CN113106391A - Multi-element hard film and preparation process thereof - Google Patents
Multi-element hard film and preparation process thereof Download PDFInfo
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- CN113106391A CN113106391A CN202110452231.6A CN202110452231A CN113106391A CN 113106391 A CN113106391 A CN 113106391A CN 202110452231 A CN202110452231 A CN 202110452231A CN 113106391 A CN113106391 A CN 113106391A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 33
- 238000004544 sputter deposition Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000010935 stainless steel Substances 0.000 claims abstract description 23
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 23
- 230000009471 action Effects 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 238000005336 cracking Methods 0.000 claims abstract description 11
- 238000000151 deposition Methods 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- 239000003513 alkali Substances 0.000 claims description 15
- 208000028659 discharge Diseases 0.000 claims description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- HSFWRNGVRCDJHI-UHFFFAOYSA-N Acetylene Chemical group C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000007747 plating Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
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- 229910021641 deionized water Inorganic materials 0.000 claims description 9
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
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- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
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- 235000011121 sodium hydroxide Nutrition 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000012495 reaction gas Substances 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000007888 film coating Substances 0.000 claims description 3
- 238000009501 film coating Methods 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 238000005546 reactive sputtering Methods 0.000 claims description 3
- 239000012686 silicon precursor Substances 0.000 claims description 3
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical group C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims 1
- 238000001755 magnetron sputter deposition Methods 0.000 abstract description 12
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 abstract description 5
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 56
- 239000011651 chromium Substances 0.000 description 24
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- 230000003213 activating effect Effects 0.000 description 2
- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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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
- C23C14/22—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
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
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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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
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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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0664—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
- 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
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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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
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
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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
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/36—Carbonitrides
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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
- C23C16/44—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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention belongs to the technical field of hard film products, in particular to a multi-element hard film and a preparation process thereof, wherein the preparation process of the multi-element hard film comprises the following specific steps: selecting a stainless steel substrate; performing bombardment treatment on the surface of the stainless steel substrate; sputtering and depositing a first film Cr layer; sputtering to generate a second film CrN layer; generating a third film CrSiN layer; and generating a fourth film CrSiCN layer. The preparation process of the multi-element hard film effectively combines magnetron sputtering and plasma-assisted chemical vapor deposition processes, so that the binding force and the hard film performance of the hard film are greatly improved. In addition, the prepared hard film is of a multi-component structure of Cr/CrN/CrSiN/CrSiCN, a precursor of organic silicon with certain saturated vapor pressure is adopted for doping Si silicon, cracking reaction is carried out under the action of plasma glow discharge, the preparation of the Si silicon in the hard film by a plasma-assisted chemical vapor deposition process and the doping of the Si silicon in the multi-component hard film are realized, and the bonding force of the structure of the multi-component hard film and the hardness of the hard film are effectively improved.
Description
Technical Field
The invention relates to the technical field of vacuum coating, in particular to a multielement hard film structure doped with silicon element and a process for preparing the multielement hard film structure by combining a vacuum magnetron sputtering process and a plasma-assisted chemical vapor deposition process.
Background
At present, in a vacuum coating process and application, a CrN film is a hard film widely applied due to superior performances of high hardness, high temperature resistance, wear resistance, oxidation resistance and the like, and is mainly applied to the following product fields:
(1) on the surface of the tool bit, the surface hardness of the tool bit can be effectively improved through surface coating modification of a CrN film, and finally the service life of the bit is prolonged;
(2) in the application of the automobile engine field, the engine piston works in the high-temperature and high-pressure environment and is very easy to damage the surface of the piston, the microhardness of the hard coating on the surface of the piston ring can meet the requirement of the surface coating of the engine piston ring through the modification of the CrN surface hard coating on the surface layer of the piston ring, the multi-target reactive magnetron sputtering and the anode layer flow type rectangular gas ion source auxiliary technology are combined, Cr/CrN/CrTiAlN/CrTiAlCN multi-layer multi-element hard films are respectively deposited on WC hard alloy and a micro drill bit, the hardness of a CrN film can be obviously improved, and the service cycle of the drill bit is prolonged.
