CN113151803A - Preparation method of boron-carbon-nitrogen film - Google Patents
Preparation method of boron-carbon-nitrogen film Download PDFInfo
- Publication number
- CN113151803A CN113151803A CN202110276691.8A CN202110276691A CN113151803A CN 113151803 A CN113151803 A CN 113151803A CN 202110276691 A CN202110276691 A CN 202110276691A CN 113151803 A CN113151803 A CN 113151803A
- Authority
- CN
- China
- Prior art keywords
- carbon
- film
- boron
- gas
- nitrogen
- 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.)
- Pending
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
- C23C16/22—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
- C23C16/36—Carbonitrides
-
- 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
- C23C16/52—Controlling or regulating the coating process
Abstract
The invention discloses a preparation method of a boron-carbon-nitrogen film, ammonia borane is used as a nitrogen source and a boron source, methane is used as a carbon source, a mixed gas of hydrogen and argon is used as a carrier gas, a copper or nickel metal film is used as a growth substrate, a single molecular layer thick BCN film is grown on the surface of the substrate through a CVD method, the carbon content in the film is regulated and controlled by the flow ratio of methane and ammonia borane steam, and then the single molecular layer films with different performances are obtained. The carbon source used in the invention, namely methane, is low in carbon content relative to other alkane gases, is the first carbon-containing origin for preparing graphene, and the nitrogen and boron source ammonia borane is commonly used as a nitrogen and boron source for preparing an h-BN monomolecular layer. The growth substrate copper and nickel are common substrates for growing graphene and h-BN monomolecular layers.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a preparation method of a boron-carbon-nitrogen film with a hexagonal structure.
Background
The graphene and the boron nitride are isoelectrons and have the same crystal structure, but the electrical properties of the graphene and the boron nitride are different, wherein the graphene is a zero band gap semiconductor, and the boron nitride is a wide band gap semiconductor. The graphene and hexagonal boron nitride (h-BN) monolayer films have similar Chemical Vapor Deposition (CVD) preparation methods, both grow on the surface of a metal catalyst under the condition of inert reducing atmosphere, and the growth temperatures are the same. The same crystal structure and the similar CVD growth method enable the three elements of carbon, boron and nitrogen to form a ternary compound Boron Carbon Nitride (BCN) on the surface of the metal catalyst, the performance of the prepared hexagonal structure material is between that of graphene and hexagonal boron nitride, and performance regulation and control can be realized through component adjustment. Experiments and theoretical calculation show that carbon, boron and nitrogen formed by the co-growth of carbon, boron and nitrogen elements have excellent mechanical, electrical, optical and biomedical performances and can be used in the fields of photocatalysis, electrochemical sensing, supercapacitors, electromagnetic wave absorption, bacteriostasis, sterilization, photoelectric detection and the like. The general preparation method of the carbon, boron and nitrogen material is to mix sources containing three elements of boron, carbon and nitrogen and perform high-temperature sintering treatment or sputtering deposition, and the prepared material is usually in the form of powder or ceramic. The two-dimensional BCN monolayer film is prepared by a chemical vapor deposition method, and can be used for the preparation and research of nano photoelectronic devices.
Disclosure of Invention
The invention provides a preparation method of a boron-carbon-nitrogen film aiming at the defects of the prior art.
The preparation method of the boron-carbon-nitrogen film comprises the following specific steps:
and (1) placing a copper film (with the size of 1.0 multiplied by 1.0 cm-2.0 multiplied by 1.0cm) as a substrate into a quartz tube in a chemical vapor deposition system (CVD).
And (2) loading 0.5-5g of ammonia borane into a quartz bubbler, connecting one end of the bubbler with carrier gas argon and hydrogen, wherein the volume of hydrogen gas accounts for 50% -100%, connecting one end of the bubbler with CVD, and loading ammonia borane vapor into the CVD through the carrier gas. The flow of the carrier gas carrying the ammonia borane vapor is controlled by a gas mass flow meter, and the flow of the carrier gas is 10-50 sccm. The heating temperature of the quartz bubbler filled with ammonia borane is 50-90 ℃.
