WO2024078227A1 - Organosilicon nanometer hydrophobic film layer and preparation method therefor - Google Patents

Organosilicon nanometer hydrophobic film layer and preparation method therefor Download PDF

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Publication number
WO2024078227A1
WO2024078227A1 PCT/CN2023/118161 CN2023118161W WO2024078227A1 WO 2024078227 A1 WO2024078227 A1 WO 2024078227A1 CN 2023118161 W CN2023118161 W CN 2023118161W WO 2024078227 A1 WO2024078227 A1 WO 2024078227A1
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film layer
hydrophobic film
preparing
nano
plasma
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PCT/CN2023/118161
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French (fr)
Chinese (zh)
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宗坚
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江苏菲沃泰纳米科技股份有限公司
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Publication of WO2024078227A1 publication Critical patent/WO2024078227A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B5/00—Electrostatic spraying apparatus; Spraying apparatus with means for charging the spray electrically; Apparatus for spraying liquids or other fluent materials by other electric means
    • B05B5/025—Discharge apparatus, e.g. electrostatic spray guns
    • B05B5/053—Arrangements for supplying power, e.g. charging power
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • 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
    • C23C16/24—Deposition of silicon 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
    • 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
    • C23C16/44—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
    • C23C16/505—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 using radio frequency discharges
    • C23C16/509—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 using radio frequency discharges using internal electrodes
    • 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
    • C23C16/515—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 using pulsed discharges
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H1/00—Contacts
    • H01H1/12—Contacts characterised by the manner in which co-operating contacts engage
    • H01H1/36—Contacts characterised by the manner in which co-operating contacts engage by sliding
    • H01H1/46—Contacts characterised by the manner in which co-operating contacts engage by sliding self-aligning contacts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/20—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy
    • H01L21/2003—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy characterised by the substrate
    • H01L21/2015—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy characterised by the substrate the substrate being of crystalline semiconductor material, e.g. lattice adaptation, heteroepitaxy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials

Definitions

  • the invention belongs to the field of chemical protective coatings, and in particular relates to an organic silicon nano-hydrophobic film layer and a preparation method thereof.
  • Hydrophobicity generally requires that the water contact angle on the surface of the material is greater than 90°.
  • hydrophobic materials are divided into two types: siloxane and fluorine-containing materials.
  • fluorine-containing materials have been widely used due to their excellent hydrophobic and oleophobic properties.
  • fluorine-containing materials can prepare a hydrophobic film layer with a maximum water contact angle of about 120°.
  • fluorine-containing materials have the disadvantages of poor friction resistance, high price, high temperature resistance and difficulty in degradation, carcinogenicity, reproductive toxicity, developmental toxicity, neurotoxicity and other toxicities, so their application is limited.
  • PFOA perfluorooctanoic acid
  • PFOS perfluorooctane sulfonic acid
  • TPCH perfluoroalkyl and polyfluoroalkyl substances
  • Plasma activation reaction organic monomer gas is deposited on the surface of the substrate.
  • This method is suitable for various substrates, and the deposited polymer protective coating is uniform, the coating preparation temperature is low, the coating thickness is thin, the stress is small, and there is almost no damage to the substrate surface and almost no effect on the substrate performance.
  • Related studies have used siloxane monomer gas in the form of plasma deposition to form a hydrophobic protective film layer on the surface of the substrate.
  • siloxane monomer gas in the form of plasma deposition to form a hydrophobic protective film layer on the surface of the substrate.
  • the existing commonly used plasma process is used for coating
  • the siloxane monomer gas is used to deposit the coating, it is easy to have a large difference in coating thickness at different positions on the substrate surface, which will affect the overall protective performance of the coating.
  • the specific embodiment of the present invention provides an organosilicon nano-hydrophobic film layer and a preparation method thereof, and the specific scheme is as follows:
  • the method for preparing the organosilicon nano hydrophobic film layer comprises the following steps:
  • the plasma reaction chamber is provided with a double electrode suitable for discharge, wherein the double electrode comprises: a central electrode provided at the center of the plasma reaction chamber and a cavity wall electrode provided at the inner wall of the plasma reaction chamber;
  • the gaseous siloxane monomer is introduced into the plasma reaction chamber from the monomer gas inlet, the double electrodes are turned on to discharge plasma into the plasma reaction chamber, and the siloxane monomer is plasma chemical vapor deposited on the surface of the substrate to form the organic silicon nano-hydrophobic film layer;
  • the siloxane monomer comprises at least one of the structures shown in the following formula (1) or (2):
  • R 1 , R 2 , R 3 , R 5 and R 6 are independently selected from hydrogen atom, halogen, C 1 -C 12 substituted or unsubstituted hydrocarbon group, C 1 -C 12 substituted or unsubstituted hydrocarbonoxy group, or C 1 -C 12 substituted or unsubstituted hydrocarbonsiloxy group, at least one of R 1 , R 2 and R 3 is not a hydrogen atom, at least one of R 5 or R 6 is not a hydrogen atom, R 4 is a C 1 -C 12 substituted or unsubstituted hydrocarbon group, or a C 1 -C 12 substituted or unsubstituted hydrocarbonsilyl group, n is an integer of 1 to 100, and m is an integer of 3 to 10.
  • the central electrode includes at least one cylindrical electrode
  • the cavity wall electrode includes at least one electrode plate.
  • the central electrode and the cavity wall electrode are electrically connected to the same power supply.
  • the plasma discharge is a pulse discharge
  • the pulse duty cycle is 0.1% to 80%
  • the pulse The frequency is 10-500Hz
  • the discharge power is 10-400W
  • the discharge time is 200-36000s.
  • the method for preparing the organic silicon nano-hydrophobic film layer further includes: arranging a gauze between the monomer air inlet and the substrate, and forming the organic silicon nano-hydrophobic film layer by plasma chemical vapor deposition on the surface of the substrate after the gaseous siloxane monomer passes through the gauze.
  • the mesh size of the gauze is 10 to 100 meshes.
  • the flow rate of the siloxane monomer is 10 to 2000 ⁇ L/min.
  • a bracket is provided in the plasma reaction chamber, a support member is provided on the bracket, the substrate is placed on the support member, and the substrate is driven to rotate in the reaction chamber by the rotation of the bracket around the central axis of the bracket and the rotation of the support member around the central axis of the support member.
  • the bracket rotates at a speed of 1 to 10 revolutions per minute
  • the support member rotates at a speed of 1 to 10 revolutions per minute.
  • the water contact angle of the organic silicon nano-hydrophobic film layer is not less than 105°.
  • the method for preparing the organic silicon nano-hydrophobic film layer further includes: before the chemical vapor deposition, evacuating to 10-200 mTorr, introducing one or a mixed gas of He, Ar, and O2 , and starting plasma discharge to pretreat the substrate.
  • R 1 , R 2 , R 3 , R 5 and R 6 are independently selected from methyl or ethyl, R 4 is methyl, ethyl or trimethylsilyl, and n is an integer of 2-10.
  • the siloxane monomer includes a siloxane monomer 1 and a siloxane monomer 2, wherein the siloxane monomer 1 has one unsaturated double bond, and the siloxane monomer 2 has at least two unsaturated double bonds.
  • the siloxane monomer 1 has a structure shown in the following formula (3):
  • R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are independently selected from hydrogen atoms or C 1 -C 4 hydrocarbon groups, at least one of R 10 , R 11 and R 12 is not a hydrogen atom, at least one of R 13 , R 14 and R 15 is not a hydrogen atom, at least one of R 16 , R 17 and R 18 is not a hydrogen atom, and p is an integer of 1 to 10.
  • R 7 , R 8 and R 9 are independently selected from hydrogen atom or methyl group
  • R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are independently selected from methyl group or ethyl group.
  • the first siloxane monomer is methacryloxypropyl tris(trimethylsiloxane)silane.
  • the siloxane monomer 2 has a structure as shown in formula (2), R 5 is a C 1 -C 4 olefin group, and R 6 is a C 1 -C 4 alkane group.
  • the second siloxane monomer is 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane.
  • a specific embodiment of the present invention further provides an organosilicon nano-hydrophobic film layer, which is prepared by the above-mentioned method for preparing the organosilicon nano-hydrophobic film layer.
  • a specific embodiment of the present invention further provides a device, at least part of the surface of the device has the above-mentioned organic silicon nano-hydrophobic film layer.
  • the organic silicon nano-hydrophobic film layer and the preparation method thereof according to the specific embodiment of the present invention are formed by plasma polymerization deposition of siloxane monomers.
  • a central electrode and a cavity wall electrode suitable for discharge are arranged in the plasma reaction chamber.
  • the central electrode and the cavity wall electrode are turned on to discharge into the plasma reaction chamber, so that the entire plasma reaction chamber is in a uniformly distributed electric field, and the gaseous siloxane monomers are activated into plasma and uniformly deposited on the surface of the substrate, effectively overcoming the problem of large differences in coating thickness at different positions on the surface of the substrate caused by the direct deposition of the gaseous siloxane monomers into the plasma chamber, while improving the wear resistance and film-forming speed of the prepared organic silicon nano-hydrophobic film layer, and at the same time improving the film quality and coating efficiency.
  • FIG1 shows a schematic structural diagram of a coating device used in a preparation method according to a specific embodiment of the present invention.
  • a specific embodiment of the present invention provides a method for preparing a hydrophobic organic silicon nano-film layer as follows, comprising the following steps:
  • the plasma reaction chamber is provided with a double electrode suitable for discharge, wherein the double electrode comprises: a central electrode provided at the center of the plasma reaction chamber and a cavity wall electrode provided at the inner wall of the plasma reaction chamber;
  • the gaseous siloxane monomers are introduced into the plasma reaction chamber from the monomer inlet, and the double electrodes are turned on to discharge plasma into the plasma reaction chamber.
  • the gaseous siloxane monomers are plasma chemical vapor deposited on the surface of the substrate to form the organic silicon nano-hydrophobic film layer.
  • the siloxane monomer comprises at least one of the structures shown in the following formula (1) or (2):
  • R 1 , R 2 , R 3 , R 5 and R 6 are independently selected from hydrogen atom, halogen, C 1 -C 12 substituted or unsubstituted hydrocarbon group, C 1 -C 12 substituted or unsubstituted hydrocarbonoxy group, or C 1 -C 12 substituted or unsubstituted hydrocarbonsiloxy group, at least one of R 1 , R 2 and R 3 is not a hydrogen atom, at least one of R 5 or R 6 is not a hydrogen atom, R 4 is a C 1 -C 12 substituted or unsubstituted hydrocarbon group, or a C 1 -C 12 substituted or unsubstituted hydrocarbonsilyl group, n is an integer of 1 to 100, and m is an integer of 3 to 10.
  • the hydrocarbon group may be an alkane group, an olefin group, an alkyne group or an aromatic hydrocarbon group
  • the substituent group may be, for example, a halogen atom, a hydroxyl group, an acyloxy group, an amino group, a nitrile group or a hydrocarbon group, etc.
  • the siloxane monomer may be, for example, diphenyldimethoxysilane, methyl orthosilicate, ethyl orthosilicate, diethylaminomethyltriethoxysilane, diethylenetriaminopropyltrimethoxysilane, 1,1,1-trimethyl-N-2-propylenepropylaminosilane, bis[3-(trimethoxysilane)] 1-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4
  • both wear resistance and hydrophobicity are taken into consideration
  • the R 1 , R 2 , R 3 , R 5 and R 6 are independently selected from methyl or ethyl, especially methyl
  • the R 4 is methyl, ethyl or trimethylsilyl, especially methyl or trimethylsilyl
  • the n is an integer of 2 to 10
  • the siloxane monomer can be, for example, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexamethylcyclotrisiloxane, hexaethylcyclotrisiloxane, octamethylcyclotetrasiloxane, octaethylcycl
  • the siloxane monomer includes siloxane monomer 1 and siloxane monomer 2, wherein the siloxane monomer 1 has one unsaturated double bond, and the siloxane monomer 2 has at least two unsaturated double bonds.
  • the siloxane monomer 1 has the structure shown in the following formula (3),
  • R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are independently selected from hydrogen atoms or C 1 -C 4 hydrocarbon groups, at least one of R 10 , R 11 and R 12 is not a hydrogen atom, at least one of R 13 , R 14 and R 15 is not a hydrogen atom, at least one of R 16 , R 17 and R 18 is not a hydrogen atom, and p is an integer of 1 to 10.
  • the R 7 , R 8 and R 9 are independently selected from hydrogen atoms or methyl groups
  • the R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are independently selected from methyl groups or ethyl groups.
  • the siloxane monomer 1 is methacryloxypropyl tris(trimethylsiloxy)silane.
  • the siloxane monomer 2 has the structure shown in the following formula (2):
  • the R 5 is a C 1 -C 4 olefin group
  • the R 6 is a C 1 -C 4 alkane group
  • the siloxane monomer 2 is 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane.
  • the molar ratio of the siloxane monomer 1 to the siloxane monomer 2 is 1:10 to 10:1, and specifically, for example, it can be 1:10, 2:10, 3:10, 4:10, 5:10, 6:10, 7:10, 8:10, 9:10, 10:10, 10:1, 10:2, 10:3, 10:4, 10:5, 10:6, 10:7, 10:8, 10:9, etc.
  • the method for preparing the organic silicon nano-hydrophobic film layer according to the specific embodiment of the present invention forms a more uniform electric field than a single electrode by providing a double electrode suitable for discharge in the plasma reaction chamber, and the plasma is more uniformly deposited on the surface of the substrate.
  • the double electrode includes a central electrode provided at the center of the plasma reaction chamber and a cavity wall electrode provided on the inner wall of the plasma reaction chamber, so that a uniform electric field is formed in the entire plasma reaction chamber during discharge.
  • the film layer is prepared on the substrate by the coating device shown in Figure 1.
  • Figure 1 shows a schematic structural diagram of the coating device used in the preparation method according to the specific embodiment of the present invention.
  • the coating device includes a plasma reaction chamber 1, which is suitable for accommodating a substrate 9.
  • the plasma reaction chamber 1 includes an inner wall 2.
  • the plasma reaction chamber 1 includes a double electrode suitable for discharge, and the double electrode includes a central electrode 3 and a cavity wall electrode 4, the central electrode 3 is arranged at the center of the plasma reaction chamber 1, and the cavity wall electrode 4 is arranged on the inner wall 2 of the plasma reaction chamber 1.
  • the central electrode 3 includes at least one cylindrical electrode
  • the cavity wall electrode 4 includes at least one electrode plate.
  • the central electrode 3 includes two cylindrical electrodes (31, 32) arranged together, one of which is grounded, and the other is connected to a power source, so as to form an electric field 33 between the two cylindrical electrodes (31, 32), so that the gaseous siloxane monomers are activated into plasma in the electric field.
  • the cavity wall electrode 4 includes at least two electrode plates, the electrode plates are connected to one end of the power source, the other end of the power source is connected to the reaction chamber, and the reaction chamber is grounded.
  • the central electrode 3 is a cylindrical electrode, and the shape of the cavity wall electrode 4 is consistent with the plasma reaction.
  • the shape of the chamber 1 corresponds to that of the chamber 1.
  • the plasma reaction chamber 1 is cylindrical, and the corresponding chamber wall electrode 4 is cylindrical.
  • the chamber wall electrode 4 includes an electrode plate, the electrode plate is cylindrical; when the chamber wall electrode 4 includes at least two electrode plates, the at least two electrode plates are respectively arc-shaped and together constitute a cylindrical shape.
  • a plurality of pores are provided on the cavity wall electrode 4 to facilitate the gaseous siloxane monomers to pass through the pores and enter the plasma reaction chamber 1 .
  • a gas extraction device is provided in the plasma reaction chamber 1 to adjust the pressure.
  • a gas extraction column is provided at the center of the plasma reaction chamber 1, and a hole is provided on the gas extraction column, and the gas extraction column is connected to a vacuum pump to extract the gas in the plasma reaction chamber 1 and control the pressure of the plasma reaction chamber 1.
  • the central electrode includes a first cylindrical electrode 31 and a second cylindrical electrode 32, and the second cylindrical electrode 32 is sleeved in the first cylindrical electrode 31.
  • a plurality of holes are provided on the second cylindrical electrode 32 to serve as a gas extraction column and to be grounded, and the first cylindrical electrode 31 is sleeved on the outside of the gas extraction column and is connected to a power source, and a plurality of holes are provided on the first cylindrical electrode 31 so that the gas passes through the gas extraction column and is extracted out of the plasma reaction chamber 1.
  • the first cylindrical electrode 31 is sleeved on the outside of the second cylindrical electrode 32, and the first cylindrical electrode 31 and the cavity wall electrode 4 can be designed to be electrically connected to the same power supply, or to be electrically connected to two power supplies respectively.
