KR101548597B1 - polyimic acid composite with dispersed dendrite Zinc oxide and high functional polyimide using same - Google Patents

Abstract

The present invention relates to a polyamic acid composition in which dendritic zinc oxide is dispersed and a polyimide using the same, wherein the polyamic acid composition is chemically bonded to the polyamic acid chain by uniformly dispersing zinc oxide in the form of dendrites, The imide is not only excellent in thermal stability but also has a low dielectric constant and residual stress and an antibacterial effect. Therefore, the polyimide in which the dendritic zinc oxide is dispersed can replace the inorganic insulating material, and in particular, it can be applied to various fields such as a semiconductor electronic device.

Description

[0001] The present invention relates to a polyamic acid composition in which a dendritic zinc oxide is dispersed and a high functional polyimide using the same.

TECHNICAL FIELD The present invention relates to a polyamic acid composition in which dendritic zinc oxide is dispersed and a polyimide using the same, and more particularly, to a high functionality polyimide in which the dendritic zinc oxide is uniformly dispersed and a method for producing the same .

The polyimide resin has excellent heat resistance, chemical resistance, electrical characteristics and mechanical properties. As a result, it is widely used as a core material for industries such as aerospace, IT, automobile, semiconductor and display.

The polyimide is widely used in various fields of high precision electronic industry including an insulating intermediate layer of an integrated circuit and a high density connecting device package as a substitute for a conventional inorganic insulating material. Especially, As the development of ultra-high speed, precision and reliability has progressed, various studies are being conducted to meet the needs of new materials such as multi-chip module and VLSI insulator in the electronic industry.

A semiconductor integrated circuit is a device in which various kinds of elements and metal wiring patterns are simultaneously formed on the surface portions of a semiconductor substrate or a glass substrate and then the leads are connected to the surfaces of these elements to have the function of an electronic circuit. An insulating film is formed between the patterns to prevent a short circuit between the device and the wiring and a signal disturbance phenomenon.

Such a semiconductor integrated circuit can dramatically improve the performance by integrating a large number of elements in a small area as possible and increasing the driving speed. The RC signal delay value, which is a product of the resistance of the wiring material and the capacitance of the insulating film, must be reduced in order to increase the integration / speed of the semiconductor circuit. In addition, signal disturbance between the metal electrode, which is a wiring material, and the semiconductor device must be prevented. Therefore, in the future, it is expected that the wiring material will be converted to copper with low electrical resistance from the current aluminum. In order to reduce the signal disturbance between the semiconductor device and the wiring material, an insulating film having a low capacitance and a low dielectric constant should be developed.

In general, SiO ₂ is used as an insulating film between the semiconductor device and the substrate. However, the insulating film including SiO ₂ has a very high dielectric constant value of about 3.9 to 4.2, which causes problems such as signal delay .

In addition, the polymer insulating film containing poly (arylene ether) described in U.S. Patent No. 5,658,994 has a dielectric constant value of 2.6 to 2.8. This is a lower value than the above-described prior art, but still has the above-described problems when used as an insulating film.

Accordingly, it is an object of the present invention to provide a polyamic acid composition in which dendritic zinc oxide is uniformly dispersed.

It is still another object of the present invention to provide a polyimide in which zinc oxide is dispersed in a highly functional dendritic form having an excellent antibacterial effect and a low dielectric constant and residual stress as well as excellent mechanical and thermal properties, .

In order to achieve the above object, the present invention provides a polyamic acid precursor composition comprising a polyamic acid precursor composition and zinc oxide in the form of dendrites, wherein the polyamic acid precursor composition is dispersed in a dendritic zinc oxide containing an organic solvent, an aromatic dianhydride and an aromatic diamine Based on the total weight of the polyamic acid composition.

According to an embodiment of the present invention, the organic solvent is any one selected from the group consisting of N-methylpyrrolidone, N, N-dimethylacetamide and dimethylformamide.

According to an embodiment of the present invention, the aromatic dianhydride may be 4,4 '- (hexafluoroisopropylidene) diphthalic dianhydride, pyromellitic dianhydride, 3,3' Benzophenone tetracarboxylic acid dianhydride, 3,3'4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3 ', 4,4'-diphenyl Sulfone tetracarboxylic acid dianhydride, and a mixture thereof.

According to an embodiment of the present invention, the aromatic diamine may be 2,2'-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 4,4'- Is selected from the group consisting of 4'-oxydianiline, 1,4-phenylene diamine, 4,4'-sulfonyl dianiline, diaminophenyl methane, and mixtures thereof.

According to an embodiment of the present invention, the solid content of the polyamic acid solution composition is 5 to 50% by weight based on the total weight of the solution.

