CN111363183B - Composite membrane and preparation method thereof - Google Patents
Composite membrane and preparation method thereof Download PDFInfo
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- CN111363183B CN111363183B CN202010116872.XA CN202010116872A CN111363183B CN 111363183 B CN111363183 B CN 111363183B CN 202010116872 A CN202010116872 A CN 202010116872A CN 111363183 B CN111363183 B CN 111363183B
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
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- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/06—Polysulfones; Polyethersulfones
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- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/18—Homopolymers or copolymers of nitriles
- C08J2433/20—Homopolymers or copolymers of acrylonitrile
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- C08J2445/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
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- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
Abstract
The invention relates to the field of electronic materials, and discloses a composite film and a preparation method thereof, wherein the method comprises the following steps: carrying out surface treatment on the low-k material base film; coating an ultralow dielectric constant material on one side of a low-k material base film to form an ultralow-k material coating; and depositing a conductive material on one side of the super-k material coating layer away from the low-k material base film to form a conductive layer, and carrying out heat treatment and curing treatment on the prepared composite film to obtain the composite film. The invention can reduce the dielectric constant and dielectric loss of the composite film and can improve the adhesion between the low-k material base film and the conductive layer.
Description
Technical Field
The invention relates to the field of electronic materials, in particular to a composite film and a preparation method thereof.
Background
With the advent of the 5G era, 5G parameters have dramatically advanced compared to 4G, since the frequency band at the high frequency of 5G has not been divided, the available bandwidth is high, and the network speed is high. Currently, the 5G frequency band of the mainstream planning in international and domestic countries can be divided into a 5G low-frequency band and a 5G high-frequency band. The 5G technical test which is currently in progress is mainly carried out at 28 GHz. Since electromagnetic waves have the characteristics that the higher the frequency, the shorter the wavelength, and the easier the attenuation in a propagation medium, the higher the frequency, the smaller the loss of the antenna material is required. This puts higher demands on the dielectric loss of the 5G high-frequency antenna material. Meanwhile, as the integration density is continuously increased in a very large scale integrated circuit, the number of layers of multilayer wiring and logic interconnection increases as the feature size of the integrated circuit becomes smaller, so that the resistance of interconnection parasitics, RC delay due to capacitance increases, which limits high speed performance and causes an increase in power consumption. Crosstalk and power consumption have become bottlenecks to be solved in the development of high-speed, high-density, low-power, and multi-functional integrated circuits. The interlayer and line dielectrics require the application of new lower dielectric constant materials to improve the integration of the device and further reduce the delay time.
PI (polyimide) films were originally used as antenna-producing materials in the 4G era. However, the loss of the PI film is obvious above 10Ghz, and the requirement of a 5G terminal cannot be met. LCP (Liquid Crystal Polymer ) is gradually used. Because LCP is expensive and complex in manufacturing cost, MPI (Modified Polyimide) is one of the mainstream choices for the material of the antenna in the early 5G era. Since the PI film has high technical threshold and material specificity, the PI film is still a major supplier in overseas at present, including Dupont, nobe, ponceau, ponka, SKCK-OLONPI in korea, damima science and technology in taiwan of domestic enterprises, and the like, and these companies basically monopolize the market of high-performance polyimide films over electronic grade polyimide films. The LCP antenna has high technical barriers in multiple links, the electronic-grade LCP material is mainly monopolized by Nissan American enterprises at present, the main production enterprises comprise Japan village and field production institute, Colorado, Gore-Tex, Baolinggi and United states DuPont company, and domestic enterprises mainly have Watt shares. However, LCP and MPI cannot meet the terminal requirements in the case of 5G high frequency (millimeter wave) due to the increased dielectric loss. There is a need to develop new materials with low dielectric constant and low dielectric loss suitable for 5G high frequency.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a composite film with low dielectric constant, low dielectric loss and high bonding performance and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
a method of making a composite membrane comprising the steps of:
carrying out surface treatment on the low-k material base film;
coating an ultra-low dielectric constant material on one side of the low-k material base film to form an ultra-k material coating;
depositing a conductive material on one side of the super-k material coating layer away from the low-k material base film to form a conductive layer, so as to obtain a prepared composite film;
and carrying out heat treatment and curing treatment on the prepared composite film to obtain the composite film.