  • the first cylindrical electrode 31 and the cavity wall electrode 4 are electrically connected to the same power supply, so that when the power is turned on, the central electrode 3 and the cavity wall electrode 4 discharge at the same time, thereby improving the discharge efficiency and the distribution uniformity of the formed electric field in the plasma reaction chamber 1, and the electric field activates the siloxane monomer to form a plasma, and the plasma undergoes chemical vapor deposition on the surface 91 of the substrate to form an organic silicon nano-hydrophobic film layer.
  • a support 5 is provided in the plasma reaction chamber 1 of the coating equipment, and a support member 6 is provided on the support 5.
  • the support frame 6 is provided with a support area 61, which is suitable for supporting a substrate 9 placed thereon.
  • the support 5 rotates around the central axis X of the support 5 and the support member 6 rotates around the central axis Y of the support member 6, thereby driving the substrate 9 to rotate in the reaction chamber.
  • the support 5 The central axis X is located at the center of the plasma reaction chamber 1 .
  • the support member 6 is arranged around the bracket 5 in more than one layer, and more than one support member 6 is arranged in each layer.
  • the support member 6 is arranged around the bracket 5 in 3 to 5 layers, and 3 to 10 support members 6 are arranged in each layer.
  • the substrate 9 is placed on the support member 6 to further increase the space utilization efficiency of the plasma reaction chamber 1, so that the organosilicon nano-hydrophobic film layer can be prepared on multiple substrate surfaces 91 at the same time.
  • the support 5 is rotated around the central axis X of the support 5 to form a revolution
  • the support 6 is rotated around the central axis Y of the support 6 to form a rotation, so as to form a planetary rotation. That is, the substrate 9 placed on the support 6 rotates and revolves in the plasma reaction chamber 1, so as to provide more consistent coating conditions for all substrates 9, thereby ensuring that all substrates obtain uniform film layers to meet the requirements of industrial mass production.
  • the rotation speed of the bracket 5 is 1 to 10 rpm, and specific examples thereof may be 1 rpm, 2 rpm, 3 rpm, 4 rpm, 6 rpm, 7 rpm, 9 rpm, or 10 rpm, etc.
  • the rotation speed of the support member 6 is 1 to 10 rpm, and specific examples thereof may be 1 rpm, 2 rpm, 3 rpm, 4 rpm, 6 rpm, 7 rpm, 9 rpm, or 10 rpm, etc.
  • a monomer release source 7 is provided on the side wall of the plasma reaction chamber 1, which is connected to the monomer supply unit 8.
  • the monomer release source 7 is provided with a monomer gas inlet 71, so that the monomer supply unit 8 provides the siloxane monomer to enter the plasma reaction chamber 1 through the monomer gas inlet 71.
  • the gaseous siloxane monomer 72 enters the plasma reaction chamber 1 through the monomer gas inlet 71.
  • the monomer gas inlet 71 can be set on the side wall adjacent to the support member 6 to reduce the distance from the gaseous siloxane monomer 72 to the substrate 9, reduce the time for the siloxane monomer chemical vapor deposition on the substrate surface 91, and thus increase the coating speed.
  • the coating equipment shown in FIG. 1 is only an example of the specific The equipment used in the preparation method of the organic silicon nano-hydrophobic film layer of the embodiment is not a limitation on the coating equipment used in the preparation method of the specific embodiment of the present invention. Based on the preparation method of the specific embodiment of the present invention, other coating equipment can be selected for coating.
  • a gauze is arranged between the monomer air inlet and the substrate. Due to the guiding effect of the gauze, the airflow distribution of the gaseous siloxane monomer entering the interior of the gauze is more uniform, so that the surface of the substrate is in contact with the gaseous siloxane monomer as the coating material.
  • the gauze is arranged in a manner of directly wrapping the gauze around the substrate support.
  • the mesh size of the gauze is 10 to 100 meshes, specifically 10 meshes, 20 meshes, 30 meshes, 50 meshes, 60 meshes, 70 meshes, 80 meshes, 90 meshes or 100 meshes, etc.
  • the specific mesh size can be adjusted according to the specific type of siloxane monomer.
  • the water contact angle of the organosilicon nano-hydrophobic film layer is not less than 105°, and can be, for example, 105°, 106°, 107°, 108°, 109°, 110°, 111°, 112°, 113°, 114°, 115°, 116°, 117°, 118°, 119°, 120°, 125°, 130°, 135°, 140°, 145° or 150°, etc.
  • the thickness of the film layer is 10 to 100 nm, for example, it can be 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, etc.
  • the flow rate of the siloxane monomer is 10 to 2000 ⁇ L/min, for example, 50 ⁇ L/min, 100 ⁇ L/min, 150 ⁇ L/min, 160 ⁇ L/min, 200 ⁇ L/min, 300 ⁇ L/min, 400 ⁇ L/min, 500 ⁇ L/min, 1000 ⁇ L/min, 1500 ⁇ L/min or 2000 ⁇ L/min.
  • the temperature of the plasma reaction chamber is controlled at 30°C to 60°C, for example, 30°C, 40°C, 45°C, 50°C, 55°C or 60°C, etc.
  • the monomer gasification temperature is 50°C to 180°C, for example, 50°C, 60°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C or 180°C, etc., and the gasification occurs under vacuum conditions.
  • the substrate in order to further improve the binding force of the organic silicon nano-hydrophobic film layer, is pretreated with continuous plasma before coating.
  • the pressure is evacuated to 10-200 mTorr, and a mixture of one or more gases selected from He, Ar, and O2 is introduced, plasma discharge is started to pre-treat the substrate, or heat, oxygen, or high-energy radiation is used.
  • the discharge in the pretreatment stage and the coating stage, is continuous discharge or pulse discharge.
  • the central electrode and the cavity wall electrode are electrically connected to the same power supply.
  • the discharge power is 50-600W, for example, 50W, 100W, 120W, 140W, 160W, 180W, 190W, 200W, 210W, 220W, 230W, 240W, 250W, 260W, 270W, 280W, 290W, 300W, 400W, 500W or 600W, etc.
  • the discharge time is 30-2400s, for example, 30s, 60s, 100s, 200s, 300s, 400s, 500s, 600s, 1000s, 1200s, 1500s, 1800s or 2400s, etc.
  • the pulse duty ratio is 0.1% to 80%, and specifically, for example, it can be 0.1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% or 80%, etc.;
  • the pulse frequency is 10 to 500 Hz, and specifically, for example, it can be 10 Hz, 20 Hz, 25 Hz, 30 Hz, 35 Hz, 40 Hz, 45 Hz, 50 Hz, 55 Hz, 60 Hz, 70 Hz, 80 Hz, 90 Hz, 100 Hz, 200 Hz, 300 Hz, 400 Hz or 500 Hz, etc.;
  • the discharge power is 10 to 500 W, For example, it can be 10W, 20W, 30W, 40W, 50W, 60W, 70W, 80W, 90W, 100W, 120W, 140W, 160W, 180W, 190W, 200W, 210W, 220W, 230W, 240W, 250W, 260W, 270W
  • the central electrode and the cavity wall electrode are electrically connected to the same power supply.
  • the discharge power is 10 to 300 W, and specifically, for example, it can be 10 W, 20 W, 30 W, 40 W, 50 W, 60 W, 70 W, 80 W, 90 W, 100 W, 120 W, 140 W, 160 W, 180 W, 190 W, 200W, 210W, 220W, 230W, 240W, 250W, 260W, 270W, 280W, 290W or 300W, etc.; discharge time 60 to 36000s, for example, 60s, 100s, 200s, 300s, 400s, 500s, 600s, 1000s, 2000s, 3000s, 5000s, 10000s, 15000s, 20000s, 25000s, 30000s or 36000s, etc.
  • the pulse duty ratio is 0.1-80%, for example, it can be 0.1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% or 80%, etc.
  • the pulse frequency is 10-500Hz, for example, it can be 10Hz, 20Hz, 25Hz, 30Hz, 35Hz, 40Hz, 45Hz, 50Hz, 55Hz, 60Hz, 70Hz, 80Hz, 90Hz, 100Hz, 200Hz, 250Hz, 300Hz, 400Hz or 500Hz, etc.
  • the discharge power is 10-400W, for example, it can be 10W, 20W, 30W, 40W, 50W, 60W, 70W, 80W, 90W, 100W, 120W, 140W, 160W, 180W, 190W, 200W, 210W, 220W, 230W, 240W, 250W, 260W, 270W, 280W, 290W, 300W or 400W, etc.
  • discharge time 200-36000s for example,
  • the plasma discharge mode can be various existing discharge modes, for example, electrodeless discharge (such as radio frequency inductively coupled discharge, microwave discharge), single electrode discharge (such as corona discharge, plasma jet formed by monopolar discharge), double electrode discharge (such as dielectric barrier discharge, bare electrode radio frequency glow discharge) and multi-electrode discharge (such as discharge using a floating electrode as the third electrode).
  • electrodeless discharge such as radio frequency inductively coupled discharge, microwave discharge
  • single electrode discharge such as corona discharge, plasma jet formed by monopolar discharge
  • double electrode discharge such as dielectric barrier discharge, bare electrode radio frequency glow discharge
  • multi-electrode discharge such as discharge using a floating electrode as the third electrode.
  • the substrate is various plastics, fabrics, glass, electrical components or optical instruments, etc.
  • the electrical component can be a printed circuit board (PCB), an electronic product or an electronic assembly semi-finished product, etc.
  • the substrate is an electronic or electrical component.
  • the substrate when the substrate is an electronic product, it can be, for example, a mobile phone, a tablet computer, a keyboard, an e-reader, a wearable device, a display, a headset, a USB data cable, a USB interface, a sound-permeable net, an earmuff or a headband, etc.
  • the substrate can also be any suitable electrical component of an electrical component, specifically, the electrical component can be a resistor, a capacitor, a transistor, a diode, an amplifier, a relay, a transformer, a battery, a fuse, an integrated circuit, a switch, an LED, an LED display, a piezoelectric element, an optoelectronic component or an antenna or an oscillator, etc.
  • the electrical component can be a resistor, a capacitor, a transistor, a diode, an amplifier, a relay, a transformer, a battery, a fuse, an integrated circuit, a switch, an LED, an LED display, a piezoelectric element, an optoelectronic component or an antenna or an oscillator, etc.
  • the specific embodiments of the present invention further provide an organosilicon nano-hydrophobic film layer.
  • the organosilicon nano-hydrophobic film layer is prepared by the above-mentioned method for preparing the organosilicon nano-hydrophobic film layer.
  • the specific embodiment of the present invention also provides a device, wherein at least part of the surface of the device has the above-mentioned organic silicon nano-hydrophobic film layer, and in some specific embodiments, part of the surface or the entire surface of the device is only coated with the above-mentioned protective coating.
  • the device is an electrical component, an optical instrument, an electronic or electrical component, etc.
  • Coating water tentacle tested according to GB/T 30447-2013 standard.
  • Film thickness test Use the American Filmetrics F20-UV-film thickness measuring instrument for testing.
  • Film forming speed test Calculate the thickness of the film formed per unit time based on the thickness of the film formed in a certain period of time.
  • Friction resistance test carried out on a wear tester, the friction material is dust-free cloth, and the water contact angle is tested before and after 1000 frictions under the conditions of 1N pressure and 50 cycles/min.
  • the Si wafer and the glass substrate are placed in a plasma reaction chamber, the substrate is placed on a support of a bracket, and the support is wrapped with a 20-mesh gauze; a double electrode is provided in the plasma reaction chamber, and the double electrode is a central electrode and a cavity wall electrode electrically connected to the same power supply for discharging into the chamber;
  • the chamber was evacuated to 20 mTorr, and helium was introduced at a flow rate of 80 sccm.
  • the chamber temperature was 45°C.
  • the chamber pressure was maintained at 20 mTorr, the helium flow rate was maintained at 80 sccm, the support and the support were turned on to rotate, the substrate was subjected to planetary motion, the support rotation speed was 2 rpm, the support rotation speed was 3 rpm, the double-electrode plasma continuous discharge was turned on, the discharge power was 100 W, and the discharge was continued for 600 s to pretreat the substrate;
  • the monomer decamethyltetrasiloxane was vaporized at a vaporization temperature of 85° C. and then introduced into the plasma chamber, the chamber pressure was maintained at 20 mTorr, the helium flow rate was maintained at 80 sccm, the bracket and the support were kept rotating, the double-electrode radio frequency plasma discharge was turned on, the radio frequency energy output mode was pulsed, and plasma chemical vapor deposition was performed on the surface of the substrate, wherein the pulse duty ratio was 25%, the pulse frequency was 200 Hz, the pulse discharge power was 120 W, the monomer flow rate was 160 ⁇ L/min, and the reaction time was 3600 s;
  • the Si wafer and the glass substrate are placed in a plasma reaction chamber, the substrate is placed on a support of a bracket, and the support is wrapped with a 20-mesh gauze; a central electrode electrically connected to a power source is provided in the plasma reaction chamber for discharging into the chamber;
  • the chamber was evacuated to 20 mTorr, helium was introduced at a flow rate of 80 sccm, and the chamber temperature was 45°C;
  • the chamber pressure was maintained at 20 mTorr, the helium flow rate was maintained at 80 sccm, the support and the support were turned on to rotate, the substrate was subjected to planetary motion, the support rotation speed was 2 rpm, the support rotation speed was 3 rpm, the central electrode plasma was turned on for continuous discharge, the discharge power was 100 W, and the discharge lasted for 600 s to pretreat the substrate;
  • the monomer decamethyltetrasiloxane was introduced into the plasma chamber after being vaporized at a vaporization temperature of 85° C., the chamber pressure was maintained at 20 mTorr, the helium flow rate was maintained at 80 sccm, the bracket and the support were kept rotating, the central electrode radio frequency plasma discharge was turned on, the radio frequency energy output mode was pulsed, and plasma chemical vapor deposition was performed on the surface of the substrate, wherein the pulse duty ratio was 25%, the pulse frequency was 200 Hz, the pulse discharge power was 120 W, the monomer flow rate was 160 ⁇ L/min, and the reaction time was 3600 s;
  • the Si wafer and the glass substrate are placed in a plasma chamber, the substrate is placed on a support of a bracket, and the support is wrapped with a 30-mesh gauze; a double electrode is provided in the plasma reaction chamber, and the double electrode is a central electrode and a cavity wall electrode electrically connected to the same power supply for discharging into the chamber;
  • the chamber was evacuated to 50 mTorr, helium was introduced at a flow rate of 70 sccm, and the chamber temperature was 50°C;
  • the chamber pressure was maintained at 50 mTorr, the helium flow rate was maintained at 70 sccm, the support and the support were turned on to rotate, the substrate was subjected to planetary motion, the support rotation speed was 1 rpm, the support rotation speed was 1.5 rpm, the double-electrode plasma continuous discharge was turned on, the discharge power was 300 W, and the discharge was continued for 300 s to pretreat the substrate;
  • the monomer octamethyltrisiloxane was vaporized at a vaporization temperature of 75° C. and then introduced into the plasma chamber, the chamber pressure was maintained at 50 mTorr, the helium flow rate was maintained at 70 sccm, the bracket and the support were kept rotating, and the double-electrode radio frequency plasma discharge was turned on.
  • the radio frequency energy output mode was pulsed, and plasma chemical vapor deposition was performed on the surface of the substrate, wherein the pulse duty ratio was 50%, the pulse frequency was 100 Hz, the pulse discharge power was 180 W, the monomer flow rate was 150 ⁇ L/min, and the reaction time was 3600 s;
  • the Si wafer and the glass substrate are placed in a plasma chamber, the substrate is placed on a support of a bracket, and the support is wrapped with a 30-mesh gauze; a central electrode electrically connected to a power source is provided in the plasma reaction chamber for discharging into the chamber;
  • the chamber was evacuated to 50 mTorr, helium was introduced at a flow rate of 70 sccm, and the chamber temperature was 50°C;
  • the chamber pressure was maintained at 50 mTorr, the helium flow rate was maintained at 70 sccm, the support and the support were turned on to rotate, the substrate was subjected to planetary motion, the support rotation speed was 1 rpm, the support rotation speed was 1.5 rpm, the central electrode plasma was turned on for continuous discharge, the discharge power was 300 W, and the discharge lasted for 300 s to pretreat the substrate;
  • the monomer octamethyltrisiloxane was vaporized at a vaporization temperature of 75° C. and then introduced into the plasma chamber, the chamber pressure was maintained at 50 mTorr, the helium flow rate was maintained at 70 sccm, the bracket and the support were kept rotating, the central electrode radio frequency plasma discharge was turned on, the radio frequency energy output mode was pulsed, and plasma chemical vapor deposition was performed on the surface of the substrate, wherein the pulse duty ratio was 50%, the pulse frequency was 100 Hz, the pulse discharge power was 180 W, the monomer flow rate was 150 ⁇ L/min, and the reaction time was 3600 s;
  • the Si wafer and the glass substrate are placed in a plasma chamber, the substrate is placed on a support of a bracket, and the support is wrapped with a 50-mesh gauze; a double electrode is provided in the plasma reaction chamber, and the double electrode is a central electrode and a cavity wall electrode electrically connected to the same power supply for discharging into the chamber;
  • the chamber was evacuated to 100 mTorr, and helium was introduced at a flow rate of 50 sccm.
