CN116219369A - Method for preparing boron carbide film by evaporation - Google Patents

Method for preparing boron carbide film by evaporation Download PDF

Info

Publication number
CN116219369A
CN116219369A CN202310223326.XA CN202310223326A CN116219369A CN 116219369 A CN116219369 A CN 116219369A CN 202310223326 A CN202310223326 A CN 202310223326A CN 116219369 A CN116219369 A CN 116219369A
Authority
CN
China
Prior art keywords
boron
boron carbide
evaporation
gas
inert gas
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
Application number
CN202310223326.XA
Other languages
Chinese (zh)
Inventor
戴辉
刘克武
尹士平
郭晨光
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.)
Anhui Guangzhi Technology Co Ltd
Original Assignee
Anhui Guangzhi Technology Co Ltd
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 Anhui Guangzhi Technology Co Ltd filed Critical Anhui Guangzhi Technology Co Ltd
Priority to CN202310223326.XA priority Critical patent/CN116219369A/en
Publication of CN116219369A publication Critical patent/CN116219369A/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24Vacuum evaporation
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021Reactive sputtering or evaporation
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0635Carbides
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention belongs to the field of vacuum coating, and discloses a method for preparing a boron carbide film by evaporation. The method comprises the following steps: placing boron powder into a crucible of an evaporation coating machine, and placing the cleaned and dried substrate above the crucible in the evaporation coating machine; and vacuumizing the evaporation coating machine, starting an electron gun to melt and evaporate the boron powder by using a high-energy electron beam, starting an ion source, using mixed gas of heavy inert gas and carbon source gas as the ion source, generating heavy inert gas ions and carbon ions by glow discharge, and reacting the high-energy carbon ions after ionization with the evaporated boron to generate the boron carbide film. The method can prepare the boron carbide film at low temperature, and avoids the limitation caused by the need of high-temperature plating in the chemical vapor deposition method. Meanwhile, the method can be applied to an evaporator to realize continuous completion of the infrared antireflection film and the boron carbide protective film.