And (3) introducing a mixed gas of methane and hydrogen, wherein the volume of the methane accounts for 5-25%, into the CVD, controlling the gas flow by a gas mass flowmeter, and controlling the mixed gas flow to be 10-50 sccm.
And (4) closing the gas mass flow meters in the steps (2) and (3), starting a mechanical pump to vacuumize the CVD system, and heating to 950-1050 ℃, wherein the heating rate is 20-30 ℃/min. And (3) keeping the temperature for 30min after the temperature rises to 950-1050 ℃, then simultaneously starting the gas mass flow meters in the steps (2) and (3), and keeping the temperature of the CVD system for 20-60 min.
And (6) stopping heating of the CVD system, starting the tube furnace, rapidly cooling the quartz tube to room temperature in a room temperature environment, then closing the gas mass flow meters in the steps (2) and (3), taking out the copper substrate, and obtaining the BCN monomolecular layer film on the surface of the copper substrate.
The substrate in the step (1) is a copper film or a nickel film.
The quartz tube in the step (1) can also be a corundum tube.
The invention adopts ammonia borane as nitrogen and boron sources, methane as carbon sources, mixed gas of hydrogen and argon as carrier gas, a copper or nickel metal film as a growth substrate, a single molecular layer thick BCN film is grown on the surface of the substrate by a CVD method, and the carbon content in the film is regulated and controlled by the flow ratio of methane and ammonia borane vapor, so that the single molecular layer films with different performances are obtained. The carbon source used in the invention, namely methane, is low in carbon content relative to other alkane gases, is the first carbon-containing origin for preparing graphene, and the nitrogen and boron source ammonia borane is commonly used as a nitrogen and boron source for preparing an h-BN monomolecular layer. The growth substrate copper and nickel are common substrates for growing graphene and h-BN monomolecular layers.
Drawings
FIG. 1 is a schematic diagram of an apparatus embodying the present invention.
Detailed Description
As shown in figure 1, the preparation method of the boron carbon nitrogen film comprises the following specific steps:
and (1) putting a copper film with the thickness of 1.0 multiplied by 1.0cm as a substrate into a quartz tube in a chemical vapor deposition system.
And (2) loading 0.5g of ammonia borane into a quartz bubbler, wherein one end of the bubbler is connected with carrier gas argon and hydrogen, the volume of hydrogen gas accounts for 50%, the other end of the bubbler is connected with CVD, and ammonia borane vapor is loaded into the CVD through the carrier gas. The flow of the carrier gas carrying ammonia borane vapor was controlled by a gas mass flow meter at a carrier gas flow rate of 10 sccm. The quartz bubbler charged with ammonia borane was heated to 50 ℃.
And (3) introducing a mixed gas of methane and hydrogen, wherein the volume of the methane accounts for 5%, into the CVD, controlling the gas flow by a gas mass flow meter, and controlling the mixed gas flow to be 10 sccm.
And (4) closing the gas mass flow meters in the steps (2) and (3), starting a mechanical pump to vacuumize the CVD system, and heating to 950 ℃ at the heating rate of 20 ℃/min. And (3) keeping the temperature for 30min after the temperature rises to 950 ℃, then simultaneously starting the gas mass flow meters in the steps (2) and (3), and keeping the temperature of the CVD system for 20 min.
And (6) stopping heating of the CVD system, starting the tube furnace, rapidly cooling the quartz tube to room temperature in a room temperature environment, then closing the gas mass flow meters in the steps (2) and (3), taking out the copper substrate, and obtaining the BCN monomolecular layer film on the surface of the copper substrate.
Example two: the preparation method of the boron-carbon-nitrogen film comprises the following specific steps:
and (1) putting a copper film with the size of 1.5 multiplied by 1.0cm as a substrate into a corundum tube in a chemical vapor deposition system.