  • the chamber temperature was 55°C.
  • the chamber pressure was maintained at 100 mTorr, the helium flow rate was maintained at 50 sccm, the support and the support were turned on to rotate, the substrate was subjected to planetary motion, the support rotation speed was 2 rpm, the support rotation speed was 2.5 rpm, the dual-electrode plasma pulse discharge was turned on, the pulse duty cycle was 60%, the pulse frequency was 300 Hz, the discharge power was 300 W, and the discharge was continued for 300 s to pretreat the substrate;
  • the monomer tetrakis(trimethylsiloxy)silane was vaporized at a vaporization temperature of 95° C. and then introduced into the plasma chamber, the chamber pressure was maintained at 100 mTorr, the helium flow rate was maintained at 50 sccm, the bracket and the support were kept rotating, the double-electrode radio frequency plasma discharge was turned on, the radio frequency energy output mode was pulsed, and plasma chemical vapor deposition was performed on the surface of the substrate, wherein the pulse duty ratio was 35%, the pulse frequency was 250 Hz, the pulse discharge power was 200 W, the monomer flow rate was 200 ⁇ L/min, and the reaction time was 3600 s;
  • the Si wafer and the glass substrate are placed in a plasma chamber, the substrate is placed on a support of a bracket, and the support is wrapped with a 50-mesh gauze; a central electrode electrically connected to a power source is provided in the plasma reaction chamber for discharging into the chamber;
  • the chamber was evacuated to 100 mTorr, and helium was introduced at a flow rate of 50 sccm.
  • the chamber temperature was 55°C.
  • the chamber pressure was maintained at 100 mTorr, the helium flow rate was maintained at 50 sccm, the support and the support were turned on to rotate, the substrate was subjected to planetary motion, the support rotation speed was 2 rpm, the support rotation speed was 2.5 rpm, the central electrode plasma pulse discharge was turned on, the pulse duty cycle was 60%, the pulse frequency was 300 Hz, the discharge power was 300 W, and the discharge was continued for 300 s to pretreat the substrate;
  • the monomer tetrakis(trimethylsiloxy)silane was vaporized at a vaporization temperature of 95°C and then introduced into the plasma chamber, the chamber pressure was maintained at 100 mTorr, the helium flow rate was maintained at 50 sccm, the bracket and the support were kept rotating, the central electrode radio frequency plasma discharge was turned on, the radio frequency energy output mode was pulsed, and plasma chemical vapor deposition was performed on the surface of the substrate, wherein the pulse duty ratio was 35%, the pulse frequency was 250 Hz, the pulse discharge power was 200 W, the monomer flow rate was 200 ⁇ L/min, and the reaction time was 3600 s;
  • A, B, and C represent the positions of the Si wafer substrate from the farthest to the closest to the rotation axis of the support, respectively.
  • the average film forming speed of A, B, and C is calculated according to the film thickness. It can be seen from Table 1 that the film forming speed in Examples 1-3 is increased by 1.5 to 2 times compared with that in Comparative Examples 1-3.
  • the central electrode and the cavity wall electrode are discharged simultaneously, and the plasma formation rate is faster, which is more conducive to the chemical vapor deposition of the monomer on the surface of the substrate, so that the substrate coating can be completed faster and the coating efficiency is improved.

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Abstract

Provided in the specific embodiments of the present invention are an organosilicon nanometer hydrophobic film layer and a preparation method therefor. The organosilicon nanometer hydrophobic film layer is formed by the plasma polymerization deposition of a siloxane monomer. During the preparation, a gaseous siloxane monomer is introduced, and twin electrodes are turned on to realize discharging in a plasma reaction chamber, such that the siloxane monomer undergoes plasma chemical vapor deposition on the surface of a substrate to form an organosilicon nanometer hydrophobic film layer. By using the preparation method of the specific embodiments of the present invention, the problem of large differences in the thickness of a film layer at different locations on a surface of a substrate caused by the deposition of a siloxane monomer introduced into a plasma chamber can be effectively overcome, and the coating speed and the wear resistance of the film layer are thereby improved.

Description

一种有机硅纳米疏水膜层及其制备方法A kind of organic silicon nano hydrophobic film layer and preparation method thereof
本申请要求于2022年10月12日提交中国专利局、申请号为202211246102.2、发明名称为“一种有机硅纳米疏水膜层及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application filed with the China Patent Office on October 12, 2022, with application number 202211246102.2 and invention name “A Silicone Nano-Hydrophobic Film Layer and Its Preparation Method”, the entire contents of which are incorporated by reference into this application.
技术领域Technical Field
本发明属于化学防护涂层领域，具体涉及一种有机硅纳米疏水膜层及其制备方法。The invention belongs to the field of chemical protective coatings, and in particular relates to an organic silicon nano-hydrophobic film layer and a preparation method thereof.
背景技术Background technique
疏水性一般要求材料表面水接触角大于90°，目前广泛使用的疏水材料分为硅氧烷类和含氟类两类材料，其中含氟类材料因其优异的疏水疏油性能得到了广泛的应用。在光滑的表面，含氟类材料可制备最高水接触角约为120°的疏水膜层，然而含氟材料具有耐摩擦性差，价格昂贵，耐高温且不易降解，具有致癌性、生殖毒性、发育毒性、神经毒性等多种毒性的缺点，因此其应用受到了限制。欧盟POPs法规要求禁止使用全氟辛酸(PFOA)和全氟辛烷磺酸(PFOS)及其衍生物，美国包装法案TPCH要求全氟烷基和多氟烷基物质(PFAS)不得检出。因此硅氧烷类材料是取代含氟类材料的首选材料，人们越来越重视硅烷类疏水材料的研究。Hydrophobicity generally requires that the water contact angle on the surface of the material is greater than 90°. Currently, the widely used hydrophobic materials are divided into two types: siloxane and fluorine-containing materials. Among them, fluorine-containing materials have been widely used due to their excellent hydrophobic and oleophobic properties. On a smooth surface, fluorine-containing materials can prepare a hydrophobic film layer with a maximum water contact angle of about 120°. However, fluorine-containing materials have the disadvantages of poor friction resistance, high price, high temperature resistance and difficulty in degradation, carcinogenicity, reproductive toxicity, developmental toxicity, neurotoxicity and other toxicities, so their application is limited. The EU POPs regulations require the prohibition of the use of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) and their derivatives, and the US Packaging Act TPCH requires that perfluoroalkyl and polyfluoroalkyl substances (PFAS) must not be detected. Therefore, siloxane materials are the preferred materials to replace fluorine-containing materials, and people are paying more and more attention to the research of silane hydrophobic materials.
利用等离子体活化反应有机单体气体在基材表面进行沉积，这种方法适用于各种基材，且沉积的聚合物防护涂层均匀，涂层制备温度低，涂层厚度薄、应力小，对基材表面几乎没有损伤和基材性能几乎没有影响，已有相关研究将硅氧烷类单体气体采用等离子体沉积的形式在基材表明形成疏水防护膜层，但是采用现有常用的等离子工艺进行涂层时，以硅氧烷类单体气体进行沉积涂层时容易在基材表面不同位置的涂层厚度差异较大，进而会影响涂层的整体防护性能。 Plasma activation reaction organic monomer gas is deposited on the surface of the substrate. This method is suitable for various substrates, and the deposited polymer protective coating is uniform, the coating preparation temperature is low, the coating thickness is thin, the stress is small, and there is almost no damage to the substrate surface and almost no effect on the substrate performance. Related studies have used siloxane monomer gas in the form of plasma deposition to form a hydrophobic protective film layer on the surface of the substrate. However, when the existing commonly used plasma process is used for coating, when the siloxane monomer gas is used to deposit the coating, it is easy to have a large difference in coating thickness at different positions on the substrate surface, which will affect the overall protective performance of the coating.
发明内容Summary of the invention
本发明的具体实施方式提供一种有机硅纳米疏水膜层及其制备方法，具体方案如下：The specific embodiment of the present invention provides an organosilicon nano-hydrophobic film layer and a preparation method thereof, and the specific scheme is as follows:
所述有机硅纳米疏水膜层的制备方法，包括以下步骤：The method for preparing the organosilicon nano hydrophobic film layer comprises the following steps:
将基材置于等离子体反应腔室内，所述等离子体反应腔室内设有适于放电的双电极，所述双电极包括：设于所述等离子体反应腔室的中心的中心电极与设于所述等离子体反应腔室的内壁的腔壁电极；Placing a substrate in a plasma reaction chamber, wherein the plasma reaction chamber is provided with a double electrode suitable for discharge, wherein the double electrode comprises: a central electrode provided at the center of the plasma reaction chamber and a cavity wall electrode provided at the inner wall of the plasma reaction chamber;
气态的硅氧烷类单体由所述单体进气口通入所述等离子体反应腔室内，开启所述双电极向所述等离子体反应腔室内等离子体放电，所述硅氧烷类单体在所述基材表面等离子体化学气相沉积形成所述有机硅纳米疏水膜层；The gaseous siloxane monomer is introduced into the plasma reaction chamber from the monomer gas inlet, the double electrodes are turned on to discharge plasma into the plasma reaction chamber, and the siloxane monomer is plasma chemical vapor deposited on the surface of the substrate to form the organic silicon nano-hydrophobic film layer;
所述硅氧烷类单体包括下式(1)或(2)所示结构至少一种，
The siloxane monomer comprises at least one of the structures shown in the following formula (1) or (2):
式(1)或(2)中，R1、R2、R3、R5和R6分别独立的选自于氢原子、卤素、C1-C12的取代或非取代烃基、C1-C12的取代或非取代烃氧基、或C1-C12的取代或非取代烃基硅氧基，所述R1、R2和R3中至少一个不为氢原子，所述R5或R6中至少一个不为氢原子，R4为C1-C12的取代或非取代烃基、或C1-C12的取代或非取代烃基硅基，n为1～100的整数，m为3～10的整数。In formula (1) or (2), R 1 , R 2 , R 3 , R 5 and R 6 are independently selected from hydrogen atom, halogen, C 1 -C 12 substituted or unsubstituted hydrocarbon group, C 1 -C 12 substituted or unsubstituted hydrocarbonoxy group, or C 1 -C 12 substituted or unsubstituted hydrocarbonsiloxy group, at least one of R 1 , R 2 and R 3 is not a hydrogen atom, at least one of R 5 or R 6 is not a hydrogen atom, R 4 is a C 1 -C 12 substituted or unsubstituted hydrocarbon group, or a C 1 -C 12 substituted or unsubstituted hydrocarbonsilyl group, n is an integer of 1 to 100, and m is an integer of 3 to 10.
可选的，所述中心电极包括至少一圆筒电极，所述腔壁电极包括至少一块的电极板。Optionally, the central electrode includes at least one cylindrical electrode, and the cavity wall electrode includes at least one electrode plate.
可选的，所述中心电极与所述腔壁电极与同一电源电连接。Optionally, the central electrode and the cavity wall electrode are electrically connected to the same power supply.
可选的，所述等离子体放电为脉冲放电，脉冲占空比为0.1％～80％，脉冲 频率为10～500Hz，放电功率为10～400W，放电时间为200～36000s。Optionally, the plasma discharge is a pulse discharge, the pulse duty cycle is 0.1% to 80%, and the pulse The frequency is 10-500Hz, the discharge power is 10-400W, and the discharge time is 200-36000s.
可选的，所述有机硅纳米疏水膜层的制备方法还包括：在所述单体进气口与基材之间设置纱网，所述气态的硅氧烷类单体经过纱网后在所述基材表面等离子体化学气相沉积形成所述有机硅纳米疏水膜层。Optionally, the method for preparing the organic silicon nano-hydrophobic film layer further includes: arranging a gauze between the monomer air inlet and the substrate, and forming the organic silicon nano-hydrophobic film layer by plasma chemical vapor deposition on the surface of the substrate after the gaseous siloxane monomer passes through the gauze.
可选的，所述纱网的网格大小为10～100目。Optionally, the mesh size of the gauze is 10 to 100 meshes.
可选的，所述硅氧烷类单体的流速为10～2000μL/min。Optionally, the flow rate of the siloxane monomer is 10 to 2000 μL/min.
可选的，所述等离子体反应腔室内设置支架，所述支架上设置支撑件，所述基材置于所述支撑件上，由所述支架绕所述支架的中心轴旋转和所述支撑件绕所述支撑件的中心轴旋转带动所述基材在反应腔室内旋转运动。Optionally, a bracket is provided in the plasma reaction chamber, a support member is provided on the bracket, the substrate is placed on the support member, and the substrate is driven to rotate in the reaction chamber by the rotation of the bracket around the central axis of the bracket and the rotation of the support member around the central axis of the support member.
可选的，所述支架旋转的转速为1～10转/min，所述支撑件旋转的转速为1～10转/min。Optionally, the bracket rotates at a speed of 1 to 10 revolutions per minute, and the support member rotates at a speed of 1 to 10 revolutions per minute.
可选的，所述有机硅纳米疏水膜层的水接触角不小于105°。Optionally, the water contact angle of the organic silicon nano-hydrophobic film layer is not less than 105°.
可选的，所述有机硅纳米疏水膜层的制备方法还包括：在所述化学气相沉积前，抽真空至10～200毫托，并通入气体He、Ar、O2中的一种或几种的混合气体，开启等离子体放电对所述基材进行预处理。Optionally, the method for preparing the organic silicon nano-hydrophobic film layer further includes: before the chemical vapor deposition, evacuating to 10-200 mTorr, introducing one or a mixed gas of He, Ar, and O2 , and starting plasma discharge to pretreat the substrate.
可选的，所述R1、R2、R3、R5和R6分别独立的选自于甲基或乙基，R4为甲基、乙基或三甲基硅基，所述n为2～10的整数。Optionally, R 1 , R 2 , R 3 , R 5 and R 6 are independently selected from methyl or ethyl, R 4 is methyl, ethyl or trimethylsilyl, and n is an integer of 2-10.
可选的，所述硅氧烷单体包括硅氧烷单体一和硅氧烷单体二，其中所述硅氧烷单体一具有一个不饱和双键，所述硅氧烷单体二具有至少两个不饱和双键。Optionally, the siloxane monomer includes a siloxane monomer 1 and a siloxane monomer 2, wherein the siloxane monomer 1 has one unsaturated double bond, and the siloxane monomer 2 has at least two unsaturated double bonds.
可选的，所述硅氧烷单体一具有下式(3)所示结构，
Optionally, the siloxane monomer 1 has a structure shown in the following formula (3):
式(3)中，R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17和R18分别独立的选自于氢原子或C1-C4的烃基，R10、R11和R12中至少一个不为氢原子，R13、R14和R15中至少一个不为氢原子，R16、R17和R18中至少一个不为氢原子，p为1～10的整数。In formula (3), R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are independently selected from hydrogen atoms or C 1 -C 4 hydrocarbon groups, at least one of R 10 , R 11 and R 12 is not a hydrogen atom, at least one of R 13 , R 14 and R 15 is not a hydrogen atom, at least one of R 16 , R 17 and R 18 is not a hydrogen atom, and p is an integer of 1 to 10.
可选的，所述R7、R8和R9分别独立的选自于氢原子或甲基，所述R10、R11、R12、R13、R14、R15、R16、R17和R18分别独立的选自于甲基或乙基。Optionally, R 7 , R 8 and R 9 are independently selected from hydrogen atom or methyl group, and R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are independently selected from methyl group or ethyl group.
可选的，所述硅氧烷单体一为甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷。Optionally, the first siloxane monomer is methacryloxypropyl tris(trimethylsiloxane)silane.
可选的，所述硅氧烷单体二具有式(2)所示结构，所述R5为C1-C4的烯烃基，所述R6为C1-C4的烷烃基。Optionally, the siloxane monomer 2 has a structure as shown in formula (2), R 5 is a C 1 -C 4 olefin group, and R 6 is a C 1 -C 4 alkane group.
可选的，所述硅氧烷单体二为1,3,5,7-四乙烯基-1,3,5,7-四甲基环四硅氧烷。Optionally, the second siloxane monomer is 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane.
本发明的具体实施方式还提供一种有机硅纳米疏水膜层，所述有机硅纳米疏水膜层由以上所述的有机硅纳米疏水膜层的制备方法制备获得。A specific embodiment of the present invention further provides an organosilicon nano-hydrophobic film layer, which is prepared by the above-mentioned method for preparing the organosilicon nano-hydrophobic film layer.