Description

Method for preparing boron carbide film by evaporation
Technical Field
The invention belongs to the field of vacuum coating, and particularly relates to a method for preparing a boron carbide film by evaporation.
Background
Boron carbide (B) 4 C) Is one of the hardest superhard materials in nature, and has hardness inferior to that of diamond. Boron carbide has wide application prospect in the fields of machinery, electronics, coating films and the like by virtue of excellent physical properties. The boron carbide film has high permeability in an infrared spectrum region; the advantages of high melting point, low density, high damage threshold and the like are thatAn ideal protective material for infrared optical lenses.
The preparation method of the boron carbide film mainly comprises a Chemical Vapor Deposition (CVD) method and a Physical Vapor Deposition (PVD) method, wherein the chemical vapor deposition method is used for depositing a film at a very high temperature (about 1000 ℃), and many substrates cannot be deposited at the very high temperature, so that the selection range of substrate materials is limited. Physical Vapor Deposition (PVD) includes magnetron sputtering, reactive sputtering, etc., which can be performed at a relatively low substrate temperature, but most of the deposited boron carbide films are amorphous, difficult to realize crystalline structures, and not sufficiently high in hardness.
Chinese patent publication No. CN101314842a discloses a method for preparing boron carbide film by electron beam evaporation technique. The method can prepare amorphous boron carbide films, boron carbide films with polycrystalline structures, boron carbide films with different B, C component proportions, and the prepared boron carbide films have smooth surfaces, compact films and good uniformity. However, the method needs to obtain the boron carbide material in advance, and the boron carbide material is sintered at a high temperature of 1400-1600 ℃ in the preparation process, so that the mixed uniformity of carbon and boron is poor, and elemental carbon or boron is generated during evaporation coating instead of the compound of the elemental carbon and the boron, thereby influencing the performance of the finally prepared boron carbide film.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for preparing a boron carbide film by evaporation, which can prepare the boron carbide film at low temperature and avoid the limitation caused by the need of high-temperature plating in a Chemical Vapor Deposition (CVD) method. Meanwhile, the method can be applied to an evaporator to realize continuous completion of the infrared antireflection film and the boron carbide protective film.
In order to achieve the purpose of the invention, the specific technical scheme is as follows:
a method for preparing a boron carbide film by evaporation, comprising the following steps:
placing boron powder into a crucible of an evaporation coating machine, and placing the cleaned and dried substrate above the crucible in the evaporation coating machine; and vacuumizing the evaporation coating machine, starting an electron gun to melt and evaporate the boron powder by using a high-energy electron beam, starting an ion source, using mixed gas of heavy inert gas and carbon source gas as the ion source, generating heavy inert gas ions and carbon ions by glow discharge, and reacting the high-energy carbon ions after ionization with the evaporated boron to generate the boron carbide film.
Preferably, the purity of the boron powder is not less than 99.9%.
Preferably, the heavy inert gas is at least one of helium, neon, argon, krypton and xenon; the carbon source gas is at least one of methane, butane and acetylene; the substrate is one of a silicon substrate, a germanium substrate, a zinc sulfide substrate or a zinc selenide substrate.
Preferably, helium is selected as the heavy inert gas; and the carbon source gas is methane.
Preferably, the ion source used is a hall source.
Preferably, in the mixed gas used by the ion source, the volume ratio of the heavy inert gas is 1% -20%, and the volume ratio of the carbon source gas is 80% -99%.
Preferably, the evaporation coating machine is vacuumized to a vacuum degree of 2.0 x 10 -3 Pa or below.
Preferably, the temperature of the substrate is controlled to be 130-200 ℃ during film coating.
Preferably, the evaporation rate of the boron powder after melting is set to 2-10 angstroms per second.
Preferably, the ion source parameter is; the neutralization current is 0.3-0.6A, the neutralization gas flow is 5-8 sccm, the anode voltage is 110-200V, and the anode current is 1.5-3A.
Compared with the prior art, the invention has the beneficial effects that:
according to the technical scheme, the boron carbide film can be prepared at low temperature, and the limitation caused by the high-temperature plating required by a Chemical Vapor Deposition (CVD) method is avoided. Meanwhile, the method can be applied to an evaporator to realize continuous completion of the infrared antireflection film and the boron carbide protective film.
The invention does not need to prefabricate the boron carbide film material in advance, the film plating process is completed by adopting full chemical reaction, and no elemental material exists.
Detailed Description
The present invention will be described more fully hereinafter with reference to the preferred embodiments for the purpose of facilitating understanding of the present invention, but the scope of protection of the present invention is not limited to the specific embodiments described below.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1
The embodiment provides a method for preparing a boron carbide film by evaporation, which comprises the following steps:
(1) The germanium sheet with the thickness of 2 mm and the diameter of 25 mm is dried after ultrasonic cleaning, so that the film stripping caused by dirt on the surface of the lens is avoided;
