WO2020233481A1 - 疏水性的低介电常数膜及其制备方法 - Google Patents

疏水性的低介电常数膜及其制备方法 Download PDF

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WO2020233481A1
WO2020233481A1 PCT/CN2020/090120 CN2020090120W WO2020233481A1 WO 2020233481 A1 WO2020233481 A1 WO 2020233481A1 CN 2020090120 W CN2020090120 W CN 2020090120W WO 2020233481 A1 WO2020233481 A1 WO 2020233481A1
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Prior art keywords
dielectric constant
constant film
hydrophobic low
compound
film according
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PCT/CN2020/090120
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English (en)
French (fr)
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宗坚
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江苏菲沃泰纳米科技有限公司
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Priority to US17/595,435 priority Critical patent/US20220145460A1/en
Priority to MYPI2021006718A priority patent/MY196443A/en
Priority to JP2021568370A priority patent/JP7381609B2/ja
Priority to KR1020217040820A priority patent/KR20220008321A/ko
Priority to EP20810537.9A priority patent/EP3971321A4/en
Publication of WO2020233481A1 publication Critical patent/WO2020233481A1/zh

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    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0486—Operating the coating or treatment in a controlled atmosphere
    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0493—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases using vacuum
    • 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
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/03—Metal processing
    • H05K2203/0392—Pretreatment of metal, e.g. before finish plating, etching

Definitions

  • the present invention relates to the field of ultra-large-scale integrated circuit manufacturing. Specifically, it relates to a hydrophobic low-dielectric constant film and a preparation method thereof.
  • the Clausius-Mossotti equation provides two directions for reducing the dielectric constant of materials: one is to reduce the polarity of the material itself, including electronic polarization, ion polarization, molecular dipolarization, and space charge polarization; the other is to reduce Material molecular density.
  • the latter method is mainly to produce porous materials by introducing nano- and micro-sized pores into the material.
  • this method often leads to a substantial decrease in the thermal conductivity and mechanical properties of the material. What is more serious is that due to the capillary effect, etc. Porous materials are easier to absorb water, making them unsuitable for use in the dielectric layer of electronic components.
  • fluorocarbon materials have excellent heat resistance, chemical resistance and weather resistance.
  • the bond energy of C-F bond (440kJ/mol) is higher than that of C-H, C-O, and C-C, and C-F bond has a smaller polarizability than C-H bond. This is mainly due to the small radius of the F atom and the concentration of negative charges, which enables it to tightly confine the electron cloud to a small area centered on the nucleus, resulting in a low polarization rate.
  • the introduction of F atoms can also increase the free volume of the material.
  • the unit constituting the fluorocarbon material has a symmetrical structure
  • the polarities of the C-F bonds distributed on both sides of the C-C main chain are cancelled out, making the whole molecule in a non-polar state, which can further reduce the dielectric constant of the material.
  • such materials often have the disadvantage of difficult processing.
  • the dielectric constant of PTFE can be as low as about 2.1, and its water absorption and chemical stability are very good.
  • PECVD plasma-enhanced chemical vapor deposition
  • one or more organosilicon compounds are introduced into a plasma-enhanced chemical vapor deposition (PECVD) technology.
  • PECVD plasma-enhanced chemical vapor deposition
  • a porogen is introduced into the chamber, and the one or more organosilicon compounds react with the porogen under constant radio frequency power conditions to deposit a low-k film on one of the chambers.
  • the low-k film is further subjected to high-temperature annealing post-treatment to substantially remove the porogen on the low-k film.
  • polyarylene sulfide and a copolymer of tetrafluoroethylene and perfluoroethylenically unsaturated compound are used as raw materials, and after mixing and kneading, they are extruded containing fluororesin with a dielectric constant of 3.0. ⁇ 4.0 resin combined insulation layer.
  • the low dielectric constant insulating layer prepared by this method is above the micron level, and is not suitable for application in large-scale integrated circuits.
  • An advantage of the present invention is to provide a hydrophobic low-dielectric constant film and a preparation method thereof, which adopts a plasma enhanced chemical vapor deposition (PECVD) method and uses materials with low polarizability as reactants to form a non-porous structure
  • the nano film has a low dielectric constant and has good hydrophobicity.
  • An advantage of the present invention is to provide a hydrophobic low-dielectric constant film and a preparation method thereof.
  • the fluoropolymer or fluorosilicon polymer with low surface energy has good hydrophobic properties.
  • the static contact of water on its surface is The angle is large, suitable for use in electronic devices.
  • One advantage of the present invention is to provide a hydrophobic low-dielectric constant film and a preparation method thereof.
  • the units constituting the fluorocarbon material have an asymmetric structure, which is easy to process and easy to reshape.
  • One advantage of the present invention is to provide a hydrophobic low-dielectric constant mode and a preparation method thereof, which adopts a PECVD process to form a nano-scale film with a small thickness and is suitable for application in large-scale integrated circuits.
  • An advantage of the present invention is to provide a hydrophobic low-dielectric constant film and a preparation method thereof, which does not require high-temperature annealing treatment and will not affect electronic products, and is suitable for application in electronic products and large-scale integrated circuits.
  • An advantage of the present invention is to provide a hydrophobic low-dielectric constant film and a preparation method thereof.
  • the performance of the nano film prepared by the PECVD method is well controllable. It can finely adjust the amount of reactants and the number of reactants.
  • the ratio between the two and the process parameters in the vapor deposition process can obtain nano-films with different properties.
  • One advantage of the present invention is to provide a hydrophobic low-dielectric constant film and a preparation method thereof, which can adjust the mechanical properties, water resistance, and corrosion resistance of the low-dielectric constant film by selecting reactants.
  • One advantage of the present invention is to provide a hydrophobic low-dielectric constant film and a preparation method thereof, which adopts a dynamic coating method, so that the low-dielectric constant film is more uniformly attached to the substrate, reducing the substrate coating at different positions The difference solves the problem of uneven thickness caused by different concentrations of deposits in different areas of the substrate.
  • An advantage of the present invention is to provide a hydrophobic low-dielectric constant film and a preparation method thereof.
  • a multifunctional cross-linking agent By adding a multifunctional cross-linking agent, the raw material of the low-dielectric constant film is directly cross-linked during the polymerization deposition process, and the density is High, good mechanical properties, saving the thermal annealing treatment process in the mass production process and the resulting costs.
  • An advantage of the present invention is to provide a hydrophobic low-dielectric constant film and a preparation method thereof, which utilize plasma to excite chemical reactions, which can avoid the disadvantage of requiring high-specificity conditions for activation between raw materials in conventional chemical reactions.
  • one aspect of the present invention provides a hydrophobic low-dielectric constant film, which is characterized in that it is formed by one or more fluorine-containing compounds A by a plasma-enhanced chemical vapor deposition method.
  • the one or more fluorine-containing compounds comprise compounds having the general formula C x Si y O m H n F 2x+2y-n+2 or C x Si y O m H n F 2x+2y-n , Where x is an integer from 1-20, y is an integer from 0-8, m is an integer from 0-6, and n is 0, 3, 6, 7, 9, 10, 12, 13, 15, 16, 17, 19 .
  • the hydrophobic low-dielectric constant film is formed by the vapor deposition reaction of the compound A and a crosslinker compound B.
  • the hydrophobic low dielectric constant film is formed by the vapor deposition reaction of the compound A and a compound C with a large steric hindrance volume.
  • the hydrophobic low dielectric constant film is formed by the vapor deposition reaction of the compound A, a crosslinker compound B, and a compound C with a large steric hindrance volume. Constant film.
  • hydrophobic low-dielectric constant film wherein x is an integer of 1-10, y is an integer of 0-6, and m is an integer of 0-3.
  • hydrophobic low dielectric constant film wherein the molar ratio of the compound A is greater than 35%.
  • hydrophobic low-dielectric constant film wherein the compound A is selected from the group consisting of: tetrafluoroethylene, hexafluoropropylene, hexafluoroethane, hexafluoropropylene oxide, 1H, 1H, 2H, One or more of 2H-perfluorooctyltriethoxysilane, trimethylfluorosilane, and octafluorobutene.
  • hydrophobic low dielectric constant film wherein the compound B is selected from the group consisting of butadiene, perfluorobutadiene, pentadiene, 1,2-epoxy-5-hexene One or more of hexadiene and heptadiene.
  • hydrophobic low dielectric constant film wherein the compound C is selected from the group consisting of cyclohexane, toluene, xylene, vinylbenzene, divinylbenzene, dicyclopentadiene, naphthalene, One or more of pyridine.
  • hydrophobic low-dielectric constant film according to an embodiment, wherein the compound B is a bifunctional or multifunctional molecule containing an unsaturated carbon-carbon double bond.
  • the compound C is selected from the group consisting of cycloalkanes, aromatic hydrocarbons, fused ring aromatic hydrocarbons, and aromatic heterocycles.
  • hydrophobic low dielectric constant film wherein the range of k value of the hydrophobic low dielectric constant film is selected from: 1.8-1.9, 1.9-2.0, 2.0-2.1, 2.1-2.2, 2.2 ⁇ 2.3, 2.3 ⁇ 2.4, 2.4 ⁇ 2.5, 2.5 ⁇ 2.6, 2.6 ⁇ 2.7 or 2.7 ⁇ 2.8.
  • hydrophobic low-dielectric constant film according to an embodiment, wherein the static contact angle of the hydrophobic low-dielectric constant film is selected from: 110°-115°, 115°-120°, 120°-125 °, 125° ⁇ 130°, 130° ⁇ 135° or 135° ⁇ 140°.
  • hydrophobic low-dielectric constant film wherein the range of Young's modulus of the hydrophobic low-dielectric constant film is selected from: 6-7GPa, 7-8GPa, 8-9GPa, 9 ⁇ 10GPa, 10-11GPa, 11-12GPa, 12-13GPa, 13-14GPa or 14-15GPa.