本发明的具体实施方式还提供一种器件，所述器件的至少部分表面具以上所述的有机硅纳米疏水膜层。A specific embodiment of the present invention further provides a device, at least part of the surface of the device has the above-mentioned organic silicon nano-hydrophobic film layer.
本发明具体实施方式的有机硅纳米疏水膜层及其制备方法，所述有机硅纳米疏水膜层由硅氧烷类单体等离子体聚合沉积形成，制备过程中，通过在 等离子体反应腔室内设有适于放电的中心电极和腔壁电极，开启中心电极与腔壁电极向等离子体反应腔放电，使整个等离子体反应腔室内处于均匀分布的电场，气态硅氧烷类单体被激活为等离子体并均匀的沉积于基材表面，有效克服气态硅氧烷类单体直接进入等离子腔室沉积引起的基材表面不同位置的涂层厚度差异较大的问题，同时提升了所制备的有机硅纳米疏水膜层的耐磨性能和成膜速度，同时提高了膜层质量和镀膜效率。The organic silicon nano-hydrophobic film layer and the preparation method thereof according to the specific embodiment of the present invention are formed by plasma polymerization deposition of siloxane monomers. A central electrode and a cavity wall electrode suitable for discharge are arranged in the plasma reaction chamber. The central electrode and the cavity wall electrode are turned on to discharge into the plasma reaction chamber, so that the entire plasma reaction chamber is in a uniformly distributed electric field, and the gaseous siloxane monomers are activated into plasma and uniformly deposited on the surface of the substrate, effectively overcoming the problem of large differences in coating thickness at different positions on the surface of the substrate caused by the direct deposition of the gaseous siloxane monomers into the plasma chamber, while improving the wear resistance and film-forming speed of the prepared organic silicon nano-hydrophobic film layer, and at the same time improving the film quality and coating efficiency.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1示出了根据本发明的具体实施方式的制备方法采用的镀膜设备的结构示意图。FIG1 shows a schematic structural diagram of a coating device used in a preparation method according to a specific embodiment of the present invention.
具体实施方式Detailed ways
本发明的发明人在研究中发现，气态的硅氧烷类单体直接进入等离子腔室等离子体激发在基材上聚合沉积形成膜层时，可能由于气态硅氧烷类单体扩散较慢的原因，基材表面不同位置的涂层厚度差异比较多，通过在等离子体反应腔室内设置适于放电的双电极，并且使基材在反应腔室中旋转运动，可使所述硅氧烷类单体均匀分布于基材表面不同位置，从而有效降低所述涂层厚度差异，因此，本发明的具体实施方式提供一种如下的有机硅纳米疏水膜层的制备方法，包括以下步骤：The inventors of the present invention have found in their research that when gaseous siloxane monomers directly enter the plasma chamber and are excited by plasma to polymerize and deposit on the substrate to form a film layer, the coating thickness at different positions on the substrate surface may vary greatly due to the slow diffusion of the gaseous siloxane monomers. By arranging a double electrode suitable for discharge in the plasma reaction chamber and rotating the substrate in the reaction chamber, the siloxane monomers can be evenly distributed at different positions on the substrate surface, thereby effectively reducing the coating thickness difference. Therefore, a specific embodiment of the present invention provides a method for preparing a hydrophobic organic silicon nano-film layer as follows, comprising the following steps:
将基材置于等离子体反应腔室内，所述等离子体反应腔室内设有适于放电的双电极，所述双电极包括：设于所述等离子体反应腔室的中心的中心电极与设于所述等离子体反应腔室的内壁的腔壁电极；Placing a substrate in a plasma reaction chamber, wherein the plasma reaction chamber is provided with a double electrode suitable for discharge, wherein the double electrode comprises: a central electrode provided at the center of the plasma reaction chamber and a cavity wall electrode provided at the inner wall of the plasma reaction chamber;
气态的硅氧烷类单体由所述单体进气口通入所述等离子体反应腔室内，开启所述双电极向所述等离子体反应腔室内等离子体放电，所述气态的硅氧烷类单体在所述基材表面等离子体化学气相沉积形成所述有机硅纳米疏水膜层。 The gaseous siloxane monomers are introduced into the plasma reaction chamber from the monomer inlet, and the double electrodes are turned on to discharge plasma into the plasma reaction chamber. The gaseous siloxane monomers are plasma chemical vapor deposited on the surface of the substrate to form the organic silicon nano-hydrophobic film layer.
本发明具体实施方式的有机硅纳米疏水膜层的制备方法，所述硅氧烷类单体包括下式(1)或(2)所示结构至少一种，
In the method for preparing the organic silicon nano-hydrophobic film layer according to the specific embodiment of the present invention, the siloxane monomer comprises at least one of the structures shown in the following formula (1) or (2):
式(1)或(2)中，R1、R2、R3、R5和R6分别独立的选自于氢原子、卤素、C1-C12的取代或非取代烃基、C1-C12的取代或非取代烃氧基、或C1-C12的取代或非取代烃基硅氧基，所述R1、R2和R3中至少一个不为氢原子，所述R5或R6中至少一个不为氢原子，R4为C1-C12的取代或非取代烃基、或C1-C12的取代或非取代烃基硅基，n为1～100的整数，m为3～10的整数。本发明的具体实施方式中，所述烃基可以是烷烃基、烯烃基、炔烃基或芳烃基，所述取代基例如可以是卤素原子、羟基、酰氧基、胺基、腈基或烃氧基等等，作为具体的举例，所述硅氧烷类单体例如可以是二苯基二甲氧基硅烷、正硅酸甲酯、正硅酸乙酯、二乙胺基甲基三乙氧基硅烷、二乙烯三胺基丙基三甲氧基硅烷、1,1,1-三甲基-N-2-丙烯丙胺基硅烷、双[3-(三甲氧基硅基)丙基]乙二胺、五甲基二硅氧烷、六甲基二硅氧烷、六甲氧基二硅氧烷、六苯基二硅氧烷、乙烯基五甲基二硅氧烷、1-乙烯基-1133-四甲基二硅氧烷、1,3-辛基四甲基二硅氧烷、1,1,3,3-四甲基-1,3-二苯基二硅氧烷、1,1,3,3-四甲基二硅氧烷、1,3-二乙烯基四甲基二硅氧烷、1,3-双(氯甲基)四甲基二硅氧烷、1,3-二氯四甲基二硅氧烷、1,3-双(4-羟基丁基)四甲基二硅氧烷、1,3-双(3-氰丙基)四甲基二硅氧烷、1,3-二甲基四乙烯基二硅氧烷、13-二甲氧基-1133-四甲基二硅氧烷、1,1,1,3,3,5,5-七甲基三硅氧烷、1,1,1,3,5,5,5-七甲基三硅氧烷、1,1,5,5-四甲基-3,3-二苯基三硅氧烷、1,1,3,3,5,5-六甲基三硅氧烷、3-[[二甲基(乙烯基)硅烷基]氧]-1,1,5,5-四甲基-3-苯基-1,5-二乙烯基三硅氧烷、1,5-二氯-1,1,3,3,5,5-六甲基三硅氧烷、八甲基三硅氧烷、十甲基四硅氧烷、1,1,1,3,5,7,7,7-八甲基四硅氧烷、1,1,3,3,5,5,7,7-八甲基四硅氧烷、1,7-二氯-1,1,3,3,5,5,7,7-八甲基四硅氧烷、十二甲基五硅氧 烷、十甲基二氢五硅氧烷、十四甲基六硅氧烷、1,1,3,3,5,5,7,7,9,9,11,11-十二甲基六硅氧烷、十六烷基七硅氧烷、1,1,3,3,5,5,7,7,9,9,11,11,13,13-十四甲基七硅氧烷、1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,15-十六甲基八硅氧烷、聚二甲基硅氧烷、聚甲基氢硅氧烷、聚二甲基硅氧烷氢化物封端、聚苯甲基硅氧烷、乙烯基封端二甲基聚硅氧烷、苯基三(三甲基硅氧烷基)硅烷、乙烯基三(三甲基硅氧烷基)硅烷、甲基三(三甲基硅氧烷基)硅烷、乙基三(三甲基硅氧烷基)硅烷、1,1,1,3,5,7,7,7-八甲基-3,5-二(三甲基硅烷氧基)四硅氧烷、1,3-二苯基-1,3-双(三甲基硅氧基)二硅氧烷、烯丙基三(三甲基硅氧基)硅烷、四(三甲基硅氧基)硅烷、(3-氯丙基)三(三甲基硅氧基)硅烷、甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷、六甲基环三硅氧烷、六乙基环三硅氧烷、六苯基环三硅氧烷、六乙基环三硅氧烷、2,4,6-三乙基-2,4,6-三甲基环三硅氧烷、1,3,5-三乙烯基-1,3,5-三甲基环三硅氧烷、2,4,6-三甲基环三硅氧烷、三甲基-1,3,5-三苯基环三硅氧烷、2,4,6-三乙烯基-2,4,6-三甲基环三硅氧烷、八甲基环四硅氧烷、八苯基环四硅氧烷、2,2,4,4-四甲基-6,6,8,8-四苯基环四硅氧烷、十甲基环五硅氧烷、2,4,6,8-四甲基-2,4,6,8-四乙烯基环四硅氧烷、1,3,5,7-四乙烯基-1,3,5,7-四甲基环四硅氧烷、1,3,5,7-四甲基环四硅氧烷、2,4,6,8-四甲基环四硅氧烷、2,4,6,8-四甲基-2-[3-(环氧乙烷基甲氧基)丙基]环四硅氧烷、2,4-二乙烯基-2,4,6,6,8,8-六甲基环四硅氧烷、五甲基五乙烯基环五硅氧烷、2,4,6,8,10-五甲基环五硅氧烷、十二甲基环六硅氧烷、六甲基六乙烯基环六硅氧烷、十六甲基环辛硅氧烷或十八甲基环壬硅氧烷等等。In formula (1) or (2), R 1 , R 2 , R 3 , R 5 and R 6 are independently selected from hydrogen atom, halogen, C 1 -C 12 substituted or unsubstituted hydrocarbon group, C 1 -C 12 substituted or unsubstituted hydrocarbonoxy group, or C 1 -C 12 substituted or unsubstituted hydrocarbonsiloxy group, at least one of R 1 , R 2 and R 3 is not a hydrogen atom, at least one of R 5 or R 6 is not a hydrogen atom, R 4 is a C 1 -C 12 substituted or unsubstituted hydrocarbon group, or a C 1 -C 12 substituted or unsubstituted hydrocarbonsilyl group, n is an integer of 1 to 100, and m is an integer of 3 to 10. In a specific embodiment of the present invention, the hydrocarbon group may be an alkane group, an olefin group, an alkyne group or an aromatic hydrocarbon group, and the substituent group may be, for example, a halogen atom, a hydroxyl group, an acyloxy group, an amino group, a nitrile group or a hydrocarbon group, etc. As a specific example, the siloxane monomer may be, for example, diphenyldimethoxysilane, methyl orthosilicate, ethyl orthosilicate, diethylaminomethyltriethoxysilane, diethylenetriaminopropyltrimethoxysilane, 1,1,1-trimethyl-N-2-propylenepropylaminosilane, bis[3-(trimethoxysilane)] 1-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2-(4-(2- , 1,3-bis(4-hydroxybutyl)tetramethyldisiloxane, 1,3-bis(3-cyanopropyl)tetramethyldisiloxane, 1,3-dimethyltetravinyldisiloxane, 13-dimethoxy-1133-tetramethyldisiloxane, 1,1,1,3,3,5,5-heptamethyltrisiloxane, 1,1,1,3,5,5,5-heptamethyltrisiloxane, 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 3-[[di Methyl(vinyl)silyl]oxy]-1,1,5,5-tetramethyl-3-phenyl-1,5-divinyltrisiloxane, 1,5-dichloro-1,1,3,3,5,5-hexamethyltrisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1,7-dichloro-1,1,3,3,5,5,7,7-octamethyltetrasiloxane, dodecamethylpentasiloxane alkane, decamethyldihydrogenpentasiloxane, tetradecamethylhexasiloxane, 1,1,3,3,5,5,7,7,9,9,11,11-dodecamethylhexasiloxane, hexadecylheptasiloxane, 1,1,3,3,5,5,7,7,9,9,11,11,13,13-tetradecamethylheptasiloxane, 1,1,3,3,5,5,7,7,9,9,11,11,13,13,15,15-hexadecamethyloctasiloxane, polydimethylsiloxane, polymethylhydrogensiloxane, polydimethylsiloxane hydride terminated, polyphenylmethylsiloxane, vinyl terminated dimethylpolysiloxane, phenyl tris(trimethylsiloxane) tris(trimethylsiloxy)silane, vinyl tris(trimethylsiloxy)silane, methyl tris(trimethylsiloxy)silane, ethyl tris(trimethylsiloxy)silane, 1,1,1,3,5,7,7,7-octamethyl-3,5-bis(trimethylsiloxy)tetrasiloxane, 1,3-diphenyl-1,3-bis(trimethylsiloxy)disiloxane, allyl tris(trimethylsiloxy)silane, tetra(trimethylsiloxy)silane, (3-chloropropyl) tris(trimethylsiloxy)silane, methacryloxypropyl tris(trimethylsiloxy)silane, hexamethylcyclotrisiloxane, hexaethylcyclotrisiloxane, hexaphenylcyclotrisiloxane trisiloxane, hexaethylcyclotrisiloxane, 2,4,6-triethyl-2,4,6-trimethylcyclotrisiloxane, 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane, 2,4,6-trimethylcyclotrisiloxane, trimethyl-1,3,5-triphenylcyclotrisiloxane, 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane, octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, 2,2,4,4-tetramethyl-6,6,8,8-tetraphenylcyclotetrasiloxane, decamethylcyclopentasiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane cyclotetrasiloxane, 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, 2,4,6,8-tetramethyl-2-[3-(oxiranylmethoxy)propyl]cyclotetrasiloxane, 2,4-divinyl-2,4,6,6,8,8-hexamethylcyclotetrasiloxane, pentamethylpentavinylcyclopentasiloxane, 2,4,6,8,10-pentamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, hexamethylhexavinylcyclohexasiloxane, hexadecylcyclooctylsiloxane or octadecylcyclononasiloxane, and the like.
本发明具体实施方式的有机硅纳米疏水膜层的制备方法，在一些具体实施方式中，兼顾耐磨性与疏水性，所述R1、R2、R3、R5和R6分别独立的选自于甲基或乙基，特别是甲基，所述R4为甲基、乙基或三甲基硅基，特别是甲基或三甲基硅基，所述n为2～10的整数，所述硅氧烷类单体例如可以是六甲基二硅氧烷、八甲基三硅氧烷、十甲基四硅氧烷、十二甲基五硅氧烷、十四甲基六硅氧烷、六甲基环三硅氧烷、六乙基环三硅氧烷、八甲基环四硅氧烷、八乙基环四硅氧烷、十甲基环五硅氧烷或十二甲基环六硅氧烷等等。 In the method for preparing the organic silicon nano-hydrophobic film layer according to the specific embodiment of the present invention, in some specific embodiments, both wear resistance and hydrophobicity are taken into consideration, the R 1 , R 2 , R 3 , R 5 and R 6 are independently selected from methyl or ethyl, especially methyl, the R 4 is methyl, ethyl or trimethylsilyl, especially methyl or trimethylsilyl, the n is an integer of 2 to 10, and the siloxane monomer can be, for example, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexamethylcyclotrisiloxane, hexaethylcyclotrisiloxane, octamethylcyclotetrasiloxane, octaethylcyclotetrasiloxane, decamethylcyclopentasiloxane or dodecamethylcyclohexasiloxane, and the like.
