CN113637216B - Low-dielectric polyimide with ZIF-8 surface modified and preparation method thereof - Google Patents
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Abstract
The invention relates to a low dielectric polyimide with a ZIF-8 surface modified and a preparation method thereof. The low dielectric polyimide with ZIF-8 surface is uniformly covered with ZIF-8, the cross section is composed of a large number of honeycomb micropores, and the density is lower than 0.25g/cm 3 The porosity is more than 70%, the dielectric constant is less than 1.50 at 1kHz, the dielectric loss is less than 0.0040 at 1kHz, the elongation at break is more than 80%, the tensile strength is more than 10MPa, the water absorption rate of standing in water for 72h is less than 0.02%, and the dielectric constant increase rate of standing in an environment with 80% of humidity for 7 days is less than 0.1%. The low dielectric polyimide with the surface modified ZIF-8 is prepared from polyimide by a phase inversion method, and the ZIF-8 is generated in situ on the surface of a polyimide film by zinc nitrate in a polyimide solution in a film forming process and dimethyl imidazole in the solution in the phase inversion process. The low dielectric polyimide with the ZIF-8 modified surface can be used as a low dielectric constant material to be applied to the field of interlayer dielectric materials for interconnection assembly.
Description
Technical Field
The invention relates to a low dielectric polyimide with a ZIF-8 surface modification and a preparation method thereof, belonging to the field of manufacturing of organic dielectric materials. The low dielectric polyimide can be used as a low dielectric constant material to be applied to the field of interlayer dielectric materials for interconnection assembly.
Background
With the rapid development of the high-speed communication field in recent years, the application size of electronic components is continuously tending to be miniaturized, the chip integration level in a large-scale integrated circuit is remarkably improved, the density of chip interconnection lines is increased, the resistance in the lines and the capacitance in the wiring are increased, the signal resistance-capacitance delay effect is generated, and the signal transmission speed and the signal loss are affected, so that the electronic components become new designs for the development of the integrated circuit in the directions of high speed, high density, low energy consumption and multiple functions. The delay time of signal transmission is generally proportional to the resistance of the conductor itself, to its dielectric constant value, and to the ratio of the length to the thickness of the conductor. Therefore, in order to shorten the delay time of signal transmission, a material having a low self-resistance value and a low dielectric constant value may be selected, or the self-resistance and the dielectric constant of the material may be reduced by other methods, or the distance between the conductors may be widened. However, since the distance between the wires is not easily widened, it is important to reduce the dielectric constant of the wires in order to reduce the delay time of signal transmission. When other conditions are consistent through calculation, when the dielectric constant value of the packaging wire is changed from 4.0 to 2.5, the speed of the wire for transmitting information can be changed to 2.6 times of the original speed, and if the dielectric constant of the wire can be further reduced, the speed of the wire for transmitting information can be obviously improved. Therefore, in order to meet the requirement of high integration of integrated circuits and to increase the signal transmission speed, high-density signal lines in the package are required to be electrically insulated from each other, and dielectric materials with dielectric constant values as low as possible should be selected as interlayer insulating materials for integrated circuits so as to ensure that the minimum electrical interaction signals can be normally transmitted in adjacent lines. In addition, with the development of flexible electronic materials, various polymer materials have been used to improve flexibility and stretchability of devices. Flexible polymers with easy processability are expected to be used as low dielectric matrix materials. In addition, according to the performance index requirement of the dielectric constant material, on the premise of reducing the dielectric constant value as much as possible, the leakage current of the low dielectric material is ensured not to be too high, and the voltage dissipation coefficient is ensured not to be too large. Since the dielectric constant of water is 80, it is ensured that the dielectric constant material has a low water absorption so that the value of the dielectric material can be maintained at a low value. In addition, since the dielectric constant material is often required to operate in a high temperature environment, the dielectric material is also subjected to a plurality of thermal cycling processes in the very large scale integrated circuit system, so that the performance of the dielectric material cannot be seriously degraded at high temperature.
