CN113667158A - Low-dielectric polyimide-based composite film and preparation method and application thereof - Google Patents
Low-dielectric polyimide-based composite film and preparation method and application thereof Download PDFInfo
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
The invention relates to the technical field of low-dielectric polyimide composite materials, in particular to a low-dielectric polyimide-based composite film and a preparation method and application thereof. The polyimide film with low dielectric constant is prepared according to the following steps: preparing polyamic acid solution from pyromellitic dianhydride and 4,4' -diaminodiphenyl, adding nano cage-type phenyl silsesquioxane, and imidizing to obtain low-dielectric polyimide composite film and low-dielectric polyimideThe base composite film can be applied to the preparation of electronic device packaging materials and interlayer dielectric materials of integrated circuits. The invention adopts nano cage type phenyl silsesquioxane to dope and the obtained product is 100 to 106Within the Hz frequency test range, the composite film with the dielectric constant of 2.2-2.5 and the dielectric loss factor of 0.0011-0.0073 is obtained, and has good mechanical properties, simple process, easily purchased raw materials and low cost.
Description
Technical Field
The invention belongs to the technical field of low-dielectric polyimide composite materials, and particularly relates to a low-dielectric polyimide-based composite film and a preparation method and application thereof.
Background
The rapid development of information technology and the increasing social demand have made higher and higher demands on miniaturization and ultrahigh integration of devices. With the increasing integration and miniaturization of Ultra Large Scale Integrated (ULSI) devices, the increasing density of transistors, the increasing inductance-capacitance effect between wires, the increasing interconnection delay of circuit signals caused by the mutual influence of wire currents, and the increasing crosstalk and power loss, the bottleneck for further increasing the speed of integrated circuits has been reached, mainly because of the conventional SiO2And (k is 3.9-4.2) as a dielectric material between lines and between layers in a microelectronic circuit, and the dielectric property of the material cannot meet the requirement. Research shows that the adoption of the material with the ultralow dielectric constant (1owk) as the insulating medium between metal wires and between layers can effectively reduce the interconnection delay, crosstalk and energy consumption of circuits, thereby realizing the novel low dielectric (k)<2.5) and ultralow dielectric (k is less than or equal to 2.0) interlayer dielectric materials are especially important to develop and apply.
There are various methods for reducing the dielectric constant of dielectric materials, and the introduction of pore structures into the dielectric matrix is a very effective approach. Porous materials include inorganic and organic porous materials, and compared with inorganic porous dielectric materials, organic polymer materials generally have good electrical insulation properties (i.e., low loss and low leakage current), good mechanical properties (i.e., high adhesion and high flexibility), and meanwhile, the electronic polarization of organic polymers is generally low, so that the porous organic polymers have good application prospects in the field of microelectronics as low dielectric materials, and have attracted extensive attention. Among the materials, polyimide film materials are considered as ideal insulating medium materials in microelectronic devices due to low dielectric constant and good thermal and chemical stability, and are used as one member of organic polymer families, and polyimide not only has the commonness of organic polymer compounds such as low density of organic polymers, rich types of molecular monomers, flexible and diverse synthetic methods, easy functional regulation, excellent mechanical properties, low moisture absorption rate and the like, but also has the unique advantages of high glass transition temperature (400 ℃), good thermal and chemical stability and the like, so that polyimide is called 'gold' in super engineering clinker and is used as a packaging material in the field of microelectronics, and the insulating medium materials in ultra-large scale integrated circuits have very attractive application prospects.
The molecular chain of the polyimide is a polar chain, and the dielectric property of certain rigid chain polyimide has anisotropy due to the orientation effect, so that the low dielectric property of the polyimide is not outstanding, particularly, the dielectric constant of a commercial Kapton film is between 3.5 and 3.8 although the Kapton film has excellent mechanical property, so that the requirement of the integrated circuit on the interlayer dielectric low dielectric constant medium cannot be met; aiming at the problem that the fluorinated low dielectric polyimide film is synthesized by using expensive fluorine-containing dianhydride or diamine monomers as raw materials at present, a preparation method of the polyimide film with simple synthesis process, low cost and ultralow dielectric constant is required to be found, and particularly, the polyimide film material with k less than or equal to 2.5 and D less than or equal to 0.003 is required.
