CN112143020A - Water-resistant low-dielectric polyimide composite film and preparation method and application thereof - Google Patents
Water-resistant low-dielectric polyimide composite film and preparation method and application thereof Download PDFInfo
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 107
- 239000004642 Polyimide Substances 0.000 title claims abstract description 99
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000004530 micro-emulsion Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 238000004377 microelectronic Methods 0.000 claims abstract description 5
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims description 44
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- -1 polyethylene Polymers 0.000 claims description 9
- 229920000573 polyethylene Polymers 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- XRWMGCFJVKDVMD-UHFFFAOYSA-M didodecyl(dimethyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCC XRWMGCFJVKDVMD-UHFFFAOYSA-M 0.000 claims description 2
- 239000010408 film Substances 0.000 claims description 2
- 238000005266 casting Methods 0.000 claims 1
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- 239000003292 glue Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000001338 self-assembly Methods 0.000 description 3
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- DEZTWKPPXJNRMY-UHFFFAOYSA-N dimethyl(pentacosan-13-yl)azanium bromide Chemical compound [Br-].C(CCCCCCCCCCC)C([NH+](C)C)CCCCCCCCCCCC DEZTWKPPXJNRMY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 2
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- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 1
- 239000005770 Eugenol Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 1
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- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000003518 norbornenyl group Chemical class C12(C=CC(CC1)C2)* 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—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
- C08J2383/04—Polysiloxanes
- C08J2383/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—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 C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J2483/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
Abstract
The invention discloses a water-resistant low-dielectric polyimide composite film and a preparation method and application thereof, and particularly relates to the technical field of low-dielectric materials. Selecting proper POSS and dosage, dissolving the POSS, amphiphilic substance and polyimide in an organic solvent to prepare an organic solution containing POSS, mixing and emulsifying the organic solution and deionized water according to a proportion to prepare a microemulsion containing both polyimide and POSS, pouring the microemulsion on a proper substrate under a certain condition, self-assembling a micron-sized water phase in the organic solution to present ordered hexagonal stacking arrangement, and completely volatilizing the water phase and the organic solvent to obtain the ordered multistage porous water-resistant low-dielectric polyimide composite film. The preparation method has the advantages of simple and convenient operation, low cost, no toxicity, no template residue, easy structure control and the like, and the composite film is applied to the fields of microelectronics and 5G as a packaging material under a higher humidity environment.
Description
Technical Field
The invention relates to the technical field of low dielectric materials, in particular to a water-resistant low dielectric polyimide composite film and a preparation method and application thereof.
Background
With the rapid development of electronic packaging, microelectronics, especially 5G communication technology, the high-performance low-dielectric material can reduce crosstalk noise, energy loss, signal delay and the like between lines, so that the integrity, accuracy and speed of signal transmission can be ensured, and a great deal of research attention is attracted. Organic polymers have significant advantages over conventional inorganic low dielectric materials, in which polyimides are widely used due to their excellent dielectric properties, thermal stability and mechanical properties. However, commercial polyimides typically have dielectric constants greater than 3, which cannot meet the increasing demands of microelectronics and 5G applications. Therefore, it is highly desirable to develop a method for reducing the dielectric constant of polyimide films. Meanwhile, the water drops have high dielectric constant, and the adsorption on the surface of the low dielectric material can cause the damage of the dielectric property of the material, and influence the property and the service life of the material.
In general, reducing the dipole strength and number of dipoles is considered to be two effective methods of reducing the dielectric constant of polymer materials. In order to reduce the dipole strength of the polymer, some low polarizability groups are often introduced, wherein C-F bonds are most common, and the introduction is also beneficial to improving the hydrophobicity and water resistance of the film. Feng et al combine fluorinated graphene and fluorinated polyimide (J.Mater.chem.C., 2018,6, 6378-6384), and achieve simultaneous reduction of the dielectric constant and water absorption of the film by introducing fluorine-containing substituents. Fang et al prepared fluorinated norbornene from fluorinated bio-based eugenol (ACS Sustainable chem. Eng.2019,7, 4078-. Although the introduction of C — F bonds has a significant effect on the reduction of the dielectric constant, and even the water absorption of the polymer film, it generally involves complicated synthesis steps, expensive experimental raw materials and low yield, and may cause deterioration of other properties of the film.