In one embodiment, the material of the low-k material based film includes at least one of PTFE, PSF, PPO, PPS, PEEK, PEK, PEKK, PEKEKK, PEEKK, PI, and MPI.
In one embodiment, the ultra-low dielectric constant material comprises at least one of Nanoglass, HSQ, SiLK, BCB, FOx, MSQ, HOSP, Black Diamond, Coral, and Aurora.
In one embodiment, the conductive material includes at least one of a liquid metal, a nano metal paste, a metal target, graphene, and a conductive polymer.
In one embodiment, the liquid metal includes at least one of liquid gallium, liquid rubidium, liquid cesium and liquid mercury, the nano metal paste includes at least one of nano silver paste, nano copper paste, nano gold paste, nano aluminum paste and nano nickel paste, the metal target includes at least one of gold target, silver target, copper target, nickel target, aluminum target, titanium target and stainless steel target, and the conductive polymer includes at least one of PAN and PPy.
In one embodiment, the surface treatment is a plasma surface treatment or a surface porosity treatment.
In one embodiment, the plasma surface treatment is a dc plasma treatment or an ac plasma treatment, and the surface porosity treatment is a laser drilling treatment or an etching treatment.
In one embodiment, the coating method is spin coating, brush coating, dip coating, or flow coating.
In one embodiment, the deposition method is 3D printing, screen printing, physical vapor deposition, or vacuum plating.
A composite membrane, comprising:
a low-k material base film subjected to surface treatment;
a super-k material coating coated on one side of the low-k material base film; and
a conductive layer deposited on a side of the ultra-k material coating away from the low-k material base film.
Compared with the prior art, the invention has at least the following advantages:
the surface treatment is carried out on the low-k material base film to improve the surface cohesiveness of the low-k material base film; through the super-k material coating, the dielectric constant and the dielectric loss of the composite film can be reduced, and meanwhile, the adhesion between the low-k material base film and the conducting layer can be improved, so that the low-k material base film and the conducting layer are firmly adhered together; then the composite film has excellent conductive function through the conductive layer; and then the stress of the composite film is eliminated through curing treatment and heat treatment, and the performance of the composite film is improved. The dielectric constant of the composite film obtained in the way is in the range of 1.3-2.2, and the dielectric loss can reach 10 at high frequency (28GHz) -4 The grade is applied to high-frequency electronic materials, the integration level of devices can be improved, the delay time is shortened, and the crosstalk and the energy consumption are reduced.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a flow chart illustrating steps of a method for preparing a composite membrane according to an embodiment of the present invention.
Fig. 2 is a schematic structural diagram of a composite membrane according to an embodiment of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
It will be understood that when an element is referred to as being "secured to" another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "left," "right," and the like as used herein are for illustrative purposes only and do not denote a single embodiment.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In one embodiment, referring to fig. 2, a composite film 10 includes a surface-treated low-k material base film 110, a super-k material coating layer 120, and a conductive layer 130, wherein the super-k material coating layer 120 is coated on one side of the low-k material base film 110; the conductive layer 130 is deposited on a side of the ultra-k material coating 120 away from the low-k material base film 110.