本发明具体实施方式的有机硅纳米疏水膜层的制备方法，在一些具体实施方式中，考虑到所述有机硅纳米疏水膜层具有更好的耐磨性能，所述硅氧烷单体包括硅氧烷单体一和硅氧烷单体二，其中所述硅氧烷单体一具有一个不饱和双键，所述硅氧烷单体二具有至少两个不饱和双键。进一步，在一些具体实施方式中，所述硅氧烷单体一具有下式(3)所示结构，
In the method for preparing the organic silicon nano-hydrophobic film layer of the specific embodiment of the present invention, in some specific embodiments, considering that the organic silicon nano-hydrophobic film layer has better wear resistance, the siloxane monomer includes siloxane monomer 1 and siloxane monomer 2, wherein the siloxane monomer 1 has one unsaturated double bond, and the siloxane monomer 2 has at least two unsaturated double bonds. Further, in some specific embodiments, the siloxane monomer 1 has the structure shown in the following formula (3),
式(3)中，R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17和R18分别独立的选自于氢原子或C1-C4的烃基，R10、R11和R12中至少一个不为氢原子，R13、R14和R15中至少一个不为氢原子，R16、R17和R18中至少一个不为氢原子，p为1～10的整数。进一步，在一些具体实施方式中，所述R7、R8和R9分别独立的选自于氢原子或甲基，所述R10、R11、R12、R13、R14、R15、R16、R17和R18分别独立的选自于甲基或乙基，进一步，在一些具体实施方式中，所述硅氧烷单体一为甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷，进一步，在一些具体实施方式中，所述硅氧烷单体二具有下式(2)所示结构，
In formula (3), R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are independently selected from hydrogen atoms or C 1 -C 4 hydrocarbon groups, at least one of R 10 , R 11 and R 12 is not a hydrogen atom, at least one of R 13 , R 14 and R 15 is not a hydrogen atom, at least one of R 16 , R 17 and R 18 is not a hydrogen atom, and p is an integer of 1 to 10. Further, in some specific embodiments, the R 7 , R 8 and R 9 are independently selected from hydrogen atoms or methyl groups, and the R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are independently selected from methyl groups or ethyl groups. Further, in some specific embodiments, the siloxane monomer 1 is methacryloxypropyl tris(trimethylsiloxy)silane. Further, in some specific embodiments, the siloxane monomer 2 has the structure shown in the following formula (2):
所述R5为C1-C4的烯烃基，所述R6为C1-C4的烷烃基，进一步，在一些 具体实施方式中，所述硅氧烷单体二为1,3,5,7-四乙烯基-1,3,5,7-四甲基环四硅氧烷。本发明的一些具体实施方式中，所述硅氧烷单体一与硅氧烷单体二的摩尔比为1:10～10:1,具体的例如可以是1:10、2:10、3:10、4:10、5:10、6:10、7:10、8:10、9:10、10:10、10:1、10:2、10:3、10:4、10:5、10:6、10:7、10:8、10:9等等。The R 5 is a C 1 -C 4 olefin group, the R 6 is a C 1 -C 4 alkane group, and further, in some In a specific embodiment, the siloxane monomer 2 is 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane. In some specific embodiments of the present invention, the molar ratio of the siloxane monomer 1 to the siloxane monomer 2 is 1:10 to 10:1, and specifically, for example, it can be 1:10, 2:10, 3:10, 4:10, 5:10, 6:10, 7:10, 8:10, 9:10, 10:10, 10:1, 10:2, 10:3, 10:4, 10:5, 10:6, 10:7, 10:8, 10:9, etc.
本发明具体实施方式的有机硅纳米疏水膜层的制备方法，通过在等离子体反应腔室内设有适于放电的双电极，相比单电极形成更均匀的电场，等离子体更均匀的沉积于基材表面。所述双电极包括设于所述等离子体反应腔室的中心的中心电极与设于所述等离子体反应腔室的内壁的腔壁电极，因此，在放电时整个等离子体反应腔形成均匀的电场。The method for preparing the organic silicon nano-hydrophobic film layer according to the specific embodiment of the present invention forms a more uniform electric field than a single electrode by providing a double electrode suitable for discharge in the plasma reaction chamber, and the plasma is more uniformly deposited on the surface of the substrate. The double electrode includes a central electrode provided at the center of the plasma reaction chamber and a cavity wall electrode provided on the inner wall of the plasma reaction chamber, so that a uniform electric field is formed in the entire plasma reaction chamber during discharge.
本发明具体实施方式的有机硅纳米疏水膜层的制备方法，在一些具体的实施方式中，通过图1所示的镀膜设备在基材上制备膜层。参考图1，图1示出了根据本发明的具体实施方式的制备方法采用的镀膜设备的结构示意图。所述镀膜设备包括等离子体反应腔室1，适于容纳基材9。所述等离子体反应腔室1包括内壁2。等离子体反应腔室1包括适于放电的双电极，所述双电极包括中心电极3和腔壁电极4，中心电极3设于等离子体反应腔室1的中心，腔壁电极4设于等离子体反应腔室1的内壁2。In the method for preparing the organosilicon nano-hydrophobic film layer according to the specific embodiment of the present invention, in some specific embodiments, the film layer is prepared on the substrate by the coating device shown in Figure 1. Referring to Figure 1, Figure 1 shows a schematic structural diagram of the coating device used in the preparation method according to the specific embodiment of the present invention. The coating device includes a plasma reaction chamber 1, which is suitable for accommodating a substrate 9. The plasma reaction chamber 1 includes an inner wall 2. The plasma reaction chamber 1 includes a double electrode suitable for discharge, and the double electrode includes a central electrode 3 and a cavity wall electrode 4, the central electrode 3 is arranged at the center of the plasma reaction chamber 1, and the cavity wall electrode 4 is arranged on the inner wall 2 of the plasma reaction chamber 1.
本发明具体实施方式的有机硅纳米疏水膜层的制备方法，在一些具体实施方式中，所述中心电极3包括至少一圆筒电极，所述腔壁电极4包括至少一块的电极板。In the method for preparing the organic silicon nano-hydrophobic film layer according to the specific embodiment of the present invention, in some specific embodiments, the central electrode 3 includes at least one cylindrical electrode, and the cavity wall electrode 4 includes at least one electrode plate.
本发明具体实施方式的有机硅纳米疏水膜层的制备方法，在一些具体实施方式中，中心电极3包括两个套设在一起的圆筒电极(31，32)，其中一个圆筒电极接地，另一个圆筒电极与电源连通，以便在两个圆筒电极(31，32)之间形成电场33，使气态硅氧烷类单体在电场中被激活为等离子体。腔壁电极4包括至少两块电极板，所述电极板与电源的一端连通，电源的另一端连接反应腔体，反应腔体接地。In the method for preparing the organic silicon nano-hydrophobic film layer according to the specific embodiment of the present invention, in some specific embodiments, the central electrode 3 includes two cylindrical electrodes (31, 32) arranged together, one of which is grounded, and the other is connected to a power source, so as to form an electric field 33 between the two cylindrical electrodes (31, 32), so that the gaseous siloxane monomers are activated into plasma in the electric field. The cavity wall electrode 4 includes at least two electrode plates, the electrode plates are connected to one end of the power source, the other end of the power source is connected to the reaction chamber, and the reaction chamber is grounded.
本发明具体实施方式的有机硅纳米疏水膜层的制备方法，在一些具体实施方式中，中心电极3为圆筒电极，腔壁电极4的形状与所述等离子体反应 腔室1的形状相对应，具体例如，等离子体反应腔室1为圆柱状，对应的腔壁电极4呈圆柱状，当腔壁电极4包括一块电极板时，该一块电极板呈圆柱状；当腔壁电极4包括至少两块电极板时，该至少两块电极板分别为圆弧板状且共同构成圆柱状。In the method for preparing the organic silicon nano-hydrophobic film layer according to the specific embodiment of the present invention, in some specific embodiments, the central electrode 3 is a cylindrical electrode, and the shape of the cavity wall electrode 4 is consistent with the plasma reaction. The shape of the chamber 1 corresponds to that of the chamber 1. For example, the plasma reaction chamber 1 is cylindrical, and the corresponding chamber wall electrode 4 is cylindrical. When the chamber wall electrode 4 includes an electrode plate, the electrode plate is cylindrical; when the chamber wall electrode 4 includes at least two electrode plates, the at least two electrode plates are respectively arc-shaped and together constitute a cylindrical shape.
本发明具体实施方式的有机硅纳米疏水膜层的制备方法，在一些具体实施方式中，腔壁电极4上设有多个孔隙，以便于气态硅氧烷类单体穿过其进入等离子体反应腔室1内。In some specific embodiments of the method for preparing the organosilicon nano-hydrophobic film layer according to the specific embodiment of the present invention, a plurality of pores are provided on the cavity wall electrode 4 to facilitate the gaseous siloxane monomers to pass through the pores and enter the plasma reaction chamber 1 .
本发明具体实施方式的有机硅纳米疏水膜层的制备方法，等离子体反应腔室1内设有抽气装置以调节压力，在一些具体实施方式中，等离子体反应腔室1的中心位置设有抽气柱，抽气柱上设有孔隙，并连通真空泵，以将等离子体反应腔室1中的气体抽出，控制等离子体反应腔室1的压力。在一些具体实施方式中，所述中心电极包括第一圆筒电极31和第二圆筒电极32，第二圆筒电极32套设于第一圆筒电极31内。在一些具体实施例中，第二圆筒电极32上设有多个孔隙，以作为抽气柱并接地，第一圆筒电极31套设于抽气柱的外侧并与电源连通，第一圆筒电极31上设有多个孔隙，以便气体穿过进入抽气柱被抽出等离子体反应腔室1。In the method for preparing the organic silicon nano-hydrophobic film layer according to the specific embodiment of the present invention, a gas extraction device is provided in the plasma reaction chamber 1 to adjust the pressure. In some specific embodiments, a gas extraction column is provided at the center of the plasma reaction chamber 1, and a hole is provided on the gas extraction column, and the gas extraction column is connected to a vacuum pump to extract the gas in the plasma reaction chamber 1 and control the pressure of the plasma reaction chamber 1. In some specific embodiments, the central electrode includes a first cylindrical electrode 31 and a second cylindrical electrode 32, and the second cylindrical electrode 32 is sleeved in the first cylindrical electrode 31. In some specific embodiments, a plurality of holes are provided on the second cylindrical electrode 32 to serve as a gas extraction column and to be grounded, and the first cylindrical electrode 31 is sleeved on the outside of the gas extraction column and is connected to a power source, and a plurality of holes are provided on the first cylindrical electrode 31 so that the gas passes through the gas extraction column and is extracted out of the plasma reaction chamber 1.
本发明具体实施方式的有机硅纳米疏水膜层的制备方法，在一些具体实施方式中，第一圆筒电极31套设在第二圆筒电极32的外侧，第一圆筒电极31和腔壁电极4可以设计为与同一电源电连接，或分别与两个电源电连接。在一些具体实施方式中，第一圆筒电极31与腔壁电极4与同一电源电连接，从而在电源开启时，所述中心电极3与所述腔壁电极4同时放电，提高了放电效率和形成的电场在等离子体反应腔室1中的分布均匀性，所述电场激活硅氧烷类单体为等离子体，等离子体在基材表面91发生化学气相沉积，形成有机硅纳米疏水膜层。In the method for preparing the organic silicon nano-hydrophobic film layer of the specific embodiment of the present invention, in some specific embodiments, the first cylindrical electrode 31 is sleeved on the outside of the second cylindrical electrode 32, and the first cylindrical electrode 31 and the cavity wall electrode 4 can be designed to be electrically connected to the same power supply, or to be electrically connected to two power supplies respectively. In some specific embodiments, the first cylindrical electrode 31 and the cavity wall electrode 4 are electrically connected to the same power supply, so that when the power is turned on, the central electrode 3 and the cavity wall electrode 4 discharge at the same time, thereby improving the discharge efficiency and the distribution uniformity of the formed electric field in the plasma reaction chamber 1, and the electric field activates the siloxane monomer to form a plasma, and the plasma undergoes chemical vapor deposition on the surface 91 of the substrate to form an organic silicon nano-hydrophobic film layer.
继续参考图1，镀膜设备的等离子体反应腔室1内设有支架5，所述支架5上设有支撑件6，支撑架6上设有支撑区61，适于对置于其上的基材9进行支撑，在基材表面91制备有机硅纳米膜层的过程中，由所述支架5绕所述支架5的中心轴X旋转和所述支撑件6绕所述支撑件6的中心轴Y旋转，从而带动所述基材9在反应腔室内旋转运动。在一些具体实施方式中，支架5的 中心轴X位于等离子体反应腔室1的中心。Continuing to refer to FIG. 1 , a support 5 is provided in the plasma reaction chamber 1 of the coating equipment, and a support member 6 is provided on the support 5. The support frame 6 is provided with a support area 61, which is suitable for supporting a substrate 9 placed thereon. During the process of preparing the organic silicon nanofilm layer on the substrate surface 91, the support 5 rotates around the central axis X of the support 5 and the support member 6 rotates around the central axis Y of the support member 6, thereby driving the substrate 9 to rotate in the reaction chamber. In some specific embodiments, the support 5 The central axis X is located at the center of the plasma reaction chamber 1 .
本发明具体实施方式的有机硅纳米疏水膜层的制备方法，在一些具体实施方式中，所述支撑件6环绕所述支架5布置一层以上，每层布置1个以上，具体的例如所述支撑件6环绕所述支架5布置3～5层，每层布置3～10个支撑件6，所述基材9置于所述支撑件6上，以进一步增加等离子体反应腔室1的空间利用效率，以便可以实现同时给多个基材表面91制备有机硅纳米疏水膜层。In the method for preparing an organosilicon nano-hydrophobic film layer according to a specific embodiment of the present invention, in some specific embodiments, the support member 6 is arranged around the bracket 5 in more than one layer, and more than one support member 6 is arranged in each layer. For example, the support member 6 is arranged around the bracket 5 in 3 to 5 layers, and 3 to 10 support members 6 are arranged in each layer. The substrate 9 is placed on the support member 6 to further increase the space utilization efficiency of the plasma reaction chamber 1, so that the organosilicon nano-hydrophobic film layer can be prepared on multiple substrate surfaces 91 at the same time.
本发明具体实施方式的有机硅纳米疏水膜层的制备方法，在一些具体实施方式中，通过所述支架5绕所述支架5的中心轴X旋转形成公转，通过所述支撑件6绕所述支撑件6的中心轴Y旋转形成自转，以形成行星式旋转，也就是说，被放置于所述支撑件6上的所述基材9在所述等离子体反应腔室1内既进行自转，又进行公转，以便为所有的基材9提供一致性更高的镀膜条件，从而确保所有的基材获得均匀性一致的膜层，以便满足工业化批量化生产的要求。In the method for preparing the organosilicon nano-hydrophobic film layer according to the specific embodiment of the present invention, in some specific embodiments, the support 5 is rotated around the central axis X of the support 5 to form a revolution, and the support 6 is rotated around the central axis Y of the support 6 to form a rotation, so as to form a planetary rotation. That is, the substrate 9 placed on the support 6 rotates and revolves in the plasma reaction chamber 1, so as to provide more consistent coating conditions for all substrates 9, thereby ensuring that all substrates obtain uniform film layers to meet the requirements of industrial mass production.
本发明具体实施方式的有机硅纳米疏水膜层的制备方法，在一些具体实施方式中，所述支架5旋转的转速为1～10转/min，具体的例如可以是1转/min、2转/min、3转/min、4转/min、6转/min、7转/min、9转/min或10转/min等等，所述支撑件6旋转的转速为1～10转/min，具体的例如可以是1转/min、2转/min、3转/min、4转/min、6转/min、7转/min、9转/min或10转/min等等。In the method for preparing a silicone nano-hydrophobic film layer according to a specific embodiment of the present invention, in some specific embodiments, the rotation speed of the bracket 5 is 1 to 10 rpm, and specific examples thereof may be 1 rpm, 2 rpm, 3 rpm, 4 rpm, 6 rpm, 7 rpm, 9 rpm, or 10 rpm, etc., and the rotation speed of the support member 6 is 1 to 10 rpm, and specific examples thereof may be 1 rpm, 2 rpm, 3 rpm, 4 rpm, 6 rpm, 7 rpm, 9 rpm, or 10 rpm, etc.
继续参考图1，等离子体反应腔室1的侧壁上设有单体释放源7，其与单体供应单元8相连通，单体释放源7设有单体进气口71，以便于单体供应单元8提供硅氧烷类单体通过单体进气口71进入等离子体反应腔室1中。在镀膜过程中，气态的硅氧烷类单体72通过单体进气口71进入等离子体反应腔室1。在一些具体的实施方式中，单体进气口71有多个，均匀分布于等离子体反应腔室1的侧壁上。单体进气口71可以设置于与支撑件6相邻的侧壁上，以减少气态硅氧烷类单体72到基材9的距离，减少硅氧烷类单体化学气相沉积在基材表面91的时间，从而提高镀膜速度。Continuing to refer to FIG. 1 , a monomer release source 7 is provided on the side wall of the plasma reaction chamber 1, which is connected to the monomer supply unit 8. The monomer release source 7 is provided with a monomer gas inlet 71, so that the monomer supply unit 8 provides the siloxane monomer to enter the plasma reaction chamber 1 through the monomer gas inlet 71. During the coating process, the gaseous siloxane monomer 72 enters the plasma reaction chamber 1 through the monomer gas inlet 71. In some specific embodiments, there are multiple monomer gas inlets 71, which are evenly distributed on the side wall of the plasma reaction chamber 1. The monomer gas inlet 71 can be set on the side wall adjacent to the support member 6 to reduce the distance from the gaseous siloxane monomer 72 to the substrate 9, reduce the time for the siloxane monomer chemical vapor deposition on the substrate surface 91, and thus increase the coating speed.