On the other hand, in order to reduce the number of dipoles, bulky groups and molecules are often introduced into the polymer chain to increase its free volume, thereby reducing the material density. Zhang et al achieved varying reductions in the dielectric constant of polyimide films by introducing varying numbers of benzene rings (J.Mater.chem.C,2017,5, 12807-12815) in the polyimide side chains. Researchers also consider fully utilizing the secondary relaxation of polymers to increase the free volume thereof when designing the molecules of the polymers, thereby achieving effective reduction of the dielectric constant of the polymers (Macromolecules,2019,52, 4601-4609). Similar to the C-F bond, the introduction of these bulky groups can also involve complicated preparation processes, high cost and low yield, and the introduction of certain groups can also affect the water resistance of the film.
The introduction of porous structures is another effective method to reduce the density of materials, and the dielectric constant of polymer films is effectively reduced due to the presence of a large amount of air with a dielectric constant of 1 in the porous structures (int.j.mol.sci.,2013,14, 8698-. Common methods for preparing porous structures include colloid templating, soft etching, phase separation, and inorganic particle templating (Macromolecules,2013,46, 2275-. However, these methods usually involve complicated and harsh template removal steps and suffer from incomplete template removal and uncontrollable porous structures.
So the research on preparing the low dielectric polyimide film with excellent water resistance is particularly important.
Disclosure of Invention
The invention aims to provide a water-resistant low-dielectric polyimide composite film, a preparation method and application thereof, and aims to solve the problems of complex steps, high cost, low yield, uncontrollable use and structure of toxic substances and the like in the preparation method of the low-dielectric polyimide film in the prior art.
The invention selects proper polyimide and dosage, amphiphilic substance and dosage, cage type Polysilsesquioxane (POSS) and dosage, water phase proportion, temperature and humidity conditions and the like, and utilizes the self-assembly process of the water phase in the POSS-containing polyimide organic solution to prepare the multistage porous polyimide/POSS composite film.
In order to achieve the purpose, the invention provides the following scheme: the invention provides a water-resistant low-dielectric polyimide composite film, which comprises cage-type Polysilsesquioxane (POSS) and a micron-sized porous structure. The micron-sized porous structure comprises an upper layer of holes and a lower layer of holes, wherein the upper layer of holes are good in uniformity and order, the pore diameter is about 2-3 mu m, and the periphery of each hole is surrounded by six other holes to form a honeycomb-like structure; the lower layer holes have poor size uniformity and are not arranged orderly; meanwhile, cage type polysemiloxane is distributed on a framework of a micron-scale porous structure, and then nanometer-level hollow holes are introduced to form a multi-level hole structure. The dielectric constant of the porous composite film is 2.3-2.65; the water absorption of the porous composite film is 0.6-0.7%.
As a further optimization of the invention, the POSS is an octavinyl-POSS.
The invention also provides a preparation method of the water-resistant low-dielectric polyimide composite film, which comprises the following steps:
(1) simultaneously dissolving cage-type polysilsesquioxane, amphiphilic substance and polyimide in an organic solvent to prepare an organic solution containing cage-type polysilsesquioxane;
(2) mixing deionized water with the organic solution containing the cage-type polysilsesquioxane prepared in the step (1), emulsifying and filtering to prepare a micro-emulsion containing the cage-type polysilsesquioxane;
(3) pouring the micro emulsion containing the cage-type polysilsesquioxane prepared in the step (2) on a proper substrate to obtain the polyimide composite film.
As a further optimization of the invention, the concentration of the polyimide in the organic solution in the step (1) is 0.1-20 mg/mL; the concentration of the cage-type polysilsesquioxane in the organic solution is 0.01-10 mg/mL; the concentration of the amphiphilic substance in the organic solution is 0.001-1 mg/mL.