It should be noted that in the composite film 10 of the present invention, the low-k material base film 110 is made of polymer insulating film materials such as PTFE, PSF, PPO, PPS, PEEK, PEK, PEKK, PEEKK, PI, and MPI, which contain low dielectric groups, such as aromatic polymers, fluorine-containing groups, and silicon-containing groups, so that the low dielectric constant and low dielectric loss of the composite film itself are achieved, and the composite film has excellent electrical properties, chemical corrosion resistance, and heat resistance, and has a wide temperature range, low water absorption, and small dielectric property change in a high frequency range, and is very suitable for being used as a 5G high frequency material, such as PTFE, PSF, PPO, PPS, PEEK, PEKK, PI, and MPIThe substrate material of (1). However, the bonding force between the polymer insulating film material and the metal material is very poor, so that the bonding force between the low-k material base film 110 and the conductive layer 130 is very poor, and the application of the composite film in microelectronic circuits is greatly limited, and if the problem of poor adhesion between the low-k material base film 110 and the conductive layer 130 can be solved, the composite film 10 can replace LCP and MPI materials, and becomes a future development trend in the 5G and 6G times. The ultra-k material coating 120 of the present invention uses materials with ultra-low dielectric constant and ultra-low dielectric loss, such as Nanoglass, HSQ, SiLK, BCB, FOx, MSQ, HOSP, Black Diamond, Coral, and Aurora, which have high adhesive strength, so that the surface treatment and the ultra-k material coating 120 can reduce the dielectric constant and dielectric loss of the composite film 10, and can improve the adhesion between the low-k material base film 110 and the conductive layer 130, so that the low-k material base film 110 and the conductive layer 130 are firmly adhered together. The dielectric constant of the composite film 10 thus obtained is in the range of 1.3 to 2.2, and the dielectric loss can reach 10 at high frequency (28GHz) -4 The grade is applied to high-frequency electronic materials, the integration level of devices can be improved, the delay time is shortened, and the crosstalk and the energy consumption are reduced.
In order to further reduce the dielectric constant and dielectric loss of the composite film 10, and improve the mechanical strength, compressive strength, tensile strength, electrical insulation performance, chemical resistance, heat resistance and service temperature range of the composite film 10, in one embodiment, the material of the low-k material base film 110 includes at least one of PTFE, PSF, PPO, PPS, PEEK, PEK, PEKK, PEKEKK, PEEKK, PI and MPI. For example, the material of the low-k material base film 110 includes a common mixture of PTFE, PSF, PPO, PPS, PEEK, PEK, PEKK, PEEKK, PI, and MPI. For example, the material of the low-k material base film 110 includes PTFE, PSF, PPO, PPS, PEEK, PEK, PEKK, PEKEKK, PEEKK, PI, or MPI. Thus, the high molecular insulation film materials such as PTFE (polytetrafluoroethylene), PSF (polysulfone), PPO (poly 2, 6-dimethyl-1, 4-phenylene oxide), PPS (polyphenylene sulfide), PEEK (polyether ether ketone), PEK (polyether ketone), PEKK (polyether ketone), PEEKK (polyether ether ketone), PI (polyimide), MPI (polyimide resin) and the like are selected, and contain low dielectric groups such as aromatic polymer, fluorine-containing groups, silicon-containing groups and the like, so that the high molecular insulation film materials have low dielectric constant and low dielectric loss, and also have excellent mechanical strength, compressive strength, tensile strength, electrical insulation performance, chemical corrosion resistance and heat resistance, wide use temperature range, low water absorption, small dielectric property change in high frequency range, and the dielectric constant and the dielectric loss of the composite film 10 can be further reduced, the mechanical strength, compressive strength, tensile strength, electrical insulation properties, chemical resistance, heat resistance and service temperature range of the composite film 10 are improved.