And (2) putting 2g of ammonia borane into a quartz bubbler, wherein one end of the bubbler is connected with carrier gas argon and hydrogen, the volume of hydrogen accounts for 70%, the other end of the bubbler is connected with CVD, and ammonia borane vapor is loaded into the CVD through the carrier gas. The flow of the carrier gas carrying ammonia borane vapor was controlled by a gas mass flow meter at a carrier gas flow rate of 30 sccm. The quartz bubbler charged with ammonia borane was heated to a temperature of 70 ℃.
And (3) introducing a mixed gas of methane and hydrogen, wherein the volume of the methane accounts for 20%, into the CVD, controlling the gas flow by a gas mass flow meter, and controlling the mixed gas flow to be 30 sccm.
And (4) closing the gas mass flow meters in the steps (2) and (3), starting a mechanical pump to vacuumize the CVD system, and heating to 1000 ℃ at the heating rate of 25 ℃/min. And (3) keeping the temperature for 30min after the temperature rises to 1000 ℃, then simultaneously starting the gas mass flow meters in the steps (2) and (3), and keeping the temperature of the CVD system for 40 min.
And (6) stopping heating of the CVD system, starting the tube furnace, rapidly cooling the corundum tube to room temperature in a room temperature environment, then closing the gas mass flow meters in the steps (2) and (3), taking out the copper substrate, and obtaining the BCN monomolecular layer film on the surface of the copper substrate.
Example three: the preparation method of the boron-carbon-nitrogen film comprises the following specific steps:
the method comprises the following steps of (1) putting a nickel film with the size of 2.0 multiplied by 1.0cm as a substrate into a quartz tube in a chemical vapor deposition system.
And (2) putting 5g of ammonia borane into a quartz bubbler, wherein one end of the bubbler is connected with carrier gas argon and hydrogen, the volume of hydrogen accounts for 100%, the other end of the bubbler is connected with CVD, and ammonia borane vapor is loaded into the CVD through the carrier gas. The flow of the carrier gas carrying ammonia borane vapor was controlled by a gas mass flow meter at a carrier gas flow rate of 50 sccm. The quartz bubbler charged with ammonia borane was heated to a temperature of 90 ℃.
And (3) introducing a mixed gas of methane and hydrogen, wherein the volume of the methane accounts for 25%, into the CVD, controlling the gas flow through a gas mass flow meter, and controlling the mixed gas flow to be 50 sccm.
And (4) closing the gas mass flow meters in the steps (2) and (3), starting a mechanical pump to vacuumize the CVD system, and heating to 1050 ℃ at the heating rate of 30 ℃/min. And (3) keeping the temperature for 30min after the temperature is increased to 1050 ℃, then simultaneously starting the gas mass flow meters in the steps (2) and (3), and keeping the temperature of the CVD system for 60 min.
And (6) stopping heating of the CVD system, starting the tube furnace, rapidly cooling the quartz tube to room temperature in a room temperature environment, then closing the gas mass flow meters in the steps (2) and (3), taking out the nickel substrate, and obtaining the BCN monomolecular layer film on the surface of the nickel substrate.