Polyimide is widely applied to the fields of electronic materials, aerospace, communication, national defense, military and the like due to good heat resistance, corrosion resistance, insulativity and excellent mechanical properties. Polyimide has high-temperature-resistant recycling performance; the self-lubricating performance is good; the mechanical properties are excellent; the flame retardant grade reaches UL 94 grade; the radiation resistance is good; the insulation performance is stable; polyimide has good dielectric property, dielectric constant is about 3.4, and the dielectric constant can be reduced to about 2.5 by introducing fluorine element into a polyimide system or dispersing air nano-size into polyimide. Dielectric loss of 10 -3 The dielectric strength is 100-300kV/mm, the volume resistance is 1017Ω cm, and the performances can be kept at a higher level in a wide temperature range and frequency range, which has important scientific significance and wide practical value for developing high-performance dielectric polymers. The invention utilizes the preparation of the high-performance polyimide material firstly and then the delayThe honeycomb porous structure is introduced into the polyimide matrix by the phase inversion method, so that the dielectric constant is reduced, good mechanical flexibility is obtained, meanwhile, the super-hydrophobic ZIF-8 is generated on the surface of the polyimide film in situ in the film forming process by the phase inversion method, the water absorption of the film is reduced to ensure the stability of the low dielectric constant, and the polyimide porous material with stable low dielectric constant is obtained.
Disclosure of Invention
The invention aims to overcome the defects of the existing low dielectric constant material such as poor mechanical property, low dielectric environment stability and the like and the defects of the technology such as relatively high dielectric constant of high-performance materials such as polyimide and the like, and provides the low dielectric polyimide with the ZIF-8 surface modified and the preparation method thereof, so that the batch preparation of the low dielectric constant polyimide is realized, the problem of high dielectric constant of the existing polyimide is solved, and the application range of the polyimide in the field of high-speed communication is widened. Has great significance for the polyimide low dielectric material in the scientific research and application fields. Specifically, polyimide and zinc nitrate which is a precursor of ZIF-8 are mixed and then dissolved in a polar solvent to obtain a mixed solution, then the mixed solution is poured on a glass plate, and the glass plate and the solution on the surface of the glass plate are soaked in ethanol solution in which dimethyl imidazole is dissolved. Zinc nitrate and dimethyl imidazole dissolved in ethanol solution in the film forming process generate ZIF-8 in situ on the surface of the polyimide film, the polyimide solution is converted into a polyimide film through phase conversion in the dimethyl imidazole ethanol solution, and the polyimide film is fully washed in pure water after being rolled, and is dried in vacuum to obtain the polyimide with low dielectric constant.
The low dielectric polyimide with the ZIF-8 modified surface is characterized in that: the low dielectric polyimide section of the surface modification ZIF-8 has a honeycomb porous structure, the surface of the honeycomb porous structure is modified with a layer of ZIF-8, and the density of the low dielectric polyimide of the surface modification ZIF-8 is lower than 0.25g/cm 3 Porosity greater than 70%, dielectric constant less than 1.5 at 1kHz, dielectric loss less than 0.004 at 1kHz, elongation at break greater than 80%, tensile strength greater than 10MPa, water absorption rate of less than 0.02% when left standing in water for 72h, and humidity of 80%The dielectric constant increase rate is less than 0.1% when the material is left standing for 7 days in the environment.
The preparation method of the low dielectric polyimide with the ZIF-8 modified surface is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) Preparation of polyimide and pore-forming agent zinc nitrate mixed solution: adding polyimide into a polar solvent to obtain a solution with the concentration of 10-20wt%, adding a pore-forming agent zinc nitrate, and mechanically stirring for 1-3 h at 100-300 r/min until the polyimide and the pore-forming agent are completely dissolved to obtain a polyimide and pore-forming agent mixed solution; the polar solvent is one of N-methyl pyrrolidone, N-dimethylformamide and N, N-dimethylacetamide; the mass ratio of the pore-forming agent zinc nitrate to polyimide is 1: 5-20;
(2) Preparation of ZIF-8/polyimide porous film: pouring the polyimide and the pore-forming agent zinc nitrate mixed solution obtained in the step (1) onto a glass plate, scraping a liquid film of 100-1000 mu m by a wet film preparation device, then soaking the glass plate and the liquid film on the surface of the glass plate together in an ethanol solution dissolved with 0.2-2 wt% of dimethyl imidazole for 0.5-3 hours, stripping the glass plate, and then continuously soaking the glass plate in deionized water for 1-3 days to obtain a ZIF-8/polyimide porous film;
(3) Preparation of low dielectric polyimide with surface modified ZIF-8: and (3) placing the ZIF-8/polyimide porous membrane prepared in the step (2) on an ultra-clean workbench for 1-4 h to drain water on the surface of the membrane, then placing the membrane in a vacuum oven at 80-150 ℃ for vacuum drying for 5-24 h, and naturally cooling to room temperature to obtain the low-dielectric polyimide with the surface modified with the ZIF-8.