In order to further reduce the dielectric constant and dielectric loss of the composite film 10 and improve the adhesion between the low-k material base film 110 and the conductive layer 130, in one embodiment, the material of the super-k material coating layer 120 includes at least one of Nanoglass, HSQ, SiLK, BCB, FOx, MSQ, HOSP, Black Diamond, Coral, and Aurora. For example, the ultra-low dielectric constant material includes a common mixture of Nanoglass, HSQ, SiLK, BCB, FOx, MSQ, HOSP, Black Diamond, Coral, and Aurora. For example, the ultra-low dielectric constant material includes Nanoglass, HSQ, SiLK, BCB, FOx, MSQ, HOSP, Black Diamond, Coral, or Aurora. Among them, Nanoglass is an aerogel-based low dielectric constant material that is introduced by Nanopore and Honeywell, and has a minimum dielectric constant of 1.3. FOx is an HSQ-based low dielectric constant material developed by Dow Chemical with a dielectric constant of 2.9. MSQ is an abbreviation of methylsilsequioxane, and is a silicon-based polymer material with a dielectric constant of 2.5-2.9. HSQ is hydrosiloxane, which is also a silicon-based polymer material, and the dielectric constant is 2.5-2.9. HOSP is a low dielectric constant material based on a mixture of organic and silicon oxides, as derived by Honeywell. Black Diamond is a low dielectric constant material based on chemical vapor deposition of carbon-doped silicon oxide, with a dielectric constant of 2.4, as introduced by applied materials, Inc. Coral is a low dielectric constant material based on chemical vapor deposition of carbon-doped silicon oxide, with a dielectric constant of 2.7, derived by Novellus. Aurora is a low dielectric constant material based on chemical vapor deposition of carbon-doped silicon oxide, with a dielectric constant of 2.7, introduced by ASM International. SiLK, a low dielectric constant material developed by Dow Chemical and widely used in integrated circuit production at present, is an aromatic thermosetting organic material containing unsaturated bonds, no fluorine, no oxygen and nitrogen, and having a dielectric constant of 2.6. BCB is benzocyclobutene resin, and the dielectric constant is 2.6. Thus, the materials with ultralow dielectric constant and ultralow dielectric loss, such as Nanoglass, HSQ, SiLK, BCB, FOx, MSQ, HOSP, Black Diamond, Coral, and Aurora, are selected, and have high adhesive force, so that the dielectric constant and the dielectric loss of the composite film 10 can be further reduced, and the adhesive property between the low-k material base film 110 and the conductive layer 130 can be improved, so that the low-k material base film 110 and the conductive layer 130 are firmly adhered together.
In order to further improve the conductivity of the composite film 10, in an embodiment, the material of the conductive layer 130 includes at least one of a liquid metal, a nano-metal paste, a metal target, graphene, and a conductive polymer. For example, the conductive material includes a liquid metal, a nano metal paste, a metal target, graphene, or a conductive polymer. For example, the liquid metal includes at least one of liquid gallium, liquid rubidium, liquid cesium, and liquid mercury, e.g., the liquid metal includes a common mixture of liquid gallium, liquid rubidium, liquid cesium, and liquid mercury. For example, the liquid metal includes liquid gallium, liquid rubidium, liquid cesium, or liquid mercury. For example, the nano-metal paste includes at least one of a nano-silver paste, a nano-copper paste, a nano-gold paste, a nano-aluminum paste, and a nano-nickel paste, for example, the nano-metal paste includes a common mixture of a nano-silver paste, a nano-copper paste, a nano-gold paste, a nano-aluminum paste, and a nano-nickel paste. For example, the nano metal paste includes a nano silver paste, a nano copper paste, a nano gold paste, a nano aluminum paste, or a nano nickel paste. For example, the metal target includes at least one of a gold target, a silver target, a copper target, a nickel target, an aluminum target, a titanium target, and a stainless steel target, for example, the metal target includes a common mixture of a gold target, a silver target, a copper target, a nickel target, an aluminum target, a titanium target, and a stainless steel target. For example, the metal target includes a gold target, a silver target, a copper target, a nickel target, an aluminum target, a titanium target, or a stainless steel target. For example, the conductive polymer includes at least one of PAN and PPy. For example, the conductive polymer includes a common mixture of PAN and PPy. For example, the conductive polymer includes PAN or PPy. Thus, the conductive material with excellent conductivity is selected, so that the conductivity of the composite film 10 can be further improved.
Referring to fig. 1 and 2, a method for preparing a composite film 10 includes the following steps:
s110, a surface treatment is performed on the low-k material base film 110.