Claims (4)
1. The preparation method of the boron-carbon-nitrogen film is characterized by comprising the following specific steps:
step (1), a copper film is taken as a substrate and is placed into a quartz tube in a chemical vapor deposition system;
step (2), ammonia borane is loaded into a quartz bubbler, one end of the bubbler is connected with carrier gas argon hydrogen, wherein the volume of hydrogen gas accounts for 50% -100%, the other end of the bubbler is connected with a chemical vapor deposition system, and ammonia borane vapor is loaded into the chemical vapor deposition system through the carrier gas; controlling the flow of a carrier gas carrying ammonia borane vapor by a gas mass flow meter, wherein the flow of the carrier gas is 10-50 sccm; heating a quartz bubbler filled with ammonia borane at the temperature of between 50 and 90 ℃;
step (3), introducing a mixed gas of methane and hydrogen, wherein the volume of the methane accounts for 5-25%, into a chemical vapor deposition system, and controlling the gas flow through a gas mass flow meter, wherein the flow of the mixed gas is 10-50 sccm;
step (4), closing the gas mass flow meters in the steps (2) and (3), starting a mechanical pump to vacuumize the chemical vapor deposition system, heating to 950-1050 ℃, and controlling the heating rate to be 20-30 ℃/min; after the temperature is increased to 950-1050 ℃, the temperature is kept for 30min, then the gas mass flow meters in the steps (2) and (3) are started simultaneously, and the chemical vapor deposition system keeps the temperature for 20-60 min;
and (6) stopping heating the chemical vapor deposition system, starting the tube furnace, cooling the quartz tube to room temperature in a room temperature environment, then closing the gas mass flow meters in the steps (2) and (3), taking out the copper substrate, and obtaining the BCN monomolecular layer film on the surface of the copper substrate.
2. The method for preparing a boron-carbon-nitrogen film as claimed in claim 1, wherein: the substrate was replaced with a nickel film.
3. The method for preparing a boron-carbon-nitrogen film as claimed in claim 1, wherein: the quartz tube is replaced by a corundum tube.
4. The method for preparing a boron-carbon-nitrogen film as claimed in claim 1, wherein: the size of the copper film is 1.0 multiplied by 1.0cm to 2.0 multiplied by 1.0 cm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110276691.8A CN113151803A (en) | 2021-03-15 | 2021-03-15 | Preparation method of boron-carbon-nitrogen film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110276691.8A CN113151803A (en) | 2021-03-15 | 2021-03-15 | Preparation method of boron-carbon-nitrogen film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113151803A true CN113151803A (en) | 2021-07-23 |
Family
ID=76887495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110276691.8A Pending CN113151803A (en) | 2021-03-15 | 2021-03-15 | Preparation method of boron-carbon-nitrogen film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113151803A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115261819A (en) * | 2022-07-25 | 2022-11-01 | 天津师范大学 | Preparation and analysis evaluation method of modified graphene protective film deposited on surface of string |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102285660A (en) * | 2010-06-21 | 2011-12-21 | 三星电子株式会社 | Graphene substituted with boron and nitrogen , method of fabricating the same, and transistor having the same |
| CN104480574A (en) * | 2014-10-30 | 2015-04-01 | 中国人民解放军国防科学技术大学 | Boron-carbon-nitrogen nano-paper and preparation method thereof |
| CN107706274A (en) * | 2017-10-25 | 2018-02-16 | 中国工程物理研究院电子工程研究所 | It is a kind of based on preparation method of the hexagonal boron nitride graphene composite bed as the epitaxy of gallium nitride structure of cushion |
| CN109161844A (en) * | 2018-08-03 | 2019-01-08 | 吉林大学 | A kind of boron carbon nitrogen film and preparation method thereof of the highly oriented boron nitride nanometer crystalline substance of envelope |
| CN109196139A (en) * | 2016-01-08 | 2019-01-11 | 南洋理工大学 | Boron nitride material and preparation method thereof |
| CN109920718A (en) * | 2017-12-13 | 2019-06-21 | 常州国成新材料科技有限公司 | A method of preparing graphene-boron nitride laminated film |