As a further optimization of the invention, the amphiphilic substance in the step (1) is one or more of cetyl trimethyl ammonium bromide, didodecyl dimethyl ammonium bromide or polyethylene oxide-polypropylene oxide-polyethylene oxide; the organic solvent is one or more of carbon disulfide, tetrahydrofuran or dichloromethane.
As a further optimization of the method, the volume ratio of the organic solution containing the cage-type polysilsesquioxane in the step (2) to the deionized water is 5: 1-50: 1.
As a further optimization of the invention, in the step (2), the filtration is organic filtration, the filter head used in the organic filtration is an organic filter head, and the size of the organic filter head is 150-300 nm.
As a further optimization of the invention, in the step (3), the ambient humidity is 30-50%, and the ambient temperature is 25-35 ℃.
As a further optimization of the invention, the substrate in the step (3) is a polyimide flat film, glass, mica or a silicon wafer.
An application of a water-resistant low-dielectric polyimide composite film as a packaging material in the fields of microelectronics and 5G.
As a further optimization of the invention, the application is as an encapsulating material in an environment with an ambient humidity above 75%.
The invention selects proper POSS and dosage, and dissolves the POSS, amphiphilic substance and polyimide in an organic solvent to prepare an organic solution containing POSS, the organic solution is mixed and emulsified with deionized water according to a certain proportion to prepare a microemulsion containing polyimide and POSS at the same time, the microemulsion is poured on a proper substrate under certain temperature and humidity conditions, micron-sized water phase is self-assembled in the organic solution to present ordered hexagonal stacking arrangement, and the ordered multi-stage porous water-resistant low-dielectric polyimide composite film is obtained after the water phase and the organic solvent are completely volatilized. The method for preparing the porous structure by using the self-assembly process of the microemulsion as the template is simpler and more convenient and cheaper, does not involve an additional template removal step, and avoids the influence of incomplete template removal on the performance of the film. More importantly, the convenient and fast introduction of the functional substance can be realized by a method of dissolving in the organic phase of the microemulsion in advance. Due to the remarkable advantages of cage type Polysilsesquioxane (POSS) in reducing the dielectric constant and the water absorption of the polymer material, the POSS can be dissolved in the organic phase of the microemulsion in advance, and then the POSS can be quickly introduced into a porous structure. The porous structure and POSS are organically combined, which is beneficial to the reduction of the dielectric constant and the improvement of the water resistance of the polyimide film.
The invention discloses the following technical effects:
the invention discloses a water-resistant low-dielectric polyimide composite film and a preparation method thereof; a micron-sized porous structure is formed in the composite film, the porosity is 21% -33.5%, the porous structure is multilayer, the uniformity and the orderliness of holes in the upper layer are good, the pore diameter is 2-3 mu m, the periphery of each hole is surrounded by other six holes to form a honeycomb-like structure, the composite film has excellent water resistance and low dielectric property, the dielectric constant of the composite film is 2.3-2.65, and the dielectric constant of the composite film is 21.13% -31.55% lower than that of a polyimide flat film with the dielectric constant of 3.36; the water absorption of the composite film is 0.6-0.7%, which is reduced by 75-78.57% compared with the water absorption of 2.80% of the polyimide flat film.
The invention organically combines the porous structure and POSS by utilizing the self-assembly process of the water phase in the microemulsion, realizes the synchronous introduction of POSS while preparing the ordered porous structure by dissolving POSS in the organic phase in advance, has the advantages of simple and convenient operation, low cost, no toxicity, no template residue, easy structure control and the like compared with other methods for preparing the porous structure and introducing POSS, and can realize the precise regulation and control of the structure and the performance of the composite film by changing the dosage of each substance and environmental conditions.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
FIG. 1 is a scanning electron microscope photograph of a polyimide composite film obtained in example 1;
FIG. 2 is a comparison of dielectric constants of a polyimide composite film obtained in example 1 and a polyimide flat film obtained in comparative example 1;
FIG. 3 is a comparison of the water absorption rates of the polyimide composite film obtained in example 1 and the polyimide flat film obtained in comparative example 1.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
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. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
(1) An organic solution containing POSS was prepared by dissolving 12mg of polyimide, 6mg of octavinyl-POSS, and 0.12mg of polyethylene oxide-polypropylene oxide-polyethylene oxide in 10mL of methylene chloride.
