CN114196937A - Hydrophilic amorphous carbon film and preparation method thereof - Google Patents

Hydrophilic amorphous carbon film and preparation method thereof Download PDF

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Publication number
CN114196937A
CN114196937A CN202111544750.1A CN202111544750A CN114196937A CN 114196937 A CN114196937 A CN 114196937A CN 202111544750 A CN202111544750 A CN 202111544750A CN 114196937 A CN114196937 A CN 114196937A
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carbon film
film
amorphous carbon
silicon
plasma
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吴春春
杨挺
王涛
张云飞
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ZJU Hangzhou Global Scientific and Technological Innovation Center
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ZJU Hangzhou Global Scientific and Technological Innovation Center
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0605—Carbon
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/221—Ion beam deposition
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5826—Treatment with charged particles
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5826—Treatment with charged particles
    • C23C14/5833—Ion beam bombardment
    • 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
    • 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
    • C23C16/56—After-treatment

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Carbon And Carbon Compounds (AREA)
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Abstract

The invention provides a hydrophilic amorphous carbon film and a preparation method thereof, and relates to a preparation technology of a metal coating material. The hydrophilic amorphous carbon film is a silicon-containing diamond-like carbon film, and the preparation method of the hydrophilic amorphous carbon film comprises the steps of doping silicon atoms in the amorphous carbon film, and then activating the film by plasma oxygen or oxygen ion beams. The invention overcomes the defects of the prior art, and the prepared film has excellent corrosion resistance and permanent hydrophilicity, so that the coating can be applied to the surface hydrophilic modification of three types of medical instruments.

