CN116479398A - Diamond film and preparation method thereof - Google Patents
Diamond film and preparation method thereof Download PDFInfo
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- CN116479398A CN116479398A CN202310488614.8A CN202310488614A CN116479398A CN 116479398 A CN116479398 A CN 116479398A CN 202310488614 A CN202310488614 A CN 202310488614A CN 116479398 A CN116479398 A CN 116479398A
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- diamond film
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- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 161
- 239000010432 diamond Substances 0.000 title claims abstract description 161
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 54
- 239000011701 zinc Substances 0.000 claims abstract description 52
- 239000000758 substrate Substances 0.000 claims abstract description 43
- 230000007704 transition Effects 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims description 19
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 238000010884 ion-beam technique Methods 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 abstract description 9
- 230000001070 adhesive effect Effects 0.000 abstract description 9
- 238000002834 transmittance Methods 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 230000008646 thermal stress Effects 0.000 abstract description 5
- 238000009835 boiling Methods 0.000 abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 22
- 238000000576 coating method Methods 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 238000000151 deposition Methods 0.000 description 13
- 239000011787 zinc oxide Substances 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 230000006872 improvement Effects 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000004050 hot filament vapor deposition Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000002131 composite material Substances 0.000 description 4
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000013077 target material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021423 nanocrystalline silicon Inorganic materials 0.000 description 1
- 239000002113 nanodiamond Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
-
- 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
- C23C14/0611—Diamond
-
- 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
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron 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
- C23C14/5806—Thermal treatment
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5873—Removal of material
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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
- C23C16/27—Diamond only
- C23C16/271—Diamond only using hot filaments
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- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention relates to the technical field of diamond films, in particular to a diamond film and a preparation method thereof, wherein the preparation method comprises the following steps: s1, preparing a layer of zinc-doped diamond film on the surface of a substrate; s2, carrying out high-temperature treatment on the zinc-doped diamond film in an inert atmosphere to evaporate part of zinc to form a porous structure, so as to obtain the zinc-doped porous diamond film; s3, preparing a layer of pure diamond film on the surface of the zinc-doped porous diamond film. According to the invention, zinc is doped in the diamond film by utilizing the characteristic of relatively low boiling point of zinc, part of zinc can be evaporated by heating to form a porous structure, and the porous structure is used as a transition layer, so that the thermal stress can be released by utilizing the porous structure, and the influence of the difference of thermal expansion coefficients between a substrate and the diamond film can be relieved, thereby remarkably improving the adhesive force, the hardness and the wear-resistant service life of the diamond film, and having good light transmittance.
Description
Technical Field
The invention relates to the technical field of diamond films, in particular to a diamond film and a preparation method thereof.
Background
The diamond film is a surface functional material with various excellent performances such as high hardness, low friction coefficient, high wear resistance and corrosion resistance, wide light transmission range, excellent biocompatibility and the like. Therefore, the diamond film has great application potential in the fields of marine ship industry, aerospace engineering, automobiles, printing, biological medicine and the like. Coating adhesion and surface finish are major factors affecting the apparent performance of CVD diamond coatings in wear-resistant antifriction devices. The difference of the thermal expansion coefficient and lattice constant of diamond and the matrix material causes certain internal stress of the deposited diamond coating, so that the coating adhesive force is reduced and the coating is easy to fall off. Because the temperature of the substrate is high, about 850 ℃ when the CVD method is used for depositing the diamond film, the thermal expansion coefficient of the diamond is smaller and is generally only 1/3-1/4 of that of the substrate material, and larger internal stress can be generated in the coating after cooling shrinkage. Reducing thermal stress between the diamond film and the substrate by the transition layer is an effective means.
For example, patent CN201911017635.1 discloses a method for preparing a tungsten carbide transition layer-silicon doped diamond composite coating on a steel substrate. Aiming at low carbon steel, low alloy steel and the like as matrixes, firstly adopting a Plasma Enhanced Chemical Vapor Deposition (PECVD) method to deposit a nano tungsten carbide coating, then adopting a hot wire chemical vapor deposition method to deposit a nanocrystalline silicon doped diamond coating on the tungsten carbide coating to form a double-layer transition layer, and then depositing an intrinsic micron or nano diamond coating on the surface of the silicon doped diamond coating. The method solves the problem that the CVD diamond coating cannot be directly deposited due to the overlarge difference between the thermal expansion coefficient of the steel matrix and that of diamond, so that the steel matrix can be used for replacing the conventional hard alloy to deposit the diamond coating. However, this method requires two transition layers, too many deposition interfaces can reduce film stability, and tungsten carbide results in lower transparency.