Generally, the hard chromium nitride film is usually prepared by PVD, such as DC magnetron sputtering, medium frequency magnetron sputtering, high power pulse magnetron sputtering, hot cathode arc plating or ion arc plating. From the industrial point of view, the hot cathode arc plating or ion arc plating technique is widely used due to its advantages of high ionization rate, fast growth rate, good film-substrate binding force, low production cost, etc. The hardness of the hard film can be improved to a certain degree by doping silicon element in the hard film, a silicon target is sputtered simultaneously in the sputtering process of the chromium nitride film in the magnetron sputtering, multiple groups of target materials are co-sputtered to form a multi-element hard film doped with the silicon element to be deposited on the surface of the substrate, van der Waals force action is adopted between film layers prepared by magnetron sputtering, the binding force is not enough, and the content of the doped silicon element and the repeatability of the process are difficult to control due to the influence of process parameters of the magnetron sputtering silicon target.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the multi-element hard film and the preparation process thereof, and the preparation process of the multi-element hard film effectively combines magnetron sputtering and plasma-assisted chemical vapor deposition processes, so that the bonding force and the hard film performance of the hard film are greatly improved.
In order to achieve the technical purpose, the invention is realized according to the following technical scheme:
the invention relates to a preparation process of a multi-element hard film, which comprises the following specific steps:
(1) selecting a stainless steel substrate;
(2) bombarding the surface of the stainless steel substrate in a plating chamber in a column arc plating mode;
(3) sputtering and depositing a Cr layer of a first film layer: ionizing and bombarding the surface of a Cr target by Ar under the action of a medium-frequency power supply, and sputtering and depositing a Cr layer;
(4) sputtering to generate a second film CrN layer: ar and N are input into the coating chamber2Ionizing sputtering gas, and sputtering the surface of the Cr target under the action of a medium-frequency power supply to generate a CrN layer;
(5) generating a third film CrSiN layer: continuously inputting Ar and N into the film coating chamber2Ionizing sputtering gas, sputtering Cr target under the action of medium-frequency power supply, introducing organosilicon precursor through liquid mass flowmeter, cracking organosilicon monomer under the action of glow of medium-frequency power supply, and separating silicon element, sputtered Cr and ionized N2Generating a CrSiN layer under the combined action;
(6) generating a fourth film CrSiCN layer: adding C2H2And acetylene reaction gas is used for realizing cracking of C2H2 and an organic silicon precursor and sputtering of a Cr target under the action of a medium-frequency power supply to generate a CrSiCN layer.
As a further improvement of the above technology, the specific process of selecting the stainless steel substrate in the step (1) is as follows: selecting a stainless steel substrate, firstly wiping off particles remained on the surface of the substrate after polishing by absorbent cotton containing petroleum ether, then removing the remaining petroleum ether by ethanol, then rubbing the surface by absorbent cotton containing 5% of caustic soda solution and calcium carbonate powder, removing oil stains on the surface of the substrate, and then flushing the caustic soda and the calcium carbonate powder on the surface of the substrate by deionized water; and then repeating the operation once again, washing the residual alkali liquor by using 4% dilute hydrochloric acid, finally washing the alkali liquor by using deionized water, then respectively carrying out ultrasonic treatment in acetone, alcohol and deionized water for 10 minutes, finally blowing the alkali liquor by using a nitrogen gun, placing the alkali liquor in a 110 ℃ blast oven for 8 minutes, and wrapping the alkali liquor by using an aluminum foil for later use after cooling.