  • Another aspect of the present invention provides a method for preparing a hydrophobic low dielectric constant film, which is characterized in that it comprises the steps of:
  • a hydrophobic low dielectric constant film is vapor-deposited on a substrate in the chamber by the reaction of the one or more fluorine-containing compounds.
  • the method for preparing a hydrophobic low-dielectric constant film further includes the step of introducing a crosslinker compound B into the reaction chamber of the reaction device.
  • the method for preparing a hydrophobic low-dielectric constant film further includes the step of introducing a compound C with a large steric hindrance volume into the reaction chamber of the reaction device.
  • the method for preparing a hydrophobic low-dielectric constant film further includes the step of introducing a crosslinker compound B and a compound C with a large steric hindrance volume into the reaction chamber of the reaction device.
  • the method for preparing a hydrophobic low-dielectric constant film includes the step of operating the substrate so that the substrate is in a moving state in the reaction chamber.
  • the method for preparing a hydrophobic low-dielectric constant film further includes the step of cleaning the substrate.
  • the method further includes a step of: evacuating the reaction chamber.
  • the plasma source gas is selected from: inert gas or fluorocarbon.
  • the plasma source gas is selected from: helium or carbon tetrafluoride.
  • the input power density of the reaction device ranges from 0.0001 W/L to 10 W/L.
  • the temperature of the cavity of the reaction device ranges from 10 to 100°C.
  • the substrate is selected from one of: a PCB board, a circuit board of a mobile phone antenna, and a mobile phone FPC.
  • FIG. 1 is a block diagram of the preparation process of a low dielectric constant film according to an embodiment of the present invention.
  • references to "one embodiment”, “embodiments”, “exemplary embodiments”, “various embodiments”, “some embodiments”, etc. indicate that such embodiments describing the invention may include specific features, structures, or characteristics , But not every embodiment must include this feature, structure or characteristic. In addition, some embodiments may have some, all, or none of the described features of other embodiments.
  • the invention provides a hydrophobic low dielectric constant film and a preparation method thereof.
  • the hydrophobic low dielectric constant film or coating contains oxygen, carbon and fluorine.
  • the hydrophobic low dielectric constant film contains oxygen, carbon, fluorine and silicon.
  • the hydrophobic low dielectric constant film contains hydrogen, oxygen, carbon, fluorine and silicon.
  • the thickness of the hydrophobic low-dielectric constant film is nanometer-scale, and the thickness range is for example but not limited to 10 to 2000 nm.
  • the hydrophobic low dielectric constant film has good dielectric properties.
  • the k value of the hydrophobic low dielectric constant film is less than 3.2.
  • the k value of the hydrophobic low dielectric constant film ranges from 1.8 to 2.8.
  • the range of k value of the hydrophobic low-dielectric constant film is selected from: 1.8-1.9, 1.9-2.0, 2.0-2.1, 2.1-2.2, 2.2-2.3, 2.3-2.4, 2.4-2.5, 2.5- 2.6, 2.6 ⁇ 2.7 or 2.7 ⁇ 2.8.
  • the dielectric loss of the hydrophobic low dielectric constant film is less than 0.0001.
  • the hydrophobic low-dielectric constant film has good hydrophobic performance, and the static contact angle of water attached to the hydrophobic low-dielectric constant film is greater than 100°.
  • the static contact angle of the hydrophobic low dielectric constant film ranges from 110° to 140°.
  • the static contact angle of the hydrophobic low-dielectric constant film is selected from: 110°-115°, 115°-120°, 120°-125°, 125°-130°, 130°-135° or 135° ⁇ 140°.
  • the static contact angle of the hydrophobic low dielectric constant film is 111°, 116°, 123°, 128°, 129°, 132°, 133°, thereby making the hydrophobic low dielectric constant
  • the constant film has good corrosion resistance.
  • the hydrophobic low-dielectric constant film has good mechanical properties, for example, the Young's modulus of the hydrophobic low-dielectric constant film is greater than 6 GPa.
  • the range of Young's modulus of the hydrophobic low dielectric constant film is selected from: 6-7GPa, 7-8GPa, 8-9GPa, 9-10GPa, 10-11GPa, 11-12GPa, 12-13GPa, 13 ⁇ 14GPa or 14 ⁇ 15GPa.
  • the hydrophobic low dielectric constant film is formed on the surface of a substrate by a plasma enhanced chemical vapor deposition (PECVD) method.
  • PECVD plasma enhanced chemical vapor deposition
  • the raw materials constituting the hydrophobic low-dielectric constant film are deposited on the surface of the substrate through a PECVD process, and the hydrophobic low-dielectric constant film is formed on the surface of the substrate.
  • the hydrophobic low dielectric constant film is deposited on the surface of the LSI board, thereby improving the RC delay phenomenon of the LSI board.
  • the hydrophobic low dielectric constant film is formed by a PECVD method by a plasma reaction device.
  • the substrate is placed in the reaction chamber of the plasma reaction device, and then reactants are introduced into the reaction chamber, and plasma discharge is performed to generate plasma.
  • the substrate is exposed to the reactant gas atmosphere, so that the hydrophobic low-dielectric constant film is deposited on the surface of the substrate.
  • the substrate is exemplified but not limited to a PCB board, a circuit board of a mobile phone antenna, and a mobile phone FPC.
  • the plasma enhanced chemical vapor deposition (PECVD) method generates plasma progeny through glow discharge, and the discharge method includes microwave discharge, radio frequency discharge, ultraviolet, and electric spark discharge.
  • the use of the PECVD method can avoid the shortcomings of requiring highly specific conditions for activation between raw materials in conventional chemical reactions, and the PECVD method uses a wide range of materials.
  • Plasma uses electrons and ions to directly bombard the active sites of the reactants for reactive activation.
  • the activation capacity is closely related to the energy of the electrons and ions in the plasma, and this can be convenient by controlling the input power size, input power time and other parameters. To control.
  • the reactant gas can be a chemical substance that is a gas at normal temperature and pressure, or it can be a vapor formed by a liquid substance with a boiling point below 350° C. under normal pressure through decompression, heating, and the like.
  • the reactant gas is composed of two or more mixtures.
  • the hydrophobic low-dielectric constant film uses a fluorine-containing compound A and a multifunctional compound B as reactants to form the hydrophobic low-dielectric constant through a PECVD process membrane.
  • the compound A and the compound B may be passed in at the same time or sequentially.
  • a plasma-enhanced chemical vapor deposition (PECVD) method is used to form a non-porous structured nano-film with a low-polarizability material as a reactant, which has a low dielectric constant, and Has good hydrophobicity.
  • PECVD plasma-enhanced chemical vapor deposition
  • the hydrophobic low-dielectric constant film has a low surface energy fluoropolymer or fluorosilicon polymer, has good hydrophobic characteristics, and has a large static contact angle when water is on its surface, and is suitable for application in electronic devices.
  • the hydrophobic low-dielectric constant film constitutes the unit of the fluorocarbon material in an asymmetric structure, which is easy to process and easy to re-mold.
  • the fluorine-containing compound A has the general formula C x Si y O m H n F 2x+2y-n+2 or C x Si y O m H n F 2x+2y-n , where x is 1-20 Integer, y is an integer of 0-8, m is an integer of 0-6, and n is 0, 3, 6, 7, 9, 10, 12, 13, 15, 16, 17, 19.
  • the oxygen content in the low dielectric constant film should be controlled, and in order to reduce the dielectric constant in the low dielectric constant film, the fluorine content should be relatively high, preferably , X is an integer of 1-10, y is an integer of 0-6, and m is an integer of 0-3.
  • the compound B is a bifunctional or multifunctional molecule, such as a diene, a perfluorodiene, or an olefin containing an epoxy group.
  • the hydrophobic low dielectric constant film uses a fluorine-containing compound A and a compound C with a large steric hindrance volume as reactants, and the hydrophobic low dielectric constant film is formed through a PECVD process. Constant film.
  • the compound A and the compound C may be passed in at the same time or sequentially.
  • the compound C may be an aromatic hydrocarbon containing a benzene ring, a fluorine-substituted aromatic hydrocarbon, or cyclohexane.
  • the compound C may be a cycloalkane, an aromatic hydrocarbon, a fused ring aromatic hydrocarbon, or an aromatic heterocycle.
  • the hydrophobic low-dielectric constant film uses the fluorine-containing compound A, the compound B, and the compound C as reactants to form the hydrophobic Low dielectric constant film.
  • the compound A, the compound B, and the compound C can be passed in simultaneously or sequentially.
  • the total inflow of the compound A accounts for more than 35%, preferably, the total inflow of the compound A accounts for more than 40%, and the proportion here refers to the molar ratio.
  • the compound A is selected from the combination: tetrafluoroethylene, hexafluoropropylene, hexafluoroethane, hexafluoropropylene oxide, 1H,1H,2H,2H-perfluorooctyltriethoxysilane, trimethyl One or more of fluorosilane and octafluorobutene.
  • the compound B is selected from a combination: one or more of butadiene, perfluorobutadiene, pentadiene, 1,2-epoxy-5-hexene, hexadiene, and heptadienekind.
  • the compound C is selected from a combination: one or more of cyclohexane, toluene, xylene, vinylbenzene, divinylbenzene, dicyclopentadiene, naphthalene, and pyridine.
  • the compound B when used as a reactant, the compound acts as a cross-linking agent to enhance the density of the hydrophobic low-dielectric constant film.
  • the bonds between the molecules of the compound A and the compound B or between the molecules of the reactant A, the compound B and the compound C are made closer, so that the The hydrophobic low dielectric constant film has good mechanical properties, such as a larger Young's modulus.