(2) Then in the step (1), the organic solution is mixed in a ratio of 10: 1 and deionized water, oscillating for 5min, and filtering with a 200nm organic filter head to prepare the POSS-containing microemulsion.
(3) Pouring the microemulsion prepared in the step (2) on a cleaned silicon chip under the conditions of 25 ℃ and 40% of humidity, and completely volatilizing the organic solvent and water to prepare the polyimide composite film with the upper layer of holes with the diameter of about 2.5 microns.
FIG. 1 is a scanning electron microscope photograph of the polyimide composite film obtained in this example, in which the porosity is 28.4%, the holes are distributed in multiple layers, the average diameter of the holes in the upper layer is 2.5 μm, and almost every hole is surrounded by six other holes to form a honeycomb-like structure, and the uniformity and order of the holes in the lower layer are slightly inferior to those in the holes in the upper layer.
FIG. 2 is a comparison of the dielectric constant of the polyimide composite film prepared in this example with that of the flat polyimide film prepared in comparative example 1, and the dielectric constant of the polyimide film was reduced from 3.36 to 2.42 by 27.63% due to the introduction of the porous structure and POSS.
FIG. 3 is a comparison of the water absorption rates of the polyimide composite film prepared in the present example and the polyimide flat film prepared in comparative example 1, wherein the water absorption rate of the polyimide film is reduced from 2.80% to 0.6% and 78.43% due to the introduction of the porous structure and POSS.
Example 2
The preparation method is the same as example 1, except that the mass of the octavinyl-POSS in the step (1) is changed to 1.2mg, the polyimide composite film with the average diameter of the upper layer pores of 2.47 mu m is prepared, the porosity is 22.1%, compared with the polyimide flat film, the dielectric constant is reduced from 3.36 to 2.62, the dielectric constant is reduced by 22%, and the water absorption is reduced from 2.80% to 0.67% and reduced by 75.96%.
Example 3
The preparation method is the same as example 1, except that the mass of the octavinyl-POSS in the step (1) is changed to 2.4mg, the polyimide composite film with the average diameter of the upper layer pores of 2.6 μm is prepared, the porosity is 23.9%, compared with the polyimide flat film, the dielectric constant is reduced from 3.36 to 2.53, and is reduced by 24.74%, and the water absorption is reduced from 2.80% to 0.65%, and is reduced by 76.85%.
Example 4
The preparation method is the same as example 1, except that the mass of the octavinyl-POSS in the step (1) is changed to 3.6mg, the polyimide composite film with the average diameter of the upper layer holes of 2.58 μm is prepared, the porosity is 26.2%, compared with the polyimide flat film, the dielectric constant is reduced to 2.49 from 3.36, and is reduced by 25.78%, and the water absorption is reduced to 0.62% from 2.80%, and is reduced by 77.75%.
Example 5
The preparation method is the same as example 1, except that the weight of POSS in the step (1) is changed into 4.8mg, the polyimide composite film with the average diameter of the upper layer holes of 2.62 μm is prepared, the porosity is 29.7%, compared with the polyimide flat film, the dielectric constant is reduced to 2.47 from 3.36, the dielectric constant is reduced to 26.44%, and the water absorption is reduced to 0.61% from 2.80%, and the dielectric constant is reduced to 78.07%.
Example 6
The preparation method is the same as example 1, only the dichloromethane in the step (1) is changed into carbon disulfide, the polyimide composite film with the average diameter of the upper layer holes being 1.82 μm and forming a structure similar to a honeycomb shape and the uniformity and the order of the lower layer holes being slightly poorer than those of the upper layer holes is prepared, the porosity is 21.8%, compared with the polyimide flat film, the dielectric constant is reduced from 3.36 to 2.65, the dielectric constant is reduced by 21.13%, the water absorption is reduced from 2.80% to 0.66%, and the water absorption is reduced by 76.43%.