As a further improvement of the above technology, the specific process of performing the bombardment treatment on the surface of the stainless steel substrate in the step (2) is as follows: firstly adopting a column arc to carry out bombardment treatment on the surface of a base material in a coating chamber, wherein the discharge treatment conditions of the column arc are as follows: the vacuum degree is 2-10Pa, the discharge voltage is 1000V-5000V, and the discharge treatment time is 5-15 minutes under the normal temperature condition, so as to achieve the purpose of activating the surface of the base material. Specifically, the vacuum degree in the coating chamber is preferably 5Pa, the discharge voltage is preferably 3000V, and the discharge treatment time is 10 minutes at normal temperature.
As a further improvement of the above technology, in the step (3) of sputter depositing the first film Cr layer, the medium frequency power supply is 40kHz, and the thickness of the Cr layer is in the range of 5nm to 100 nm. Specifically, the thickness of the first film layer Cr layer is preferably 10 nm.
As a further improvement of the above technology, in the sputtering formation of the second film layer CrN layer in the step (4), the content of Ar is 55sccm, and N is2The content of (A) is controlled by a gas mass flow meter, and the numerical value range of the content of (A) is 5sccm to 50 sccm; the thickness of the CrN layer ranges from 500nm to 5000 nm. Specifically, the content of Ar is 55sccm, and the thickness of the CrN layer is 1000nm. As a further improvement of the above technique, in the step (5) for forming the third film layer CrSiN layer, the flow rate of the acetylene gas is in the range of 5sccm to 50sccm,the preferred flow rate is 10 sccm; the thickness of the CrSiCN layer ranges from 500nm to 5000nm, and the preferred thickness is 1000nm. Ar and N in the process2The Si element is derived from the cracking of the organosilicon monomer during the reactive sputtering process, the organosilicon monomer can be Tetramethylsilane (TEOS), Hexamethylsilane (HMDSO), octamethylsilane, or tetrahydrosilane (SiH) with reference to the gas flow in step (4) above4) The input amount of organosilane is controlled by a liquid mass flow meter, the selected flow range is 3sccm to 50sccm, the preferred flow value is 5sccm, the thickness range of the CrSiN layer is 500nm to 5000nm, and the preferred thickness is 1000 nm;
the invention also discloses a multi-element hard film prepared by the preparation process of the multi-element hard film, which comprises a stainless steel substrate, and a first film Cr layer, a second film CrN layer, a third film CrSiN layer and a fourth film CrSiCN layer on the surface of the stainless steel substrate. The multi-element hard film has multiple film layers, and the film layers are connected by chemical bonds, so that the hardness of the hard film is improved, the binding force of the film layers is enhanced, the process flow is simplified, and the multi-element hard film is suitable for industrial production and application.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation process of the multi-element hard film effectively combines magnetron sputtering and plasma-assisted chemical vapor deposition processes, thereby greatly improving and improving the binding force and the hard film hardness performance of the hard film, simplifying the process flow and being widely applicable to industrial production and application;
(2) according to the multi-element hard film, the film layers are connected by chemical bonds, so that the hardness of the hard film is improved, the binding force of the film layers is enhanced, and various performances of the film such as high hardness, high temperature resistance, wear resistance, oxidation resistance and the like are ensured.
Drawings
The invention is described in detail below with reference to the following figures and specific embodiments:
fig. 1 is a schematic structural view of a multicomponent hard film according to the present invention.
Detailed Description
As shown in fig. 1, the multi-element hard film of the present invention sequentially comprises a stainless steel substrate 1, and a first film Cr layer 2, a second film CrN layer 3, a third film CrSiN layer 4 and a fourth film CrSiCN layer 5 on the surface of the stainless steel substrate 1, wherein the stainless steel substrate 1 has a size of 40mmx40mm, the first film Cr layer 2 has a thickness of 10nm, the second film CrN layer 3 has a thickness of 1000nm, and the third film CrSiN layer 4 has a thickness of 1000nm.