In the present invention, the adhesion of the surface of the low-k material base film 110 is improved by surface-treating the low-k material base film 110. For example, the surface treatment is a plasma surface treatment. Thus, through plasma surface treatment, the chemical composition and the structure of the polymer on the surface layer of the low-k material base film 110 are changed by utilizing plasma, and hydrophilic groups are generated to improve the wettability and the hydrophilicity of the surface of the low-k material base film 110; and through the etching effect of the plasma, some tiny macroscopic invisible nano-scale grooves and protruding nano-scale short and thin stripes are formed on the surface of the low-k material base film 110 to improve the roughness of the surface of the low-k material base film 110, so that the adhesive property of the surface of the low-k material base film 110 is comprehensively improved, and the adhesion between the low-k material base film 110 and the conductive layer 130 is further improved. For example, the plasma surface treatment is a direct-current plasma treatment or an alternating-current plasma treatment. This can improve the adhesion property of the surface of the low-k material base film 110. For example, the surface treatment is a surface porous treatment. Thus, a plurality of micron-sized micropores are formed on the surface of the low-k material base film 110 through surface porous treatment, so that the ultra-low dielectric constant material can be immersed into the low-k material base film 110, the bonding area and the bonding depth between the ultra-k material coating 120 and the low-k material base film 110 are increased, and the bonding property between the low-k material base film 110 and the conductive layer 130 is improved; while the dielectric constant and dielectric loss of the low-k material based film 110 can be reduced by the plurality of micropores. For example, the surface porous treatment is a laser drilling treatment or an etching treatment. This improves the adhesion between the low-k material base film 110 and the conductive layer 130, and reduces the dielectric constant and dielectric loss of the low-k material base film 110.
In order to further improve the adhesion performance of the surface of the low-k material base film, in an embodiment, the operation of performing plasma treatment on the low-k material base film specifically includes: sequentially carrying out ultrasonic cleaning operation and drying operation on the low-k material base film; arranging a conductive active mesh enclosure in a container, putting the low-k material base film into the conductive active mesh enclosure, and then sealing the container; vacuumizing the container, and introducing a treatment gas into the container; the container is provided with a conductive container wall, and plasma equipment transmits electricity to the conductive container wall and the conductive active mesh enclosure, so that the conductive container wall is an anode, the conductive active mesh enclosure is a cathode, the processing gas is ionized to generate plasma, and the low-k material base film is subjected to plasma processing. Introducing new hydrophilic hydroxyl groups on the surface of the low-k material base film through plasma treatment so as to improve the wettability and the hydrophilicity of the surface of the low-k material base film; and some tiny macroscopic invisible nano-scale grooves and protruding nano-scale short and fine stripes are formed on the low-k material base film to improve the roughness of the surface of the low-k material base film, so that the bonding performance of the surface of the low-k material base film can be further improved.
In order to further improve the processing effect of the plasma processing, in one embodiment, the plasma device is a dc plasma device or an ac plasma device, for example, the rf output by the dc plasma device is 100MHz to 100GHz, for example, the rf output by the dc plasma device is 50GHz, for example, the microwave output by the ac plasma device is 1GHz or more. For example, the AC plasma device outputs microwaves of 1GHz, 5GHz, 10GHz, 50GHz or 100 GHz. For example, the distance between the low-k material base film and the conductive active mesh cover is 5mm to 100 mm. For example, the low-k material base film is 50mm away from the conductive active mesh. For example, the processing pressure of the plasma processing is 10 to 500 Pa. For example, the processing pressure of the plasma treatment is 2500 Pa. For example, the treatment temperature of the plasma treatment is 50 ℃ to 250 ℃. For example, the processing temperature of the plasma treatment is 150 ℃. For example, the plasma treatment is performed for a treatment time of 5min to 5 hours. For example, the processing time of the plasma treatment is 2.5 h. For example, the process gas includes at least one of argon, nitrogen, hydrogen, methane, and oxygen. For example, the material of the conductive container wall includes at least one of stainless steel, copper, silver, nickel and aluminum. For example, the material of the conductive active mesh enclosure includes at least one of stainless steel, copper, silver, nickel and aluminum. This can further improve the processing effect of the plasma processing.
