CN117801331A - High-frequency low-dielectric hydrophobic polyimide composite film and preparation method and application thereof - Google Patents
High-frequency low-dielectric hydrophobic polyimide composite film and preparation method and application thereof Download PDFInfo
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Abstract
本发明公开了一种高频低介电疏水聚酰亚胺复合膜及其制备方法和应用，通过制备粒径均匀的空心二氧化硅微球，采用接枝疏水基团的硅烷偶联剂对空心二氧化硅微球表面进行有机改性，得到具有疏水效应且与聚酰亚胺基体相容性好的空心二氧化硅微球。接着通过物理掺杂的方法将疏水改性空心二氧化硅微球分散在聚酰胺酸溶液中，经酰亚胺化后得到聚酰亚胺复合膜。该薄膜具有低介电常数、低热膨胀系数、高疏水等优异特性，可以在高频高速基材等领域广泛使用。
The invention discloses a high-frequency low-dielectric hydrophobic polyimide composite film and a preparation method and application thereof. Hollow silica microspheres with uniform particle size are prepared, and the surface of the hollow silica microspheres is organically modified by a silane coupling agent grafted with a hydrophobic group to obtain hollow silica microspheres with a hydrophobic effect and good compatibility with a polyimide matrix. Then, the hydrophobically modified hollow silica microspheres are dispersed in a polyamic acid solution by a physical doping method, and a polyimide composite film is obtained after imidization. The film has excellent properties such as low dielectric constant, low thermal expansion coefficient, and high hydrophobicity, and can be widely used in the fields of high-frequency and high-speed substrates.
Description
Technical Field
The invention belongs to the field of low dielectric materials, and particularly relates to a high-frequency low-dielectric hydrophobic polyimide composite film, and a preparation method and application thereof.
Background
At present, high-frequency microwave communication technologies such as 5G technology and the like promote revolutionary development in the fields of radar systems, satellite communication, artificial intelligence and the like. However, with the increase of frequency, the problems of high signal delay or loss, crosstalk noise and the like caused by the conventional interlayer dielectric materials are increasingly prominent, and further integration and development of electronic devices are greatly hindered. Polyimide is considered as an ideal choice for microwave devices because of its excellent mechanical/thermal properties, good corrosion and radiation resistance, outstanding electrical insulation, and relatively low cost, as an interlayer dielectric material for a wide range of applications. However, polyimide has not been able to meet the requirements for high frequency communications with relatively high dielectric constants (3.1 to 3.8) and high dielectric losses. Therefore, lowering the dielectric constant of polyimide is currently an urgent issue.
The hollow silica microsphere has the advantages of simple synthesis process, easy surface functionalization, good chemical inertness, good thermal stability and the like, and the hollow cavity structure inside contains a large amount of air with the dielectric constant of 1, so that the introduction of the hollow silica microsphere into polyimide is beneficial to reducing the dielectric constant of the hollow silica microsphere under a high-frequency working condition. However, the dispersibility of the hollow silica microspheres and the polyimide matrix is poor, and the phenomenon of clustering and the like is easy to occur, so that the original excellent properties of polyimide are greatly influenced.
In order to enhance the dispersibility of hollow silica microspheres in polyimide matrices, researchers modified the silica surface. The existing modification modes are mainly amino modification, and have been reported in the related fields, such as Zhou Hong (Materials Science and Engineering B, dielectric properties of polyimide/SiO) 2 hollow spheres composite films with ultralow dielectric constant[J]Nano-scale hollow SiO with aminopropyl trimethoxysilane silane coupling agent of 203 (2016) 13-18) et al 2 Ball modification to obtain amino nano hollow SiO 2 Ball, and preparing the corresponding polyimide composite film. Although the introduction of the amino group can increase the compatibility of the silicon dioxide and polyimide, the amino group belongs to a polar group, so that the reduction of the dielectric constant of the polyimide composite film is hindered to a certain extent, and the amino group belongs to a hydrophilic group, so that the integrated circuit device is not beneficial to long-term use in a humid environment.
Disclosure of Invention
The invention aims to increase the dispersibility of hollow silica microspheres in a polyimide matrix through hydrophobic modification, improve the low dielectric property, low thermal expansion coefficient property and hydrophobic property of original polyimide under a high-frequency working condition, and provide a high-frequency low-dielectric hydrophobic polyimide composite film and a preparation method thereof.