In view of the foregoing, there is a need for an improved diamond film and method of making the same that addresses the above-described problems.
Disclosure of Invention
The invention aims to provide a diamond film and a preparation method thereof, wherein a layer of porous diamond film or a zinc oxide doped porous diamond film is prepared between a substrate and the diamond film as a transition layer, and the porous structure can be utilized to release thermal stress, so that the influence of the difference of thermal expansion coefficients between the substrate and the diamond film is relieved, the adhesive force, the hardness and the wear-resistant service life of the diamond film are obviously improved, and the diamond film has good light transmittance.
In order to achieve the above object, the present invention provides a method for preparing a diamond film, comprising the steps of:
s1, preparing a layer of zinc-doped diamond film on the surface of a substrate;
s2, carrying out high-temperature treatment on the zinc-doped diamond film in an inert atmosphere to evaporate part of zinc to form a porous structure, so as to obtain the zinc-doped porous diamond film;
s3, preparing a layer of pure diamond film on the surface of the zinc-doped porous diamond film.
As a further improvement of the present invention, step S2 further includes: and (3) performing thermal oxidation treatment on the zinc-doped porous diamond film to obtain a zinc oxide-doped porous diamond film, and performing step S3.
As a further improvement of the present invention, the thermal oxygen treatment includes: treating in air at 200-400 deg.c for 1-3 hr;
or treating for 1-3h in an atmosphere with the volume ratio of oxygen to nitrogen of 10% -90% -30% -70% and at the temperature of 200-400 ℃.
As a further improvement of the invention, the molar content of zinc atoms in the zinc-doped diamond film is 0.1% -10%; the evaporated zinc in the high temperature treatment accounts for 1% -99% of the original doped zinc.
As a further improvement of the invention, the molar content of zinc atoms in the zinc-doped diamond film is 2% -6%; the evaporated zinc in the high temperature treatment accounts for 10% -80% of the original doped zinc.
As a further improvement of the invention, the temperature of the high-temperature treatment is 910-1100 ℃, and the inert atmosphere is nitrogen or helium.
As a further improvement of the invention, the zinc-doped porous diamond film is obtained by one or more methods of linear ion beam, magnetron sputtering and vacuum cathode arc;
and/or the substrate is a silicate substrate, a silicon carbide substrate, a silicon nitride substrate or a monocrystalline silicon substrate, and the substrate temperature is 700-900 ℃.
As a further improvement of the invention, the thickness of the zinc-doped porous diamond film is 0.05-5 mu m, and the thickness of the diamond film is 0.05-10 mu m.
Further, the invention also provides a diamond film, which comprises a substrate, a transition layer and a diamond film; the transition layer is a zinc-doped porous diamond film or a zinc oxide-doped porous diamond film.
As a further improvement of the present invention, the diamond film is produced by the production method according to any one of claims 1 to 8.
The beneficial effects of the invention are as follows:
1. according to the preparation method of the diamond film, the porous diamond film or the zinc oxide doped porous diamond film is prepared between the substrate and the diamond film to serve as the transition layer, the porous structure can be used for releasing thermal stress, and the influence of the difference of thermal expansion coefficients between the substrate and the diamond film is relieved, so that the adhesive force, the hardness and the wear-resistant service life of the diamond film are remarkably improved, and the diamond film has good light transmittance.
2. The invention utilizes the characteristic of low boiling point of zinc, and can remove part of zinc to form a porous structure by heating, and the preparation method is simple. And more free space can be provided for thermal expansion by utilizing the multiple holes, and the thermal expansion coefficients of zinc or zinc oxide, a substrate and a diamond film are regulated and controlled by regulating and controlling the contents of the zinc or zinc oxide and the substrate and the diamond film, so that the adhesive force of the diamond film is improved.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a diamond film, which comprises a substrate, a transition layer and a diamond film; the transition layer is a zinc-doped porous diamond film or a zinc oxide-doped porous diamond film.