Example 7
The preparation method is the same as example 1, except that the dichloromethane in the step (1) is changed into tetrahydrofuran, the polyimide composite film with the average diameter of the upper layer holes being 5 μm is prepared, the porosity is 30.5%, compared with the polyimide flat film, the dielectric constant is reduced from 3.36 to 2.4, and is reduced by 28.57%, and the water absorption is reduced from 2.80% to 0.6% and is reduced by 78.57%.
Example 8
The preparation method is the same as example 1, except that polyethylene oxide-polypropylene oxide-polyethylene oxide in the step (1) is changed into hexadecyl trimethyl ammonium bromide, the polyimide composite film with the average diameter of the upper layer holes of 3.5 μm is prepared, the porosity is 28.8%, compared with the polyimide flat film, the dielectric constant is reduced from 3.36 to 2.41, and is reduced by 28.27%, and the water absorption is reduced from 2.80% to 0.615%, and is reduced by 78.04%.
Example 9
The preparation method is the same as example 1, except that the polyethylene oxide-polypropylene oxide-polyethylene oxide in the step (1) is changed into didodecyltrimethylammonium bromide, the polyimide composite film with the average diameter of the upper layer holes of 3.8 μm is prepared, the porosity is 29.8%, compared with the polyimide flat film, the dielectric constant is reduced from 3.36 to 2.41, and is reduced by 28.27%, and the water absorption is reduced from 2.80% to 0.625%, and is reduced by 77.68%.
Example 10
The preparation method is the same as example 1, except that the mass of the polyimide in the step (1) is changed into 1mg, the polyimide composite film with the average diameter of the upper layer holes of 5.8 μm is prepared, the porosity is 32.8%, compared with the polyimide flat film, the dielectric constant is reduced from 3.36 to 2.35, the water absorption is reduced by 30.06%, and the water absorption is reduced from 2.80% to 0.65%, and the water absorption is reduced by 76.79%.
Example 11
The preparation method is the same as example 1, except that the mass of the polyimide in the step (1) is changed to 200mg, the polyimide composite film with the average diameter of the upper layer holes of 1.25 μm is prepared, the porosity is 21%, compared with the polyimide flat film, the dielectric constant is reduced from 3.36 to 2.65, the dielectric constant is reduced by 21.13%, and the water absorption is reduced from 2.80% to 0.68% and reduced by 75.71%.
Example 12
The preparation method is the same as example 1, except that the POSS mass in the step (1) is changed into 0.1mg, the polyimide composite film with the average diameter of the upper layer holes of 2.68 μm is prepared, the porosity is 21.7%, compared with the polyimide flat film, the dielectric constant is reduced from 3.36 to 2.64, the dielectric constant is reduced by 21.43%, and the water absorption is reduced from 2.80% to 0.7%, and the water absorption is reduced by 75%.
Example 13
The preparation method is the same as example 1, except that the POSS mass in the step (1) is changed into 100mg, the polyimide composite film with the average diameter of the upper layer pores of 2.3 μm is prepared, the porosity is 33.5%, compared with the polyimide flat film, the dielectric constant is reduced from 3.36 to 2.34, the water absorption is reduced by 30.36%, and the water absorption is reduced from 2.80% to 0.615%, and is reduced by 78.04%.
Example 14
The preparation method is the same as example 1, except that the mass of the polyethylene oxide-polypropylene oxide-polyethylene oxide in the step (1) is changed to 10mg, the polyimide composite film with the average diameter of the upper layer holes of 1.5 μm is prepared, the porosity is 21.5%, compared with the polyimide flat film, the dielectric constant is reduced from 3.36 to 2.63 and is reduced by 21.73%, and the water absorption is reduced from 2.80% to 0.675% and is reduced by 75.89%.
Example 15
The preparation method is the same as example 1, except that the mass of the polyethylene oxide-polypropylene oxide-polyethylene oxide in the step (1) is changed to 0.01mg, the polyimide composite film with the average diameter of the upper layer pores being 3 μm is prepared, the porosity is 22.5%, compared with the polyimide flat film, the dielectric constant is reduced from 3.36 to 2.6 and is reduced by 22.62%, and the water absorption is reduced from 2.80% to 0.625% and is reduced by 77.68%.