The invention has the beneficial effects that: the low-dielectric polyimide with the surface modified ZIF-8 prepared by the invention has a large number of honeycomb micropores, and can effectively reduce the dielectric constant of the system. The density of the low dielectric polyimide with the surface modified ZIF-8 is adjustable and is lower than 0.25g/cm by adjusting the content of a pore-forming agent zinc nitrate 3 The porosity is more than 70%, the dielectric constant of the super-hydrophobic low-dielectric polyimide is less than 1.50 at 1kHz, the dielectric loss is less than 0.0040 at 1kHz, the water absorption rate of the super-hydrophobic low-dielectric polyimide after standing for 72h in water is less than 0.020%, and the water absorption rate of the super-hydrophobic low-dielectric polyimide is 80% by adjusting the density of the super-hydrophobic low-dielectric polyimideThe dielectric constant of the super-hydrophobic low-dielectric polyimide is increased by less than 0.10 percent after being stood for 7 days in a wet environment, the super-hydrophobic low-dielectric polyimide also has excellent mechanical flexibility, the elongation at break is more than 80 percent, and the requirement of an interlayer insulating material for integrated circuits in large-scale integrated circuits is met. The preparation method of the surface modified ZIF-8 low-dielectric polyimide is simple and is easy to realize industrialization.
Drawings
FIG. 1 is a SEM image of a low dielectric polyimide surface of a surface modified ZIF-8
FIG. 2 is a cross-sectional SEM image of a low dielectric polyimide with surface modification ZIF-8
Detailed Description
The following examples of the preparation method of the present invention are presented for illustration of the present invention and are not to be construed as limiting the scope of the claims.
Example 1
(1) Preparation of polyimide and pore-forming agent zinc nitrate mixed solution: 10g of fluorinated polyimide is added into 90g of N, N-dimethylformamide to obtain a solution with the concentration of 10wt%, then 0.1g of zinc nitrate is added, and the solution is mechanically stirred for 1h at 100r/min until the solution is completely dissolved, so as to obtain a polyimide and zinc nitrate mixed solution;
(2) Preparation of ZIF-8/polyimide porous film: pouring the polyimide and the pore-forming agent zinc nitrate mixed solution obtained in the step (1) onto a glass plate, scraping a 200 mu m liquid film by a wet film preparation device, soaking the glass plate and the liquid film on the surface of the glass plate together in 200mL of 2.5wt% dimethyl imidazole ethanol solution for 1h, and then continuously soaking in the dimethyl imidazole/ethanol mixed solution for 2 days to obtain a ZIF-8/polyimide porous film;
(3) Preparation of low dielectric polyimide with surface modified ZIF-8: and (3) placing the ZIF-8/polyimide porous membrane prepared in the step (2) on an ultra-clean workbench for 4 hours to drain water on the surface of the membrane, then placing the membrane in a vacuum oven at 100 ℃ for vacuum drying for 12 hours, and naturally cooling to room temperature to obtain the low-dielectric polyimide with the surface modified with the ZIF-8.
The density of the low dielectric polyimide of the subsurface-modified ZIF-8 is 0.25g/cm 3 The porosity is 70%, the surface and the section morphology of the super-hydrophobic low-dielectric polyimide are shown in the attached figures 1 and 2, the dielectric constant of the low-dielectric polyimide of the surface modification ZIF-8 is 1.50 at 1kHz, the dielectric loss is 0.0040 at 1kHz, the water absorption rate of the low-dielectric polyimide is 0.02% after standing in water for 72 hours, the dielectric constant increase rate of the low-dielectric polyimide is 0.10% after standing for 7 days in an environment with 80% of humidity, the elongation at break of the low-dielectric polyimide of the surface modification ZIF-8 is 80%, and the tensile strength is 10MPa.