In order to further reduce the dielectric constant and dielectric loss of the composite film 10, in one embodiment, the material of the low-k material base film 110 includes at least one of PTFE, PSF, PPO, PPS, PEEK, PEK, PEKK, PEEKK, PI, and MPI. Thus, the polymer insulation film materials such as PTFE, PSF, PPO, PPS, PEEK, PEK, PEKK, PEKEKK, PEEKK, PI, MPI and the like are selected, and the polymer insulation film materials contain low dielectric groups such as aromatic polymers, fluorine-containing groups, silicon-containing groups and the like, so that the polymer insulation film materials have low dielectric constant and low dielectric loss, and also have excellent electrical property, chemical corrosion resistance, heat resistance, wide use temperature range, low water absorption and small dielectric property change in a high frequency range, the dielectric constant and the dielectric loss of the composite film 10 can be further reduced, the electrical property, the chemical corrosion resistance, the heat resistance and the use temperature range of the composite film 10 are further improved, and the water absorption of the composite film 10 is further reduced.
And S120, coating an ultralow dielectric constant material on one side of the low-k material base film 110 to form an ultralow-k material coating 120.
It should be noted that, according to the present invention, the ultra-low dielectric constant material is coated on one side of the low-k material base film 110 to form the ultra-k material coating layer 120, and the ultra-k material coating layer 120 is used to reduce the dielectric constant and dielectric loss of the composite film 10, and at the same time, the adhesion between the low-k material base film 110 and the conductive layer 130 can be improved, so that the low-k material base film 110 and the conductive layer 130 are firmly adhered together. For example, the coating method is spin coating, brush coating, dip coating or flow coating. This reduces the dielectric constant and dielectric loss of the composite film 10, and improves the adhesion between the low-k material base film 110 and the conductive layer 130.
In order to further reduce the dielectric constant and dielectric loss of the composite film 10 and further improve the adhesion between the low-k material base film 110 and the conductive layer 130, in one embodiment, the ultra-low dielectric constant material includes at least one of Nanoglass, HSQ, SiLK, BCB, FOx, MSQ, HOSP, Black Diamond, Coral, and Aurora. Thus, materials with ultralow dielectric constant and ultralow dielectric loss, such as Nanoglass, HSQ, SiLK, BCB, FOx, MSQ, HOSP, Black Diamond, Coral, Aurora and the like, are selected, and the materials also have high adhesive force, so that the dielectric constant and the dielectric loss of the composite film 10 can be further reduced, and the adhesion between the low-k material base film 110 and the conductive layer 130 is further improved, so that the low-k material base film 110 and the conductive layer 130 are firmly adhered together.
And S130, depositing a conductive material on one side of the ultra-k material coating layer 120 away from the low-k material base film 110 to form a conductive layer 130, thereby obtaining a prepared composite film.
In addition, the invention deposits the conductive material on the side of the ultra-k material coating layer 120 away from the low-k material base film 110 to form the conductive layer 130, so as to obtain a prepared composite film; the conductive layer 130 enables the composite film 10 to have a conductive function, and can be applied to high-frequency antenna materials, thereby improving the integration level of devices, reducing the delay time, and reducing crosstalk and energy consumption. For example, the deposition method is 3D printing, screen printing, physical vapor deposition, or vacuum plating. This can improve the conductivity of the composite film 10.
In order to further improve the conductivity of the composite film 10, in an embodiment, the conductive material includes at least one of a liquid metal, a nano-metal paste, a metal target, graphene, and a conductive polymer. For example, the liquid metal includes at least one of liquid gallium, liquid rubidium, liquid cesium, and liquid mercury. For example, the nano metal paste includes at least one of nano silver paste, nano copper paste, nano gold paste, nano aluminum paste, and nano nickel paste. For example, the metal target includes at least one of a gold target, a silver target, a copper target, a nickel target, an aluminum target, a titanium target, and a stainless steel target. For example, the conductive polymer includes at least one of PAN and PPy. Thus, the conductive material with excellent conductivity is selected, so that the conductivity of the composite film 10 can be further improved.
And S140, carrying out heat treatment and curing treatment on the prepared composite film to obtain the composite film 10.
It should be noted that the present invention crosslinks the ultralow dielectric constant material by curing treatment, and improves the comprehensive properties of the composite film 10, such as heat resistance, corrosion resistance, adhesiveness, etc.; and then the stress of the composite film 10 is eliminated by heat treatment, so that the performance of the composite film 10 is further improved.