Example 16
The preparation method is the same as example 1, except that the volume ratio of the organic solution to the deionized water in the step (2) is changed to 5:1, the polyimide composite film with the average diameter of the upper layer holes of 5 μm is prepared, the porosity is 28.9%, compared with the polyimide flat film, the dielectric constant is reduced to 2.4 from 3.36, the dielectric constant is reduced to 28.57%, and the water absorption is reduced to 0.618% from 2.80%, and the dielectric constant is reduced to 77.93%.
Example 17
The preparation method is the same as example 1, except that the volume ratio of the organic solution to the deionized water in the step (2) is changed to 50:1, the polyimide composite film with the average diameter of the upper layer holes of 2 μm is prepared, the porosity is 27.5%, compared with the polyimide flat film, the dielectric constant is reduced to 2.45 from 3.36, the dielectric constant is reduced to 27.08%, and the water absorption is reduced to 0.65% from 2.80%, and the dielectric constant is reduced to 76.79%.
Example 18
The preparation method is the same as example 1, except that the silicon wafer in the step (3) is changed into a polyimide flat film, the polyimide composite film with the average diameter of the upper layer holes of 2.61 μm is prepared, the porosity is 28%, compared with the polyimide flat film, the dielectric constant is reduced from 3.36 to 2.43, the dielectric constant is reduced by 27.68%, and the water absorption is reduced from 2.80% to 0.61% and reduced by 78.21%.
Example 19
The preparation method is the same as example 1, except that the silicon wafer in the step (3) is changed into glass, the polyimide composite film with the average diameter of the upper layer holes of 2.59 mu m is prepared, the porosity is 28.2%, compared with the polyimide flat film, the dielectric constant is reduced from 3.36 to 2.435, the dielectric constant is reduced by 27.53%, and the water absorption is reduced from 2.80% to 0.618%, and the water absorption is reduced by 77.93%.
Example 20
The preparation method is the same as example 1, except that the silicon wafer in the step (3) is changed into mica, the polyimide composite film with the average diameter of the upper layer holes of 2.58 μm is prepared, the porosity is 27.8%, compared with the polyimide flat film, the dielectric constant is reduced from 3.36 to 2.59, the dielectric constant is reduced by 22.92%, and the water absorption is reduced from 2.80% to 0.62% and reduced by 77.86%.
Example 21
The preparation method is the same as example 1, except that the polyethylene oxide-polypropylene oxide-polyethylene oxide in the step (1) is changed into a mixture of didodecyltrimethylammonium bromide and polyethylene oxide-polypropylene oxide-polyethylene oxide (mass ratio is 1: 1), and the polyimide composite film with the average diameter of the upper layer holes of 3.5 μm is prepared, the porosity is 27.8%, compared with the polyimide flat film, the dielectric constant is reduced from 3.36 to 2.52, and is reduced by 25%, the water absorption is reduced from 2.80% to 0.61%, and is reduced by 78.21%.
Example 22
The preparation method is the same as example 1, except that dichloromethane in the step (1) is changed into a mixture of dichloromethane and carbon disulfide (the volume ratio is 1: 1), a porous structure with the average diameter of upper-layer holes of 2.2 mu m is prepared, the porosity is 25.5%, the dielectric constant is reduced to 2.59 from 3.36 compared with the polyimide flat film, the dielectric constant is reduced to 22.92%, the water absorption is reduced to 0.63% from 2.80%, and the water absorption is reduced to 77.5%.