The invention provides a high-frequency low-dielectric hydrophobic polyimide composite film and a preparation method thereof, comprising the following steps:
1) Vacuum drying the hollow silica microspheres;
2) Dispersing the hollow silica microspheres obtained in the step 1) into an organic solvent, adding 5-30 g of silane coupling agent, stirring and reacting for 12-24 hours under water bath heating, centrifuging after the reaction is finished, washing with the organic solvent, and drying to obtain the hydrophobic hollow silica microspheres;
3) And (3) mixing the hydrophobic hollow silica microspheres into the polyamic acid solution, stirring and carrying out ultrasonic treatment, spreading a wet film of the polyamic acid/hydrophobic hollow silica microspheres by a film scraping machine, and calcining to obtain the polyimide/hydrophobic hollow silica microsphere composite film.
In the step 1), the hollow silica microspheres have a diameter of submicron order and a shell thickness of 20-100 nm.
In the preferred embodiment, in the step 2), the organic solvent is one or more of methanol, ethanol, ethylene glycol, n-propanol, isopropanol, toluene, xylene, trimethylbenzene, cyclohexane, n-hexane, cyclopentane, petroleum ether, and heptane.
In the preferred technical scheme, in the step 2), the silane coupling agent is one or more of dimethyl dichlorosilane, methyltrioxysilane, ethyltrioxysilane, propyltrioxysilane, propenyl trioxysilane, methyltrimethoxysilane and methyltriethoxysilane.
As a preferable technical scheme, in the step 2), the water bath temperature is 30-80 ℃, and the stirring speed is 200-700 rap/min.
As a preferable technical scheme, in the step 3), the solid content of the polyamic acid solution is 10 to 30 weight percent.
As a preferable technical scheme, in the step 3), the mass ratio of the hydrophobic hollow silica microspheres to the polyamic acid is 1 (1-99).
As a preferable technical scheme, in the step 3), the stirring time is 0.5-1.0 h; the ultrasonic time is 0.5-1.0 h.
As a preferable technical scheme, in the step 3), the calcination means that the calcination temperature is gradually increased from room temperature to 200-400 ℃ and the temperature rising speed is 0.5-15 ℃ min -1 And maintaining the temperature at the highest calcination temperature for 0 to 360 minutes to complete the thermal imidization.
The invention also provides the high-frequency low-dielectric hydrophobic polyimide composite film prepared by the method. According to the embodiment of the invention, after the hollow silica microspheres are subjected to hydrophobic modification, the dispersibility of silica in the polyimide matrix can be improved, and the high-frequency dielectric constant (from 3.50 to 2.16; 8.2-12.4 GHz) of the original polyimide can be reduced better. Furthermore, the introduction of the inorganic filler can reduce the thermal expansion coefficient of polyimide (from 32.0ppm/K to 26.6 ppm/K). In addition, the hydrophobic component can be introduced to raise the contact angle of the film surface with water (from 72.7 degrees to 110.0 degrees) and reduce the water absorption rate of the polyimide film (from 3.14 percent to 1.6 percent).
The invention also provides application of the high-frequency low-dielectric hydrophobic polyimide composite film as an interlayer dielectric material in reducing the dielectric constant of a high-frequency high-speed circuit.
The beneficial effects of the invention are as follows: the invention adopts the means of carrying out surface hydrophobic modification on the hollow silica microspheres, and overcomes the problem that the hollow silica microspheres are easy to cluster in a polyimide matrix, thereby obtaining lower dielectric constant, reducing the thermal expansion coefficient of polyimide, and simultaneously improving the integral hydrophobic property of the polyimide film by introducing hydrophobic components, so that the hollow silica microspheres have better application prospect in the field of 5G electronic devices.
Drawings
FIG. 1 is a cross-sectional TEM image of the polyimide/hydrophobic hollow silica microsphere composite film of example 1;
FIG. 2 is a cross-sectional TEM image of a polyimide/hollow silica microsphere composite film of comparative example 2;
FIG. 3 is a graph of dielectric properties of test 1 versus example 1 and comparative examples 1, 2;
FIG. 4 is a graph showing the thermal expansion coefficients of test 2 for example 1 and comparative examples 1 and 2;
FIG. 5 is a graph of surface contact angle performance test for test 3 pairs of example 1 and comparative example 1, comparative example 2;
FIG. 6 is a graph showing the water absorption performance of test 4 pairs of example 1, comparative example 1 and comparative example 2.