  • the compound B is a multifunctional crosslinking agent, and the functional group can be a carbon-carbon double bond, a carbon-carbon triple bond, an epoxy group, etc., preferably a carbon-carbon double bond and an epoxy group as the crosslinking functional group. Since the carbon-carbon double bond and epoxy group have double bond reaction and ring-opening reaction respectively, the molecular structure remains saturated, which is beneficial to improve the hydrophobicity and symmetry of the molecule.
  • the compound C when used as a reactant, the compound C has a large steric hindrance volume, which increases the free volume of the polymer in the hydrophobic low-dielectric constant film, which is beneficial to increase the molecular weight Hydrophobicity.
  • the addition amount of the compound A, the compound B and/or the compound C and the ratio between the reactants can be adjusted. And the process parameters in vapor deposition to obtain nano-films with different properties.
  • the requirements for their dielectric materials are often all-round and multi-level.
  • the mechanical properties of the coating, the waterproofness of the coating, the corrosion resistance of the coating, and the chemical resistance of the coating are all required.
  • different reactants can be selected and combined to meet this requirement.
  • the hydrophobic low-permittivity nano film of the present invention does not need to undergo thermal annealing treatment to eliminate stress after the deposition is completed, so as to improve the density and density of the film.
  • the invention uses a crosslinking agent with multifunctional groups to directly crosslink the low-dielectric constant coating material in the polymerization deposition process, which improves the compactness and saves the thermal annealing treatment process and the resulting cost in the large-scale production process. . It does not require high-temperature annealing treatment, will not affect electronic products, and is suitable for applications in electronic products and large-scale integrated circuits.
  • the PECVD process is performed in a dynamic manner, that is, the substrate is moved in the reaction chamber.
  • this movement can be a circular movement in the cavity.
  • the operation mode of the substrate may include multiple modes.
  • the substrate may revolve around the center of the substrate with the center point of the reaction chamber as a reference point or a predetermined axis. The axis or a predetermined axis rotates, or the base body rotates around two axes in the horizontal and vertical directions.
  • the volume of the vacuum reaction chamber of the selected reaction device is not less than 100L, and the input power density of the plasma generation method used is in the range of 0.0001W/L to 10W/L, so that Adapt to large-scale production applications, and reduce production costs.
  • the radio frequency discharge electrode of the reaction device is composed of a plurality of symmetrical electrode plates, so that the hydrophobic low dielectric constant film deposited on the surface of the substrate can be more uniform.
  • a plasma source gas when preparing the hydrophobic low-dielectric constant film, a plasma source gas needs to be added to promote plasma generation.
  • the plasma source gas is exemplified but not limited to inert gas and fluorocarbon.
  • the type of the plasma source gas needs to be determined according to the added reactants, that is, the compound A, the compound B, and the compound C.
  • the inert gas is helium.
  • carbon tetrafluoride is selected as the fluorocarbon.
  • FIG. 1 is a block diagram of the preparation process of a hydrophobic low dielectric constant film according to an embodiment of the present invention.
  • the hydrophobic low dielectric constant film may be formed by vapor deposition by a plasma reaction device.
  • the method for preparing the hydrophobic low dielectric constant film includes the steps:
  • the one or more fluorine-containing compounds react to vapor-deposit a hydrophobic low-dielectric constant film on a substrate in the reaction chamber.
  • the hydrophobic low dielectric constant film is formed by vapor deposition of a fluorine-containing compound A and a crosslinker compound B.
  • the step 101 may include the step of introducing a fluorine-containing compound A and a crosslinker compound B into the reaction chamber of the reaction device.
  • the fluorine-containing compound A is selected from combinations: tetrafluoroethylene, hexafluoropropylene, hexafluoroethane, hexafluoropropylene oxide, 1H,1H,2H,2H-perfluorooctyltriethoxysilane, trimethyl One or more of fluorosilane and octafluorobutene.
  • the cross-linking agent compound B is selected from a combination: one or more of butadiene, perfluorobutadiene, pentadiene, 1,2-epoxy-5-hexene, hexadiene, and heptadienekind.
  • the hydrophobic low-dielectric constant film is formed by vapor deposition of a fluorine-containing compound A and a compound C having a large steric hindrance volume.
  • the step 101 may include the step of introducing the fluorine-containing compound A and the compound C with a large hindered volume into the reaction chamber of the reaction device.
  • the fluorine-containing compound A is selected from combinations: tetrafluoroethylene, hexafluoropropylene, hexafluoroethane, hexafluoropropylene oxide, 1H,1H,2H,2H-perfluorooctyltriethoxysilane, trimethyl One or more of fluorosilane and octafluorobutene.
  • the compound C with a large steric hindrance volume is selected from a combination: one or more of cyclohexane, toluene, xylene, vinylbenzene, divinylbenzene, dicyclopentadiene, naphthalene, and pyridine.
  • the hydrophobic low-dielectric constant film is formed by vapor deposition of a fluorine-containing compound A, a crosslinker compound B, and a compound C having a large steric hindrance volume.
  • the step 101 may include the step of introducing the fluorine-containing compound A, the cross-linking agent compound B, and the compound C with a large hindered volume into the reaction chamber of the reaction device.
  • the fluorine-containing compound A is selected from combinations: tetrafluoroethylene, hexafluoropropylene, hexafluoroethane, hexafluoropropylene oxide, 1H,1H,2H,2H-perfluorooctyltriethoxysilane, trimethyl One or more of fluorosilane and octafluorobutene.
  • the crosslinking agent compound B is selected from a combination: one or more of butadiene, perfluorobutadiene, pentadiene, 1,2-epoxy-5-hexene, hexadiene, and heptadienekind.
  • the compound C with large steric hindrance volume is selected from the group consisting of one or more of cyclohexane, toluene, xylene, vinylbenzene, divinylbenzene, dicyclopentadiene, naphthalene, and pyridine.
  • the plasma source gas introduced in the step 102 is exemplified but not limited to inert gas and fluorocarbon. Such as helium, carbon tetrafluoride.
  • the method for preparing the hydrophobic low-dielectric constant film may further include the step of: 104: operating the substrate.
  • the substrate is in a moving state in the reaction chamber. This movement can be a circular movement in the cavity.
  • the operation mode of the substrate may include multiple modes.
  • the substrate may revolve around the center of the substrate with the center point of the reaction chamber as a reference point or a predetermined axis.
  • the axis or a predetermined axis rotates, or the base body rotates around two axes in the horizontal and vertical directions.
  • the step 104 may be before the step 103.
  • the substrate Before the step 101, the substrate may also be pre-treated.
  • the substrate needs to be cleaned before the chemical vapor deposition is performed on the substrate. Dust, moisture, grease, etc. on the surface of the substrate will adversely affect the deposition effect.
  • the substrate is cleaned with acetone or isopropanol first, and then placed in a drying oven to dry.
  • the preparation process of the hydrophobic low-dielectric constant film may be: (1) Prepare the substrate, and clean the substrate before performing chemical vapor deposition on the substrate. Dust, moisture, grease, etc. on the surface of the substrate will adversely affect the deposition effect. First clean the substrate with acetone or isopropanol, and then put it in a drying oven to dry. (2) Chemical vapor deposition on the substrate to prepare nano-film.
  • the reactant gas can be passed in simultaneously with the plasma source, or the substrate can be pretreated for 1-1200s after the plasma source is passed in, and then the reactant gas can be passed in according to the process parameters; (c) set the vacuum reaction The chamber pressure and temperature, and different reactant gases are introduced at the same time, the plasma generation power is adjusted to 1 ⁇ 500W, the cavity temperature is adjusted to 10 ⁇ 100°C, plasma chemical vapor deposition is performed, and the reaction is stopped after the reaction is completed Material gas, raise the cavity pressure to normal pressure.
  • the volume of the selected vacuum reaction chamber is not less than 100L, and the input power density of the plasma generation method used is in the range of 0.0001W/L to 10W/L.
  • a low dielectric constant nano film or nano coating applied to a PCB board and a preparation method thereof go through the following steps:
  • the pre-treatment stage discharge frequency is 500 Hz
  • discharge power is 10 W
  • discharge time is 100 s.
  • tetrafluoroethylene, butadiene, and toluene are simultaneously introduced, and chemical vapor deposition is performed on the surface of the substrate to prepare a nano-coating.
  • the feed speeds of the three reactive monomers were 150 ⁇ L/min, 20 ⁇ L/min, 5 ⁇ L/min, and the feed time was 2000s respectively.
  • a low-dielectric constant nano-coating applied to the protection of mobile phone antennas and a preparation method thereof go through the following steps:
  • the discharge frequency is 433MHz
  • the discharge power is 100W
  • the discharge time is 100s.
  • hexafluoroethane, butadiene, and vinylbenzene are simultaneously introduced, and chemical vapor deposition is performed on the surface of the substrate to prepare a nano-coating.
  • the feed rate of the three reactive monomers were 250 ⁇ L/min, 10 ⁇ L/min, 5 ⁇ L/min, and the feed time was 3000s respectively.
  • a low-dielectric constant nano-coating applied to the protection of mobile phone antennas and a preparation method thereof go through the following steps:
  • the pre-treatment stage discharge frequency is 2450MHz, discharge power 400W, and discharge time 200s.
  • hexafluoropropylene oxide, pentadiene, and cyclohexane are simultaneously introduced, and chemical vapor deposition is performed on the surface of the substrate to prepare a nano-coating.
  • the feed rate of the three reactive monomers were 350 ⁇ L/min, 30 ⁇ L/min, 5 ⁇ L/min, and the feed time was 3000s respectively.
  • a low-dielectric constant nano-coating applied to FPC protection of mobile phones and a preparation method thereof go through the following steps:
  • the pre-treatment stage discharge frequency is 2450MHz, discharge power 400W, and discharge time 200s.