The invention relates to a preparation process of a multi-element hard film, which comprises the following specific steps:
(1) selecting a stainless steel substrate 1: firstly, using absorbent cotton containing petroleum ether to wipe off particles remained on the surface of a stainless steel substrate 1 after polishing, then using ethanol to remove the remaining petroleum ether, then using absorbent cotton containing 5% of caustic soda solution and calcium carbonate powder to rub the surface, removing oil stains on the surface of the substrate, and then using deionized water to wash the caustic soda and the calcium carbonate powder on the surface of the substrate; and then repeating the operation once again, washing the residual alkali liquor by using 4% dilute hydrochloric acid, finally washing the alkali liquor by using deionized water, then respectively carrying out ultrasonic treatment in acetone, alcohol and deionized water for 10 minutes, finally blowing the alkali liquor by using a nitrogen gun, placing the alkali liquor in a 110 ℃ blast oven for 8 minutes, and wrapping the alkali liquor by using an aluminum foil for later use after cooling.
(2) Bombarding the surface 1 of the stainless steel substrate in a plating chamber by adopting a column arc plating mode, wherein the column arc discharge treatment conditions are as follows: the vacuum degree is 2-10Pa, the discharge voltage is 1000V-5000V, and the discharge treatment is carried out for 5-15 minutes under the condition of normal temperature, so as to achieve the purpose of activating the surface of the base material. Specifically, the vacuum degree in the coating chamber is preferably 5Pa, the discharge voltage is preferably 3000V, and the discharge treatment time is 10 minutes at normal temperature.
(3) Sputtering and depositing a first film Cr layer 2: and (3) ionizing and bombarding the surface of the Cr target by Ar under the action of a medium-frequency power supply, and sputtering and depositing a Cr layer 2, wherein the Cr layer 2 is a transition layer, and the thickness of the Cr layer 2 ranges from 5nm to 100nm, and is preferably 10 nm.
(4) Sputtering to generate a second film CrN layer 3: ar and N are input into the coating chamber2Ionizing sputtering gas, and applying medium frequency power supply at 40kHzThen, sputtering Cr target surface to generate CrN layer 3, the variation condition of N content in CrN layer 3 is set as a fixed value by gas mass flowmeter according to Ar content, preferably, Ar content is 55sccm, N2The content of (A) is controlled by a gas mass flow meter, and the numerical value range of the content of (A) is 5sccm to 50 sccm; the thickness of the CrN layer 3 ranges from 500nm to 5000nm, with a preferred thickness of 1000nm.
(5) And generating a third film CrSiN layer 4: continuously inputting Ar and N into the film coating chamber2Ionizing sputtering gas, sputtering Cr target under the action of 40kHz intermediate frequency power supply, introducing organosilicon precursor through a liquid mass flowmeter, cracking organosilicon monomer under the action of glow of the intermediate frequency power supply, and separating the produced silicon element, sputtered Cr and ionized N2Generating a CrSiN layer 4 under the combined action; ar and N in the process2The Si element is derived from the cracking of the organosilicon monomer during the reactive sputtering process, the organosilicon monomer can be Tetramethylsilane (TEOS), Hexamethylsilane (HMDSO), octamethylsilane, or tetrahydrosilane (SiH) with reference to the gas flow in step (4) above4) One or more organosilicon precursors. The input amount of organosilane is controlled by a liquid mass flow meter, the selected flow range is 3sccm to 50sccm, the preferred flow value is 5sccm, the thickness range of the CrSiN layer 4 is 500nm to 5000nm, and the preferred thickness is 1000nm.
(6) And generating a fourth film CrSiCN layer 5: adding C2H2Acetylene reaction gas under the action of medium-frequency power supply to realize C2H2Cracking of the organic silicon precursor and sputtering of a Cr target to generate a CrSiCN layer 5. Adding C2H2Acetylene reaction gas under the action of medium-frequency power supply to realize C2H2Cracking of the organosilicon precursor and sputtering of the Cr target, with simultaneous formation of a CrSiCN layer 5, in which step acetylene C is added2H2Acetylene C as a reaction gas with controlled input by an acetylene gas mass flow meter2H2The flow rate of the gas ranges from 5sccm to 50sccm, and the preferred flow rate is 10 sccm; the thickness of the CrSiCN layer ranges from 500nm to 5000nm, and the preferred thickness is 1000nm.