(2) Placing boron powder with purity not less than 99.9% into a crucible of an evaporation coating machine, placing the cleaned germanium sheet into a fixture of the evaporation coating machine, adjusting the position to be right above an opening of the crucible, and vacuumizing the cavity to 2.0x10 -3 Setting the heating temperature of the coating to 150 ℃ below Pa pressure;
(3) Starting an electron gun to melt boron powder after the vacuum and the temperature reach, slowly increasing the beam current of the electron gun from 0 watt to 300 watt, avoiding the film material from splashing due to the instant rise of the temperature when the power is increased too fast, and setting the evaporation rate to 2 angstrom per second after the boron powder is melted;
(4) Starting an ion source (Hall source) while evaporating boron powder, setting parameters of 0.3A of neutralization current, 5sccm of neutralization gas flow, 180V of anode voltage and 2A of anode current, and setting the gas inlet ratio of the ion source to methane with the volume ratio of 90% and argon with the volume ratio of 10%;
(5) The thickness of the boron carbide film is determined according to the coating speed multiplied by the time, and the embodiment is provided with: the 2 angstrom rate lasts for 1 kilosecond, and a boron carbide film with the thickness of 200 nanometers is obtained;
(6) And standing for 20 minutes after coating is completed, cooling, releasing stress, and taking out the germanium sheet to obtain the boron carbide film with corresponding thickness.
Example 2
The embodiment provides a method for preparing a boron carbide film by evaporation, which comprises the following steps:
(1) A silicon wafer with the thickness of 2 mm and the diameter of 25 mm is wiped clean by polishing solution, acetone and alcohol, so that the surface of a lens is prevented from being stained to cause stripping;
(2) Placing boron powder with purity not less than 99.9% into a crucible of an evaporation coating machine, placing the cleaned silicon wafer into a working fixture of the evaporation coating machine, adjusting the position to be right above an opening of the crucible, and vacuumizing the cavity to 1.5 x 10 -3 Setting the heating temperature of the coating to 160 ℃ below Pa pressure;
(3) And after the vacuum and the temperature reach, an electron gun is started to melt boron powder, the beam current of the electron gun is slowly increased from 0 watt to 300 watt, and the phenomenon that the film material is splashed due to the instant rising of the temperature when the power is increased too fast is avoided. Setting the evaporation rate to 3 angstroms per second after the boron powder is melted;
(4) The boron powder is evaporated, meanwhile, the ion source is started to set parameters of 0.5 ampere of neutralization current, 8sccm of neutralization gas flow, 200 volts of anode voltage and 2.4 amperes of anode current, and the ion source gas is set to be introduced with the proportion of methane of 95% and argon of 5%;
(5) The thickness of the boron carbide film is determined according to the coating speed multiplied by the time, and the embodiment is provided with: the 3 angstrom rate lasts for 1 kilosecond, and a boron carbide film with the thickness of 300 nanometers is obtained;
(6) And standing for 30 minutes after coating is completed, cooling, releasing stress, and taking out the silicon wafer to obtain the boron carbide film with corresponding thickness.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. A method for preparing a boron carbide film by evaporation, which is characterized by comprising the following steps:
placing boron powder into a crucible of an evaporation coating machine, and placing the cleaned and dried substrate above the crucible in the evaporation coating machine; and vacuumizing the evaporation coating machine, starting an electron gun to melt and evaporate the boron powder by using a high-energy electron beam, starting an ion source, using mixed gas of heavy inert gas and carbon source gas as the ion source, generating heavy inert gas ions and carbon ions by glow discharge, and reacting the high-energy carbon ions after ionization with the evaporated boron to generate the boron carbide film.
2. The method of claim 1, wherein the boron powder has a purity of not less than 99.9%.
3. The method of claim 1, wherein the heavy inert gas is selected from at least one of helium, neon, argon, krypton, xenon; the carbon source gas is at least one of methane, butane and acetylene; the substrate is one of a silicon substrate, a germanium substrate, a zinc sulfide substrate or a zinc selenide substrate.
4. The method of claim 1, wherein the heavy inert gas is helium; and the carbon source gas is methane.
5. The method of claim 1, wherein the ion source used is a hall source.
6. The method according to any one of claims 1 to 5, wherein the mixed gas used in the ion source has a weight of 1% to 20% by volume of inert gas and a carbon source gas of 80% to 99% by volume of inert gas.
7. The method of claim 1, wherein the evaporation coater is evacuated to a vacuum level of 2.0 x 10 -3 Pa or below.
8. The method of claim 1, wherein the substrate temperature is controlled to be 130-200 ℃ during the coating.
9. The method of claim 1, wherein the boron powder is melted and evaporated at a rate of 2 to 10 angstroms per second.
10. The method of claim 1, wherein the ion source parameter is; the neutralization current is 0.3-0.6A, the neutralization gas flow is 5-8 sccm, the anode voltage is 110-200V, and the anode current is 1.5-3A.
CN202310223326.XA 2023-03-09 2023-03-09 Method for preparing boron carbide film by evaporation Pending CN116219369A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310223326.XA CN116219369A (en) 2023-03-09 2023-03-09 Method for preparing boron carbide film by evaporation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310223326.XA CN116219369A (en) 2023-03-09 2023-03-09 Method for preparing boron carbide film by evaporation