In order to further relieve the stress of the composite film 10 and further improve the performance of the composite film 10, in one embodiment, the heat treatment temperature is 100 ℃ to 150 ℃, for example, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃ or 150 ℃. In this way, the stress of the composite film 10 can be further eliminated, and the performance of the composite film 10 can be further improved. For example, the temperature of the curing treatment is 25 ℃ to 250 ℃, for example, the temperature of the curing treatment is 25 ℃, 50 ℃, 75 ℃, 100 ℃, 125 ℃, 150 ℃, 175 ℃, 200 ℃, 225 ℃ or 250 ℃.
Compared with the prior art, the invention has at least the following advantages:
the invention improves the adhesive property of the surface of the low-k material base film 110 by carrying out surface treatment on the low-k material base film 110; then, the ultra-k material coating 120 can reduce the dielectric constant and dielectric loss of the composite film 10, and can improve the adhesion between the low-k material base film 110 and the conductive layer 130, so that the low-k material base film 110 and the conductive layer 130 are firmly adhered together; then the composite film 10 has an excellent conductive function through the conductive layer 130; and then the stress of the composite film 10 is eliminated through curing treatment and heat treatment, so that the performance of the composite film 10 is improved. The dielectric constant of the composite film 10 is 1.3-2.2, and the dielectric loss can reach 10 at high frequency (28GHz) -4 Grade, applied to high-frequency electronic materials, can improve the integration level of devices and reduce the costSmall delay time, reduced crosstalk and power consumption.
The following are detailed description of the embodiments
Example 1
And S111, carrying out direct current plasma treatment on the low-k material base film, wherein the low-k material base film is made of PTFE.
And S121, spin-coating Nanoglass on one side of the low-k material base film to form a super-k material coating.
S131, screen printing nano silver paste on one side surface of the super-k material coating layer, which is far away from the low-k material base film, to form a conductive layer, so that a prepared composite film is obtained.
And S141, carrying out heat treatment and curing treatment on the prepared composite film to obtain the composite film.
Example 2
And S112, carrying out laser drilling treatment on the low-k material base film, wherein the low-k material base film is made of PPO.
S122, dip-coating SiLK on one side of the low-k material base film to form a super-k material coating.
S132, vacuum plating a gold target material on one side surface of the super-k material coating layer away from the low-k material base film to form a conductive layer, and obtaining a prepared composite film.
And S142, carrying out heat treatment and curing treatment on the prepared composite film to obtain the composite film.
Example 3
S113, carrying out alternating current plasma treatment on the low-k material base film, wherein the low-k material base film is made of PSF.
S123, brushing HSQ on one side of the low-k material base film to form a super-k material coating.
And S133, 3D printing liquid gallium on one side surface of the super-k material coating layer, which is far away from the low-k material base film, to form a conductive layer, so as to obtain a prepared composite film.
And S143, carrying out heat treatment and curing treatment on the prepared composite film to obtain the composite film.
Example 4
S114, etching the low-k material base film, wherein the low-k material base film is made of PEEK.
And S124, flow-coating BCB on one side of the low-k material base film to form a super-k material coating.
And S134, screen-printing graphene on one side of the super-k material coating layer away from the low-k material base film to form a conductive layer, so as to obtain a prepared composite film.
And S144, carrying out heat treatment and curing treatment on the prepared composite film to obtain the composite film.
Example 5
And S115, carrying out direct current plasma treatment on the low-k material base film, wherein the material of the low-k material base film is PI.
And S125, coating MSQ on one side of the low-k material base film by brushing to form a super-k material coating.
And S135, carrying out vacuum plating on PAN on one side of the ultra-k material coating layer away from the low-k material base film to form a conductive layer, so as to obtain a prepared composite film.
And S145, carrying out heat treatment and curing treatment on the prepared composite film to obtain the composite film.
Comparative example 1
And brushing an epoxy resin adhesive on one side of the low-k material base film to form an adhesive layer, and screen-printing nano-silver slurry on one side of the adhesive layer, which is far away from the low-k material base film, to form a conductive layer to obtain a prepared composite film. And carrying out heat treatment and curing treatment on the prepared composite film to obtain the composite film.