Disclosure of Invention
Aiming at the technical defects, the invention provides a low dielectric polyimide-based composite film, a preparation method and application thereof, solves the defects of the prior art, and provides a polyimide-based composite film which is low in cost, simple in process and ultra-low in dielectric constant.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a low-dielectric polyimide-based composite film comprises the following steps:
preparing a polyimide acid solution by adopting 4,4' -diaminodiphenyl ether and pyromellitic dianhydride;
adding nano cage-type phenyl silsesquioxane into the polyimide acid solution obtained in the step (1), and stirring for 2-3 hours in an ice bath environment to obtain a mixed solution;
step (3), after the mixed solution obtained in the step (2) is uniformly coated to form a film, placing the coated glass sheet into a vacuum drying box, preserving heat for 10h at the temperature of 60-70 ℃, preserving heat for 6h at the temperature of 100-;
the mass fraction of the nano cage-type phenyl silsesquioxane in the low dielectric polyimide-based composite film is 5-30%.
Preferably, in the step (3), the mass fraction of the nano cage-type phenyl silsesquioxane in the low dielectric polyimide-based composite film is 15-25%.
Preferably, in the step (3), the mass fraction of the nano cage-type phenyl silsesquioxane in the low dielectric polyimide-based composite film is 25%.
Preferably, the viscosity coefficient of the polyimide acid solution in the step (1) is 9000-10000 CP.
Preferably, in the step (1), the polyimide acid solution is prepared according to the following steps: dissolving 4,4' -diaminodiphenyl ether in a nonpolar solvent in an argon atmosphere, then adding pyromellitic dianhydride, and stirring for 6-8h in an ice bath environment to obtain a polyimide acid solution.
Preferably, the non-polar solvent is selected from N, N '-dimethylformamide or N, N' -dimethylacetamide.
Preferably, in the polyimide acid solution, the molar ratio of 4,4 '-diaminodiphenyl ether to pyromellitic dianhydride is 1:1, and the total solid content of 4,4' -diaminodiphenyl ether and pyromellitic dianhydride is 10%.
Preferably, the invention also protects the low dielectric polyimide-based composite film prepared by the preparation method, namely the polyimide-based composite filmWhen the mass fraction of the rice cage type phenyl silsesquioxane in the low dielectric polyimide-based composite film is 25 percent, the mass fraction is 100 to 10 percent6In the Hz frequency test range, the dielectric constant is measured as follows: k is more than or equal to 2.2 and less than or equal to 2.5, and the dielectric loss factor D is more than or equal to 0.0011 and less than or equal to 0.0073.
The invention also protects the application of the low dielectric polyimide-based composite film in the preparation of electronic device packaging materials and interlayer dielectric materials of integrated circuits.
Compared with the prior art, the invention has the beneficial effects that:
1. the nano cage-type phenyl silsesquioxane particles are uniformly dispersed in the polyimide film to play two roles, namely introducing a hole structure into a polyimide matrix and reducing the number of polarized molecules in unit volume; on the other hand, the dielectric local effect of the nanoparticles inhibits the polarization of matrix electron cloud in the polyimide matrix material, which is in contact with the nanoparticles, so that the dielectric constant and the dielectric loss of the polyimide film are effectively reduced by adding the nano cage type phenyl silsesquioxane into the polyimide matrix, and meanwhile, the synthesized polyimide-based composite film keeps good mechanical properties.
2. The low dielectric constant polyimide film obtained by the invention obtains the optimal sample on the basis of keeping good mechanical property, and the optimal sample is realized at 104In the range of the Hz frequency test, the dielectric constant k is 2.37 and the dielectric loss factor D is 0.0018.
3. The invention adopts a copolymerization method, and the dianhydride and the diamine are used as the raw materials for synthesizing the commercial Kapton film, thereby ensuring the good mechanical property of the synthesized polyimide film; the viscosity coefficient of the polyimide acid solution is limited to 9000-10000CP, when the viscosity coefficient is less than 9000CP, the polymerization degree is low, the mechanical property of the polyimide film is influenced, and when the viscosity coefficient is more than 10000CP, the industrial processing production is not easy to realize; in addition, the dianhydride and the diamine are easily purchased and commercialized raw materials, and the cost is low.