Publications (1)

Publication Number Publication Date
CN116219369A true CN116219369A (en) 2023-06-06

Family

ID=86585488

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310223326.XA Pending CN116219369A (en) 2023-03-09 2023-03-09 Method for preparing boron carbide film by evaporation

Country Status (1)

Country Link
CN (1) CN116219369A (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001106585A (en) * 1999-08-03 2001-04-17 Ion Engineering Research Institute Corp Treating method for improving resistance to oxidation at high temperature of carbon material
CN1653867A (en) * 2002-05-08 2005-08-10 达纳公司 Plasma-assisted coating
CN105543803A (en) * 2015-12-16 2016-05-04 中国科学院深圳先进技术研究院 Diamond/boron carbide composite coating of hard alloy substrate and preparation method thereof
CN114481030A (en) * 2022-01-26 2022-05-13 苏州闻道电子科技有限公司 Solid neutron conversion layer and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001106585A (en) * 1999-08-03 2001-04-17 Ion Engineering Research Institute Corp Treating method for improving resistance to oxidation at high temperature of carbon material
CN1653867A (en) * 2002-05-08 2005-08-10 达纳公司 Plasma-assisted coating
CN105543803A (en) * 2015-12-16 2016-05-04 中国科学院深圳先进技术研究院 Diamond/boron carbide composite coating of hard alloy substrate and preparation method thereof
CN114481030A (en) * 2022-01-26 2022-05-13 苏州闻道电子科技有限公司 Solid neutron conversion layer and preparation method and application thereof

Similar Documents

Publication Publication Date Title
US5723188A (en) Process for producing layers of cubic boron nitride
CN107142463A (en) A kind of plasma activated chemical vapour deposition and magnetron sputtering or the compound coating method of ion plating
GB2171726A (en) A method for reactive evaporation deposition of layers of oxides nitrides oxynitrides and carbides
KR20150053959A (en) Method for manufacturing a metal-borocarbide layer on a substrate
CN113832430A (en) Preparation method of diamond-based amorphous carbon-yttrium oxide gradient composite antireflection film
EP4419726A1 (en) Method for forming hard and ultra-smooth a-c by sputtering
CN105951051A (en) Method of preparing graded refractive index antireflection film by adopting oblique sputtering process
Moll et al. Activated reactive ion plating (ARIP)
EP1239056A1 (en) Improvement of a method and apparatus for thin film deposition, especially in reactive conditions
CN116219369A (en) Method for preparing boron carbide film by evaporation
Martin Ionization-assisted evaporative processes: techniques and film properties
CN114540779B (en) Composite cathode, magnetron sputtering coating equipment and coating method
CN113151797B (en) Ion cleaning process based on ta-C film plated on surface of hard alloy
Pulker Ion plating as an industrial manufacturing method
WO2002070776A1 (en) Deposition process
KR20150076467A (en) Aluminum coating layer with controllable structure and the method thereof
CN111647859A (en) Preparation process of Zr-Ti-B-N nano composite coating in reducing atmosphere
CN109957757B (en) Method for preparing ultra-thick Ti-Al-C ternary coating by two-step PVD (physical vapor deposition) technology
CN108411265A (en) A kind of preparation method of low stress dense coating
US4089990A (en) Battery plate and method of making
Degout et al. High current density triode magnetron sputtering
CN101153379A (en) Method for producing transparent Mgo film and obtained product
CN112831769B (en) Composite antireflection film for infrared optical product and preparation method thereof
CN118516649A (en) Method for preparing nanocrystalline WC film by magnetron sputtering pure WC compound target material
US8568905B2 (en) Housing and method for making the same

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