According to an embodiment of the present invention, the dendritic zinc oxide used for the polyamic acid composition in which the dendritic zinc oxide is dispersed is used in an amount of from 5 to 100 wt% based on the total solid content of the polyamic acid precursor composition %. ≪ / RTI >

According to another embodiment of the present invention, the polyamic acid composition in which the dendritic zinc oxide is dispersed has a dielectric constant of 1.5 to 2.0.

According to another aspect of the present invention, there is provided a polyimide prepared by using a polyamic acid solution composition in which dendritic zinc oxide is dispersed.

According to another aspect of the present invention, there is provided a method for preparing a polyimide in which dendritic zinc oxide is dispersed, comprising the steps of:

I) preparing zinc oxide in the form of dendrites,

Ii) mixing the polyamic acid precursor composition and the dendritic zinc oxide,

Iii) polymerizing the mixed solution to prepare a polyamic acid composition in which dendritic zinc oxide is dispersed, and

Iv) curing the polyamic acid to produce polyimide.

According to an embodiment of the present invention, the step i) is characterized in that zinc powder having a particle diameter of 1 to 10 m is charged into a crucible and heated.

According to an embodiment of the present invention, the heating condition in step (i) is performed at 700 to 1000 ° C for 10 to 100 minutes.

According to an embodiment of the present invention, the polyamic acid precursor includes an organic solvent, an aromatic dianhydride, and an aromatic diamine, and the step ii) is carried out by mixing the organic solvent and zinc oxide in the form of dendritic Mixing; Ii-2) adding and mixing aromatic dianhydride and aromatic diamine to the mixed solution; And ii-3) polymerizing the polymer.

According to an embodiment of the present invention, the manufacturing method further comprises: (v) cooling and precipitating a polyimide solution in which dendritic zinc oxide is dispersed to powder.

According to an embodiment of the present invention, in the step iv), the curing is performed by thermosetting or chemical curing.

According to an embodiment of the present invention, the thermosetting is performed by a stepwise heating process at 80 ° C for 1 hour, 150 ° C for 30 minutes, 200 ° C for 30 minutes, 250 ° C for 30 minutes and 350 ° C for 2 hours .

According to the present invention, the polyamic acid composition is uniformly dispersed in dendritic zinc oxide and chemically bonded to the polyamic acid chain. Therefore, the polyimide using the polyimide composition is excellent in thermal stability, low in dielectric constant and residual stress, Effect. Therefore, the polyimide in which the dendritic zinc oxide is dispersed can replace the inorganic insulating material, and in particular, it can be applied to various fields such as a semiconductor electronic device.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a photograph of a polyimide thin film dispersed in zinc oxide in the form of dendrites according to the present invention, taken by a scanning electron microscope. FIG.
FIG. 2 is a graph showing the results of thermal gravimetric analysis to confirm the thermal stability of the polyimide thin film in which the dendritic zinc oxide is dispersed and the polyimide thin film according to the comparative example according to the production example of the present invention.

Hereinafter, the present invention will be described in more detail.

The present invention provides a polyamic acid composition further comprising zinc oxide in the form of dendrites. This is because by dispersing the dendritic zinc oxide in the polyamic acid precursor composition, it is possible to more uniformly disperse zinc oxide in a dendritic form, and as a result, the dielectric constant and the electrostatic capacity are low, .

Also, in order to form the polyamic acid precursor composition in the present invention, an organic solvent, an aromatic dianhydride, and an aromatic diamine are included, and the organic solvent includes N-methylpyrrolidone, N, N-dimethylacetamide, and dimethylformamide And the aromatic dianhydride may be any one selected from the group consisting of 4,4'- (hexafluoroisopropylidene) diphthalic dianhydride, pyromellitic dianhydride, 3,3'4,4 Benzophenone tetracarboxylic dianhydride, 3,3'4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3`, 4,4`- Diphenylsulfone tetracarboxylic acid dianhydride, diphenylsulfone tetracarboxylic acid dianhydride, and mixtures thereof, and the aromatic diamine may be any one selected from the group consisting of 2,2'-bis (3-amino-4-hydroxyphenyl) Fluoropropane, 4,4'-oxydianiline , 3,4'-oxydianiline, 1,4-phenylene diamine, 4,4'-sulfonyl dianiline, diaminophenyl methane, and mixtures thereof.

The dendritic zinc oxide used for the polyamic acid composition in which the dendritic zinc oxide is dispersed may be contained in an amount of 5 to 100% by weight based on the total weight of the solid content in the polyamic acid precursor composition, When the content of zinc oxide in the form of zinc oxide is within the above range, zinc oxide in the form of dendrites can form a stable and uniformly dispersed polyamic acid composition.