4. The invention utilizes a physical blending method to mix the nano cage-type phenyl silsesquioxane particles into the synthetic polyamic acid solution, and has simple process and easy operation.
Drawings
FIG. 1 is a flow chart showing the synthesis of polyimide-based composite films according to examples 1 to 8 of the present invention;
FIG. 2 is a graph showing FT-IR absorption spectra of polyimide-based composite films of examples 1 and 4 to 8 of the present invention and a polyimide film of comparative example 1;
FIG. 3 is a dielectric-spectrum graph of polyimide-based composite films according to examples 1 and 4 to 8 of the present invention and a polyimide film according to comparative example 1;
FIG. 4 is a graph showing a comparison of mechanical properties of polyimide-based composite films according to examples 1 and 4 to 8 of the present invention and a polyimide film according to comparative example 1, wherein (a) is tensile strength; (b) is the tensile modulus; (c) the elongation at break.
Detailed Description
The following detailed description of specific embodiments of the invention is provided, but it should be understood that the scope of the invention is not limited to the specific embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. The experimental methods described in the examples of the present invention are all conventional methods unless otherwise specified.
The following experimental methods and detection methods, unless otherwise specified, are conventional methods; the following reagents and starting materials are all commercially available unless otherwise specified.
Example 1
A preparation method of a low-dielectric polyimide-based composite film comprises the following steps:
step (1), according to the standard that the total solid content of 4,4 '-diaminodiphenyl ether and pyromellitic dianhydride is 10%, respectively weighing 4,4' -diaminodiphenyl ether (ODA, 98% analytical purity), pyromellitic dianhydride (PDMA, 99% analytical purity) and N, N '-dimethylformamide (DMF, not less than 99.9% analytical purity), selecting a 50mL round-bottomed flask, filling argon gas as protective gas, firstly dissolving 4,4' -diaminodiphenyl ether in N, N '-dimethylformamide solution, adding Pyromellitic Dianhydride (PDMA) after 4,4' -diaminodiphenyl ether (ODA) is completely dissolved, stirring for 6 hours in ice bath environment, and synthesizing polyimide acid solution (PAA solution);
step (2), adding nano cage-type phenyl silsesquioxane (phenyl POSS particles) into the polyimide acid solution obtained in the step (1), sealing the flask, placing the flask into an ice-water mixture, and magnetically stirring for 2 hours to obtain a mixed solution, wherein the phenyl POSS particles in the mixed solution are uniformly distributed in the PAA solution;
step (3), uniformly coating the mixed solution on a cleaned glass sheet, then placing the coated glass sheet in a vacuum drying oven, vacuumizing, preserving heat for 10 hours at 70 ℃, 6 hours at 120 ℃, 6 hours at 200 ℃, 2 hours at 300 ℃, removing organic solvent and water, closing the oven, naturally cooling to room temperature, taking out, soaking the film in hot water, stripping off the film from the glass sheet, drying and preserving to obtain the low dielectric polyimide-based composite film;
wherein the mass fraction of the nano cage-type phenyl silsesquioxane in the low dielectric polyimide-based composite film is 5%.