  • hexafluoropropylene oxide, 1,2-epoxy-5-hexene, and dicyclopentadiene are simultaneously introduced, and chemical vapor deposition is performed on the surface of the substrate to prepare a nano-coating.
  • the feed speeds of the three reactive monomers were 400 ⁇ L/min, 20 ⁇ L/min, and 10 ⁇ L/min, respectively, and the feed time was 3000 s.
  • Example 1 Compared with Example 1, the monomer tetrafluoroethylene in step (4) was replaced with 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane, and other conditions were not changed.
  • the monomer toluene flow rate in step (4) is changed to 0, that is, it is not passed through, and other conditions are not changed.
  • Example 1 Compared with Example 1, the helium gas in step (3) is changed to carbon tetrafluoride, and other conditions are not changed.
  • the tetrafluoroethylene in step (4) is changed to a mixture of tetrafluoroethylene and trimethylfluorosilane, the molar ratio is 2:1, and other conditions remain unchanged.
  • the tetrafluoroethylene in step (4) is changed to a mixture of tetrafluoroethylene and trimethylfluorosilane, the molar ratio is 1:1, and other conditions remain unchanged.
  • the PCB board, the circuit board of the mobile phone antenna, and the mobile phone FPC are used as the substrates as the examples of the formation process of the hydrophobic low-dielectric constant film described in the specification.
  • plasma enhanced chemical vapor deposition can also be performed with other electronic devices as the substrate to form the hydrophobic low-dielectric constant film, and the present invention is not limited in this respect.
  • the thickness of the nano-coating is measured by the American Filmetrics F20-UV-film thickness measuring instrument.
  • the water contact angle of the nano coating is tested according to the GB/T 30447-2013 standard.
  • the dielectric constant is tested according to the recommended method of GB/T 1409-2006 for measuring the permittivity and dielectric loss factor of electrical insulating materials at power frequency, audio frequency, and high frequency (including meter wave wavelength).
  • the Young's modulus of the nano-coating is measured according to the technical specifications of JB/T 12721-2016 solid material in-situ nanoindentation/scratch tester.
  • Example Thickness/nm Contact angle/° Dielectric constant Dielectric loss Young's modulus/GPa Example 1 186 129 1.92 ⁇ 0.0001 8.78
  • Example 2 315 132 2.21 ⁇ 0.0001 9.63
  • Example 3 340 116 2.03 ⁇ 0.0001 11.22
  • Example 4 296 111 1.86 ⁇ 0.0001 6.95
  • Example 5 192 116 2.33 ⁇ 0.0001 8.96
  • Example 6 210 132 2.42 ⁇ 0.0001 13.5
  • Example 7 152 128 2.37 ⁇ 0.0001 8.36
  • Example 8 136 123 2.52 ⁇ 0.0001 12.36
  • Example 9 123 133 2.65 ⁇ 0.0001 8.30
  • Example 10 174 128 2.01 ⁇ 0.0001 3.12
  • a waterproof nano-membrane that can be applied to large-scale integrated circuits can be obtained.
  • a hydrophobic nano-film with a relative dielectric constant of about 2.0 is obtained; the density of the nano-film is increased by adding a cross-linking agent, which is embodied in the improvement of mechanical properties.

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Abstract

本发明提供一疏水性的低介电常数膜及其制备方法，其中所述低介电常数膜其由一种或多种含氟化合物A通过等离子体增强化学气相沉积方法形成，其中所述一种或多种含氟化合物包含具有通式CxSiyOmHnF2x+2y-n+2或者CxSiyOmHnF2x+2y-n的化合物，其中x为1-20的整数，y为0-8的整数，m为0-6的整数，n为0、3、6、7、9、10、12、13、15、16、17、19，由此在基体表面形成具有较低介电常数，且具有良好疏水性的纳米膜。

Description

疏水性的低介电常数膜及其制备方法 技术领域
本发明涉及超大规模集成电路制造领域，详而言之，涉及一疏水性的低介电常数膜及其制备方法。
背景技术
近些年来，随着电子信息技术的飞速发展，电子产品朝着外形轻薄、速度更快、功能更多样化、智能化程度更高的方向前进。网络速度以几何级提升，随之对电子产品信息处理能力的需求也更加明显。在这样发展趋势下，集成电路的尺寸不断缩小，芯片上集成的器件数目越来越多，集成度要求越来越高。
由于大规模集成电路的集成度越来越高，器件特征尺寸逐渐减小，导致导线电阻以及导线间和层间电容增加，引起电阻-电容(RC)延迟上升，从而出现信号传输延时、噪声干扰增强和功率损耗增大等一系列问题，这极大限制了器件的高速性能。缓解这些问题的重要方法之一就是降低介质材料的介电常数(k)。
在无线电通讯技术领域中，尤其是在GHz范围的通信技术中，具有低介电常数的低损耗材料已经引起了人们越来越广泛的关注。
Clausius-Mossotti方程为降低材料的介电常数提供了两个方向：其一是降低材料本身的极性，包括电子极化、离子极化、分子偶极化、空间电荷极化；其二是降低材料分子密度。后一种方法主要是通过在材料中引入纳微级尺寸的孔径制造多孔材料，但这种方法常常会导致材料的导热性、力学性能大幅下降，更为严重的是，由于毛细效应等作用使含孔材料更容易吸水，使其不能应用于电子元器件的介质层。