The solid content of the dendritic zinc oxide-dispersed polyamic acid composition is 5 to 50% by weight based on the total weight of the polyamic acid composition.

In addition, according to one embodiment of the present invention, the polyimide injected with zinc oxide in the form of dendrites prepared using the polyamic acid composition sprayed with the dendritic zinc oxide has a dielectric constant of 1.5 to 2.0, And an insulating film for semiconductor can be obtained by using this.

The insulating film of the present invention can be used as an interlayer dielectric (ILD) of a semiconductor device or as an intermetallic dielectric (IMD) of a metal interconnection, .

The present invention also provides a process for producing a polyimide in which dendritic zinc oxide is dispersed, comprising the steps of:

I) preparing zinc oxide in the form of dendrites,

Ii) mixing the polyamic acid precursor composition and the dendritic zinc oxide,

Iii) polymerizing the mixed solution to prepare a polyamic acid composition in which dendritic zinc oxide is dispersed, and

Iv) curing the polyamic acid to produce polyimide.

In order to prepare a polyimide in which dendritic zinc oxide is dispersed, first, a zinc powder having a particle diameter of 1 to 10 μm is put into a crucible, heated, taken out at room temperature and cooled. Through this process, oxygen and zinc To produce zinc oxide in the form of dendrites. At this time, the heating is performed at 700 to 1000 ° C for 10 to 100 minutes. Also, during the heating process, it is completely sealed to prevent the reaction between oxygen and zinc. Thereafter, when the crucible is taken out and cooled, a part of the inlet is opened to induce binding with oxygen, and the amount of oxygen can be controlled by adjusting the opening degree.

Next, mixing the polyamic acid precursor composition and the dendritic zinc oxide comprises mixing an organic solvent and zinc oxide in the form of dendrites; Adding and mixing an aromatic dianhydride and an aromatic diamine into the mixed solution; And a step of polymerizing the mixed solution, a polyamic acid composition in which dendritic zinc oxide is dispersed can be prepared. At this time, it is preferable to use an ultrasonic homogenizer for mixing.

In addition, adding and dispersing dendritic zinc oxide in the polyamic acid composition results in lower dispersity than mixing the dendritic zinc oxide in the polyamic acid precursor composition. Therefore, .

Also, the polyamic acid composition comprises an organic solvent, an aromatic dianhydride, and an aromatic diamine, wherein the organic solvent is selected from the group consisting of N-methylpyrrolidone, N, N-dimethylacetamide and dimethylformamide And the aromatic dianhydride may be any one selected from the group consisting of 4,4'- (hexafluoroisopropylidene) diphthalic dianhydride, pyromellitic dianhydride, 3,3'4,4'-benzophenonetetracar 4,3'4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylate Acid dianhydride, and mixtures thereof. The aromatic diamine may be selected from the group consisting of 2,2'-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 4'-oxydianiline, 3,4'-oxydianiline, 1,4-phenylene di It may be of any one selected from the diamine, 4,4`- sulfo nildayi aniline, diamino diphenyl methane, and mixtures thereof.

The dendritic zinc oxide-dispersed polyimide according to an embodiment of the present invention may be formed through thermal or chemical curing of the polyamic acid composition in which the dendritic zinc oxide is dispersed.

The thermal curing is performed by a stepwise heating process at 80 ° C for 1 hour, 150 ° C for 30 minutes, 200 ° C for 30 minutes, 250 ° C for 30 minutes, and 350 ° C for 2 hours, Pyridine and acetic anhydride, which are dehydrating agents, are imidized to obtain a polyimide in which dendritic zinc oxide is dispersed. This process is shown in Formula 1 below.

In this formula,

N is an integer of 50 to 100000,

Wherein Ar is an aromatic dianhydride consisting of 1 to 20 carbon atoms and 4 or more oxygen atoms.

Ar 'is a mixture of diamino groups having at least one carbon atom.

Finally, in order to obtain the polyimide powder in which the dendritic zinc oxide is dispersed, the polyimide solution in which the zinc oxide in the dendritic form is dispersed can be cooled, precipitated, and then pulverized.

When the polyamic acid composition in which the dendritic zinc oxide is dispersed is spin-coated on a semiconductor device or a metal wiring, and then thermally cured, a hard film-like insulating film can be obtained. The insulating film for a semiconductor on a film thus produced can lower the dielectric constant and improve the physical properties of the device. Further, the dielectric constant required for the interlayer material for semiconductors can be reduced.