Example 2
(1) Preparation of polyimide and pore-forming agent zinc nitrate mixed solution: 10g of fluorinated polyimide is added into 90g of N, N-dimethylformamide to obtain a solution with the concentration of 10wt%, then 1g of zinc nitrate is added, and the solution is mechanically stirred for 1h at 100r/min until the solution is completely dissolved, so as to obtain a polyimide and zinc nitrate mixed solution;
(2) Preparation of ZIF-8/polyimide porous film: consistent with step (2) of example 1;
(3) Preparation of low dielectric polyimide with surface modified ZIF-8: consistent with step (3) of example 1;
the density of the low dielectric polyimide of the subsurface-modified ZIF-8 is 0.23g/cm 3 The porosity was 75%, the dielectric constant of the surface-modified ZIF-8 low-dielectric polyimide was 1.48 at 1kHz, the dielectric loss was 0.0039 at 1kHz, the water absorption rate after standing in water for 72 hours was 0.018%, the dielectric constant growth rate after standing in an environment of 80% humidity for 7 days was 0.09%, the elongation at break of the surface-modified ZIF-8 low-dielectric polyimide was 84%, and the tensile strength was 11MPa.
Example 3
(1) Preparation of polyimide and pore-forming agent zinc nitrate mixed solution: 10g of fluorinated polyimide is added into 90g of N, N-dimethylformamide to obtain a solution with the concentration of 10wt%, then 1g of zinc nitrate is added, and the solution is mechanically stirred for 1h at 100r/min until the solution is completely dissolved, so as to obtain a polyimide and zinc nitrate mixed solution;
(2) Preparation of ZIF-8/polyimide porous film: preparation of ZIF-8/polyimide porous film: pouring the polyimide and the pore-forming agent zinc nitrate mixed solution obtained in the step (1) onto a glass plate, scraping a 200 mu m liquid film by a wet film preparation device, then soaking the glass plate and the liquid film on the surface of the glass plate together in 200mL of 5wt% dimethyl imidazole ethanol solution for 1h, and then continuously soaking in the dimethyl imidazole/ethanol mixed solution for 2 days to obtain a ZIF-8/polyimide porous film;
(3) Preparation of low dielectric polyimide with surface modified ZIF-8: consistent with step (3) of example 1;
the density of the low dielectric polyimide of the subsurface-modified ZIF-8 is 0.22g/cm 3 The porosity was 78%, the dielectric constant of the low dielectric polyimide of the surface-modified ZIF-8 was 1.45 at 1kHz, the dielectric loss was 0.0032 at 1kHz, the water absorption rate of the low dielectric polyimide was 0.015% when left standing in water for 72 hours, the dielectric constant increase rate was 0.07% when left standing in an environment of 80% humidity for 7 days, the elongation at break of the low dielectric polyimide of the surface-modified ZIF-8 was 89%, and the tensile strength was 13MPa.
Example 4
(1) Preparation of polyimide and pore-forming agent zinc nitrate mixed solution: 10g of fluorinated polyimide is added into 90g of N, N-dimethylformamide to obtain a solution with the concentration of 10wt%, 3g of zinc nitrate is added, and the solution is mechanically stirred for 1h at 100r/min until the solution is completely dissolved, so as to obtain a polyimide and zinc nitrate mixed solution;
(2) Preparation of ZIF-8/polyimide porous film: preparation of ZIF-8/polyimide porous film: pouring the polyimide and the pore-forming agent zinc nitrate mixed solution obtained in the step (1) onto a glass plate, scraping a 200 mu m liquid film by a wet film preparation device, soaking the glass plate and the liquid film on the surface of the glass plate together in 200mL of 7.5wt% dimethyl imidazole ethanol solution for 1h, and then continuously soaking in the dimethyl imidazole/ethanol mixed solution for 2 days to obtain a ZIF-8/polyimide porous film;
(3) Preparation of low dielectric polyimide with surface modified ZIF-8: consistent with step (3) of example 1;
the density of the low dielectric polyimide of the subsurface-modified ZIF-8 is 0.20g/cm 3 The porosity is 82%, the dielectric constant of the low dielectric polyimide of the surface modified ZIF-8 is 1.42 at 1kHz, the dielectric loss is 0.0031 at 1kHz, and the surface modified ZIF-8 is placed in water for 72hThe water absorption rate of the low dielectric polyimide was 0.015%, the dielectric constant increase rate after standing for 7 days in an environment of 80% moisture was 0.05%, the elongation at break of the low dielectric polyimide of the surface-modified ZIF-8 was 94%, and the tensile strength was 12MPa.