一些研究表明，氟碳材料具有优良的耐热性、耐化学药品性和耐候性。C-F键的键能(440kJ/mol)比C-H、C-O、C-C的键能均要高，C-F键比C-H键有更小的极化率。这主要是由于F原子半径小，负电荷集中，使它能将电子云紧紧地限制在以原子核为中心的小区域内，导致其极化率低。引入F原子同时还可以增加材料的自由体积。当构成氟碳材料的单元具有对称结构时，分布在C-C主链 两侧C-F键的极性被相互抵消，使整个分子呈非极性状态，可进一步降低材料的介电常数。但是这类材料往往存在加工困难的缺点，比如聚四氟乙烯介电常数可以低至2.1左右，且吸水性、化学稳定性均很好，但其加工困难，难以二次成型，限制了其在电子产品上的应用。
此外，在已有的一些研究中，采用等离子体增强化学气相沉积(PECVD)技术来制备低介电常数的纳米膜，举例地，将一种或多种有机硅化合物引入一等离子体增强化学气相沉积腔室中，并且引入一成孔剂到腔室内，在恒定射频功率条件下使得该一种或多种有机硅化合物与该成孔剂反应，以沉积一低k膜在该腔室的一基板上，进一步，对此低k膜进行高温退火后处理，以基本上移出此低k膜上的成孔剂。但是在这种方式中，首选需要引入成孔剂形成孔隙来降低介电常数，孔隙不利于材料的疏水性，其次，其需要进行高温退火来移除成孔剂，不利于低介电常数膜在电子产品的应用。
另外，在一些研究中，以聚亚芳基硫醚和四氟乙烯与全氟烯键式不饱和化合物的共聚物为原材料，通过混合混炼之后挤出包含氟树脂、对介电常数为3.0～4.0的树脂组合绝缘层。该方法所制备的低介电常数绝缘层为微米级以上，不适合应用于大规模集成电路中。
这里的陈述仅提供与本发明有关的背景信息，而不必然地构成现有技术。
发明内容
本发明的一个优势在于提供一疏水性的低介电常数膜及其制备方法，其采用等离子体增强化学气相沉积(PECVD)方法，以含低极化率的材料为反应物，形成非孔隙结构的纳米膜，具有较低的介电常数，以及具有良好的疏水性。
本发明的一个优势在于提供一疏水性的低介电常数膜及其制备方法，其具有低表面能的氟聚合物或氟硅聚合物，具有良好的疏水特性，水在其表面时的静态接触角大，适于应用于电子器件。
本发明的一个优势在于提供一疏水性的低介电常数膜及其制备方法，其构成氟碳材料的单元呈非对称结构，加工容易，容易二次成型。
本发明的一个优势在于提供一疏水性的低介电常数模及其制备方法，其采用PECVD工艺形成纳米级薄膜，厚度小，适于应用于大规模集成电路。
本发明的一个优势在于提供一疏水性的低介电常数膜及其制备方法，其不需 要高温退火处理，不会对电子产品产生影响，适于应用于电子产品以及大规模集成电路。
本发明的一个优势在于提供一疏水性的低介电常数膜及其制备方法，其采用PECVD法制备的纳米膜性能可控性好，其可以通过精细地调控反应物的加入量、反应物之间的比例、气相沉积过程中的工艺参数获得不同性能的纳米膜。
本发明的一个优势在于提供一疏水性的低介电常数膜及其制备方法，其可以通过选择反应物，调控低介电常数膜的力学性能、防水性、抗腐蚀性。
本发明的一个优势在于提供一疏水性的低介电常数膜及其制备方法，其采用动态镀膜的方法，使得所述低介电常数膜更加均匀地附着于基体，减少了基体在不同位置镀膜的差异，解决了基体不同区域沉积物的浓度不同导致厚度不均匀的问题。
本发明的一个优势在于提供一疏水性的低介电常数膜及其制备方法，其通过加入多官能团的交联剂，使得低介电常数膜的原料直接在聚合沉积过程中交联，致密性高，力学性能较好，节省了了大规模生产过程中的热退火处理工序以及由此产生的费用。
本发明的一个优势在于提供一疏水性的低介电常数膜及其制备方法，其利用等离子体激发化学反应，可以避免常规化学反应中原料之间需要高特定性条件进行激活的缺点。
为了实现本发明的上述至少一个优势，本发明的一方面提供一疏水性的低介电常数膜，其特征在于，其由一种或多种含氟化合物A通过等离子体增强化学气相沉积方法形成，其中所述一种或多种含氟化合物包含具有通式C xSi yO mH nF 2x+2y-n+2或者C xSi yO mH nF 2x+2y-n的化合物，其中x为1-20的整数，y为0-8的整数，m为0-6的整数，n为0、3、6、7、9、10、12、13、15、16、17、19。
根据一个实施例所述的疏水性的低介电常数膜，其由所述化合物A和一交联剂化合物B气相沉积反应形成所述疏水性的低介电常数膜。
根据一个实施例所述的疏水性的低介电常数膜，其由所述化合物A和一具有大位阻体积的化合物C气相沉积反应形成所述疏水性的低介电常数膜。
根据一个实施例所述的疏水性的低介电常数膜，其由所述化合物A、一交联剂化合物B以及一具有大位阻体积的化合物C气相沉积反应形成所述疏水性的 低介电常数膜。
根据一个实施例所述的疏水性的低介电常数膜，其中x为1-10的整数，y为0-6的整数，m为0-3的整数。
根据一个实施例所述的疏水性的低介电常数膜，其中所述化合物A的摩尔占比大于35％。
根据一个实施例所述的疏水性的低介电常数膜，其中所述化合物A选自组合：四氟乙烯、六氟丙烯、六氟乙烷、六氟环氧丙烷、1H,1H,2H,2H-全氟辛基三乙氧基硅烷、三甲基氟硅烷、八氟丁烯中的一种或几种。
根据一个实施例所述的疏水性的低介电常数膜，其中所述化合物B选自组合：丁二烯、全氟丁二烯、戊二烯、1,2-环氧-5-己烯、己二烯、庚二烯中的一种或几种。
根据一个实施例所述的疏水性的低介电常数膜，其中所述化合物C选自组合：环己烷、甲苯、二甲苯、乙烯基苯、二乙烯基苯、双环戊二烯、萘、吡啶中的一种或几种。
根据一个实施例所述的疏水性的低介电常数膜，其中所述化合物B是含有不饱和碳碳双键的双官能团或者多官能团分子。
根据一个实施例所述的疏水性的低介电常数膜，其中所述化合物C选自：环烷烃、芳烃、稠环芳烃、芳杂环。
根据一个实施例所述的疏水性的低介电常数膜，其中所述疏水性的低介电常数膜的k值范围选自：1.8～1.9、1.9～2.0、2.0～2.1、2.1～2.2、2.2～2.3、2.3～2.4、2.4～2.5、2.5～2.6、2.6～2.7或2.7～2.8。
根据一个实施例所述的疏水性的低介电常数膜，其中所述疏水性的低介电常数膜的静态接触角选自：110°～115°、115°～120°、120°～125°、125°～130°、130°～135°或135°～140°。
根据一个实施例所述的疏水性的低介电常数膜，其中所述疏水性的低介电常数膜的杨氏模量范围选自：6～7GPa、7～8GPa、8～9GPa、9～10GPa、10～11GPa、11～12GPa、12～13GPa、13～14GPa或14～15GPa。
本发明的另一方面提供一疏水性低介电常数膜制备方法，其特征在于，包括步骤：
(A)引入包含有通式结构C xSi yO mH nF 2x+2y-n+2或者C xSi yO mH nF 2x+2y-n的一种 或多种含氟化合物A至反应装置的反应腔室内；
(B)引入等离子源气体至所述反应腔室内；和
(C)在预定功率下，由所述一种或多种含氟化合物反应而在腔室内的一基体上气相沉积疏水性的低介电常数膜。
根据一个实施例所述的疏水性的低介电常数膜的制备方法，其还包括步骤：引入一交联剂化合物B至反应装置的反应腔室内。
根据一个实施例所述的疏水性的低介电常数膜的制备方法，其还包括步骤：引入一具有大位阻体积的化合物C至反应装置的反应腔室内。
根据一个实施例所述的疏水性的低介电常数膜的制备方法，其中还包括步骤：引入一交联剂化合物B和一具有大位阻体积的化合物C至反应装置的反应腔室内。
根据一个实施例所述的疏水性的低介电常数膜的制备方法，其包括步骤：运转所述基体，以使得所述基体在所述反应腔室内处于运动的状态。
根据一个实施例所述的疏水性的低介电常数膜的制备方法，其还包括步骤：清洁处理所述基体。
根据一个实施例所述的疏水性的低介电常数膜的制备方法，其中在步骤(A)之前还包括步骤：对所述反应腔室抽真空。
根据一个实施例所述的疏水性的低介电常数膜的制备方法，其中所述等离子源气体选自：惰性气体或者碳氟化合物。
根据一个实施例所述的疏水性的低介电常数膜的制备方法，其中所述等离子源气体选自：氦气或四氟化碳。
根据一个实施例所述的疏水性的低介电常数膜的制备方法，其中所述反应装置的输入功率密度范围在0.0001W/L～10W/L。
根据一个实施例所述的疏水性的低介电常数膜的制备方法，其中所述反应装置的腔体温度范围为10～100℃。
根据一个实施例所述的疏水性的低介电常数膜的制备方法，其中所述基体选自：PCB板、手机天线的电路板、手机FPC中的一种。
附图说明
图1是根据本发明的一个实施例的低介电常数膜的制备过程框图。
具体实施方式
以下描述用于揭露本发明以使本领域技术人员能够实现本发明。以下描述中的优选实施例只作为举例，本领域技术人员可以想到其他显而易见的变型。在以下描述中界定的本发明的基本原理可以应用于其他实施方案、变形方案、改进方案、等同方案以及没有背离本发明的精神和范围的其他技术方案。
本领域技术人员应理解的是，在本发明的揭露中，术语“纵向”、“横向”、“上”、“下”、“前”、“后”、“左”、“右”、“竖直”、“水平”、“顶”、“底”、“内”、“外”等指示的方位或位置关系是基于附图所示的方位或位置关系，其仅是为了便于描述本发明和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方位、以特定的方位构造和操作，因此上述术语不能理解为对本发明的限制。
可以理解的是，术语“一”应理解为“至少一”或“一个或多个”，即在一个实施例中，一个元件的数量可以为一个，而在另外的实施例中，该元件的数量可以为多个，术语“一”不能理解为对数量的限制。
对“一个实施例”、“实施例”、“示例实施例”、“各种实施例”、“一些实施例”等的引用指示这样的描述本发明的实施例可包括特定特征、结构或特性，但是不是每个实施例必须包括该特征、结构或特性。此外，一些实施例可具有对其它实施例的描述的特征中的一些、全部或没有这样的特征。
本发明提供一疏水性的低介电常数膜及其制备方法。所述疏水性的低介电常数膜或者涂层含氧、碳和氟。举例地，所述疏水性的低介电常数膜含氧、碳、氟和硅。举例地，所述疏水性的低介电常数膜含氢、氧、碳、氟和硅。所述疏水性的低介电常数膜的厚度为纳米级尺寸，其厚度范围举例地但不限于10～2000nm。