Example 2
A preparation method of a low-dielectric polyimide-based composite film comprises the following steps:
step (1), according to the standard that the total solid content of 4,4 '-diaminodiphenyl ether and pyromellitic dianhydride is 10%, respectively weighing 4,4' -diaminodiphenyl ether (ODA, 98% analytical purity), pyromellitic dianhydride (PDMA, 99% analytical purity) and N, N '-dimethylformamide (DMF, not less than 99.9% analytical purity), selecting a 50mL round-bottomed flask, filling argon gas as protective gas, firstly dissolving 4,4' -diaminodiphenyl ether in N, N '-dimethylformamide solution, adding Pyromellitic Dianhydride (PDMA) after 4,4' -diaminodiphenyl ether (ODA) is completely dissolved, stirring for 7 hours in ice bath environment, and synthesizing polyimide acid solution (PAA solution);
step (2), adding nano cage-type phenyl silsesquioxane (phenyl POSS particles) into the polyimide acid solution obtained in the step (1), sealing the flask, placing the flask into an ice-water mixture, and magnetically stirring for 2.5 hours to obtain a mixed solution, wherein the phenyl POSS particles in the mixed solution are uniformly distributed in the PAA solution;
step (3), uniformly coating the mixed solution on a cleaned glass sheet, then placing the coated glass sheet in a vacuum drying oven, vacuumizing, preserving heat for 10 hours at 65 ℃, 6 hours at 110 ℃, 6 hours at 205 ℃, 2 hours at 310 ℃, removing organic solvent and water, closing the oven, naturally cooling to room temperature, taking out, soaking the film in hot water, stripping off the film from the glass sheet, drying and preserving to obtain the low dielectric polyimide-based composite film;
wherein the mass fraction of the nano cage-type phenyl silsesquioxane in the low dielectric polyimide-based composite film is 5%.
Example 3
A preparation method of a low-dielectric polyimide-based composite film comprises the following steps:
step (1), according to the standard that the total solid content of 4,4 '-diaminodiphenyl ether and pyromellitic dianhydride is 10%, respectively weighing 4,4' -diaminodiphenyl ether (ODA, 98% analytical purity), pyromellitic dianhydride (PDMA, 99% analytical purity) and N, N '-dimethylformamide (DMF, no less than 99.9% analytical purity), selecting a 50mL round-bottomed flask, filling argon gas as protective gas, firstly dissolving 4,4' -diaminodiphenyl ether in N, N '-dimethylformamide solution, adding Pyromellitic Dianhydride (PDMA) after 4,4' -diaminodiphenyl ether (ODA) is completely dissolved, stirring for 8 hours in ice bath environment, and synthesizing polyimide acid solution (PAA solution);
step (2), adding nano cage-type phenyl silsesquioxane (phenyl POSS particles) into the polyimide acid solution obtained in the step (1), sealing the flask, placing the flask into an ice-water mixture, and magnetically stirring for 3 hours to obtain a mixed solution, wherein the phenyl POSS particles in the mixed solution are uniformly distributed in the PAA solution;
step (3), uniformly coating the mixed solution on a cleaned glass sheet, then placing the coated glass sheet in a vacuum drying oven, vacuumizing, preserving heat for 10 hours at 60 ℃, 6 hours at 100 ℃, 6 hours at 210 ℃, 2 hours at 330 ℃, removing organic solvent and water, closing the oven, naturally cooling to room temperature, taking out, soaking the film in hot water, stripping off the film from the glass sheet, drying and preserving to obtain the low dielectric polyimide-based composite film;
wherein the mass fraction of the nano cage-type phenyl silsesquioxane in the low dielectric polyimide-based composite film is 5%.
Example 4
The same procedure as in example 1 was followed, except that the nano cage-type phenylsilsesquioxane was replaced with 10% by mass in the low dielectric polyimide-based composite film.
Example 5
The same procedure as in example 1 was followed, except that the nano cage-type phenylsilsesquioxane was substituted at 5% to 15% by mass in the low dielectric polyimide-based composite film.
Example 6
The same procedure as in example 1 was followed, except that the nano cage-type phenylsilsesquioxane was substituted at 5% to 20% by mass in the low dielectric polyimide-based composite film.
Example 7
The same procedure as in example 1 was followed, except that the nano cage-type phenylsilsesquioxane was replaced by 25% in the mass fraction of the low dielectric polyimide-based composite film.
Example 8
The same procedure as in example 1 was followed, except that the nano cage-type phenylsilsesquioxane was replaced with 30% by mass in the low dielectric polyimide-based composite film.