Further, the invention provides a preparation method of the diamond film, which comprises the following steps:
s1, preparing a layer of zinc-doped diamond film on the surface of a substrate;
s2, carrying out high-temperature treatment on the zinc-doped diamond film in an inert atmosphere to evaporate part of zinc to form a porous structure, so as to obtain the zinc-doped porous diamond film;
s3, preparing a layer of pure diamond film on the surface of the zinc-doped porous diamond film.
On the one hand, the thermal expansion coefficient of zinc is different from that of the substrate and the diamond film, so that the thermal expansion coefficient between layers can be adjusted; on the other hand, the formed porous structure can provide more free space for thermal expansion, so that the adhesive force of the porous structure on the substrate is high, and the adhesive force of the diamond film on the surface of the porous structure is improved; in addition, the porous structure can be formed only by heating, and the method is simple and easy to operate.
Preferably, step S2 further comprises: and (3) performing thermal oxidation treatment on the zinc-doped porous diamond film to obtain a zinc oxide-doped porous diamond film, and performing step S3. The thermal expansion coefficient of zinc oxide is changed, the doped zinc or zinc oxide can be selected according to the type of the substrate and the actual requirement, and the flexibility is high. Furthermore, during oxidation, the incorporation of oxygen atoms can provide a certain adjustment of the porous structure and thus the structure of the transition layer.
The thermal oxygen treatment includes: treating in air at 200-400 deg.c for 1-3 hr;
or treating for 1-3h in an atmosphere with the volume ratio of oxygen to nitrogen of 10% -90% -30% -70% and at the temperature of 200-400 ℃. Preferably at 200-300 ℃. Zinc and oxygen undergo oxidation reaction under the action of heat to produce zinc oxide. Since the diamond film itself is resistant to high temperatures, the heat treatment of the present invention does not affect the diamond film itself. It can be seen that the present invention ingeniously utilizes the respective characteristics of diamond film and zinc.
The molar content of zinc atoms in the zinc-doped diamond film is 0.1% -10%, preferably 2% -6%. The doping amount of zinc is not easy to be excessive so as not to influence the integrity of the diamond film.
The high temperature treatment evaporates from 1% to 99%, preferably from 10% to 80% of the original doped zinc. The structure of the transition layer is adjusted by the porosity and the residual zinc content to optimize its adhesion.
The temperature of the high-temperature treatment is 910-1100 ℃, and the inert atmosphere is nitrogen or helium. The high temperature treatment temperature is above the boiling point of zinc to evaporate the zinc.
The zinc-doped diamond film is obtained by one or more methods of linear ion beam, magnetron sputtering and vacuum cathode arc.
The substrate is a silicate substrate, a silicon carbide substrate, a silicon nitride substrate or a monocrystalline silicon substrate, and the temperature of the substrate is 700-900 ℃; the thickness of the diamond film is 0.05-5 mu m; the thickness of the diamond film is 0.05-10 mu m.
Example 1
A diamond film prepared by the steps of:
s1, preparing a zinc-doped diamond film with the thickness of 0.6 mu m on the surface of a silicon nitride substrate by adopting a linear ion beam composite magnetron sputtering technology:
the magnetron sputtering source is provided with a zinc target material for depositing metallic zinc, a carbon-containing air source is introduced into the linear ion beam source for depositing the diamond film, and the magnetron sputtering source and the linear ion source are simultaneously started in the film plating process, so that the deposition of the zinc-doped diamond film is realized. Wherein the molar content of zinc is 4%.