Detailed Description
The invention is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Example 1:
a preparation method of a high-frequency low-dielectric hydrophobic polyimide composite film comprises the following specific steps:
1) 0.5g of hollow silica microspheres are taken and dried in vacuum at 120 ℃ for 24 hours in a vacuum oven.
2) Adding the silicon spheres after the treatment of 1) into 100mL of isopropanol, adding 12.8g of dimethyl dichlorosilane, stirring and reacting at the rate of 500rap/min for 24h in a water bath environment at 60 ℃, centrifuging at the rate of 600 rap/min for 1 time, washing with absolute ethyl alcohol for 4 times, and drying at 100 ℃ for 12h to obtain the methyl grafted hydrophobic hollow silicon dioxide microspheres.
3) Taking 3g of polyamide acid/N, N-dimethylacetamide mixed solution with the mass fraction of 20%, adding 0.067g of hydrophobic hollow silica microspheres, performing ultrasonic dispersion for 1h, and paving a polyamide acid/hydrophobic hollow silica microsphere wet film with the thickness of 300 mu m by a film scraping machine. And (3) placing the wet film into a muffle furnace, carrying out imidization at the temperature rising speed of 5 ℃/min and the temperature of 200 ℃ and 300 ℃ for 1 hour, and naturally cooling to obtain the polyimide/hydrophobic hollow silica microsphere composite film with the thickness of about 40 mu m. The hydroxyl groups on the surface of the hydrophobic hollow silica microspheres are replaced by methyl groups, and the hydrophobic hollow silica microspheres in the polyimide composite film are distributed uniformly, as shown in figure 1.
Example 2:
a preparation method of a high-frequency low-dielectric hydrophobic polyimide composite film comprises the following specific steps:
1) 0.5g of hollow silica microspheres are taken and dried in vacuum at 120 ℃ for 24 hours in a vacuum oven.
2) Adding the hollow silica microspheres treated in the step 1) into 100mL of toluene, adding 0.1M methyltriethoxysilane, stirring and reacting for 24 hours at a rate of 500rap/min in a water bath environment at 60 ℃, centrifuging for 1 time at a rate of 600 rap/min, washing for 4 times by using absolute ethyl alcohol, and drying for 12 hours at 100 ℃ to obtain the ethyl grafted hydrophobic hollow silica microspheres.
3) 3g of PAA/DMAc mixed solution with the mass fraction of 20% is taken, 0.067g of hydrophobic hollow silica microsphere is added, ultrasonic dispersion is carried out for 1h, and a polyamide acid/hydrophobic hollow silica microsphere wet film with the thickness of 300 mu m is paved by a film scraping machine. And (3) placing the wet film into a muffle furnace, carrying out imidization at the temperature rising speed of 5 ℃/min and the temperature of 200 ℃ and 300 ℃ for 1 hour, and naturally cooling to obtain the polyimide/hydrophobic hollow silica microsphere composite film with the thickness of about 40 mu m. The hydroxyl groups on the surface of the hydrophobic hollow silica microspheres are replaced by ethyl groups, and the hydrophobic hollow silica microspheres in the polyimide composite film are distributed uniformly, and are similar to those in FIG. 1.
Example 3:
a preparation method of a high-frequency low-dielectric hydrophobic polyimide composite film comprises the following specific steps:
1) 0.5g of hollow silica microspheres are taken and dried in vacuum at 120 ℃ for 24 hours in a vacuum oven.
2) Adding the silicon spheres after the treatment of 1) into 100mL of toluene, adding 12.8g of dimethyl dichlorosilane, stirring and reacting at the rate of 500rap/min for 24h in a water bath environment of 60 ℃, centrifuging for 1 time at 600 rap/min, washing with toluene for 4 times, and drying for 12h at 100 ℃ to obtain the methyl grafted hydrophobic hollow silicon dioxide microspheres.
3) 3g of PAA/DMAc mixed solution with the mass fraction of 20% is taken, 0.067g of hydrophobic hollow silica microsphere is added, ultrasonic dispersion is carried out for 1h, and a polyamide acid/hydrophobic hollow silica microsphere wet film with the thickness of 300 mu m is paved by a film scraping machine. And (3) placing the wet film into a muffle furnace, carrying out imidization at the temperature rising speed of 5 ℃/min and the temperature of 200 ℃ and 300 ℃ for 1 hour, and naturally cooling to obtain the polyimide/hydrophobic hollow silica microsphere composite film with the thickness of about 40 mu m. The hydroxyl groups on the surface of the hydrophobic hollow silica microspheres are replaced by methyl groups, and the hydrophobic hollow silica microspheres in the polyimide composite film are distributed uniformly, similar to the one in figure 1.
