5.0 × 10-3Pa；
3) utilize magnetic force transmission lever and substrate push bracket that substrate is sent on coating chamber sample stage, when background pressure is in super
(it is better than 8 × 10 under high vacuum-7When Pa), opens plasma enhancing system and plasma cleaning is carried out to substrate until system vacuum
Degree is stablized；Plasma system is closed simultaneously to carrying out silicon to 550 DEG C；
4) it when cleaning is completed and silicon is to assigned temperature, begins through mass flowmenter control and is passed through N2/B
(OCH3)3Or N2/B2H3Mix precursor gas；
5) it is again turned on plasma enhancing auxiliary presoma and cracks and start to deposit hexagonal boron nitride, closed after deposition
Precursor gas and fast cooling.
Claims (6)
1. the system that a kind of plasma enhanced chemical vapor deposition prepares two-dimensional material, it is characterised in that：The system comprises
Vacuum system, substrate heating system, plasma enhancing system and air inlet pipeline；The vacuum system includes vacuum pump (1), plating
Membrane cavity room (11) and sample introduction chamber (12) are connected by pipeline with valve between two vacuum chambers；In coating chamber (11) and
Air inlet, gas outlet and multiple observation windows are respectively equipped on sample introduction chamber (12)；Sample introduction chamber (12) is internally provided with lining
Bottom push bracket (14), substrate push bracket (14) are connect with magnetic force transmission lever (13)；Substrate heating system is set in coating chamber (11),
Substrate heating system includes sample stage (2), and be separately mounted to upper heater (21) above and below sample stage and it is lower plus
Hot device (22)；The plasma enhancing system contains plasma generator (3)；Top crown (32) and bottom crown (31) are respectively
Upper and lower surface in sample stage, and plasma external in coating chamber (11) with setting by lead respectively are set
Generator (3) connects.
2. the system that a kind of plasma enhanced chemical vapor deposition as described in claim 1 prepares two-dimensional material, feature
It is：The air inlet pipeline include precursor gas pipeline (41), auxiliary gas piping (42), protective gas pipeline (43) and
Mixing chamber (4)；The presoma air inlet pipeline (41) is divided into two-way, wherein (41a) independent control is passed through vacuum cavity all the way
Above internal sample stage (2), this gas piping (41a) is equipped with expansion regulating mechanism；Another way (41b) and auxiliary flue
Road (42) and protective gas pipeline (43) are passed through coating chamber (12) after mixing chamber (4) mixing.
3. the system that a kind of plasma enhanced chemical vapor deposition as described in claim 1 prepares two-dimensional material, feature
It is：The plasma enhancing system uses low-temperature plasma energy source, carried out using radio frequency discharge or microwave discharge etc.
Gas ions enhance.
4. the system that a kind of plasma enhanced chemical vapor deposition as described in claim 1 prepares two-dimensional material, feature
It is：The upper heater (21) and lower heater (22) uses resistance wire or infrared heating device.
5. a kind of plasma enhanced chemical vapor deposition using system as claimed in claim 1 or 2 prepares two-dimensional material
Method, it is characterised in that this method comprises the following steps：
1) it places the substrate into before sample introduction chamber, is cleaned；
2) after placing the substrate into sample introduction chamber, then start to be evacuated, vacuum degree is made to be at least up to 5.0 × 10-3Pa；
3) utilize magnetic force transmission lever and substrate push bracket that substrate is sent on coating chamber sample stage, when background pressure is at least 8
×10-7When Pa, opens plasma enhancing system and plasma cleaning is carried out to substrate until system vacuum is stablized；Close etc. from
Daughter enhances system, while to silicon to 30 DEG C to 600 DEG C；
4) when cleaning is completed and silicon is to assigned temperature, the mixed gas of protective gas and auxiliary gas is passed through into quality
Flowmeter control is passed through coating chamber, precursor gas by mass flowmenter control independent gas circuit be passed through it is above sample stage or logical
It crosses mixing chamber and is passed through coating chamber；
5) it is again turned on plasma enhancing system, auxiliary enhancing is carried out during substrate growth to two-dimensional material；
6) two-dimensional material closes precursor gas and auxiliary gas after substrate growth, and is carried out under protective gas atmosphere
Cooling.