需要说明的是，图1所示的镀膜设备，仅为举例说明根据本发明的具体 实施方式的有机硅纳米疏水膜层的制备方法中所采用的设备，并非是对本发明的具体实施方式的制备方法所采用的镀膜设备的限制。基于本发明的具体实施方式的制备方法，可以选用其他镀膜设备进行镀膜。It should be noted that the coating equipment shown in FIG. 1 is only an example of the specific The equipment used in the preparation method of the organic silicon nano-hydrophobic film layer of the embodiment is not a limitation on the coating equipment used in the preparation method of the specific embodiment of the present invention. Based on the preparation method of the specific embodiment of the present invention, other coating equipment can be selected for coating.
本发明具体实施方式的有机硅纳米疏水膜层的制备方法，在一些具体实施方式中，在单体进气口与基材之间设置纱网，由于纱网的导流作用，进入纱网内部的气态硅氧烷类单体的气流分布更加均匀，以便基材表面接触均匀的作为镀膜材料的气态硅氧烷类单体，在一些具体实施方式中，所述纱网的设置方式采用直接将纱网包裹基材支撑件的方式。在一些具体实施方式中，所述纱网的网格大小为10～100目，具体的可以是10目、20目、30目、50目、60目、70目、80目、90目或100目等等，对于具体的网格大小可根据具体的硅氧烷类单体种类进行调节。In the method for preparing the organic silicon nano-hydrophobic film layer of the specific embodiment of the present invention, in some specific embodiments, a gauze is arranged between the monomer air inlet and the substrate. Due to the guiding effect of the gauze, the airflow distribution of the gaseous siloxane monomer entering the interior of the gauze is more uniform, so that the surface of the substrate is in contact with the gaseous siloxane monomer as the coating material. In some specific embodiments, the gauze is arranged in a manner of directly wrapping the gauze around the substrate support. In some specific embodiments, the mesh size of the gauze is 10 to 100 meshes, specifically 10 meshes, 20 meshes, 30 meshes, 50 meshes, 60 meshes, 70 meshes, 80 meshes, 90 meshes or 100 meshes, etc. The specific mesh size can be adjusted according to the specific type of siloxane monomer.
本发明具体实施方式的有机硅纳米疏水膜层的制备方法，在一些具体实施方式中，所述有机硅纳米疏水膜层的水接触角不小于105°，具体的例如可以是105°、106°、107°、108°、109°、110°、111°、112°、113°、114°、115°、116°、117°、118°、119°、120°、125°、130°、135°、140°、145°或150°等等。The preparation method of the organosilicon nano-hydrophobic film layer according to the specific embodiment of the present invention, in some specific embodiments, the water contact angle of the organosilicon nano-hydrophobic film layer is not less than 105°, and can be, for example, 105°, 106°, 107°, 108°, 109°, 110°, 111°, 112°, 113°, 114°, 115°, 116°, 117°, 118°, 119°, 120°, 125°, 130°, 135°, 140°, 145° or 150°, etc.
本发明具体实施方式的有机硅纳米疏水膜层的制备方法，在一些具体实施方式中，所述膜层的厚度为10～100nm，具体的例如可以是10nm、20nm、30nm、40nm、50nm、60nm、70nm、80nm、90nm、100nm等等。In the method for preparing the organic silicon nano-hydrophobic film layer of the specific embodiment of the present invention, in some specific embodiments, the thickness of the film layer is 10 to 100 nm, for example, it can be 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, etc.
本发明具体实施方式的有机硅纳米疏水膜层的制备方法，在一些具体实施方式中，所述硅氧烷类单体的流速为10～2000μL/min，具体例如可以是50μL/min、100μL/min、150μL/min、160μL/min、200μL/min、300μL/min、400μL/min、500μL/min、1000μL/min、1500μL/min或2000μL/min等等；等离子体反应腔室的温度控制在30℃～60℃，具体例如可以是30℃、40℃、45℃、50℃、55℃或60℃等等；单体气化温度为50℃～180℃，具体例如可以是50℃、60℃、70℃、75℃、80℃、85℃、90℃、95℃、100℃、110℃、120℃、130℃、140℃、150℃、160℃、170℃或180℃等等，且是在真空条件下发生气化。In the method for preparing the organic silicon nano-hydrophobic film layer according to the specific embodiment of the present invention, in some specific embodiments, the flow rate of the siloxane monomer is 10 to 2000 μL/min, for example, 50 μL/min, 100 μL/min, 150 μL/min, 160 μL/min, 200 μL/min, 300 μL/min, 400 μL/min, 500 μL/min, 1000 μL/min, 1500 μL/min or 2000 μL/min. /min, etc.; the temperature of the plasma reaction chamber is controlled at 30°C to 60°C, for example, 30°C, 40°C, 45°C, 50°C, 55°C or 60°C, etc.; the monomer gasification temperature is 50°C to 180°C, for example, 50°C, 60°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C or 180°C, etc., and the gasification occurs under vacuum conditions.
本发明具体实施方式的有机硅纳米疏水膜层的制备方法，在一些具体实施方式中，为进一步提高所述有机硅纳米疏水膜层的结合力，在一些具体实施方式中，在涂层前对所述基材采用连续等离子体进行预处理，具体预处理 方式例如，抽真空至10～200毫托，并通入气体He、Ar、O2中的一种或几种的混合气体，开启等离子体放电对所述基材进行预处理，或者采用热、氧或高能辐射等方式等等。In some embodiments of the present invention, in order to further improve the binding force of the organic silicon nano-hydrophobic film layer, the substrate is pretreated with continuous plasma before coating. For example, the pressure is evacuated to 10-200 mTorr, and a mixture of one or more gases selected from He, Ar, and O2 is introduced, plasma discharge is started to pre-treat the substrate, or heat, oxygen, or high-energy radiation is used.
本发明具体实施方式的有机硅纳米疏水膜层的制备方法，在一些具体实施方式中，在预处理阶段和镀膜阶段，放电采用连续放电或脉冲放电。In some specific embodiments of the method for preparing the organic silicon nano-hydrophobic film layer according to the specific embodiment of the present invention, in the pretreatment stage and the coating stage, the discharge is continuous discharge or pulse discharge.
本发明具体实施方式的有机硅纳米疏水膜层的制备方法，在一些具体实施方式中，所述中心电极和腔壁电极与同一电源电连接，在预处理阶段，使用连续放电时，放电功率为50～600W，具体例如可以是50w、100w、120W、140W、160W、180W、190W、200W、210W、220W、230W、240W、250W、260W、270W、280W、290W、300W、400W、500W或600W等等；放电时间为30～2400s，具体例如可以是30s、60s、100s、200s、300s、400s、500s、600s、1000s、1200s、1500s、1800s或2400s等等。使用脉冲放电时，脉冲占空比0.1％～80％，具体例如可以是0.1％、5％、10％、15％、20％、25％、30％、35％、40％、45％、50％、55％、60％、65％、70％、75％或80％等等；脉冲频率10～500Hz，具体例如可以是10Hz、20Hz、25Hz、30Hz、35Hz、40Hz、45Hz、50Hz、55Hz、60Hz、70Hz、80Hz、90Hz、100Hz、200Hz、300Hz、400Hz或500Hz等等；放电功率为10～500W，具体例如可以是10W、20W、30W、40W、50W、60W、70W、80W、90W、100W、120W、140W、160W、180W、190W、200W、210W、220W、230W、240W、250W、260W、270W、280W、290W、300W、400W、500W等等；放电时间30～2400s，具体例如可以是30s、60s、100s、200s、300s、400s、500s、600s、1000s、1200s、1500s、1800s或2400s等等。In the method for preparing the organic silicon nano-hydrophobic film layer according to the specific embodiment of the present invention, in some specific embodiments, the central electrode and the cavity wall electrode are electrically connected to the same power supply. In the pretreatment stage, when continuous discharge is used, the discharge power is 50-600W, for example, 50W, 100W, 120W, 140W, 160W, 180W, 190W, 200W, 210W, 220W, 230W, 240W, 250W, 260W, 270W, 280W, 290W, 300W, 400W, 500W or 600W, etc.; the discharge time is 30-2400s, for example, 30s, 60s, 100s, 200s, 300s, 400s, 500s, 600s, 1000s, 1200s, 1500s, 1800s or 2400s, etc. When pulse discharge is used, the pulse duty ratio is 0.1% to 80%, and specifically, for example, it can be 0.1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% or 80%, etc.; the pulse frequency is 10 to 500 Hz, and specifically, for example, it can be 10 Hz, 20 Hz, 25 Hz, 30 Hz, 35 Hz, 40 Hz, 45 Hz, 50 Hz, 55 Hz, 60 Hz, 70 Hz, 80 Hz, 90 Hz, 100 Hz, 200 Hz, 300 Hz, 400 Hz or 500 Hz, etc.; the discharge power is 10 to 500 W, For example, it can be 10W, 20W, 30W, 40W, 50W, 60W, 70W, 80W, 90W, 100W, 120W, 140W, 160W, 180W, 190W, 200W, 210W, 220W, 230W, 240W, 250W, 260W, 270W, 280W, 290W, 300W, 400W, 500W, etc.; the discharge time is 30-2400s, for example, it can be 30s, 60s, 100s, 200s, 300s, 400s, 500s, 600s, 1000s, 1200s, 1500s, 1800s or 2400s, etc.
本发明具体实施方式的有机硅纳米疏水膜层的制备方法，在一些具体实施方式中，所述中心电极和腔壁电极与同一电源电连接，在镀膜阶段，使用连续放电时，放电功率为10～300W，具体例如可以是10W、20W、30W、40W、50W、60W、70W、80W、90W、100W、120W、140W、160W、180W、190W、200W、210W、220W、230W、240W、250W、260W、270W、280W、290W或300W等等；放电时间60～36000s，具体例如可以是60s、100s、200s、300s、400s、500s、600s、1000s、2000s、3000s、5000s、10000s、15000s、20000s、 25000s、30000s或36000s等等。使用脉冲放电时，脉冲占空比0.1～80％，具体例如可以是0.1％、5％、10％、15％、20％、25％、30％、35％、40％、45％、50％、55％、60％、65％、70％、75％或80％等等；脉冲频率10～500Hz，具体例如可以是10Hz、20Hz、25Hz、30Hz、35Hz、40Hz、45Hz、50Hz、55Hz、60Hz、70Hz、80Hz、90Hz、100Hz、200Hz、250Hz、300Hz、400Hz或500Hz等等；放电功率为10～400W，具体例如可以是10W、20W、30W、40w、50w、60w、70w、80w、90w、100w、120W、140W、160W、180W、190W、200W、210W、220W、230W、240W、250W、260W、270W、280W、290W、300W或400W等等；放电时间200～36000s，具体例如可以是200s、500s、1000s、2000s、3000s、3600s、4000s、5000s、6000s、7000s、7200s、10000s、15000s、20000s、25000s、30000s或36000s等等。In the method for preparing the organic silicon nano-hydrophobic film layer according to the specific embodiment of the present invention, in some specific embodiments, the central electrode and the cavity wall electrode are electrically connected to the same power supply. In the coating stage, when continuous discharge is used, the discharge power is 10 to 300 W, and specifically, for example, it can be 10 W, 20 W, 30 W, 40 W, 50 W, 60 W, 70 W, 80 W, 90 W, 100 W, 120 W, 140 W, 160 W, 180 W, 190 W, 200W, 210W, 220W, 230W, 240W, 250W, 260W, 270W, 280W, 290W or 300W, etc.; discharge time 60 to 36000s, for example, 60s, 100s, 200s, 300s, 400s, 500s, 600s, 1000s, 2000s, 3000s, 5000s, 10000s, 15000s, 20000s, 25000s, 30000s or 36000s, etc. When using pulse discharge, the pulse duty ratio is 0.1-80%, for example, it can be 0.1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% or 80%, etc.; the pulse frequency is 10-500Hz, for example, it can be 10Hz, 20Hz, 25Hz, 30Hz, 35Hz, 40Hz, 45Hz, 50Hz, 55Hz, 60Hz, 70Hz, 80Hz, 90Hz, 100Hz, 200Hz, 250Hz, 300Hz, 400Hz or 500Hz, etc.; the discharge power is 10-400W, for example, it can be 10W, 20W, 30W, 40W, 50W, 60W, 70W, 80W, 90W, 100W, 120W, 140W, 160W, 180W, 190W, 200W, 210W, 220W, 230W, 240W, 250W, 260W, 270W, 280W, 290W, 300W or 400W, etc.; discharge time 200-36000s, for example, it can be 200s, 500s, 1000s, 2000s, 3000s, 3600s, 4000s, 5000s, 6000s, 7000s, 7200s, 10000s, 15000s, 20000s, 25000s, 30000s or 36000s, etc.
本发明具体实施方式的有机硅纳米疏水膜层的制备方法，在一些具体实施方式中，所述等离子放电方式可以现有的各种放电方式，具体例如，无电极放电(如射频电感耦合放电、微波放电)、单电极放电(如电晕放电、单极放电所形成的等离子体射流)、双电极放电(如介质阻挡放电、裸露电极射频辉光放电)以及多电极放电(如采用浮动电极作为第三个电极的放电)。In the method for preparing the organic silicon nano-hydrophobic film layer according to the specific embodiment of the present invention, in some specific embodiments, the plasma discharge mode can be various existing discharge modes, for example, electrodeless discharge (such as radio frequency inductively coupled discharge, microwave discharge), single electrode discharge (such as corona discharge, plasma jet formed by monopolar discharge), double electrode discharge (such as dielectric barrier discharge, bare electrode radio frequency glow discharge) and multi-electrode discharge (such as discharge using a floating electrode as the third electrode).
本发明具体实施方式的有机硅纳米疏水膜层的制备方法，在一些具体实施方式中，所述基材为各种塑料、织物、玻璃、电气组件或光学仪器等。具体地，电气组件可以是印刷电路板(PCB)、电子产品或电子组装半成品等。在一些具体实施方式中，所述基材为电子或电气元器件，作为具体的非限制性举例，当所述基材是电子产品时，例如可以为手机、平板电脑、键盘、电子阅读器、可穿戴设备、显示器，耳机、USB数据线、USB接口、透音网、耳套或头带等。所述基材也可以是电气组件的任一合适的电气部件，具体地，所述电气部件可以是电阻器、电容器、晶体管、二极管、放大器、继电器、变压器、电池、熔断器、集成电路、开关、LED、LED显示器、压电元件、光电子部件或天线或振荡器等。The preparation method of the organosilicon nano hydrophobic film layer of the specific embodiment of the present invention, in some specific embodiments, the substrate is various plastics, fabrics, glass, electrical components or optical instruments, etc. Specifically, the electrical component can be a printed circuit board (PCB), an electronic product or an electronic assembly semi-finished product, etc. In some specific embodiments, the substrate is an electronic or electrical component. As a specific non-limiting example, when the substrate is an electronic product, it can be, for example, a mobile phone, a tablet computer, a keyboard, an e-reader, a wearable device, a display, a headset, a USB data cable, a USB interface, a sound-permeable net, an earmuff or a headband, etc. The substrate can also be any suitable electrical component of an electrical component, specifically, the electrical component can be a resistor, a capacitor, a transistor, a diode, an amplifier, a relay, a transformer, a battery, a fuse, an integrated circuit, a switch, an LED, an LED display, a piezoelectric element, an optoelectronic component or an antenna or an oscillator, etc.
本发明的具体实施方式还提供一种有机硅纳米疏水膜层，在一些具体实施方式中，所述有机硅纳米疏水膜层由以上所述的有机硅纳米疏水膜层的制备方法制备获得。 The specific embodiments of the present invention further provide an organosilicon nano-hydrophobic film layer. In some specific embodiments, the organosilicon nano-hydrophobic film layer is prepared by the above-mentioned method for preparing the organosilicon nano-hydrophobic film layer.
本发明的具体实施方式还提供一种器件，所述器件的至少部分表面具有以上所述的有机硅纳米疏水膜层，在一些具体实施方式中，所述器件的部分表面或全部表面仅涂覆有上述的保护涂层。在一些具体实施方式中，所述器件如前所述器件为电气组件、光学仪器、电子或电气元器件等。The specific embodiment of the present invention also provides a device, wherein at least part of the surface of the device has the above-mentioned organic silicon nano-hydrophobic film layer, and in some specific embodiments, part of the surface or the entire surface of the device is only coated with the above-mentioned protective coating. In some specific embodiments, the device is an electrical component, an optical instrument, an electronic or electrical component, etc.
以下通过具体实施例对本发明做进一步说明。The present invention is further described below by means of specific examples.