Comparative example 1:
a preparation method of a pure polyimide film comprises the following specific steps:
3g of a PAA/DMAc mixture with a mass fraction of 20% was taken and a wet polyamide acid film with a thickness of 300 μm was laid by a doctor blade machine. The film is put into a muffle furnace, imidized at the temperature rising speed of 5 ℃/min and the temperature of 200 ℃ and 300 ℃ for 1 hour, and naturally cooled to obtain the polyimide film with the thickness of about 40 mu m.
Comparative example 2:
the preparation method of the polyimide/hollow silica microsphere composite film comprises the following specific steps:
1) 0.5g of hollow silica microspheres are taken and dried in vacuum at 120 ℃ for 24 hours in a vacuum oven.
2) 3g of PAA/DMAc mixed solution with the mass fraction of 20% is taken, 0.067g of hollow silica microspheres are added, the mixture is dispersed for 1h by ultrasonic, and a polyamide acid/hollow silica microsphere wet film with the thickness of 300 mu m is paved by a film scraping machine. And (3) placing the wet film into a muffle furnace, carrying out imidization at the temperature rising speed of 5 ℃/min and the temperature of 200 ℃ and 300 ℃ for 1 hour, and naturally cooling to obtain the polyimide/hollow silica microsphere composite film with the thickness of about 40 mu m. The surface of the unmodified hollow silica microsphere is a hydroxyl group, and a large number of clusters of the unmodified hollow silica microsphere inside the polyimide composite film appear as shown in figure 2.
And (3) result detection:
example 1-polyimide/hydrophobic hollow silica microsphere composite film, comparative example 1-polyimide film, comparative example 2-polyimide/hollow silica microsphere composite film performance test method is as follows:
test 1: the dielectric properties were tested using a Agilent Technologies Inc-E5071C type vector network analyzer using a waveguide method at an X-band (8.2-12.4 GHz). The results are shown in FIG. 3: in the X wave band, the pure polyimide has a higher dielectric constant of about 3.1 to 3.7; the dielectric constant of the polyimide/hollow silica microsphere composite film is reduced by about 2.4 to 2.7 due to the introduction of air with a dielectric constant of 1; the dielectric constant of the polyimide/hydrophobic hollow silica microsphere composite film is most obviously reduced by about 1.9 to 2.3, and besides the factor of air, the internal hydrophobic hollow silica microsphere can be well dispersed in a polyimide matrix, and the factor also has a great contribution to the reduction of the dielectric constant.
Test 2: the thermal expansion coefficient was measured using a TA Instruments-Q400EM thermo-mechanical analyzer with a heating rate of 10℃min -1 The constant load was 0.05N and the sample size was 15X 3mm, and each group of samples was measured 3 times in parallel. The results are shown in FIG. 4: the linear thermal expansion coefficient of the pure polyimide is highest and is 32.2ppm/K in the same temperature range; the linear thermal expansion coefficient of the polyimide/hollow silica microsphere composite film is greatly reduced to 27.6ppm/K, which is attributed to the lower linear thermal expansion coefficient of the inorganic filler silica itself; polyimide/hydrophobic hollow IICompared with the polyimide/hollow silica microsphere composite film, the linear thermal expansion coefficient of the silica microsphere composite film is still reduced to 26.6ppm/K, and the silica microsphere composite film benefits from the fact that the hydrophobic hollow silica microsphere can be more uniformly dispersed in a polyimide matrix, and the advantage of low linear thermal expansion coefficient of the inorganic filler is fully exerted, so that the thermal expansion coefficient is the lowest.
Test 3: the surface hydrophobicity test method is thatThe hydrophobic properties were tested on a contact angle tester with a drop volume of 2 μl, a size of 2 x 2cm per membrane, and 3 times in parallel. The results are shown in FIG. 5: the surface of the pure polyimide is hydrophilic, and the contact angle with water is 72.7 degrees; the surface of the polyimide/hollow silica microsphere composite film is almost the same as polyimide, still is hydrophilic, and has a contact angle with water of 75.7 degrees; the surface of the polyimide/hydrophobic hollow silica microsphere composite film is hydrophobic, the contact angle is 110.0 degrees, and the surface hydrophobicity of the polyimide composite film is enhanced due to the introduction of the hydrophobic hollow silica microsphere, so that the contact angle with water is greatly improved.