Hereinafter, the present invention will be described in more detail with reference to examples. The following examples are provided to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

Manufacturing example  1 to 5

(1) Preparation of zinc oxide in the form of dendrites.

6 g of pure zinc powder of 10 μm or less is placed in a 50 ml aluminum crucible and fully sealed, and then heated in an electric furnace at 800 ° C. for 30 minutes. At this time, the supply of oxygen is cut off. Thereafter, the aluminum crucible is partially opened and closed immediately at room temperature to react with the heated zinc powder and oxygen. After completion of the oxidation reaction, the mixture was cooled at room temperature to obtain dendritic zinc oxide.

(2) Preparation of polyamic acid precursor in which dendrite type zinc oxide is dispersed.

10, 20, 30 and 40% by weight based on the solid content of the pure polyamic acid precursor, 10 ml of N-methylpyrrolidone was added to an Erlenmeyer flask, and dendritic zinc oxide Was dispersed in a polyamic acid solution. At this time, the stirring process was carried out at room temperature for 6 hours. Thereafter, 0.801 g (3 mmol) of 4,4'-oxydianiline was added to the polyamic acid solution in which the dendritic zinc was dispersed, stirred until completely dissolved, and 0.873 g (3 mmol) of pyromellitic dianhydride And the mixture was stirred for 24 hours under a nitrogen atmosphere at 0 ° C. Through the above process, dendritic zinc oxide was efficiently dispersed in the polyamic acid composition, and a polyamic acid composition in which dendritic zinc oxide having high viscosity was dispersed through physical chain bonding was obtained.

(3) Production of polyimide thin film

The polyamic acid composition prepared in the above step was applied to a glass plate in the form of a film and heated in an oven at 80 DEG C for 1 hour, 150 DEG C for 30 minutes, 200 DEG C for 30 minutes, 250 DEG C for 30 minutes and 350 DEG C for 2 hours Through the stepwise heating process, a polyimide thin film having imidized dendritic zinc oxide was prepared. Thereafter, the glass plate and the polyimide thin film in which the dendritic zinc oxide was dispersed were immersed in ultrapure water and dried at 80 DEG C for 24 hours. Thereafter, a glass plate and polyimide dispersed in a dendritic zinc oxide Thin film was obtained.

Comparative Example  One

(1) Polyamic acid composition

0.801 g (3 mmol) of 4,4'-oxydianiline was placed in an Erlenmeyer flask, and 10 ml of NMP was added thereto. After stirring, 0.873 g (3 mmol) of pyromellitic dianhydride was added. The polyamic acid precursor solution was stirred for 24 hours under a nitrogen atmosphere at 0 占 폚 to obtain a polyamic acid composition.

(2) Polyimide thin film

The polyamic acid composition obtained through the above process was applied to a glass plate and placed in an oven and heated at 80 ° C for 1 hour, 150 ° C for 30 minutes, 200 ° C for 30 minutes, 250 ° C for 30 minutes, and 350 ° C for 2 hours To prepare a polyimide thin film. Next, in order to separate the polyimide thin film from the glass plate, it was immersed in ultrapure water and dried at 80 DEG C for 24 hours to obtain a separated polyimide thin film.

Test Example  1. Scanning electron microscope ( SEM )

In order to confirm the surface of the polyimide thin film in which dendritic zinc oxide was dispersed according to the preparation example of the present invention, it was photographed by SEM and shown in FIGS.

Referring to FIGS. 1A and 1B, it is confirmed that the dendritic zinc oxide according to the present invention is uniformly formed on the surface of the polyimide thin film.

Test Example  2. Thermogravimetric analysis ( Thermogravimetric 분석 )

In order to confirm the thermal stability of the polyimide thin film in which the dendritic zinc oxide was dispersed according to the preparation example of the present invention, the polyimide thin film having the dendritic zinc oxide dispersed therein was heated stepwise to 800 ° C, The mass change at each step was measured.

2 is a graph showing the result of the thermogravimetric analysis, wherein (a) is a polyimide thin film in which dendritic zinc oxide is dispersed according to the preparation example 3, and (b) is a polyimide thin film according to the comparative example . Referring to this, the polyimide thin film according to the comparative example, in which the 5 wt% loss is 580 < 0 > C, and the dendritic zinc oxide-dispersed polyimide thin film according to the production example, , It can be confirmed that the polyimide thin film in which dendritic zinc oxide is dispersed according to the preparation example has better thermal stability than the polyimide thin film according to the comparative example.