实施例Example
测试方法说明Test Method Description
涂层水触角：根据GB/T 30447-2013标准进行测试。Coating water tentacle: tested according to GB/T 30447-2013 standard.
膜层厚度测试：使用美国Filmetrics F20-UV-薄膜厚度测量仪进行检测。Film thickness test: Use the American Filmetrics F20-UV-film thickness measuring instrument for testing.
成膜速度测试：根据一定时间形成的膜层厚度，计算单位时间形成的膜层厚度。Film forming speed test: Calculate the thickness of the film formed per unit time based on the thickness of the film formed in a certain period of time.
耐摩擦性能测试：在耐磨试验机上进行，摩擦材料为无尘布，在1N的压力和50cycles/min的条件下测试摩擦1000次前后的水接触角。Friction resistance test: carried out on a wear tester, the friction material is dust-free cloth, and the water contact angle is tested before and after 1000 frictions under the conditions of 1N pressure and 50 cycles/min.
实施例1Example 1
将Si片和玻璃基材放置于等离子体反应腔室内，基材放置于支架的支撑件上，使用20目纱网将支撑件包裹；等离子体反应腔室内设有双电极，所述双电极为与同一电源电连接的中心电极和腔壁电极，用于向腔室内放电；The Si wafer and the glass substrate are placed in a plasma reaction chamber, the substrate is placed on a support of a bracket, and the support is wrapped with a 20-mesh gauze; a double electrode is provided in the plasma reaction chamber, and the double electrode is a central electrode and a cavity wall electrode electrically connected to the same power supply for discharging into the chamber;
将腔室抽真空至20毫托，通入氦气，流量80sccm，腔室温度为45℃；The chamber was evacuated to 20 mTorr, and helium was introduced at a flow rate of 80 sccm. The chamber temperature was 45°C.
保持腔室气压为20毫托，保持氦气流量为80sccm，开启支架和支撑件旋转，基材进行行星运动，支架旋转速度为2转/min，支撑件旋转速度为3转/min，开启双电极等离子体连续放电，放电功率为100W，持续放电600s，对基材进行预处理；The chamber pressure was maintained at 20 mTorr, the helium flow rate was maintained at 80 sccm, the support and the support were turned on to rotate, the substrate was subjected to planetary motion, the support rotation speed was 2 rpm, the support rotation speed was 3 rpm, the double-electrode plasma continuous discharge was turned on, the discharge power was 100 W, and the discharge was continued for 600 s to pretreat the substrate;
然后，将单体十甲基四硅氧烷，在气化温度为85℃下进行气化后导入等离子体腔室内，保持腔室气压为20毫托，保持氦气流量为80sccm，保持支架和支撑件旋转，开启双电极射频等离子体放电，射频的能量输出方式为脉冲，在基材表面进行等离子体化学气相沉积，其中脉冲占空比25％，脉冲频率200Hz，脉冲放电功率为120W，单体流量为160μL/min，反应时间为3600s； Then, the monomer decamethyltetrasiloxane was vaporized at a vaporization temperature of 85° C. and then introduced into the plasma chamber, the chamber pressure was maintained at 20 mTorr, the helium flow rate was maintained at 80 sccm, the bracket and the support were kept rotating, the double-electrode radio frequency plasma discharge was turned on, the radio frequency energy output mode was pulsed, and plasma chemical vapor deposition was performed on the surface of the substrate, wherein the pulse duty ratio was 25%, the pulse frequency was 200 Hz, the pulse discharge power was 120 W, the monomer flow rate was 160 μL/min, and the reaction time was 3600 s;
镀膜完成后，充入压缩空气使腔室恢复常压，取出已镀膜基材Si片和玻璃，测试Si片膜厚列于下表1中，对玻璃耐摩擦性能测试列于下表2中。After the coating is completed, compressed air is filled to restore the chamber to normal pressure, and the coated substrate Si wafer and glass are taken out. The test of Si wafer film thickness is listed in Table 1 below, and the test of glass friction resistance is listed in Table 2 below.
对比例1Comparative Example 1
将Si片和玻璃基材放置于等离子体反应腔室内，基材放置于支架的支撑件上，使用20目纱网将支撑件包裹；等离子体反应腔室内设有与电源电连接的中心电极，用于向腔室内放电；The Si wafer and the glass substrate are placed in a plasma reaction chamber, the substrate is placed on a support of a bracket, and the support is wrapped with a 20-mesh gauze; a central electrode electrically connected to a power source is provided in the plasma reaction chamber for discharging into the chamber;
将腔室抽真空至20毫托，通入氦气，流量80sccm，腔室温度为45℃；The chamber was evacuated to 20 mTorr, helium was introduced at a flow rate of 80 sccm, and the chamber temperature was 45°C;
保持腔室气压为20毫托，保持氦气流量为80sccm，开启支架和支撑件旋转，基材进行行星运动，支架旋转速度为2转/min，支撑件旋转速度为3转/min，开启中心电极等离子体连续放电，放电功率为100W，持续放电600s，对基材进行预处理；The chamber pressure was maintained at 20 mTorr, the helium flow rate was maintained at 80 sccm, the support and the support were turned on to rotate, the substrate was subjected to planetary motion, the support rotation speed was 2 rpm, the support rotation speed was 3 rpm, the central electrode plasma was turned on for continuous discharge, the discharge power was 100 W, and the discharge lasted for 600 s to pretreat the substrate;
然后，将单体十甲基四硅氧烷，在气化温度为85℃下进行气化后导入等离子体腔室内，保持腔室气压为20毫托，保持氦气流量为80sccm，保持支架和支撑件旋转，开启中心电极射频等离子体放电，射频的能量输出方式为脉冲，在基材表面进行等离子体化学气相沉积，其中脉冲占空比25％，脉冲频率200Hz，脉冲放电功率为120W，单体流量为160μL/min，反应时间为3600s；Then, the monomer decamethyltetrasiloxane was introduced into the plasma chamber after being vaporized at a vaporization temperature of 85° C., the chamber pressure was maintained at 20 mTorr, the helium flow rate was maintained at 80 sccm, the bracket and the support were kept rotating, the central electrode radio frequency plasma discharge was turned on, the radio frequency energy output mode was pulsed, and plasma chemical vapor deposition was performed on the surface of the substrate, wherein the pulse duty ratio was 25%, the pulse frequency was 200 Hz, the pulse discharge power was 120 W, the monomer flow rate was 160 μL/min, and the reaction time was 3600 s;
镀膜完成后，充入压缩空气使腔室恢复常压，取出已镀膜基材Si片和玻璃，测试Si片膜厚列于下表1中，对玻璃耐摩擦性能测试列于下表2中。After the coating is completed, compressed air is filled to restore the chamber to normal pressure, and the coated substrate Si wafer and glass are taken out. The test of Si wafer film thickness is listed in Table 1 below, and the test of glass friction resistance is listed in Table 2 below.
实施例2Example 2
将Si片和玻璃基材放置于等离子体腔室内，基材放置于支架的支撑件上，使用30目纱网将支撑件包裹；等离子体反应腔室内设有双电极，所述双电极为与同一电源电连接的中心电极和腔壁电极，用于向腔室内放电；The Si wafer and the glass substrate are placed in a plasma chamber, the substrate is placed on a support of a bracket, and the support is wrapped with a 30-mesh gauze; a double electrode is provided in the plasma reaction chamber, and the double electrode is a central electrode and a cavity wall electrode electrically connected to the same power supply for discharging into the chamber;
将腔室抽真空至50毫托，通入氦气，流量70sccm，腔室温度为50℃；The chamber was evacuated to 50 mTorr, helium was introduced at a flow rate of 70 sccm, and the chamber temperature was 50°C;
保持腔室气压为50毫托，保持氦气流量为70sccm，开启支架和支撑件旋转，基材进行行星运动，支架旋转速度为1转/min，支撑件旋转速度为1.5转/min，开启双电极等离子体连续放电，放电功率为300W，持续放电300s，对基材进行预处理； The chamber pressure was maintained at 50 mTorr, the helium flow rate was maintained at 70 sccm, the support and the support were turned on to rotate, the substrate was subjected to planetary motion, the support rotation speed was 1 rpm, the support rotation speed was 1.5 rpm, the double-electrode plasma continuous discharge was turned on, the discharge power was 300 W, and the discharge was continued for 300 s to pretreat the substrate;
然后，将单体八甲基三硅氧烷，在气化温度为75℃下进行气化后导入等离子体腔室内，保持腔室气压为50毫托，保持氦气流量为70sccm，保持支架和支撑件旋转，开启双电极射频等离子体放电，射频的能量输出方式为脉冲，在基材表面进行等离子体化学气相沉积，其中脉冲占空比50％，脉冲频率100Hz，脉冲放电功率为180W，单体流量为150μL/min，反应时间为3600s；Then, the monomer octamethyltrisiloxane was vaporized at a vaporization temperature of 75° C. and then introduced into the plasma chamber, the chamber pressure was maintained at 50 mTorr, the helium flow rate was maintained at 70 sccm, the bracket and the support were kept rotating, and the double-electrode radio frequency plasma discharge was turned on. The radio frequency energy output mode was pulsed, and plasma chemical vapor deposition was performed on the surface of the substrate, wherein the pulse duty ratio was 50%, the pulse frequency was 100 Hz, the pulse discharge power was 180 W, the monomer flow rate was 150 μL/min, and the reaction time was 3600 s;
镀膜完成后，充入压缩空气使腔室恢复常压，取出已镀膜基材Si片和玻璃，测试Si片膜厚列于下表1中，对玻璃耐摩擦性能测试列于下表2中。After the coating is completed, compressed air is filled to restore the chamber to normal pressure, and the coated substrate Si wafer and glass are taken out. The test of Si wafer film thickness is listed in Table 1 below, and the test of glass friction resistance is listed in Table 2 below.
对比例2Comparative Example 2
将Si片和玻璃基材放置于等离子体腔室内，基材放置于支架的支撑件上，使用30目纱网将支撑件包裹；等离子体反应腔室内设有与电源电连接的中心电极，用于向腔室内放电；The Si wafer and the glass substrate are placed in a plasma chamber, the substrate is placed on a support of a bracket, and the support is wrapped with a 30-mesh gauze; a central electrode electrically connected to a power source is provided in the plasma reaction chamber for discharging into the chamber;
将腔室抽真空至50毫托，通入氦气，流量70sccm，腔室温度为50℃；The chamber was evacuated to 50 mTorr, helium was introduced at a flow rate of 70 sccm, and the chamber temperature was 50°C;
保持腔室气压为50毫托，保持氦气流量为70sccm，开启支架和支撑件旋转，基材进行行星运动，支架旋转速度为1转/min，支撑件旋转速度为1.5转/min，开启中心电极等离子体连续放电，放电功率为300W，持续放电300s，对基材进行预处理；The chamber pressure was maintained at 50 mTorr, the helium flow rate was maintained at 70 sccm, the support and the support were turned on to rotate, the substrate was subjected to planetary motion, the support rotation speed was 1 rpm, the support rotation speed was 1.5 rpm, the central electrode plasma was turned on for continuous discharge, the discharge power was 300 W, and the discharge lasted for 300 s to pretreat the substrate;
然后，将单体八甲基三硅氧烷，在气化温度为75℃下进行气化后导入等离子体腔室内，保持腔室气压为50毫托，保持氦气流量为70sccm，保持支架和支撑件旋转，开启中心电极射频等离子体放电，射频的能量输出方式为脉冲，在基材表面进行等离子体化学气相沉积，其中脉冲占空比50％，脉冲频率100Hz，脉冲放电功率为180W，单体流量为150μL/min，反应时间为3600s；Then, the monomer octamethyltrisiloxane was vaporized at a vaporization temperature of 75° C. and then introduced into the plasma chamber, the chamber pressure was maintained at 50 mTorr, the helium flow rate was maintained at 70 sccm, the bracket and the support were kept rotating, the central electrode radio frequency plasma discharge was turned on, the radio frequency energy output mode was pulsed, and plasma chemical vapor deposition was performed on the surface of the substrate, wherein the pulse duty ratio was 50%, the pulse frequency was 100 Hz, the pulse discharge power was 180 W, the monomer flow rate was 150 μL/min, and the reaction time was 3600 s;
镀膜完成后，充入压缩空气使腔室恢复常压，取出已镀膜基材Si片和玻璃，测试Si片膜厚列于下表1中，对玻璃耐摩擦性能测试列于下表2中。After the coating is completed, compressed air is filled to restore the chamber to normal pressure, and the coated substrate Si wafer and glass are taken out. The test of Si wafer film thickness is listed in Table 1 below, and the test of glass friction resistance is listed in Table 2 below.
实施例3Example 3
将Si片和玻璃基材放置于等离子体腔室内，基材放置于支架的支撑件上，使用50目纱网将支撑件包裹；等离子体反应腔室内设有双电极，所述双电极为与同一电源电连接的中心电极和腔壁电极，用于向腔室内放电； The Si wafer and the glass substrate are placed in a plasma chamber, the substrate is placed on a support of a bracket, and the support is wrapped with a 50-mesh gauze; a double electrode is provided in the plasma reaction chamber, and the double electrode is a central electrode and a cavity wall electrode electrically connected to the same power supply for discharging into the chamber;
将腔室抽真空至100毫托，通入氦气，流量50sccm，腔室温度为55℃；The chamber was evacuated to 100 mTorr, and helium was introduced at a flow rate of 50 sccm. The chamber temperature was 55°C.
保持腔室气压为100毫托，保持氦气流量为50sccm，开启支架和支撑件旋转，基材进行行星运动，支架旋转速度为2转/min，支撑件旋转速度为2.5转/min，开启双电极等离子体脉冲放电，脉冲占空比60％，脉冲频率300Hz，放电功率为300W，持续放电300s，对基材进行预处理；The chamber pressure was maintained at 100 mTorr, the helium flow rate was maintained at 50 sccm, the support and the support were turned on to rotate, the substrate was subjected to planetary motion, the support rotation speed was 2 rpm, the support rotation speed was 2.5 rpm, the dual-electrode plasma pulse discharge was turned on, the pulse duty cycle was 60%, the pulse frequency was 300 Hz, the discharge power was 300 W, and the discharge was continued for 300 s to pretreat the substrate;
然后，将单体四(三甲基硅氧基)硅烷，在气化温度为95℃下进行气化后导入等离子体腔室内，保持腔室气压为100毫托，保持氦气流量为50sccm，保持支架和支撑件旋转，开启双电极射频等离子体放电，射频的能量输出方式为脉冲，在基材表面进行等离子体化学气相沉积，其中脉冲占空比35％，脉冲频率250Hz，脉冲放电功率为200W，单体流量为200μL/min，反应时间为3600s；Then, the monomer tetrakis(trimethylsiloxy)silane was vaporized at a vaporization temperature of 95° C. and then introduced into the plasma chamber, the chamber pressure was maintained at 100 mTorr, the helium flow rate was maintained at 50 sccm, the bracket and the support were kept rotating, the double-electrode radio frequency plasma discharge was turned on, the radio frequency energy output mode was pulsed, and plasma chemical vapor deposition was performed on the surface of the substrate, wherein the pulse duty ratio was 35%, the pulse frequency was 250 Hz, the pulse discharge power was 200 W, the monomer flow rate was 200 μL/min, and the reaction time was 3600 s;
镀膜完成后，充入压缩空气使腔室恢复常压，取出已镀膜基材Si片和玻璃，测试Si片膜厚列于下表1中，对玻璃耐摩擦性能测试列于下表2中。After the coating is completed, compressed air is filled to restore the chamber to normal pressure, and the coated substrate Si wafer and glass are taken out. The test of Si wafer film thickness is listed in Table 1 below, and the test of glass friction resistance is listed in Table 2 below.
对比例3Comparative Example 3
将Si片和玻璃基材放置于等离子体腔室内，基材放置于支架的支撑件上，使用50目纱网将支撑件包裹；等离子体反应腔室内设有与电源电连接的中心电极，用于向腔室内放电；The Si wafer and the glass substrate are placed in a plasma chamber, the substrate is placed on a support of a bracket, and the support is wrapped with a 50-mesh gauze; a central electrode electrically connected to a power source is provided in the plasma reaction chamber for discharging into the chamber;
将腔室抽真空至100毫托，通入氦气，流量50sccm，腔室温度为55℃；The chamber was evacuated to 100 mTorr, and helium was introduced at a flow rate of 50 sccm. The chamber temperature was 55°C.