Test 4: the moisture absorption rate test method is to immerse the sample in ultra-pure water at 25 ℃ for 24 hours, test the mass change of the sample before and after immersion, and the sample size is 5 x 5cm, the thickness is 40+/-5 μm, and test is carried out in parallel for 3 times. The results are shown in FIG. 6: the water absorption of the pure polyimide is 3.12 percent; the polyimide/hollow silica microsphere composite film has water absorption of 7.56%, which is attributed to poor compatibility of unmodified hollow silica microspheres with polyimide matrix, a large number of hollow silica microspheres are clustered and generate pores (this phenomenon can be observed in fig. 2), thus causing capillary phenomenon, so that the water absorption is remarkably higher than that of pure polyimide; the water absorption of the polyimide/hydrophobic hollow silica microsphere composite film is 2.77%, and although partial pores are generated by introducing the hydrophobic hollow silica microsphere, the surface hydrophobicity prevents water penetration, and the overall hydrophobicity of the polyimide composite film is improved, so that the water absorption of the polyimide/hydrophobic hollow silica microsphere composite film is reduced.
In conclusion, the hydrophobic modification of the hollow silica microspheres in the invention can effectively reduce the dielectric constant and the thermal expansion coefficient of polyimide under the high-frequency working condition, increase the surface hydrophobicity of the polyimide film, reduce the water absorption of the polyimide film and be beneficial to increasing the practical value of the polyimide film in 5G high-frequency devices.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of the invention should be assessed as that of the appended claims.
Claims (10)
1. The preparation method of the high-frequency low-dielectric hydrophobic polyimide composite film is characterized by comprising the following steps of:
1) Vacuum drying the hollow silica microspheres;
2) Dispersing the hollow silica microspheres obtained in the step 1) into an organic solvent, adding 5-30 g of silane coupling agent, stirring and reacting for 12-24 hours under water bath heating, centrifuging after the reaction is finished, washing with the organic solvent, and drying to obtain the hydrophobic hollow silica microspheres;
3) And (3) mixing the hydrophobic hollow silica microspheres into the polyamic acid solution, stirring and carrying out ultrasonic treatment, spreading a wet film of the polyamic acid/hydrophobic hollow silica microspheres by a film scraping machine, and calcining to obtain the polyimide/hydrophobic hollow silica microsphere composite film.
2. The method according to claim 1, wherein in the step 1), the hollow silica microspheres are used with a diameter of submicron order and a shell thickness of 20-100 nm.
3. The method according to claim 1, wherein in the step 2), the organic solvent is one or more of methanol, ethanol, ethylene glycol, n-propanol, isopropanol, toluene, xylene, trimethylbenzene, cyclohexane, n-hexane, cyclopentane, petroleum ether, and heptane.
4. The method according to claim 1, wherein in the step 2), the silane coupling agent is one or more of dimethyldichlorosilane, methyltrioxysilane, ethyltrioxysilane, propyltrioxysilane, propenyl trioxysilane, methyltrimethoxysilane, methyltriethoxysilane.
5. The method according to claim 1, wherein in the step 2), the water bath temperature is 30-80 ℃ and the stirring rate is 200-700 rap/min.
6. The method according to claim 1, wherein in the step 3), the solid content of the polyamic acid solution is 10 to 30% by weight.
7. The method according to claim 1, wherein in the step 3), the mass ratio of the hydrophobic hollow silica microspheres to the polyamic acid is 1 (1-99).
8. The method according to claim 1, wherein in the step 3), the stirring time is 0.5 to 1.0h; the ultrasonic time is 0.5-1.0 h.
9. The method according to claim 1, wherein in the step 3), the calcination is performed at a temperature of 200 to 400 ℃ and a temperature rising rate of 0.5 to 15 ℃ min -1 And maintaining the temperature at the highest calcination temperature for 0 to 360 minutes to complete the thermal imidization.
10. The use of the high-frequency low-dielectric hydrophobic polyimide composite film prepared by the method of any one of claims 1 to 9 as an interlayer dielectric material for reducing the dielectric constant of a high-frequency high-speed circuit.
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