Experiment: 1. the dielectric constants and dielectric losses of the composite films of examples 1-5 and the composite film of comparative example 1 were measured, respectively, and the results are shown in table 1.
2. According to the GB/T9286-1998 ruled test standard, the adhesion between the conductive layers of the composite films of examples 1-5 and the composite film of comparative example 1 and the base film of the low-k material is respectively detected, and the detection results are shown in Table 1.
TABLE 1
| Comparative example 1 | Example 1 | Example 2 | Example 3 | Example 4 | |
| Dielectric constant (28GHz) | 4.30 | 1.30 | 2.20 | 2.00 | 1.80 |
| Dielectric loss (28GHz) | 0.012 | 0.0008 | 0.0009 | 0.0009 | 0.0008 |
| Grade of adhesion | Stage 2 | Level 0 | Level 0 | Level 0 | Level 0 |
As can be seen from table 1, the dielectric constant and dielectric loss of the composite film of the present invention are much lower than those of the composite film of comparative example 1, and the adhesion between the conductive layer of the present invention and the base film of low-k material is much higher than that between the conductive layer of comparative example 1 and the base film of low-k material. The dielectric constant of the composite film is within the range of 1.3-2.2, and the dielectric loss can reach 10 at high frequency (28GHz) -4 And the grade is applied to high-frequency antenna materials, so that the integration level of the device can be improved, the delay time is shortened, and the crosstalk and energy consumption are reduced.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (8)
1. A preparation method of a composite film is characterized by comprising the following steps:
carrying out surface treatment on the low-k material base film; wherein the material of the low-k material base film comprises at least one of PTFE, PSF, PPO, PPS, PEEK, PEK, PEKK, PEKEKK, PEEKK, PI and MPI;
coating an ultra-low dielectric constant material on one side of the low-k material base film to form an ultra-k material coating; wherein the ultra-low dielectric constant material comprises at least one of Nanoglass, HSQ, SiLK, BCB, FOx, MSQ, HOSP, Black Diamond, Coral, and Aurora;
depositing a conductive material on one side of the super-k material coating layer away from the low-k material base film to form a conductive layer, so as to obtain a prepared composite film;
and carrying out heat treatment and curing treatment on the prepared composite film to obtain the composite film.
2. The method of claim 1, wherein the conductive material comprises at least one of a liquid metal, a nano-metal paste, a metal target, graphene, and a conductive polymer.
3. The method of claim 2, wherein the liquid metal comprises at least one of liquid gallium, liquid rubidium, liquid cesium, and liquid mercury, the nano-metal paste comprises at least one of nano-silver paste, nano-copper paste, nano-gold paste, nano-aluminum paste, and nano-nickel paste, the metal target comprises at least one of gold target, silver target, copper target, nickel target, aluminum target, titanium target, and stainless steel target, and the conductive polymer comprises at least one of PAN and PPy.
4. A method of making a composite membrane according to any of claims 1 to 3 wherein the surface treatment is a plasma surface treatment or a surface porosity treatment.
5. A method of making a composite membrane according to claim 4 wherein the plasma surface treatment is a DC plasma treatment or an AC plasma treatment and the surface porosity treatment is a laser drilling treatment or an etching treatment.
6. A method of making a composite film according to any of claims 1 to 3 wherein said coating is spin coating, brush coating, dip coating or flow coating.
7. A method of making a composite film according to any of claims 1 to 3 wherein the deposition process is 3D printing, screen printing, physical vapour deposition or vacuum plating.
8. A composite membrane, comprising:
a low-k material base film subjected to surface treatment; the material of the low-k material base film comprises at least one of PTFE, PSF, PPO, PPS, PEEK, PEK, PEKK, PEKEKK, PEEKK, PI and MPI;
a super-k material coating coated on one side of the low-k material base film; the material of the ultra-k material coating comprises at least one of Nanoglass, HSQ, SiLK, BCB, FOx, MSQ, HOSP, Black Diamond, Coral and Aurora; and
a conductive layer deposited on a side of the ultra-k material coating away from the low-k material base film.
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