保持腔室气压为100毫托，保持氦气流量为50sccm，开启支架和支撑件旋转，基材进行行星运动，支架旋转速度为2转/min，支撑件旋转速度为2.5转/min，开启中心电极等离子体脉冲放电，脉冲占空比60％，脉冲频率300Hz，放电功率为300W，持续放电300s，对基材进行预处理；The chamber pressure was maintained at 100 mTorr, the helium flow rate was maintained at 50 sccm, the support and the support were turned on to rotate, the substrate was subjected to planetary motion, the support rotation speed was 2 rpm, the support rotation speed was 2.5 rpm, the central electrode plasma pulse discharge was turned on, the pulse duty cycle was 60%, the pulse frequency was 300 Hz, the discharge power was 300 W, and the discharge was continued for 300 s to pretreat the substrate;
然后，将单体四(三甲基硅氧基)硅烷，在气化温度为95℃下进行气化后导入等离子体腔室内，保持腔室气压为100毫托，保持氦气流量为50sccm，保持支架和支撑件旋转，开启中心电极射频等离子体放电，射频的能量输出方式为脉冲，在基材表面进行等离子体化学气相沉积，其中脉冲占空比35％，脉冲频率250Hz，脉冲放电功率为200W，单体流量为200μL/min，反应时间为3600s； Then, the monomer tetrakis(trimethylsiloxy)silane was vaporized at a vaporization temperature of 95°C and then introduced into the plasma chamber, the chamber pressure was maintained at 100 mTorr, the helium flow rate was maintained at 50 sccm, the bracket and the support were kept rotating, the central electrode radio frequency plasma discharge was turned on, the radio frequency energy output mode was pulsed, and plasma chemical vapor deposition was performed on the surface of the substrate, wherein the pulse duty ratio was 35%, the pulse frequency was 250 Hz, the pulse discharge power was 200 W, the monomer flow rate was 200 μL/min, and the reaction time was 3600 s;
镀膜完成后，充入压缩空气使腔室恢复常压，取出已镀膜基材Si片和玻璃，测试Si片膜厚列于下表1中，对玻璃耐摩擦性能测试列于下表2中。After the coating is completed, compressed air is filled to restore the chamber to normal pressure, and the coated substrate Si wafer and glass are taken out. The test of Si wafer film thickness is listed in Table 1 below, and the test of glass friction resistance is listed in Table 2 below.
表1膜厚测试结果
Table 1 Film thickness test results
表1中A、B、C分别代表Si片基材离支撑件的旋转轴最远到最近的位置。In Table 1, A, B, and C represent the positions of the Si wafer substrate from the farthest to the closest to the rotation axis of the support, respectively.
根据上表实施例1-3的膜厚测试结果可知，实施例1-3中通过中心电极和腔壁电极放电，并且同时对支架和支撑件旋转带动基材旋转，而对比例1-3中，仅通过中心电极进行放电，实施例1-3的基材表面不同位置的涂层厚度相比于对比例1-3中的结果差异更小，膜层厚度分布更均匀，膜层的均匀性与一致性明显得以改进。According to the film thickness test results of Examples 1-3 in the above table, it can be seen that in Examples 1-3, discharge is performed through the central electrode and the cavity wall electrode, and the bracket and the support are rotated at the same time to drive the substrate to rotate, while in Comparative Examples 1-3, discharge is only performed through the central electrode. The coating thickness at different positions on the substrate surface of Examples 1-3 is smaller than that in Comparative Examples 1-3, the film thickness distribution is more uniform, and the uniformity and consistency of the film layer are significantly improved.
同时，根据膜厚计算A、B、C的平均成膜速度，由表1可知，实施例1-3中的成膜速度相比对比例1-3中提高了1.5～2倍，实施例1-3中采用中心电极与腔壁电极同时放电，等离子体形成速率更快，更利于单体在基材表面的化学气相沉积，从而可以更快的完成基材镀膜，提升镀膜效率。At the same time, the average film forming speed of A, B, and C is calculated according to the film thickness. It can be seen from Table 1 that the film forming speed in Examples 1-3 is increased by 1.5 to 2 times compared with that in Comparative Examples 1-3. In Examples 1-3, the central electrode and the cavity wall electrode are discharged simultaneously, and the plasma formation rate is faster, which is more conducive to the chemical vapor deposition of the monomer on the surface of the substrate, so that the substrate coating can be completed faster and the coating efficiency is improved.
表2耐摩擦性能测试结果
Table 2 Friction resistance test results
根据上表2的结果可知，相比于对比例1-3，实施例1-3中通过中心电极和腔壁电极放电，并且同时对支架和支撑件旋转带动基材旋转，其涂覆膜层摩擦前水接触角基本一致，摩擦后实施例1-3中膜层的水接触角明显高于对比例1-3中的水接触角，表明实施例1-3中的膜层具有更为优异的耐磨性能。According to the results in Table 2 above, compared with Comparative Examples 1-3, in Examples 1-3, discharge is performed through the central electrode and the cavity wall electrode, and the bracket and the support are rotated to drive the substrate to rotate at the same time. The water contact angle of the coating film layer before friction is basically the same. After friction, the water contact angle of the film layer in Examples 1-3 is significantly higher than that in Comparative Examples 1-3, indicating that the film layer in Examples 1-3 has more excellent wear resistance.
虽然本发明披露如上，但本发明并非限定于此。任何本领域技术人员，在不脱离本发明的精神和范围内，均可作各种更动与修改，因此本发明的保护范围应当以权利要求所限定的范围为准。 Although the present invention is disclosed as above, the present invention is not limited thereto. Any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the scope defined by the claims.

Claims (20)

  1. 一种有机硅纳米疏水膜层的制备方法，其特征在于，包括以下步骤：A method for preparing an organosilicon nano-hydrophobic film layer, characterized in that it comprises the following steps:
    将基材置于等离子体反应腔室内，所述等离子体反应腔室内设有适于放电的双电极，所述双电极包括：设于所述等离子体反应腔室的中心的中心电极与设于所述等离子体反应腔室的内壁的腔壁电极；Placing a substrate in a plasma reaction chamber, wherein the plasma reaction chamber is provided with a double electrode suitable for discharge, wherein the double electrode comprises: a central electrode provided at the center of the plasma reaction chamber and a cavity wall electrode provided at the inner wall of the plasma reaction chamber;
    气态的硅氧烷类单体由所述单体进气口通入所述等离子体反应腔室内，开启所述双电极向所述等离子体反应腔室内等离子体放电，所述硅氧烷类单体在所述基材表面等离子体化学气相沉积形成所述有机硅纳米疏水膜层；The gaseous siloxane monomer is introduced into the plasma reaction chamber from the monomer gas inlet, the double electrodes are turned on to discharge plasma into the plasma reaction chamber, and the siloxane monomer is plasma chemical vapor deposited on the surface of the substrate to form the organic silicon nano-hydrophobic film layer;
    所述硅氧烷类单体包括下式(1)或(2)所示结构至少一种，
    The siloxane monomer comprises at least one of the structures shown in the following formula (1) or (2):
    式(1)或(2)中，R1、R2、R3、R5和R6分别独立的选自于氢原子、卤素、C1-C12的取代或非取代烃基、C1-C12的取代或非取代烃氧基、C1-C12的取代或非取代烃基硅氧基，所述R1、R2和R3中至少一个不为氢原子，所述R5或R6中至少一个不为氢原子，R4为C1-C12的取代或非取代烃基、或C1-C12的取代或非取代烃基硅基，n为1～100的整数，m为3～10的整数。In formula (1) or (2), R 1 , R 2 , R 3 , R 5 and R 6 are independently selected from hydrogen atom, halogen, C 1 -C 12 substituted or unsubstituted hydrocarbon group, C 1 -C 12 substituted or unsubstituted hydrocarbonoxy group, C 1 -C 12 substituted or unsubstituted hydrocarbonsiloxy group, at least one of R 1 , R 2 and R 3 is not a hydrogen atom, at least one of R 5 or R 6 is not a hydrogen atom, R 4 is a C 1 -C 12 substituted or unsubstituted hydrocarbon group, or a C 1 -C 12 substituted or unsubstituted hydrocarbonsilyl group, n is an integer of 1 to 100, and m is an integer of 3 to 10.
  2. 根据权利要求1所述的有机硅纳米疏水膜层的制备方法，其特征在于，所述中心电极包括至少一圆筒电极，所述腔壁电极包括至少一块的电极板。The method for preparing an organosilicon nano-hydrophobic film layer according to claim 1 is characterized in that the central electrode includes at least one cylindrical electrode, and the cavity wall electrode includes at least one electrode plate.
  3. 根据权利要求2所述的有机硅纳米疏水膜层的制备方法，其特征在于，所述中心电极与所述腔壁电极与同一电源电连接。The method for preparing an organosilicon nano-hydrophobic film layer according to claim 2, characterized in that the central electrode and the cavity wall electrode are electrically connected to the same power supply.
  4. 根据权利要求1所述的有机硅纳米疏水膜层的制备方法，其特征在于，所述等离子体放电为脉冲放电，脉冲占空比为0.1％～80％，脉冲频率为 10～500Hz，放电功率为10～400W，放电时间为200～36000s。The method for preparing an organosilicon nano-hydrophobic film layer according to claim 1 is characterized in that the plasma discharge is a pulse discharge, the pulse duty cycle is 0.1% to 80%, and the pulse frequency is 10～500Hz, discharge power is 10～400W, and discharge time is 200～36000s.
  5. 根据权利要求1所述的有机硅纳米疏水膜层的制备方法，其特征在于，还包括：The method for preparing an organosilicon nano-hydrophobic film layer according to claim 1, characterized in that it also includes:
    在所述单体进气口与基材之间设置纱网，所述气态的硅氧烷类单体经过纱网后在所述基材表面等离子体化学气相沉积形成所述有机硅纳米疏水膜层。A gauze is arranged between the monomer air inlet and the substrate, and the gaseous siloxane monomer passes through the gauze and is then plasma chemical vapor deposited on the surface of the substrate to form the organic silicon nano-hydrophobic film layer.
  6. 根据权利要求5所述的有机硅纳米疏水膜层的制备方法，其特征在于，所述纱网的网格大小为10～100目。The method for preparing a nano-hydrophobic organosilicon film layer according to claim 5, characterized in that the mesh size of the gauze is 10 to 100 meshes.
  7. 根据权利要求1所述的有机硅纳米疏水膜层的制备方法，其特征在于，所述硅氧烷类单体的流速为10～2000μL/min。The method for preparing an organosilicon nano-hydrophobic film layer according to claim 1 is characterized in that the flow rate of the siloxane monomer is 10 to 2000 μL/min.
  8. 根据权利要求1所述的有机硅纳米疏水膜层的制备方法，其特征在于，所述等离子体反应腔室内设置支架，所述支架上设置支撑件，所述基材置于所述支撑件上，由所述支架绕所述支架的中心轴旋转和所述支撑件绕所述支撑件的中心轴旋转带动所述基材在所述等离子体反应腔室内旋转运动。The method for preparing a silicone nano-hydrophobic film layer according to claim 1 is characterized in that a bracket is arranged in the plasma reaction chamber, a support member is arranged on the bracket, the substrate is placed on the support member, and the bracket rotates around the central axis of the bracket and the support member rotates around the central axis of the support member to drive the substrate to rotate in the plasma reaction chamber.
  9. 根据权利要求8所述的有机硅纳米疏水膜层的制备方法，其特征在于，所述支架旋转的转速为1～10转/min，所述支撑件旋转的转速为1～10转/min。The method for preparing a nano-hydrophobic organic silicon film layer according to claim 8 is characterized in that the rotation speed of the bracket is 1 to 10 rpm, and the rotation speed of the support member is 1 to 10 rpm.
  10. 根据权利要求1所述的有机硅纳米疏水膜层的制备方法，其特征在于，所述有机硅纳米疏水膜层的水接触角不小于105°。The method for preparing an organosilicon nano-hydrophobic film layer according to claim 1, characterized in that the water contact angle of the organosilicon nano-hydrophobic film layer is not less than 105°.
  11. 根据权利要求1所述的有机硅纳米疏水膜层的制备方法，其特征在于，还包括：在所述化学气相沉积前，抽真空至10～200毫托，并通入气体He、Ar、O2中的一种或几种的混合气体，开启等离子体放电对所述基材进行预处理。The method for preparing an organosilicon nano-hydrophobic film layer according to claim 1 is characterized in that it also includes: before the chemical vapor deposition, evacuating to 10 to 200 mTorr, introducing one or a mixture of He, Ar, and O2 , and starting plasma discharge to pretreat the substrate.
  12. 根据权利要求1所述的有机硅纳米疏水膜层的制备方法，其特征在于，所述R1、R2、R3、R5和R6分别独立的选自于甲基或乙基，R4为甲基、乙基或三甲基硅基，所述n为2～10的整数。The method for preparing an organosilicon nano-hydrophobic film layer according to claim 1, characterized in that R 1 , R 2 , R 3 , R 5 and R 6 are independently selected from methyl or ethyl, R 4 is methyl, ethyl or trimethylsilyl, and n is an integer of 2 to 10.
  13. 根据权利要求1所述的有机硅纳米疏水膜层的制备方法，其特征在于，所述硅氧烷类单体包括硅氧烷单体一和硅氧烷单体二，其中所述硅氧烷 单体一具有一个不饱和双键，所述硅氧烷单体二具有至少两个不饱和双键。The method for preparing an organosilicon nano-hydrophobic film layer according to claim 1, characterized in that the siloxane monomer comprises a siloxane monomer 1 and a siloxane monomer 2, wherein the siloxane The first monomer has one unsaturated double bond, and the second siloxane monomer has at least two unsaturated double bonds.
  14. 根据权利要求13所述的有机硅纳米疏水膜层的制备方法，其特征在于，所述硅氧烷单体一具有下式(3)所示结构，
    The method for preparing an organosilicon nano-hydrophobic film layer according to claim 13, characterized in that the siloxane monomer has a structure shown in the following formula (3):
    式(3)中，R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17和R18分别独立的选自于氢原子或C1-C4的烃基，R10、R11和R12中至少一个不为氢原子，R13、R14和R15中至少一个不为氢原子，R16、R17和R18中至少一个不为氢原子，p为1～10的整数。In formula (3), R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are independently selected from hydrogen atoms or C 1 -C 4 hydrocarbon groups, at least one of R 10 , R 11 and R 12 is not a hydrogen atom, at least one of R 13 , R 14 and R 15 is not a hydrogen atom, at least one of R 16 , R 17 and R 18 is not a hydrogen atom, and p is an integer of 1 to 10.
  15. 根据权利要求14所述的有机硅纳米疏水膜层的制备方法，其特征在于，所述R7、R8和R9分别独立的选自于氢原子或甲基，所述R10、R11、R12、R13、R14、R15、R16、R17和R18分别独立的选自于甲基或乙基。The method for preparing an organosilicon nano-hydrophobic film layer according to claim 14, characterized in that R7 , R8 and R9 are independently selected from hydrogen atoms or methyl groups, and R10 , R11 , R12 , R13 , R14 , R15 , R16 , R17 and R18 are independently selected from methyl groups or ethyl groups.
  16. 根据权利要求15所述的有机硅纳米疏水膜层的制备方法，其特征在于，所述硅氧烷单体一为甲基丙烯酰氧丙基三(三甲基硅氧烷基)硅烷。The method for preparing a nano-hydrophobic organic silicon film layer according to claim 15, characterized in that the first siloxane monomer is methacryloxypropyl tris(trimethylsiloxane) silane.
  17. 根据权利要求13所述的有机硅纳米疏水膜层的制备方法，其特征在于，所述硅氧烷单体二具有式(2)所示结构，所述R5为C1-C4的烯烃基，所述R6为C1-C4的烷烃基。The method for preparing an organosilicon nano-hydrophobic film layer according to claim 13, characterized in that the siloxane monomer II has a structure shown in formula (2), the R 5 is a C 1 -C 4 olefin group, and the R 6 is a C 1 -C 4 alkane group.
  18. 根据权利要求17所述的有机硅纳米疏水膜层的制备方法，其特征在于，所述硅氧烷单体二为1,3,5,7-四乙烯基-1,3,5,7-四甲基环四硅氧烷。The method for preparing an organosilicon nano-hydrophobic film layer according to claim 17, characterized in that the siloxane monomer II is 1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane.
  19. 一种有机硅纳米疏水膜层，其特征在于，所述有机硅纳米疏水膜层由权利要求1-18中任意一项所述的有机硅纳米疏水膜层的制备方法制备获得。 An organosilicon nano-hydrophobic film layer, characterized in that the organosilicon nano-hydrophobic film layer is prepared by the preparation method of the organosilicon nano-hydrophobic film layer according to any one of claims 1 to 18.
  20. 一种器件，其特征在于，所述器件的至少部分表面具有权利要求19所述的有机硅纳米疏水膜层。 A device, characterized in that at least part of the surface of the device has the organic silicon nano-hydrophobic film layer as described in claim 19.
PCT/CN2023/118161 2022-10-12 2023-09-12 Organosilicon nanometer hydrophobic film layer and preparation method therefor WO2024078227A1 (en)

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