Description

Hydrophilic amorphous carbon film and preparation method thereof
Technical Field
The invention relates to a preparation technology of a metal coating material, in particular to a hydrophilic amorphous carbon film and a preparation method thereof.
Background
Diamond-like carbon (DLC) film is a coating material used in various industrial fields because it has high hardness, lubricity, electrical resistance and good wear resistance, has a smooth surface, and can be synthesized at low temperature. In addition, the DLC film has excellent chemical stability of its surface, excellent biocompatibility and compatibility with blood, and causes no side effect when it is in contact with cells and the like in vivo.
Therefore, attempts have been made to use them as a bio-coating, for example, a surface layer of an insertion or replacement material for a living body, which requires a coating having a good hydrophilic property to prevent adhesion of a liquid (blood, etc.) on the surface and thus generation of thrombus.
At present, the diamond-like carbon film has poor hydrophilic performance, the contact angle is about 60 degrees, and the hydrophilic requirement of a third class of medical instruments is difficult to meet.
The method brings great challenges to the application of the coating, and the method is characterized in that the surface hydrophilicity of the carbon film is improved by activating the amorphous carbon film with plasma oxygen or nitrogen, but the duration of the activation is short, and the original hydrophilicity can be recovered after 24 hours.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a hydrophilic amorphous carbon film and a preparation method thereof. The corrosion resistance of the amorphous carbon film is improved by doping silicon, and the amorphous carbon film forms permanent hydrophilicity by activating oxygen atoms, so that the coating can be applied to surface hydrophilic modification of three types of medical instruments.
In order to achieve the above purpose, the technical scheme of the invention is realized by the following technical scheme:
a hydrophilic amorphous carbon film, which is a silicon-containing diamond-like carbon film containing a chemical bond of carbon atoms and silicon atoms present on the surface of the film, and the inside and the surface of the film contain silicon atoms that provide hydrophilicity to the surface of the film.
Preferably, the silicon content in the thin film ranges from 1.0 at.% to 2.5 at.%, and if the silicon content is too small, the corrosion resistance of the amorphous carbon film is low and the hydrophilicity of the surface tends to disappear, while if the silicon content exceeds 17 at.%, the size of the SiC cluster in the thin film is too large, resulting in deterioration of mechanical and chemical properties.
Preferably, the surface roughness of the thin film is 10nm to 20 nm.
Preferably, the Si-O bond proportion of the surface of the film is in the range of 30% to 60%.
The preparation method of the hydrophilic amorphous carbon film comprises the following steps:
(1) forming a thin film: doping silicon atoms into the diamond-like carbon film by using the substrate to form a silicon-doped diamond-like carbon film for later use;
(2) activation treatment: and activating the surface of the film by using plasma or ion beams to generate chemical bonds of carbon atoms and silicon atoms on the surface of the film.
Preferably, the raw material for forming the silicon-doped diamond-like carbon film in the step (1) is benzene gas and silane mixed.
Preferably, the method for preparing the silicon-doped diamond-like carbon film in the step (1) is any one or any combination of plasma chemical vapor deposition, plasma synthesis, sputtering synthesis, self-filtering arc synthesis or ion beam deposition.
Preferably, the pressure in the chamber during the plasma treatment in step (2) is in the range of 0.1Pa to 10Pa, and the bias voltage is in the range of-100V to-800V.
Preferably, when the ion beam is used to activate the surface of the film in the step (2), the pressure in the chamber is 10-7Pa-10Pa and 100V-50 kV.
Preferably, the plasma and the ion beam used in the step (2) are plasma oxygen and ion beam of oxygen, respectively.
The invention provides a hydrophilic amorphous carbon film and a preparation method thereof, and compared with the prior art, the hydrophilic amorphous carbon film has the advantages that:
the invention uses the silicon-doped DLC film with excellent corrosion resistance to replace a pure DLC film, the silicon-doped DLC film comprises silicon atoms in the form of clusters of several to dozens of nanometers, the clusters are distributed in and on the surface of the DLC film, compared with the DLC film, the invention can reduce the specific strain of the DLC film, improve the durability and the biocompatibility, and the plasma or ion beam containing oxygen excites the surface of the film to form Si-O bonds, and the oxygen atoms provide the hydrophilic performance of the coating, so that the contact angle range of the surface of the film is 0.5-20 degrees, and the good hydrophilicity is achieved.
Description of the drawings:
FIG. 1 is a photograph showing contact angles with water of samples according to various examples and comparative examples of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
preparing a silicon-doped amorphous carbon film:
(1) cleaning a glass slide substrate for 20 minutes by using an ultrasonic cleaning agent, then installing the glass slide substrate on an electrode in a vacuum reaction chamber, and cooling the glass slide substrate with water;
(2) the inside of the reaction chamber is maintained at 10 by a vacuum pump-5Introducing argon gas into the reaction chamber in vacuum, and then dry-cleaning the substrate with plasma generated by applying-400V of radio wave power to the electrodes;
(3) benzene (C)6H6) Gas and Silane (SiH)4) A gas flow ratio of 20: 1 was introduced into the chamber interior so that the Si content in the film to be formed was 1.2 at%, and then radio wave power was applied to form a Si-doped amorphous carbon film.
(4) Surface activation of the silicon-doped thin film: and putting the Si-doped amorphous film into a reactor, and then treating the surface of the Si-doped amorphous film for 10 minutes by using oxygen plasma, wherein the bias voltage in the plasma treatment is-100V, and the pressure is 10Pa, so that the activated silicon-doped amorphous carbon film is obtained.
Example 2:
preparing a silicon-doped amorphous carbon film:
(1) cleaning a glass slide substrate for 20 minutes by using an ultrasonic cleaning agent, then installing the glass slide substrate on an electrode in a vacuum reaction chamber, and cooling the glass slide substrate with water;
(2) the inside of the reaction chamber is maintained at 10 by a vacuum pump-5Introducing argon gas into the reaction chamber in vacuum, and then dry-cleaning the substrate with plasma generated by applying-400V of radio wave power to the electrodes;
(3) benzene (C)6H6) Gas and Silane (SiH)4) A gas flow ratio of 5: 1 was introduced into the chamber interior so that the Si content in the film to be formed was 17 at%, and then radio wave power was applied to form a Si-doped amorphous carbon film.
(4) Surface activation of the silicon-doped thin film: and putting the Si-doped amorphous film into a reactor, and then treating the surface of the Si-doped amorphous film for 10 minutes by using oxygen plasma, wherein the bias voltage in the plasma treatment is-800V, and the pressure is 1.33Pa, so that the activated silicon-doped amorphous carbon film is obtained.
Comparative example:
preparing an amorphous carbon film:
(1) cleaning a glass slide substrate for 20 minutes by using an ultrasonic cleaning agent, then installing the glass slide substrate on an electrode in a vacuum reaction chamber, and cooling the glass slide substrate with water;
(2) the inside of the reaction chamber is maintained at 10 by a vacuum pump-5Introducing argon gas into the reaction chamber in vacuum, and then dry-cleaning the substrate with plasma generated by applying-400V of radio wave power to the electrodes;
(3) benzene (C)6H6) Introducing gas into the chamber, and depositing to form a pure amorphous carbon film;
(4) surface activation of amorphous carbon film: and (3) putting the amorphous film into a reactor, and then treating the surface of the amorphous film for 10 minutes by using oxygen plasma, wherein the bias voltage in the plasma treatment is-800V, and the pressure is 1.33Pa, so that the finished amorphous carbon film is obtained.
And (3) detection:
the contact angle test was performed on the films obtained in the above examples 1-2 and comparative examples after 1h and 48h respectively by using a contact angle tester, and the results are shown in fig. 1, and it can be seen that after 1h of activation by oxygen atoms, the contact angles of the silicon-doped amorphous carbon film (fig. 1A) and the pure amorphous carbon film (fig. 1C) to water were 4 ° and 7 °, respectively, and after 48h of activation, the contact angle of the silicon-doped amorphous carbon film (fig. 1B) was 6.6 °, and the contact angle of the undoped amorphous carbon film was recovered to 64 °, i.e., the silicon-containing diamond-like carbon film prepared in the present application had long-lasting hydrophilic properties.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. A hydrophilic amorphous carbon film is characterized in that the hydrophilic amorphous carbon film is a silicon-containing diamond-like carbon film.
2. A hydrophilic amorphous carbon film according to claim 1, wherein: the silicon content in the thin film ranges from 1.0 at.% to 2.5 at.%.
3. A hydrophilic amorphous carbon film according to claim 1, wherein: the film surface roughness is 10nm to 20 nm.
4. A hydrophilic amorphous carbon film according to claim 1, wherein: the Si-O bond proportion of the surface of the film is 30-60%.
5. A method for preparing a hydrophilic amorphous carbon film is characterized by comprising the following steps: the preparation method of the hydrophilic amorphous carbon film comprises the following steps:
(1) forming a thin film: doping silicon atoms into the diamond-like carbon film by using the substrate to form a silicon-doped diamond-like carbon film for later use;
(2) activation treatment: and activating the surface of the film by using plasma or ion beams to generate chemical bonds of carbon atoms and silicon atoms on the surface of the film.
6. The method of claim 5, wherein: the raw material for forming the silicon-doped diamond-like carbon film in the step (1) is benzene gas and silane mixed.
7. The method of claim 5, wherein: the preparation method of the silicon-doped diamond-like carbon film in the step (1) is any one or any combination of plasma chemical vapor deposition, plasma synthesis, sputtering synthesis, self-filtering arc synthesis or ion beam deposition.
8. The method of claim 5, wherein: and (3) when the plasma is adopted for treatment in the step (2), the pressure range in the chamber is 0.1Pa to 10Pa, and the bias voltage range is-100V to-800V.
9. The method of claim 5, wherein: when the ion beam is adopted to activate the surface of the film in the step (2), the pressure in the cavity is 10-7Pa-10Pa and 100V-50 kV.
10. The method of claim 5, wherein: the plasma and the ion beam adopted in the step (2) are plasma oxygen and ion beam of oxygen respectively.
CN202111544750.1A 2021-12-16 2021-12-16 Hydrophilic amorphous carbon film and preparation method thereof Pending CN114196937A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030035444A (en) * 2001-10-31 2003-05-09 한국과학기술연구원 Silicon incorporated tetrahedral amorphous carbon film and preparation method thereof
CN101109064A (en) * 2007-08-15 2008-01-23 中国航天科技集团公司第五研究院第五一○研究所 Method of plating-manufacturing silicon doped non-hydrogen diamond membrane
CN101619455A (en) * 2008-07-03 2010-01-06 中国科学院兰州化学物理研究所 Super lubricating Si-doped diamond film preparation method
US20120190114A1 (en) * 2009-10-08 2012-07-26 Korea Institute Of Science And Technology Silicon-incorporated diamond-like carbon film, fabrication method thereof, and its use
CN104947037A (en) * 2015-05-30 2015-09-30 中国科学院宁波材料技术与工程研究所 Doped diamond-like film and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030035444A (en) * 2001-10-31 2003-05-09 한국과학기술연구원 Silicon incorporated tetrahedral amorphous carbon film and preparation method thereof
CN101109064A (en) * 2007-08-15 2008-01-23 中国航天科技集团公司第五研究院第五一○研究所 Method of plating-manufacturing silicon doped non-hydrogen diamond membrane
CN101619455A (en) * 2008-07-03 2010-01-06 中国科学院兰州化学物理研究所 Super lubricating Si-doped diamond film preparation method
US20120190114A1 (en) * 2009-10-08 2012-07-26 Korea Institute Of Science And Technology Silicon-incorporated diamond-like carbon film, fabrication method thereof, and its use
CN104947037A (en) * 2015-05-30 2015-09-30 中国科学院宁波材料技术与工程研究所 Doped diamond-like film and preparation method thereof

Non-Patent Citations (1)

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Title
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