所述疏水性的低介电常数膜具有良好的介电性能。所述疏水性的低介电常数膜的k值小于3.2。举例地，所述疏水性的低介电常数膜的k值范围为1.8～2.8。举例地，所述疏水性的低介电常数膜的k值范围选自：1.8～1.9、1.9～2.0、2.0～2.1、2.1～2.2、2.2～2.3、2.3～2.4、2.4～2.5、2.5～2.6、2.6～2.7或2.7～2.8。所述疏水性的低介电常数膜的介电损耗小于0.0001。
所述疏水性的低介电常数膜具有良好的疏水性能，水附着于所述疏水性的低介电常数膜的静态接触角大于100°。举例地，所述疏水性的低介电常数膜的静态接触角范围为110°～140°。举例地，所述疏水性的低介电常数膜的静态接触角 选自：110°～115°、115°～120°、120°～125°、125°～130°、130°～135°或135°～140°。举例地，所述疏水性的低介电常数膜的静态接触角为111°、116°、123°、128°、129°、132°、133°，由此使得所述疏水性的低介电常数膜具有良好的耐腐蚀性能。
所述疏水性的低介电常数膜具有良好的力学性能，举例地，所述疏水性的低介电常数膜的杨氏模量大于6GPa。举例地，所述疏水性的低介电常数膜的杨氏模量范围选自：6～7GPa、7～8GPa、8～9GPa、9～10GPa、10～11GPa、11～12GPa、12～13GPa、13～14GPa或14～15GPa。
根据本发明的这个实施例，所述疏水性的低介电常数膜通过等离子体增强化学气相沉积(PECVD)方法形成于一基体的表面。也就是说，构成所述疏水性的低介电常数膜的原材料经过PECVD工艺沉积于基体表面，在所述基体的表面形成所述疏水性的低介电常数膜。举例地但不限于，所述疏水性的低介电常数膜沉积于大规模集成电路板表面，从而改善所述大规模集成电路板的RC延迟现象。
更进一步，所述疏水性的低介电常数膜通过一等离子体反应装置通过PECVD方法形成。也就是说，在沉积时，将所述基体放置于所述等离子体反应装置的反应腔室中，然后向所述反应腔室中通入反应物，并且进行等离子体放电产生等离子体，将所述基体暴露在反应物气体氛围中，从而在所述基体的表面沉积形成所述疏水性的低介电常数膜。
所述基体举例地但不限于PCB板、手机天线的电路板、手机FPC。
所述等离子体增强化学气相沉积(PECVD)法通过辉光放电产生等离体子体，放电的方法包括微波放电、射频放电、紫外、电火花放电。
值得一提的是，采用PECVD方法，可以避免常规化学反应中原料之间需要高特定性条件进行激活的缺点，且PECVD方法使用的材料范围较广。等离子体是利用电子、离子直接轰击反应物的活性位置进行反应性激活，激活能力与等离子体中电子、离子的能量关系密切，而这可以通过控制输入功率的大小、输入功率的时间等参数方便地进行调控。
这种反应物气体可以是常温常压下为气体的化学物质，也可以是常压下沸点低于350℃的液态物质经过减压、加热等方式形成的蒸汽。反应物气体是两种或者两种以上的混合物组成。
在本发明的一个实施例中，所述疏水性的低介电常数膜以一含氟化合物A和一多官能团的化合物B为反应物，通过PECVD工艺，形成所述疏水性的低介 电常数膜。在制备所述疏水性的低介电常数膜时，所述化合物A和所述化合物B可以同时通入，也可以先后通入。
根据本发明的一个实施例，其采用等离子体增强化学气相沉积(PECVD)方法，以含低极化率的材料为反应物，形成非孔隙结构的纳米膜，具有较低的介电常数，以及具有良好的疏水性。
进一步，所述疏水性的低介电常数膜具有低表面能的氟聚合物或氟硅聚合物，具有良好的疏水特性，水在其表面时的静态接触角大，适于应用于电子器件。
进一步，所述疏水性的低介电常数膜构成氟碳材料的单元呈非对称结构，加工容易，容易二次成型。
进一步，所述含氟化合物A具有通式C xSi yO mH nF 2x+2y-n+2或者C xSi yO mH nF 2x+2y-n，其中x为1-20的整数，y为0-8的整数，m为0-6的整数，n为0、3、6、7、9、10、12、13、15、16、17、19。为了获得好的疏水性性能的低介电常数膜，低介电常数膜中的氧含量应该得到控制，而且为了降低低介电常数膜中的介电常数，氟含量要相对较高，优选地，x为1-10的整数，y为0-6的整数，m为0-3的整数。
举例地，所述化合物B为双官能团或者多官能团分子，如二烯烃、全氟代二烯烃或者含有环氧基团的烯烃。
在本发明的一个实施例中，所述疏水性的低介电常数膜以含氟化合物A和一具有大位阻体积的化合物C为反应物，通过PECVD工艺，形成所述疏水性的低介电常数膜。在制备所述疏水性的低介电常数膜时，所述化合物A和所述化合物C可以同时通入，也可以先后通入。举例地，所述化合物C可以是含苯环的芳烃、氟取代芳烃、环己烷。举例地，所述化合物C可以是环烷烃、芳烃、稠环芳烃、芳杂环。
在本发明的一个实施例中，所述疏水性的低介电常数膜以所述含氟化合物A、所述化合物B和所述化合物C为反应物，通过PECVD工艺，形成所述疏水性的低介电常数膜。在制备所述疏水性的低介电常数膜时，所述化合物A、所述化合物B和所述化合物C可以同时通入，也可以先后通入。
进一步，所述化合物A的总通入量占比大于35％，优选地，所述化合物A的总通入量占比大于40％，此处的占比是指摩尔比。
举例地，所述化合物A选自组合：四氟乙烯、六氟丙烯、六氟乙烷、六氟 环氧丙烷、1H,1H,2H,2H-全氟辛基三乙氧基硅烷、三甲基氟硅烷、八氟丁烯中的一种或几种。
举例地，所述化合物B选自组合：丁二烯、全氟丁二烯、戊二烯、1,2-环氧-5-己烯、己二烯、庚二烯中的一种或几种。
举例地，所述化合物C选自组合：环己烷、甲苯、二甲苯、乙烯基苯、二乙烯基苯、双环戊二烯、萘、吡啶中的一种或几种。
值得一提的是，当所述化合物B作为反应物时，所述化合物作为交联剂，增强所述疏水性的低介电常数膜的致密程度。也就是说，在沉积过程中，使得所述化合物A和所述化合物B的分子之间或所述反应物A、所述化合物B和所述化合物C的分子之间的结合更加紧密，从而使得所述疏水性的低介电常数膜具有良好的力学性能，比如具有更大的杨氏模量。
所述化合物B是一种多官能团的交联剂，官能团可以选择碳碳双键、碳碳三键、环氧基团等，优选碳碳双键、环氧基团作为交联官能团。由于碳碳双键、环氧基团发生分别发生双键反应、开环反应后，分子结构保持饱和状态，有利于提高分子的疏水性和对称性。
值得一提的是，当所述化合物C作为反应物时，所述化合物C具有大位阻体积，增加了所述疏水性的低介电常数膜中聚合物的自由体积，有利于提高分子的疏水性。
值得一提的是，在制备所述疏水性的低介电常数膜时可以通过调控所述化合物A、所述化合物B和/或所述化合物C的加入量，以及各反应物之间的比例以及气相沉积中的工艺参数来获得不同性能的纳米膜。电子产品在实际使用过程中，对其介质材料的要求往往是全方位、多层次的。比如，在大规模集成电路的制备过程，涂层的力学性能、涂层的防水性、涂层抗腐蚀性、涂层的耐化学性能等均有要求。而在本发明的实施例中，可以通过选择不同的反应物进行组合，满足这种要求。
还值得一提的是，在制备所述疏水性的低介电常数膜时，本发明的疏水性的低介电常数纳米膜沉积完成之后不需要经过热退火处理消除应力以提高薄膜致密程度和力学性能的过程。本发明是利用加入多官能团的交联剂，使低介电常数涂层原料直接在聚合沉积过程中交联，致密性提高，节省了大规模生产过程中热退火处理工序及由此产生的费用。其不需要高温退火处理，不会对电子产品产生 影响，适于应用于电子产品以及大规模集成电路。
进一步，根据本发明的一个实施例，在制备所述疏水性的低介电常数膜时，采用动态的方式进行PECVD过程，也就是说，使得所述基体在反应腔室内运动。在一个实施例中，这种运动可以是在腔体中进行圆周运动，其好处是基体可以处于相对腔体不同的位置，均匀地接受等离子体的作用并减少反应原料浓度分布不均对涂层质量的影响。在本发明的一个实施例中，所述基体的运转方式可以包括多种方式，比如，所述基体可以以反应腔室的中心点为参考点或者预定的轴线进行公转，绕所述基体的中心轴线或预定的轴线进行自转，或者，所述基体分别绕横向和纵向的两个轴分别进行转动。
进一步，根据本发明的一个实施例，所选反应装置的真空反应腔的体积不小于100L，所采用的产生等离子体方式的输入功率密度范围在0.0001W/L～10W/L，由此，可以适应大规模的生产应用，且降低生产成本。所述反应装置的射频放电的电极是由对称的多块电极板组成，由此使得所述基体表面沉积的所述疏水性的低介电常数膜可以更加均匀。
进一步，根据本发明的一个实施例，在制备所述疏水性的低介电常数膜时，需要加入一等离子源气体，以促进产生等离子体。所述等离子源气体举例地但不限于惰性气体、碳氟化合物。所述等离子源气体的类型需要根据加入的反应物，即所述化合物A、所述化合物B和所述化合物C来确定。举例地但不限于，所述惰性气体选择氦气。举例地但不限于，所述碳氟化合物选择四氟化碳。
图1是根据本发明的一个实施例的疏水性的低介电常数膜的制备过程框图。所述疏水性的低介电常数膜可以通过等离子体反应装置进行气相沉积形成。
根据本发明的一个实施例，所述疏水性的低介电常数膜的制备方法，所述方法包括步骤：
101：引入包含有通式结构C xSi yO mH nF 2x+2y-n+2或者C xSi yO mH nF 2x+2y-n的一种或多种含氟化合物至一反应装置的反应腔室内；
102：引入等离子源气体至所述反应腔室内；和
103：在预定功率下，由所述一种或多种含氟化合物反应而在反应腔室内的一基体上气相沉积疏水性的低介电常数膜。
在一个实施例中，通过含氟化合物A和一交联剂化合物B进行气相沉积形成所述疏水性的低介电常数膜。