| CN111607775A (en) * | 2019-05-09 | 2020-09-01 | 中国科学院半导体研究所 | Method for preparing two-dimensional h-BNC hybrid film with adjustable components |
-
2021
- 2021-03-15 CN CN202110276691.8A patent/CN113151803A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102285660A (en) * | 2010-06-21 | 2011-12-21 | 三星电子株式会社 | Graphene substituted with boron and nitrogen , method of fabricating the same, and transistor having the same |
| CN104480574A (en) * | 2014-10-30 | 2015-04-01 | 中国人民解放军国防科学技术大学 | Boron-carbon-nitrogen nano-paper and preparation method thereof |
| CN109196139A (en) * | 2016-01-08 | 2019-01-11 | 南洋理工大学 | Boron nitride material and preparation method thereof |
| CN107706274A (en) * | 2017-10-25 | 2018-02-16 | 中国工程物理研究院电子工程研究所 | It is a kind of based on preparation method of the hexagonal boron nitride graphene composite bed as the epitaxy of gallium nitride structure of cushion |
| CN109920718A (en) * | 2017-12-13 | 2019-06-21 | 常州国成新材料科技有限公司 | A method of preparing graphene-boron nitride laminated film |
| CN109161844A (en) * | 2018-08-03 | 2019-01-08 | 吉林大学 | A kind of boron carbon nitrogen film and preparation method thereof of the highly oriented boron nitride nanometer crystalline substance of envelope |
| CN111607775A (en) * | 2019-05-09 | 2020-09-01 | 中国科学院半导体研究所 | Method for preparing two-dimensional h-BNC hybrid film with adjustable components |
Non-Patent Citations (1)
| Title |
|---|
| CHENG-KAI CHANG ET AL.: ""Band Gap Engineering of Chemical Vapor Deposited Graphene by in Situ BN Doping"", 《ACS NANO》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115261819A (en) * | 2022-07-25 | 2022-11-01 | 天津师范大学 | Preparation and analysis evaluation method of modified graphene protective film deposited on surface of string |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109267036B (en) | Preparation of tungsten ditelluride nanowire material and tungsten ditelluride nanowire material | |
| CN113832432B (en) | Preparation method of two-dimensional compound semiconductor film | |
| CN106087051B (en) | The preparation method and its equipment of synchronous growth wafer scale AB stacking bilayer graphene | |
| JP6190562B2 (en) | Graphene growth method | |
| CN104562195A (en) | Method for growing graphene | |
| US20220081300A1 (en) | Method for efficiently eliminating graphene wrinkles formed by chemical vapor deposition | |
| CN112359421B (en) | Method for preparing layered bismuth-oxygen-selenium semiconductor film by reverse airflow method | |
| CN103469155A (en) | Method for preparing high-purity high-density WO3/S core-shell structure nano-particles | |
| KR20140052517A (en) | Hexagonal boron nitride sheet, process for preparing the sheet and electronic device comprising the sheet | |
| CN113151803A (en) | Preparation method of boron-carbon-nitrogen film | |
| CN205188486U (en) | Two dimension nanometer film preparation device | |
| CN107161988B (en) | The method of nanocrystalline graphene is prepared on a sapphire substrate | |
| CN113322522B (en) | Preparation method of large-single-domain large-area single-layer tungsten disulfide film by epitaxy | |
| CN108588713A (en) | A kind of preparation method of two dimension phosphatization molybdenum film | |
| CN110323126B (en) | Preparation method of Si/SiC/graphene material | |
| CN111547711B (en) | Preparation method of silicon carbide-based distorted multilayer graphene material | |
| CN109830413B (en) | Preparation method of GaN micron rod array/graphene field emission cathode composite material | |
| CN103498191B (en) | High purity corynebacterium crystallization FeWO 4the preparation method of/FeS nanometer nuclear shell nano-structure | |
| CN112813496A (en) | Preparation method of highly oriented pyrolytic graphite | |
| CN115058700B (en) | Preparation method of molybdenum disulfide film and molybdenum disulfide film | |
| CN115613162B (en) | Composite fiber and preparation method thereof | |
| CN114059039B (en) | Neutron direct detection 10 Low-pressure chemical vapor deposition growth device and growth method for BN material | |
| CN115626639B (en) | Large-area boron nitride/graphene vertical heterojunction film and preparation method thereof | |
| CN110484893B (en) | Preparation method of metal nanowire core-shell structure | |
| CN116254517A (en) | Preparation method of large-area BNOX |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210723 |