Example 5
(1) Preparation of polyimide and pore-forming agent zinc nitrate mixed solution: 15g of fluorinated polyimide is added into 85g of N, N-dimethylformamide to obtain a solution with the concentration of 15wt%, 3g of zinc nitrate is added, and 100r/min of mechanical stirring is carried out for 1h until the solution is completely dissolved, so as to obtain a polyimide and zinc nitrate mixed solution;
(2) Preparation of ZIF-8/polyimide porous film: consistent with step (2) of example 1;
(3) Preparation of low dielectric polyimide with surface modified ZIF-8: consistent with step (3) of example 1;
the density of the low dielectric polyimide of the subsurface-modified ZIF-8 is 0.22g/cm 3 The porosity was 80%, the dielectric constant of the low dielectric polyimide of the surface-modified ZIF-8 was 1.45 at 1kHz, the dielectric loss was 0.0034 at 1kHz, the water absorption rate of the low dielectric polyimide was 0.015% when left standing in water for 72 hours, the dielectric constant increase rate was 0.06% when left standing in an environment of 80% humidity for 7 days, the elongation at break of the low dielectric polyimide of the surface-modified ZIF-8 was 92%, and the tensile strength was 13MPa.
Claims (2)
1. A low dielectric polyimide with ZIF-8 surface modification is characterized in that: the low dielectric polyimide section of the surface modified ZIF-8 has a honeycomb porous structure, and the surface of the honeycomb porous structure is modified with a layer of ZIF-8, and the preparation steps are as follows:
(1) Preparation of polyimide and pore-forming agent zinc nitrate mixed solution: adding polyimide into a polar solvent to obtain a solution with the concentration of 10-20wt%, adding a pore-forming agent zinc nitrate, and mechanically stirring for 1-3 h at 100-300 r/min until the polyimide and the pore-forming agent are completely dissolved to obtain a polyimide and pore-forming agent mixed solution; the polar solvent is one of N-methyl pyrrolidone, N-dimethylformamide and N, N-dimethylacetamide; the mass ratio of the pore-forming agent zinc nitrate to polyimide is 1: 5-20;
(2) Preparation of ZIF-8/polyimide porous film: pouring the polyimide and the pore-forming agent zinc nitrate mixed solution obtained in the step (1) onto a glass plate, scraping a liquid film of 100-1000 mu m by a wet film preparation device, then soaking the glass plate and the liquid film on the surface of the glass plate together in an ethanol solution dissolved with 0.2-2 wt% of dimethyl imidazole for 0.5-3 hours, stripping the glass plate, and then continuously soaking the glass plate in deionized water for 1-3 days to obtain a ZIF-8/polyimide porous film;
(3) Preparation of low dielectric polyimide with surface modified ZIF-8: placing the ZIF-8/polyimide porous membrane prepared in the step (2) on an ultra-clean workbench for 1-4 h to drain water on the surface of the membrane, and then placing the membrane in 80-150 h o And C, vacuum drying 5-24 and h in a vacuum oven, and naturally cooling to room temperature to obtain the low-dielectric polyimide with the surface modified ZIF-8.
2. The surface modified ZIF-8 low dielectric polyimide of claim 1, wherein: the density of the low dielectric polyimide of the surface modified ZIF-8 is lower than 0.25g/cm 3 The porosity is more than 70%, the dielectric constant is less than 1.50 at 1kHz, the dielectric loss is less than 0.0040 at 1kHz, the elongation at break is more than 80%, the tensile strength is more than 10MPa, the water absorption rate of standing in water for 72h is less than 0.02%, and the dielectric constant increase rate of standing in an environment with 80% of humidity for 7 days is less than 0.1%.
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