在所述步骤101中可以包括步骤：引入含氟化合物A和一交联剂化合物B至反应装置的反应腔室内。所述含氟化合物A选自组合：四氟乙烯、六氟丙烯、六氟乙烷、六氟环氧丙烷、1H,1H,2H,2H-全氟辛基三乙氧基硅烷、三甲基氟硅烷、八氟丁烯中的一种或几种。所述交联剂化合物B选自组合：丁二烯、全氟丁二烯、戊二烯、1,2-环氧-5-己烯、己二烯、庚二烯中的一种或几种。
在一个实施例中，通过含氟化合物A和具有大位阻体积的化合物C进行气相沉积形成所述疏水性的低介电常数膜。
所述步骤101中可以包括步骤：引入含氟化合物A和具有大位阻体积的化合物C至反应装置的反应腔室内。所述含氟化合物A选自组合：四氟乙烯、六氟丙烯、六氟乙烷、六氟环氧丙烷、1H,1H,2H,2H-全氟辛基三乙氧基硅烷、三甲基氟硅烷、八氟丁烯中的一种或几种。所述具有大位阻体积的化合物C选自组合：环己烷、甲苯、二甲苯、乙烯基苯、二乙烯基苯、双环戊二烯、萘、吡啶中的一种或几种。
在一个实施例中，通过含氟化合物A、交联剂化合物B和具有大位阻体积的化合物C进行气相沉积形成所述疏水性的低介电常数膜。
在所述步骤101中可以包括步骤：引入含氟化合物A、交联剂化合物B和具有大位阻体积的化合物C至反应装置的反应腔室内。所述含氟化合物A选自组合：四氟乙烯、六氟丙烯、六氟乙烷、六氟环氧丙烷、1H,1H,2H,2H-全氟辛基三乙氧基硅烷、三甲基氟硅烷、八氟丁烯中的一种或几种。所述交联剂化合物B选自组合：丁二烯、全氟丁二烯、戊二烯、1,2-环氧-5-己烯、己二烯、庚二烯中的一种或几种。所述具有大位阻体积的化合物C选自组合：环己烷、甲苯、二甲苯、乙烯基苯、二乙烯基苯、双环戊二烯、萘、吡啶中的一种或几种。
所述步骤102中引入的等离子源气体举例地但不限于惰性气体、碳氟化合物。如氦气、四氟化碳。
所述述疏水性的低介电常数膜的制备方法还可以包括步骤：104：运转所述基体。也就是说，使得所述基体在所述反应腔室内处于运动的状态。这种运动可以是在腔体中进行圆周运动。在本发明的一个实施例中，所述基体的运转方式可以包括多种方式，比如，所述基体可以以反应腔室的中心点为参考点或者预定的轴线进行公转，绕所述基体的中心轴线或预定的轴线进行自转，或者，所述基体分别绕横向和纵向的两个轴分别进行转动。
所述步骤104可以在所述步骤103之前。
在所述步骤101之前还可以对所述基体进行前处理，比如，在对基体进行化学气相沉积之前，需先对基体进行洁净处理。基体表面的灰尘、水分、油脂等会对沉积效果产生不利影响。举例地，先用丙酮或者异丙醇对基体进行清洗，然后放到干燥箱干燥。
在一个实施例中，所述疏水性的低介电常数膜的制备过程可以是：(1)准备基体，在对基体进行化学气相沉积之前，需先对基体进行洁净处理。基体表面的灰尘、水分、油脂等会对沉积效果产生不利影响。先用丙酮或者异丙醇对基体进行清洗，然后放到干燥箱干燥。(2)对基体进行化学气相沉积制备纳米膜。(a)将表面洁净的基体置于等离子体设备的反应腔室内，然后对反应腔室连续抽真空，将反应腔室内的真空度抽到1～2000毫托；(b)开启运动机构，使基体在腔体中处于运动状态；通入等离子源气体，在腔体中采用射频放电或者紫外辐照等手段，使腔体内产生等离子体。反应物气体可与等离子体源同时通入，也可以在等离子体源通入后先对基体进行1-1200s的预处理，再根据工艺参数要求通入反应物气体；(c)设定真空反应腔体压力、温度，同时通入不同反应物气体，将等离子体产生功率调到1～500W，腔体温度调到10～100℃，进行等离子体化学气相沉积，反应完成后，停止通入反应物气体，升高腔体压力到常压。
一般地，所选真空反应腔的体积不小于100L，所采用的产生等离子体方式的输入功率密度范围在0.0001W/L～10W/L。
以下举例说明具体的实施例。
实施例1
本发明中一种应用于PCB板的低介电常数纳米膜或者纳米涂层及其制备方法，经过如下步骤：
(1)先用丙酮或者异丙醇对PCB基体进行清洗，用无尘布擦干，然后放到干燥箱干燥24h。
(2)将干燥好的电子器件的PCB板放置于300L等离子体真空反应腔体内，对反应腔体连续抽真空使真空度达到10毫托。
(3)通入氦气，流量为20sccm，开启脉冲等离子体放电对PCB板进行预处理，预处理阶段放电频率在500Hz，放电功率10W，放电时间为100s。
(4)然后同时通入四氟乙烯、丁二烯、甲苯，在基体表面进行化学气相沉 积制备纳米涂层。涂层制备过程中三种反应单体通入速度分别为150μL/min、20μL/min、5μL/min，通入时间分别为2000s。
(5)涂层制备结束后，通入压缩空气，使反应腔体恢复至常压，打开腔体，取出电子器件的PCB板。即在PCB板上镀了一层低介电常数的纳米涂层。
实施例2
本发明中一种应用于手机天线保护的低介电常数纳米涂层及其制备方法，经过如下步骤：
(1)先用丙酮或者异丙醇对带有手机天线的电路板进行清洗，用无尘布擦干，然后放到干燥箱干燥24h。
(2)将干燥好的手机天线电路板放置于1000L等离子体真空反应腔体内，对反应腔体连续抽真空使真空度达到50毫托。
(3)通入氦气，流量为40sccm，开启微波等离子体放电对手机天线电路板进行预处理，预处理阶段放电频率在433MHz，放电功率100W，放电时间为100s。
(4)然后同时通入六氟乙烷、丁二烯、乙烯基苯，在基体表面进行化学气相沉积制备纳米涂层。涂层制备过程中三种反应单体通入速度分别为250μL/min、10μL/min、5μL/min，通入时间分别为3000s。
(5)涂层制备结束后，通入压缩空气，使反应腔体恢复至常压，打开腔体，取出手机天线电路板。即在手机天线电路板上镀了一层低介电常数的纳米涂层。
实施例3
本发明中一种应用于手机天线保护的低介电常数纳米涂层及其制备方法，经过如下步骤：
(1)先用丙酮或者异丙醇对带有手机天线的电路板进行清洗，用无尘布擦干，然后放到干燥箱干燥24h。
(2)将干燥好的手机天线电路板放置于2000L等离子体真空反应腔体内，对反应腔体连续抽真空使真空度达到80毫托。
(3)通入氦气，流量为40sccm，开启微波等离子体放电对手机天线电路板进行预处理，预处理阶段放电频率在2450MHz，放电功率400W，放电时间为200s。
(4)然后同时通入六氟环氧丙烷、戊二烯、环己烷，在基体表面进行化学气相沉积制备纳米涂层。涂层制备过程中三种反应单体通入速度分别为 350μL/min、30μL/min、5μL/min，通入时间分别为3000s。
(5)涂层制备结束后，通入压缩空气，使反应腔体恢复至常压，打开腔体，取出手机天线电路板。即在手机天线电路板上镀了一层低介电常数的纳米涂层。
实施例4
本发明中一种应用于手机FPC保护的低介电常数纳米涂层及其制备方法，经过如下步骤：
(1)先用丙酮或者异丙醇对带有手机FPC进行清洗，用无尘布擦干，然后放到干燥箱干燥24h。
(2)将干燥好的手机FPC放置于2000L等离子体真空反应腔体内，对反应腔体连续抽真空使真空度达到80毫托。
(3)通入氦气，流量为40sccm，开启微波等离子体放电对手机FPC进行预处理，预处理阶段放电频率在2450MHz，放电功率400W，放电时间为200s。
(4)然后同时通入六氟环氧丙烷、1,2-环氧-5-己烯、双环戊二烯，在基体表面进行化学气相沉积制备纳米涂层。涂层制备过程中三种反应单体通入速度分别为400μL/min、20μL/min、10μL/min，通入时间分别为3000s。
(5)涂层制备结束后，通入压缩空气，使反应腔体恢复至常压，打开腔体，取出手机FPC。即在手机FPC上镀了一层低介电常数的纳米涂层。
实施例5
与实施例1相比，将步骤(4)中的单体四氟乙烯更换为1H,1H,2H,2H-全氟辛基三乙氧基硅烷，其他条件不改变。
实施例6
与实施例1相比，将步骤(4)中的单体甲苯流量改为0，即不通入，其他条件不改变。
实施例7
与实施例1相比，将步骤(3)中的氦气改为四氟化碳，其他条件不改变。
实施例8
与实施例1相比，将步骤(4)中的四氟乙烯改为四氟乙烯和三甲基氟硅烷的混合物，摩尔比例为2:1，其他条件不变。
实施例9
与实施例1相比，将步骤(4)中的四氟乙烯改为四氟乙烯和三甲基氟硅烷 的混合物，摩尔比例为1:1，其他条件不变。
实施例10
与实施例1相比，将步骤(4)中的丁二烯流量改为0，其他条件不变。
值得一提的是，在上述实施例中，分别以PCB板、手机天线的电路板、手机FPC为基体作为示例说明书所述疏水性的低介电常数膜的形成过程，但是在本发明的其它实施例中，也可以以其它电子器材为基体进行等离子增强化学气相沉积，形成所述疏水性的低介电常数膜，本发明在这方面并不限制。
进一步，对上述实施例的参数进行检测。
纳米涂层厚度，使用美国Filmetrics F20-UV-薄膜厚度测量仪进行检测。
纳米涂层水接触角，根据GB/T 30447-2013标准进行测试。
介电常数，根据GB/T 1409-2006测量电气绝缘材料在工频、音频、高频(包括米波波长在内)下电容率和介质损耗因数的推荐方法进行检测。
纳米涂层的杨氏模量根据JB/T 12721-2016固体材料原位纳米压痕/划痕测试仪技术规范进行测定。
附表：实施例1-10各性能参数
表一
实施例 厚度/nm 接触角/° 介电常数 介电损耗 杨氏模量/GPa
实施例1 186 129 1.92 <0.0001 8.78
实施例2 315 132 2.21 <0.0001 9.63
实施例3 340 116 2.03 <0.0001 11.22
实施例4 296 111 1.86 <0.0001 6.95
实施例5 192 116 2.33 <0.0001 8.96
实施例6 210 132 2.42 <0.0001 13.5
实施例7 152 128 2.37 <0.0001 8.36
实施例8 136 123 2.52 <0.0001 12.36