The multicomponent hard film of the invention is specifically described below according to specific experimental data:
(the organosilicon precursor is SiH4The technological parameter adopts 10sccm)
Hardness test results:
comparison table for surface hardness test (CrCN vs CrSiCN)
And (4) conclusion: the Vickers hardness of the hard film is tested under the conditions of CrCN hard films and CrSiCN hard films with the same thickness, the Vickers hardness of the CrCN hard film with the measurement result of 2859 value is improved to 3295.08 of the Vickers hardness of the CrSiCN hard film, the Vickers hardness is improved by 15.23%, the doping of Si element in magnetron sputtering generates a CrSiCN multielement hard film, and the hardness of the film can be improved to a certain extent.
The foregoing is a preferred embodiment of the present invention, and it should be understood that modifications and equivalents may be made to the technical solution of the present invention by those skilled in the art without departing from the scope of the present invention.
Claims (10)
1. A preparation process of a multi-element hard film comprises the following specific steps:
(1) selecting a stainless steel substrate;
(2) bombarding the surface of the stainless steel substrate in a plating chamber in a column arc plating mode;
(3) sputtering and depositing a Cr layer of a first film layer: ionizing and bombarding the surface of a Cr target by Ar under the action of a medium-frequency power supply, and sputtering and depositing a Cr layer;
(4) sputtering to generate a second film CrN layer: ar and N are input into the coating chamber2Ionizing sputtering gas, and sputtering the surface of the Cr target under the action of a medium-frequency power supply to generate a CrN layer;
(5) generating a third film CrSiN layer:continuously inputting Ar and N into the film coating chamber2Ionizing sputtering gas, sputtering Cr target under the action of medium-frequency power supply, introducing organosilicon precursor through liquid mass flowmeter, cracking organosilicon monomer under the action of glow of medium-frequency power supply, and separating silicon element, sputtered Cr and ionized N2Generating a CrSiN layer under the combined action;
(6) generating a fourth film CrSiCN layer: adding C2H2Acetylene reaction gas under the action of medium-frequency power supply to realize C2H2Cracking an organic silicon precursor and sputtering a Cr target to generate a CrSiCN layer.
2. The process for preparing a multicomponent hard film according to claim 1, characterized in that:
the specific process of selecting the stainless steel substrate in the step (1) is as follows: selecting a stainless steel substrate, firstly wiping off particles remained on the surface of the substrate after polishing by absorbent cotton containing petroleum ether, then removing the remaining petroleum ether by ethanol, then rubbing the surface by absorbent cotton containing 5% of caustic soda solution and calcium carbonate powder, removing oil stains on the surface of the substrate, and then flushing the caustic soda and the calcium carbonate powder on the surface of the substrate by deionized water; and then repeating the operation once again, washing the residual alkali liquor by using 4% dilute hydrochloric acid, finally washing the alkali liquor by using deionized water, then respectively carrying out ultrasonic treatment in acetone, alcohol and deionized water for 10 minutes, finally blowing the alkali liquor by using a nitrogen gun, placing the alkali liquor in a 110 ℃ blast oven for 8 minutes, and wrapping the alkali liquor by using an aluminum foil for later use after cooling.
3. The process for preparing a multicomponent hard film according to claim 1, characterized in that:
the specific process for performing the bombardment treatment on the surface of the stainless steel substrate in the step (2) is as follows: firstly adopting a column arc to carry out bombardment treatment on the surface of a base material in a coating chamber, wherein the discharge treatment conditions of the column arc are as follows: the vacuum degree is 2-10Pa, the discharge voltage is 1000V-5000V, and the discharge treatment time is 5-15 minutes under the normal temperature condition.