Comparative example 1
Preparing a polyimide flat film: sequentially adding ODA and DMAc into a three-neck flask at room temperature, accurately weighing PMDA with the same molar weight as ODA after the ODA is completely dissolved, adding into the solution in four times on average, reacting for 2 hours after each addition, keeping the temperature of the solution below 20 ℃ all the time in the adding process, continuously stirring for 2 hours after the addition is finished, obtaining polyamic acid (PAA) glue solution after full reaction, standing for defoaming, paving the PAA glue solution on a clean glass plate, placing the PAA glue solution in an oven for thermal imidization reaction, carrying out imidization gradient of 1 hour at 80 ℃,2 hours at 110 ℃,150 ℃, 0.5 hour at 200 ℃,1 hour at 250 ℃ and 0.5 hour at 300 ℃, cooling the oven temperature to room temperature, taking out the glass plate and soaking in water for a certain time, preparing a polyimide flat film with the thickness of about 20 mu m after demoulding, and obtaining the dielectric constant of 3.36 after detection, the water absorption was 2.80%.
When the composite film prepared in example 1 was placed in a high humidity environment with a humidity of 75%, the dielectric constant was only 2.5 and the increment was only 3.3%, while the dielectric constant of the polyimide flat film after moisture absorption was 3.67 and the increment was 9.43%. Therefore, the composite film prepared in example 1 of the present application can be applied to an environment with humidity higher than 75%.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. A water-resistant low-dielectric polyimide composite film is characterized by comprising cage-type polysilsesquioxane and a micron-sized porous structure, wherein the micron-sized porous structure comprises an upper layer of holes and a lower layer of holes, the upper layer of holes are uniform in size and good in order, the average pore diameter is about 2-3 mu m, the periphery of each hole is surrounded by other six holes to form a honeycomb-like structure, and the lower layer of holes are poor in size uniformity and are not arranged in order; meanwhile, the cage type polysemiloxane is distributed on a framework of a micron-sized porous structure.
2. The water-resistant low-dielectric polyimide composite film as claimed in claim 1, wherein said cage polysilsesquioxane is octavinyl-cage polysilsesquioxane.
3. The method for preparing the water-resistant low-dielectric polyimide composite film according to claim 1 or 2, comprising the steps of:
(1) simultaneously dissolving cage-type polysilsesquioxane, amphiphilic substance and polyimide in an organic solvent to prepare an organic solution containing cage-type polysilsesquioxane;
(2) mixing deionized water with the organic solution containing the cage-type polysilsesquioxane prepared in the step (1), emulsifying and filtering to prepare a micro-emulsion containing the cage-type polysilsesquioxane;
(3) pouring the microemulsion containing the cage-type polysilsesquioxane prepared in the step (2) on a substrate to obtain the polyimide composite film.
4. The method for preparing a water-resistant low-dielectric polyimide composite film according to claim 3, wherein the concentration of polyimide in the organic solution in the step (1) is 0.1-20 mg/mL; the concentration of the cage-type polysilsesquioxane in the organic solution is 0.01-10 mg/mL; the concentration of the amphiphilic substance in the organic solution is 0.001-1 mg/mL.
5. The method for preparing a water-resistant low-dielectric polyimide composite film according to claim 4, wherein the amphiphilic substance in the step (1) is one or more of cetyl trimethyl ammonium bromide, didodecyl dimethyl ammonium bromide or polyethylene oxide-polypropylene oxide-polyethylene oxide; the organic solvent is one or more of carbon disulfide, tetrahydrofuran or dichloromethane.
6. The preparation method of the water-resistant low-dielectric polyimide composite film as claimed in claim 3, wherein the volume ratio of the organic solution containing cage-type polysilsesquioxane and the deionized water in the step (2) is 5: 1-50: 1.
7. The method for preparing a water-resistant low-dielectric polyimide composite film according to claim 3, wherein the filtration in the step (2) is organic filtration, the filter head used in the organic filtration is an organic filter head, and the size of the pore in the organic filter head is 150-300 nm.
8. The preparation method of the water-resistant low-dielectric polyimide composite film according to claim 3, wherein the casting in the step (3) is carried out under the conditions that the humidity is 30-50% and the temperature is 25-35 ℃; the substrate is a polyimide flat film, glass, mica or a silicon wafer.
9. The use of a water-resistant, low dielectric polyimide composite film according to claim 1 or 2 as an encapsulation material in microelectronics and 5G applications.
10. Use according to claim 9, as encapsulating material in an environment with an ambient humidity higher than 75%.
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