S2, treating the zinc-doped diamond film in an inert atmosphere at 950 ℃ to remove 40% of the zinc-doped diamond film in a controlled manner, so as to obtain a zinc-doped porous diamond film;
s3, preparing a layer of pure diamond film with the thickness of 2 mu m on the surface of the zinc-doped porous diamond film by taking hydrogen and methane as raw materials through hot wire chemical vapor deposition. The hot filament chemical vapor deposition conditions were: the reaction chamber is vacuumized to be below 10Pa, methane with 20sccm and hydrogen with 500sccm are introduced, and the air pressure in the reaction chamber is controlled to be 1800Pa until the voltage of the heating wire is stable. 10sccm of methane, 100sccm of hydrogen and 92sccm of argon were introduced, and the pressure in the reaction chamber was controlled at 1300Pa to perform deposition.
Example 2
A diamond film prepared by the steps of:
s1, preparing a zinc-doped diamond film with the thickness of 0.6 mu m on the surface of a silicon nitride substrate by adopting a linear ion beam composite magnetron sputtering technology:
the magnetron sputtering source is provided with a zinc target material for depositing metallic zinc, a carbon-containing air source is introduced into the linear ion beam source for depositing the diamond film, and the magnetron sputtering source and the linear ion source are simultaneously started in the film plating process, so that the deposition of the zinc-doped diamond film is realized. Wherein the molar content of zinc is 4%.
S2, treating the zinc-doped diamond film in an inert atmosphere at 950 ℃ to remove 40% of the zinc-doped diamond film in a controlled manner, so as to obtain a zinc-doped porous diamond film; then, treating for 1h in air at 300 ℃ to obtain a zinc oxide doped porous diamond film;
s3, preparing a layer of pure diamond film with the thickness of 2 mu m on the surface of the zinc oxide doped porous diamond film by taking hydrogen and methane as raw materials through hot wire chemical vapor deposition.
Example 3
A diamond film was different from example 1 in that the molar content of zinc in step S1 was 0.2%. The other components are the same as those in embodiment 1, and will not be described in detail here.
Example 4
A diamond film was different from example 1 in that the molar content of zinc in step S1 was 2%. The other components are the same as those in embodiment 1, and will not be described in detail here.
Example 5
A diamond film was different from example 1 in that the molar content of zinc in step S1 was 6%. The other components are the same as those in embodiment 1, and will not be described in detail here.
Example 6
A diamond film was different from example 1 in that the molar content of zinc in step S1 was 10%. The other components are the same as those in embodiment 1, and will not be described in detail here.
Example 7
A diamond film was different from example 1 in that 5% of doped zinc was controlled to be removed in step S2. The other components are the same as those in embodiment 1, and will not be described in detail here.
Example 8
A diamond film was controlled to remove 80% of the doped zinc compared to example 1. The other components are the same as those in embodiment 1, and will not be described in detail here.
Example 9
A diamond film was treated in step S2 at 300℃for 3 hours in air to obtain a zinc oxide-doped porous diamond film, as compared with example 2. The other components are the same as those in embodiment 2, and will not be described in detail here.
Example 10
A diamond film prepared by the steps of:
s1, preparing a zinc-doped diamond film on the surface of a calcium silicate substrate by adopting a linear ion beam composite magnetron sputtering technology:
the magnetron sputtering source is provided with a zinc target material for depositing metallic zinc, a carbon-containing air source is introduced into the linear ion beam source for depositing the diamond film, and the magnetron sputtering source and the linear ion source are simultaneously started in the film plating process, so that the deposition of the zinc-doped diamond film is realized. Wherein the molar content of zinc is 4%.
S2, treating the zinc-doped diamond film in an inert atmosphere at 950 ℃ to remove 60% of the zinc-doped diamond film in a controlled manner, so as to obtain a zinc-doped porous diamond film;
s3, preparing a layer of pure diamond film on the surface of the zinc-doped porous diamond film by taking hydrogen and methane as raw materials and performing hot wire chemical vapor deposition.
Comparative example 1
A diamond film was prepared on the surface of a silicon nitride substrate directly through step S3, unlike example 1. The other components are the same as those in embodiment 1, and will not be described in detail here.
And heating the obtained diamond film with the thickness of 1cm multiplied by 1cm to 200 ℃, keeping the temperature for 1h, then cooling to room temperature, performing the cyclic treatment for 10 times, observing the surface morphology of the film, and evaluating the adhesive force and the service life of the diamond film.