4. The process for preparing a multicomponent hard film according to claim 3, characterized in that: the vacuum degree in the coating chamber is 5Pa, the voltage is 3000V, and the discharge treatment time under the normal temperature condition is 10 minutes.
5. The process for preparing a multicomponent hard film according to claim 1, characterized in that: in the sputtering deposition of the first film Cr layer in the step (3), the medium-frequency power supply is 40kHz, and the thickness range of the Cr layer is 5nm to 100 nm.
6. The process for preparing a multicomponent hard film according to claim 5, characterized in that: the thickness of the first film layer Cr layer is preferably 10 nm.
7. The process for preparing a multicomponent hard film according to claim 1, characterized in that: the sputtering of the second film layer CrN layer in the step (4) has Ar content of 55sccm and N2The content of (A) is controlled by a gas mass flow meter, and the numerical value range of the content of (A) is 5sccm to 50 sccm; the thickness of the CrN layer ranges from 500nm to 5000 nm.
8. The process for preparing a multicomponent hard film according to claim 7, characterized in that: the content of Ar is 55sccm, and the thickness of the CrN layer is 1000nm.
9. The process for preparing a multicomponent hard film according to claim 1, characterized in that:
in the step (5), Si element in the CrSiN layer is derived from cracking of an organosilicon monomer in a reactive sputtering process, and the organosilicon monomer is Tetramethylsilane (TEOS) or Hexamethylsilane (HMDSO) or octamethylsilane or tetrahydrosilane (SiH)4) The flow range of the acetylene gas is 5sccm to 50sccm, and the thickness range of the CrSiCN layer is 500nm to 5000 nm.
10. A multi-component hard film obtained by the process for preparing a multi-component hard film according to any one of claims 1 to 9, wherein: the stainless steel substrate comprises a stainless steel substrate, and a first film Cr layer, a second film CrN layer, a third film CrSiN layer and a fourth film CrSiCN layer on the surface of the stainless steel substrate.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005082823A (en) * | 2003-09-05 | 2005-03-31 | Ion Engineering Research Institute Corp | HARD NITRIDE FILM DEPOSITING METHOD USING Si-CONTAINING GAS |
| US20130056348A1 (en) * | 2011-08-31 | 2013-03-07 | Hauzer Techno Coating Bv | Vacuum coating apparatus and method for depositing nanocomposite coatings |
| CN103707568A (en) * | 2012-10-04 | 2014-04-09 | 现代自动车株式会社 | Coating material for parts of engine exhaust system and method for manufacturing the same |
| CN105568231A (en) * | 2015-12-25 | 2016-05-11 | 珠海罗西尼表业有限公司 | Method for depositing functionally-graded nano-multilayer coating on surface of steel workpiece and product comprising functionally-graded nano-multilayer coating |
| CN111910161A (en) * | 2020-07-23 | 2020-11-10 | 滨中元川金属制品（昆山）有限公司 | Preparation process of high-power unipolar pulse magnetron sputtering CrSiCN film |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005082823A (en) * | 2003-09-05 | 2005-03-31 | Ion Engineering Research Institute Corp | HARD NITRIDE FILM DEPOSITING METHOD USING Si-CONTAINING GAS |
| US20130056348A1 (en) * | 2011-08-31 | 2013-03-07 | Hauzer Techno Coating Bv | Vacuum coating apparatus and method for depositing nanocomposite coatings |
| CN103707568A (en) * | 2012-10-04 | 2014-04-09 | 现代自动车株式会社 | Coating material for parts of engine exhaust system and method for manufacturing the same |
| CN105568231A (en) * | 2015-12-25 | 2016-05-11 | 珠海罗西尼表业有限公司 | Method for depositing functionally-graded nano-multilayer coating on surface of steel workpiece and product comprising functionally-graded nano-multilayer coating |
| CN111910161A (en) * | 2020-07-23 | 2020-11-10 | 滨中元川金属制品（昆山）有限公司 | Preparation process of high-power unipolar pulse magnetron sputtering CrSiCN film |
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