Comparative example 1
The preparation method of the polyimide film comprises the following steps:
step (1), according to the standard that the total solid content of 4,4 '-diaminodiphenyl ether and pyromellitic dianhydride is 10%, respectively weighing 4,4' -diaminodiphenyl ether (ODA, 98% analytical purity), pyromellitic dianhydride (PDMA, 99% analytical purity) and N, N '-dimethylformamide (DMF, not less than 99.9% analytical purity), selecting a 50mL round-bottomed flask, filling argon gas as protective gas, firstly dissolving 4,4' -diaminodiphenyl ether in N, N '-dimethylformamide solution, adding Pyromellitic Dianhydride (PDMA) after 4,4' -diaminodiphenyl ether (ODA) is completely dissolved, stirring for 6 hours in ice bath environment, and synthesizing polyimide acid solution (PAA solution);
and (2) uniformly coating the polyimide acid solution on a cleaned glass sheet, then placing the coated glass sheet in a vacuum drying oven, vacuumizing, preserving heat at 70 ℃ for 10 hours, preserving heat at 120 ℃ for 6 hours, preserving heat at 200 ℃ for 6 hours, preserving heat at 300 ℃ for 2 hours, removing organic solvent and water, closing the oven, naturally cooling to room temperature, taking out, soaking the film in hot water, stripping the film from the glass plate, drying and preserving to obtain the polyimide film.
The polyimide-based composite films of examples 1 to 8 of the present invention were synthesized in the same manner as shown in FIG. 1.
In order to determine that the synthesized composite film is a polyimide-based film, a sample was examined using fourier infrared (FT-IR) absorption spectroscopy, and the obtained spectrum results are shown in fig. 2:
appearing at 725cm in FIG. 2-1Peak at (2), corresponding to flexural vibration absorption of imido C ═ O double bond, 1376cm-1The peak at (a) is related to the C-N stretching vibration absorption of the imino group, 1724cm-1And 1780cm-1Peaks at (a) are due to symmetric carbonyl stretching vibration and imino asymmetric vibration, respectively; the peak appears at 3072cm-1The vibration belongs to the stretching vibration of C-H on a benzene ring; furthermore, 1431cm in the spectrum-1The tensile vibration peak intensity of the C-bond is gradually increased, which is mainly caused by the high content of benzene ring in the phenyl POSS particles, so the infrared spectrum shows that the polyamic acid is imidized into polyimide; compared with a polyimide film not doped with POSS, the FTIR spectrum of the doped film is 1200-1000 cm-1Shows a broad and strong absorption peak due to the asymmetric tensile absorption of Si-O-Si in the phenyl POSS particles, confirming the presence of phenyl POSS particles in the polyimide.
In order to investigate the low dielectric properties of the low dielectric polyimide-based composite films synthesized by the method of the present invention, dielectric-spectrum measurements at room temperature were performed on examples 1, 4 to 8 and comparative samples, and the results are shown in fig. 3;
the dielectric constant and loss of the composite film in FIG. 3 decreased with increasing phenyl POSS particle content until the phenyl POSS particle content reached 25 wt%; when the content of phenyl POSS particles is 25%, the dielectric constant of the film is lowest, and the film has good dielectric-frequency spectrum stability at 10%4The dielectric constant under Hz is only 2.37, the dielectric loss is only 0.0018, and the dielectric constant is obviously improved compared with the dielectric constant of 3.89 and the dielectric loss of 0.011 of the undoped polyimide film under the frequency; when POSS content reaches 30 wt%, dielectric constant and dielectric loss rise sharply again, which is mainly related to agglomeration of phenyl POSS particles upon overdoping.
To investigate the mechanical properties of the phenyl POSS particle doped polyimide based composite films synthesized by the method of the present invention, mechanical property measurements at room temperature were performed on examples 1, 4-8 and comparative samples, and the results are shown in fig. 4:
in FIG. 4, as the content of POSS particles increases, the tensile strength of the film is reduced from 170.12MPa of PI/POSS-0 to 50.23MPa, the tensile modulus is increased from 1.41GPa of PI/POSS-0 to 3.51GPa of PI/POSS-30, and the elongation at break is reduced from 10.17% of PI/POSS-0 to 2.0% of PI/POSS-30; the tensile strength of a sample with the doping amount of 25% is 56.42MPa, the tensile film amount is 3.1GPa, the elongation at break is 2.2%, and the sample still has good mechanical properties under the condition that the low dielectric property is remarkably improved.