TABLE 1 Performance test results of the diamond films prepared in examples 1 to 10 and comparative example 1
| Examples | Transmittance (%) | Surface topography |
| 1 | 69.8 | Basically has no crack and no warp falling off |
| 2 | 69.6 | Basically has no crack and no warp falling off |
| 3 | 70.1 | More cracks, no warpage and falling off |
| 4 | 70.0 | Small amount of cracks, no warpage and falling off |
| 5 | 69.5 | Basically has no crack and no warp falling off |
| 6 | 69.1 | Small amount of cracks, no warpage and falling off |
| 7 | 69.7 | Small amount of cracks, no warpage and falling off |
| 8 | 69.9 | Basically has no crack and no warp falling off |
| 9 | 69.2 | Small amount of cracks, no warpage and falling off |
| 10 | 69.7 | Basically has no crack and no warp falling off |
| Comparative example 1 | 70.2 | Generating more cracks and generating warping and falling off |
As can be seen from Table 1, the diamond film prepared by the invention has light transmittance close to that of the film without the transition layer (close to the theoretical light transmittance of the diamond film), which indicates that the transition layer also has better light transmittance. It can be seen that doping with small amounts of zinc or zinc oxide has little effect on light transmittance. From the surface morphology, it can be seen that the addition of the transition layer can significantly improve the thermal stability of the film. Therefore, the transition layer of the invention still takes the diamond film as a main body, and utilizes the doped zinc or zinc oxide and the porous structure to regulate and control the thermal expansion coefficient, thereby relieving the thermal stress, not only ensuring the light transmittance of the diamond film, but also improving the adhesive force and the service life of the diamond film. The transition layer has similar properties to diamond, so that the performance of the diamond film can be improved, and the hardness of the diamond film is basically consistent with that of natural diamond.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the 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 scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the diamond film is characterized by comprising the following steps:
s1, preparing a layer of zinc-doped diamond film on the surface of a substrate;
s2, carrying out high-temperature treatment on the zinc-doped diamond film in an inert atmosphere to evaporate part of zinc to form a porous structure, so as to obtain the zinc-doped porous diamond film;
s3, preparing a layer of pure diamond film on the surface of the zinc-doped porous diamond film.
2. The method for preparing a diamond film according to claim 1, wherein step S2 further comprises: and (3) performing thermal oxidation treatment on the zinc-doped porous diamond film to obtain a zinc oxide-doped porous diamond film, and performing step S3.
3. The method of producing a diamond film according to claim 2, wherein the thermal oxygen treatment comprises: treating in air at 200-400 deg.c for 1-3 hr;
or treating for 1-3h in an atmosphere with the volume ratio of oxygen to nitrogen of 10% -90% -30% -70% and at the temperature of 200-400 ℃.
4. The method of producing a diamond film according to claim 1, wherein the zinc atom molar content in the zinc-doped porous diamond film is 0.1% to 10%; the evaporated zinc in the high temperature treatment accounts for 1% -99% of the original doped zinc.
5. The method of producing a diamond film according to claim 4, wherein the zinc atom molar content of the zinc-doped diamond film is 2% to 6%; the evaporated zinc in the high temperature treatment accounts for 10% -80% of the original doped zinc.
6. The method for preparing a diamond film according to claim 1, wherein the high temperature treatment is performed at a temperature of 910 to 1100 ℃, and the inert atmosphere is nitrogen or helium.
7. The method for preparing the diamond film according to claim 1, wherein the zinc-doped diamond film is obtained by one or more methods of linear ion beam, magnetron sputtering, vacuum cathodic arc;
and/or the substrate is a silicate substrate, a silicon carbide substrate, a silicon nitride substrate or a monocrystalline silicon substrate, and the substrate temperature is 700-900 ℃.
8. The method of manufacturing a diamond film according to claim 1, wherein the thickness of the zinc-doped porous diamond film is 0.05 to 5 μm and the thickness of the diamond film is 0.05 to 10 μm.
9. A diamond film, which is characterized by comprising a substrate, a transition layer and a diamond film; the transition layer is a zinc-doped porous diamond film or a zinc oxide-doped porous diamond film.
10. The diamond film according to claim 9, wherein the diamond film is produced by the production method according to any one of claims 1 to 8.
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