Test Example  3. Measurement of dielectric constant ( Dielectric test )

In order to confirm the effect of the dendritic zinc oxide content on the dielectric constant of the polyimide thin film, the dielectric constant of the polyimide thin film according to the content of the dispersed dendritic zinc oxide according to the preparation example And the dielectric constant of the polyimide thin film according to the comparative example was measured and compared. The dielectric constant was measured using an RCL meater, and the composition ratios of the preparation examples and comparative examples are shown in Table 1 in more detail.

Content of zinc oxide in dendritic form (wt.%) Dielectric Constant Comparative Example 1
(PMDA-ODA) - 2.93 Comparative Example 2
(Kepton®) - 3 Production Example 1 5 2.71 Production Example 2 10 1.92 Production Example 3 20 2.04 Production Example 4 30 2.37 Production Example 5 40 2.56

According to Table 1, the dielectric constant of the dendritic zinc oxide-dispersed polyimide thin film according to Production Examples 1 to 5 was 1.92, and the dielectric constant of the polyimide thin film according to Comparative Example 1 was 2.93. It was confirmed that the dielectric constant of the polyimide thin film in which dendritic zinc oxide was dispersed was lower. It is expected that the dendritic zinc oxide acts as an empty space between the polyimide chains.

Claims (15)

A polyamic acid precursor composition comprising an organic solvent, an aromatic dianhydride and an aromatic diamine; And zinc oxide in the form of dendrites,
The dendritic zinc oxide is contained in an amount of 5 to 40% by weight based on the total weight of the solid content in the polyamic acid precursor composition,
Wherein the dendritic zinc oxide is uniformly dispersed and bound to the polyamic acid chain. The dendritic zinc oxide-dispersed polyamic acid composition of claim 1, wherein the dendritic zinc oxide is dispersed uniformly and bound to the polyamic acid chain. The method according to claim 1,
Wherein the organic solvent is any one selected from the group consisting of N-methylpyrrolidone, N, N-dimethylacetamide, and dimethylformamide. The method according to claim 1,
Wherein the aromatic dianhydride is selected from the group consisting of 4,4'- (hexafluoroisopropylidene) diphthalic dianhydride, pyromellitic dianhydride, 3,3'4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic dianhydride, and mixtures thereof Wherein the dendritic zinc oxide is dispersed in the polyamic acid composition. The method according to claim 1,
The aromatic diamine may be selected from the group consisting of 2,2'-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane, 4,4'-oxydianiline, 3,4'- Wherein the dendritic zinc oxide is dispersed in a dendritic form, wherein the zinc oxide is selected from the group consisting of phenylenediamine, 4,4'-sulfonyldianiline, diaminophenylmethane, and mixtures thereof. The method according to claim 1,
Wherein the solid content in the polyamic acid precursor composition is in the range of 5 to 50 wt% based on the total weight of the polyamic acid composition. delete A polyimide in which zinc oxide in the form of dendrites is dispersed using the polyamic acid composition in which the dendritic zinc oxide according to claim 1 is dispersed. 8. The method of claim 7,
Wherein the polyimide in which the dendritic zinc oxide is dispersed has a dielectric constant of 1.9 to 2.7. I) heating the zinc powder to produce zinc oxide in the form of dendrites;
Ii) mixing the polyamic acid precursor composition of claim 2 with zinc oxide in the dendritic form;
Iii) polymerizing the mixed solution to prepare a polyamic acid composition in which dendritic zinc oxide is dispersed; And
Iv) curing the polyamic acid to prepare a polyimide,
Wherein the heating in the step (i) is performed at 700 to 1000 ° C for 10 to 100 minutes. The method for producing polyimide according to claim 1, wherein the zinc oxide is dispersed in the dendritic state. 10. The method of claim 9,
Wherein the zinc powder of step (i) has a particle diameter of 1 to 10 μm. delete 10. The method of claim 9,
The step ii) comprises the steps of: ii-1) mixing an organic solvent and zinc oxide in the form of dendrites; Ii-2) adding and mixing aromatic dianhydride and aromatic diamine to the mixed solution; And ii-3) polymerizing the dendritic zinc oxide. 10. The method of claim 9,
And (v) cooling and precipitating a polyimide solution in which dendritic zinc oxide is dispersed, and pulverizing the resulting polyimide solution into a dendritic zinc oxide-dispersed polyimide. 10. The method of claim 9,
Wherein the curing in step iv) is a thermal curing or a chemical curing. ≪ RTI ID = 0.0 > 11. < / RTI > 15. The method of claim 14,
The thermal curing is carried out by a stepwise heating process at 80 DEG C for 1 hour, 150 DEG C for 30 minutes, 200 DEG C for 30 minutes, 250 DEG C for 30 minutes and 350 DEG C for 2 hours. The dendritic zinc A process for producing polyimide in which an oxide is dispersed.

Images