In conclusion, the phenyl POSS particle doped polyimide composite film provided by the invention effectively improves the low dielectric property of the polyimide film through the doping of the phenyl POSS particles, and greatly reduces the dielectric constant value and the dielectric loss value of the polyimide film, so that the phenyl POSS particle doped polyimide composite film provided by the invention can be used as a packaging material of electronic devices in the electronic industry field, and an interlayer dielectric material in an integrated circuit has a wide application prospect.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (9)
1. A preparation method of a low-dielectric polyimide-based composite film is characterized by comprising the following steps:
preparing a polyimide acid solution by adopting 4,4' -diaminodiphenyl ether and pyromellitic dianhydride;
adding nano cage-type phenyl silsesquioxane into the polyimide acid solution obtained in the step (1), and stirring for 2-3 hours in an ice bath environment to obtain a mixed solution;
step (3), after the mixed solution obtained in the step (2) is uniformly coated to form a film, placing the coated glass sheet into a vacuum drying box, preserving heat for 10h at the temperature of 60-70 ℃, preserving heat for 6h at the temperature of 100-;
the mass fraction of the nano cage-type phenyl silsesquioxane in the low dielectric polyimide-based composite film is 5-30%.
2. The method for preparing a low dielectric polyimide-based composite film according to claim 1, wherein in the step (3), the mass fraction of the nano cage-type phenylsilsesquioxane in the low dielectric polyimide-based composite film is 15-25%.
3. The method for preparing a low dielectric polyimide-based composite film according to claim 1, wherein in the step (3), the mass fraction of the nano cage-type phenylsilsesquioxane in the low dielectric polyimide-based composite film is 25%.
4. The method for preparing a low dielectric polyimide-based composite film as defined in claim 1, wherein the polyimide solution in step (1) has a viscosity coefficient of 9000-10000 CP.
5. The method for preparing a low dielectric polyimide-based composite film according to claim 1, wherein in the step (1), the polyimide acid solution is prepared according to the following steps: dissolving 4,4' -diaminodiphenyl ether in a nonpolar solvent in an argon atmosphere, then adding pyromellitic dianhydride, and stirring for 6-8h in an ice bath environment to obtain a polyimide acid solution.
6. The method for preparing a low dielectric polyimide-based composite film according to claim 5, wherein the non-polar solvent is selected from N, N '-dimethylformamide or N, N' -dimethylacetamide.
7. The method of claim 5, wherein the polyimide-based solution has a molar ratio of 4,4 '-diaminodiphenyl ether to pyromellitic dianhydride of 1:1, and a total solid content of 4,4' -diaminodiphenyl ether and pyromellitic dianhydride of 10%.
8. A low dielectric polyimide-based composite film prepared by the preparation method of any one of claims 1 to 7, wherein when the mass fraction of the nano cage-type phenyl silsesquioxane in the low dielectric polyimide-based composite film is 25%, the mass fraction is 100 to 106In the Hz frequency test range, the dielectric constant is measured as follows: k is more than or equal to 2.2 and less than or equal to 2.5, and the dielectric loss factor D is more than or equal to 0.0011 and less than or equal to 0.0073.
9. The use of the low dielectric polyimide-based composite film of claim 8 in the preparation of electronic device packaging materials and interlayer dielectric materials for integrated circuits.
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| CN114316591A (en) * | 2021-12-31 | 2022-04-12 | 浙江中科玖源新材料有限公司 | Dimensionally stable low-dielectric polyimide film and preparation method and application thereof |
| CN116179075A (en) * | 2023-03-08 | 2023-05-30 | 中国地质大学（北京） | POSS modified polyimide insulating paint, preparation method and application |
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| CN116179075A (en) * | 2023-03-08 | 2023-05-30 | 中国地质大学（北京） | POSS modified polyimide insulating paint, preparation method and application |
| CN116179075B (en) * | 2023-03-08 | 2023-10-13 | 中国地质大学（北京） | POSS modified polyimide insulating paint, preparation method and application |
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