实施例9 123 133 2.65 <0.0001 8.30
实施例10 174 128 2.01 <0.0001 3.12
采用本发明的技术，可获得能应用于大规模集成电路的防水纳米膜。利用等 离子体化学气相沉积法，获得了相对介电常数在2.0左右的疏水纳米膜；通过添加交联剂使纳米膜的致密度得到提高，其具体体现在力学性能的提升上。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。
本领域的技术人员应理解，上述描述及附图中所示的本发明的实施例只作为举例而并不限制本发明。本发明的目的已经完整并有效地实现。本发明的功能及结构原理已在实施例中展示和说明，在没有背离所述原理下，本发明的实施方式可以有任何变形或修改。

Claims (44)

  1. 一疏水性的低介电常数膜，其由一种或多种含氟化合物A通过等离子体增强化学气相沉积方法形成，其中所述一种或多种含氟化合物包含具有通式C xSi yO mH nF 2x+2y-n+2或者C xSi yO mH nF 2x+2y-n的化合物，其中x为1-20的整数，y为0-8的整数，m为0-6的整数，n为0、3、6、7、9、10、12、13、15、16、17、19。
  2. 根据权利要求1所述的疏水性的低介电常数膜，其由所述化合物A和一交联剂化合物B气相沉积反应形成所述疏水性的低介电常数膜。
  3. 根据权利要求1所述的疏水性的低介电常数膜，其由所述化合物A和一具有大位阻体积的化合物C气相沉积反应形成所述疏水性的低介电常数膜。
  4. 根据权利要求1所述的疏水性的低介电常数膜，其由所述化合物A、一交联剂化合物B以及一具有大位阻体积的化合物C气相沉积反应形成所述疏水性的低介电常数膜。
  5. 根据权利要求1-4任一所述的疏水性的低介电常数膜，其中x为1-10的整数，y为0-6的整数，m为0-3的整数。
  6. 根据权利要求2-4任一所述的疏水性的低介电常数膜，其中所述化合物A的摩尔占比大于35％。
  7. 根据权利要求1-4任一所述的疏水性的低介电常数膜，其中所述化合物A选自组合：四氟乙烯、六氟丙烯、六氟乙烷、六氟环氧丙烷、1H,1H,2H,2H-全氟辛基三乙氧基硅烷、三甲基氟硅烷、八氟丁烯中的一种或几种。
  8. 根据权利要求1至4任一所述的疏水性的低介电常数膜，其中所述化合物A选自组合四氟乙烯、六氟乙烷、六氟环氧丙烷、1H,1H,2H,2H-全氟辛基三乙氧基硅烷中的一种或者几种。
  9. 根据权利要求1至4任一所述的疏水性的低介电常数膜，其中所述化合物A为四氟乙烯加三甲基氟硅烷的混合物。
  10. 根据权利要求2或4所述的疏水性的低介电常数膜，其中所述化合物B选自组合：丁二烯、全氟丁二烯、戊二烯、1,2-环氧-5-己烯、己二烯、庚二烯中的一种或几种。
  11. 根据权利要求2或4所述的疏水性的低介电常数膜，其中所述化合物B 选自组合丁二烯、戊二烯、1,2-环氧-5-己烯中的一种或者几种。
  12. 根据权利要求3或4所述的疏水性的低介电常数膜，其中所述化合物C选自组合：环己烷、甲苯、二甲苯、乙烯基苯、二乙烯基苯、双环戊二烯、萘、吡啶中的一种或几种。
  13. 根据权利要求3或4所述的疏水性的低介电常数膜，其中所述化合物C选自组合甲苯、乙烯基苯、环己烷、双环戊二烯中的一种或者几种。
  14. 根据权利要求2或4所述的疏水性的低介电常数膜，其中所述化合物B是含有不饱和碳碳双键的双官能团或者多官能团分子。
  15. 根据权利要求3或4所述的疏水性的低介电常数膜，其中所述化合物C选自：环烷烃、芳烃、稠环芳烃、芳杂环。
  16. 根据权利要求1-4任一所述的疏水性的低介电常数膜，其中所述疏水性的低介电常数膜的k值范围选自：1.8～1.9、1.9～2.0、2.0～2.1、2.1～2.2、2.2～2.3、2.3～2.4、2.4～2.5、2.5～2.6、2.6～2.7或2.7～2.8。
  17. 根据权利要求1-4任一所述的疏水性的低介电常数膜，其中所述疏水性的低介电常数膜的静态接触角选自：110°～115°、115°～120°、120°～125°、125°～130°、130°～135°或135°～140°。
  18. 根据权利要求1-4任一所述的疏水性的低介电常数膜，其中所述疏水性的低介电常数膜的杨氏模量范围选自：6～7GPa、7～8GPa、8～9GPa、9～10GPa、10～11GPa、11～12GPa、12～13GPa、13～14GPa或14～15GPa。
  19. 一疏水性低介电常数膜制备方法，包括步骤：
    (A)引入包含有通式结构C xSi yO mH nF 2x+2y-n+2或者C xSi yO mH nF 2x+2y-n的一种或多种含氟化合物A至反应装置的反应腔室内；
    (B)引入等离子源气体至所述反应腔室内；和
    (C)在预定功率下，由所述一种或多种含氟化合物反应而在反应腔室内的一基体上气相沉积疏水性的低介电常数膜。
  20. 根据权利要求19所述的疏水性的低介电常数膜的制备方法，其还包括步骤：引入一交联剂化合物B至反应装置的反应腔室内。
  21. 根据权利要求19所述的疏水性的低介电常数膜的制备方法，其还包括步骤：引入一具有大位阻体积的化合物C至反应装置的反应腔室内。
  22. 根据权利要求19所述的疏水性的低介电常数膜的制备方法，其中还包 括步骤：引入一交联剂化合物B和一具有大位阻体积的化合物C至反应装置的反应腔室内。
  23. 根据权利要求19所述的疏水性的低介电常数膜的制备方法，其包括步骤：运转所述基体，以使得所述基体在所述反应腔室内处于运动的状态。
  24. 根据权利要求19所述的疏水性的低介电常数膜的制备方法，其还包括步骤：清洁处理所述基体。
  25. 根据权利要求19所述的疏水性的低介电常数膜的制备方法，其中在步骤(A)之前还包括步骤：对所述反应腔室抽真空。
  26. 根据权利要求19-25任一所述的疏水性的低介电常数膜的制备方法，其中x为1-10的整数，y为0-6的整数，m为0-3的整数。
  27. 根据权利要求20-22任一所述的疏水性的低介电常数膜的制备方法，其中所述化合物A的摩尔占比大于35％。
  28. 根据权利要求19-25任一所述的疏水性的低介电常数膜的制备方法，其中所述化合物A选自组合：四氟乙烯、六氟丙烯、六氟乙烷、六氟环氧丙烷、1H,1H,2H,2H-全氟辛基三乙氧基硅烷、三甲基氟硅烷、八氟丁烯中的一种或几种。
  29. 根据权利要求19至25任一所述的疏水性的低介电常数膜的制备方法，其中所述化合物A选自组合四氟乙烯、六氟乙烷、六氟环氧丙烷、1H,1H,2H,2H-全氟辛基三乙氧基硅烷中的一种或者几种。
  30. 根据权利要求19至25任一所述的疏水性的低介电常数膜的制备方法，其中所述化合物A为四氟乙烯加三甲基氟硅烷的混合物。
  31. 根据权利要求20或22所述的疏水性的低介电常数膜的制备方法，其中所述化合物B选自组合：丁二烯、全氟丁二烯、戊二烯、1,2-环氧-5-己烯、己二烯、庚二烯中的一种或几种。
  32. 根据权利要求20或22所述的疏水性的低介电常数膜的制备方法，其中所述化合物B选自组合丁二烯、戊二烯、1,2-环氧-5-己烯中的一种或者几种。
  33. 根据权利要求21或22所述的疏水性的低介电常数膜的制备方法，其中所述化合物C选自组合：环己烷、甲苯、二甲苯、乙烯基苯、二乙烯基苯、双环戊二烯、萘、吡啶中的一种或几种。
  34. 根据权利要求21或22所述的疏水性的低介电常数膜的制备方法，其中所述化合物C选自组合甲苯、乙烯基苯、环己烷、双环戊二烯中的一种或者 几种。
  35. 根据权利要求20或22所述的疏水性的低介电常数膜的制备方法，其中所述化合物B是含有不饱和碳碳双键的双官能团或者多官能团分子。
  36. 根据权利要求21或22所述的疏水性的低介电常数膜的制备方法，其中所述化合物C选自：环烷烃、芳烃、稠环芳烃、芳杂环。
  37. 根据权利要求19-25任一所述的疏水性的低介电常数膜的制备方法，其中所述疏水性的低介电常数膜的k值范围选自：1.8～1.9、1.9～2.0、2.0～2.1、2.1～2.2、2.2～2.3、2.3～2.4、2.4～2.5、2.5～2.6、2.6～2.7或2.7～2.8。
  38. 根据权利要求19-25任一所述的疏水性的低介电常数膜的制备方法，其中所述疏水性的低介电常数膜的静态接触角选自：110°～115°、115°～120°、120°～125°、125°～130°、130°～135°或135°～140°。
  39. 根据权利要求19-25任一所述的疏水性的低介电常数膜的制备方法，其中所述疏水性的低介电常数膜的杨氏模量范围选自：6～7GPa、7～8GPa、8～9GPa、9～10GPa、10～11GPa、11～12GPa、12～13GPa、13～14GPa或14～15GPa。
  40. 根据权利要求19-25任一所述的疏水性的低介电常数膜的制备方法，其中所述等离子源气体选自：惰性气体或者碳氟化合物。
  41. 根据权利要求19-25任一所述的疏水性的低介电常数膜的制备方法，其中所述等离子源气体选自：氦气或四氟化碳。
  42. 根据权利要求19-25任一所述的疏水性的低介电常数膜的制备方法，其中所述反应装置的输入功率密度范围在0.0001W/L～10W/L。
  43. 根据权利要求19-25任一所述的疏水性的低介电常数膜的制备方法，其中所述反应装置的腔体温度范围为10～100℃。
  44. 根据权利要求19-25任一所述的疏水性的低介电常数膜的制备方法，其中所述基体选自：PCB板、手机天线的电路板、手机FPC中的一种。
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