6. the method that a kind of plasma enhanced chemical vapor deposition as claimed in claim 5 prepares two-dimensional material, feature
It is：The two-dimensional material includes：Simple substance two-dimensional nano crystal, stratiform transient metal chalcogenide compound, laminated metal halogenation are closed
Object, layered metal oxide and transition metal carbide and nitride；The substrate is using metal material, inorganic non-metallic material
Material or high molecular material.
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 true CN108342716A (en) | 2018-07-31 |
| CN108342716B 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) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107675141A (en) * | 2017-10-25 | 2018-02-09 | 南昌大学 | A kind of device for being used to prepare nitride material |
| 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 |
| CN109536930A (en) * | 2018-12-27 | 2019-03-29 | 合肥百思新材料研究院有限公司 | A kind of the multi-source two-dimensional material Preparation equipment and its working method of PE enhancing |
| CN109580325A (en) * | 2018-11-17 | 2019-04-05 | 金华职业技术学院 | A kind of method of sedimentation preparation of film sample |
| 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 |
| 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 (2)
| 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 |
| 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 |
-
2017
- 2017-12-28 CN CN201711461217.2A patent/CN108342716B/en active Active
Patent Citations (2)
| 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 |
| 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 |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107675141A (en) * | 2017-10-25 | 2018-02-09 | 南昌大学 | A kind of device for being used to prepare nitride material |
| CN107675141B (en) * | 2017-10-25 | 2023-08-04 | 南昌大学 | Device for preparing nitride material |
| CN109580325A (en) * | 2018-11-17 | 2019-04-05 | 金华职业技术学院 | A kind of method of sedimentation preparation of film sample |
| 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 |
| CN109536930A (en) * | 2018-12-27 | 2019-03-29 | 合肥百思新材料研究院有限公司 | A kind of the multi-source two-dimensional material Preparation equipment and its working method of PE enhancing |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108342716B (en) | 2020-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108342716A (en) | Plasma enhanced chemical vapor deposition prepares the system and method for two-dimensional material | |
| CN103981507B (en) | A kind of graphene preparation method | |
| CN102102220B (en) | Preparation method of graphene on diamond (111) surface | |
| CN108977795B (en) | Device and method for preparing silicon carbide coating by using electric coupling chemical vapor deposition method | |
| CN106756870B (en) | A kind of method of plasma enhanced chemical vapor deposition growth graphene | |
| CN105800602B (en) | Copper particle is remotely catalyzed the method for directly growing graphene on an insulating substrate | |
| CN103193224B (en) | Method for preparing graphene film on nonmetallic substrate at low temperature | |
| CN103121670A (en) | Method for low-temperature growth of graphene by remote plasma reinforced atomic layer deposition | |
| CN103346073B (en) | A kind of preparation method of beta-silicon carbide thin film | |
| CN106609392A (en) | Two-dimension nano-film preparation device and method | |
| CN109722641A (en) | Diamond/graphene composite heat conduction film and preparation method thereof and cooling system | |
| CN101831633A (en) | Method for preparing composite film of graphene and amorphous carbon | |
| CN104313684A (en) | Method for preparing hexagonal boron nitride (h-BN) two-dimensional atomic crystal | |
| CN111826714B (en) | Method for enhancing CVD diamond heteroepitaxial nucleation based on radio frequency power supply applied bias voltage | |
| CN104495829A (en) | Method for preparing graphene film on low-temperature substrate | |
| CN104144531A (en) | High heating carbon crystal plate and manufacturing method thereof | |
| CN110562983B (en) | Efficient preparation device and preparation method of high-performance wave-absorbing material | |
| CN108597993A (en) | A kind of Direct Bonding method of gallium nitride/diamond | |
| CN104195522B (en) | Preparation method of glass fiber cotton felt with high thermal conductivity | |
| CN103183336A (en) | Preparation method of large-area graphene on Si substrate based on Ni film annealing | |
| CN108910868B (en) | Method for preparing graphene dendrite on insulating substrate | |
| CN103915319A (en) | Method for manufacturing graphene device through moved CVD graphene | |
| CN111647873B (en) | Three-dimensional continuous network hydrophilic boron-doped diamond heat radiator and preparation method and application thereof | |
| CN101844752A (en) | High-mass pyrolysis BN crucible and preparation method thereof | |
| CN110408911B (en) | Controllable preparation device and method for large-area thin film |
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 |