KR20030085166A - Composition Comprising Positive-Type Photosenstive Polyimide Precusors - Google Patents

Abstract

PURPOSE: A positive photosensitive polyimide precursor composition, a photosensitive insulation or protection coating using the composition and a semiconductor device using the composition are provided, to improve the residue ratio, the physical properties, the color and the film shrinkage. CONSTITUTION: The positive photosensitive polyimide precursor composition comprises a soluble polyimide represented by the formula 1 which contains at least one repeating unit and whose at least one end is terminated by a reactive end-capping monomer; a polyamide acid represented by the formula 5 which contains at least one repeating unit and whose at least one end is terminated by a reactive end-capping monomer; a dissolution inhibitor substituted with a group capable of dissociated by an acid; a photoacid generator; and a polar solvent, wherein X is a tetravalent aromatic or aliphatic organic group; Y is a divalent aromatic or aliphatic organic group; and m is an integer of 1 or more.

Description

Positive photosensitive polyimide precursor composition {Composition Comprising Positive-Type Photosenstive Polyimide Precusors}

The present invention relates to a composition comprising a positive photosensitive polyimide precursor, more specifically, a soluble polyimide comprising at least one repeating unit represented by the following formula (1); A polyamic acid represented by Formula 5 below, including one or more repeating units; Dissolution inhibitors; Photoacid generators; And it relates to a photosensitive polyimide precursor composition comprising a polar solvent.

Recently, in the semiconductor device field mainly on semiconductors and liquid crystal display devices, as the movement of high integration, high density, high reliability, and high speed of electronic devices are rapidly spreading, there is an attempt to take advantage of the advantages of organic materials that are easy to process and high purity. Research is actively underway. However, in order for the organic polymer to be used in these fields, it must be thermally stable even at a temperature of 200 ° C or higher in the device manufacturing process.

In addition to the excellent electrical properties such as high heat resistance, excellent mechanical strength, low dielectric constant and high insulation, the polyimide resin has good flattening properties of the coating surface, has a very low content of impurities which degrades the reliability of the device, and is easily made into fine shapes. There are advantages to it.

As a method of synthesizing polyimide, it is a two-stage condensation polymerization method in which the diamine component and the dianhydride component have the same polarity as N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMAc) and dimethylformamide (DMF). It is common to polymerize in an organic solvent to obtain a polyimide precursor solution, which is coated on a silicon wafer or glass, and then cured by heat treatment. Commercialized polyimide products for electronic materials are supplied in the form of polyimide precursor solution or polyimide film, and are mainly supplied in the form of polyimide precursor solution in the semiconductor device field.

1 is a cross-sectional structure of a semiconductor device to which a polyimide resin is applied to a buffer coating film. In resin-encapsulated large-scale integrated circuits (LSI), cracks occur in the passivation film of the chip due to shrinkage of the resin after the encapsulation, and thermal stress caused by the difference in the thermal expansion coefficient between the chip and the resin. It can also be damaged. In order to solve this problem, a buffer layer made of polyimide is formed between the chip and the encapsulant. The thickness of the buffer layer is 10 μm or more to serve as a buffer, and the thicker the thickness, the better the buffering effect and the higher the yield of the semiconductor product.

As shown in FIG. 1, the polyimide layer is required to form fine patterns such as inter-electrode connections and wire bonding pads. In order to form a via hole in the polyimide layer, a conventional method of coating and etching a photoresist on an existing non-photosensitive polyimide film has been widely used, but recently, a photosensitive polyimide having a photosensitive function in the polyimide itself is used. Many attempts have been made to apply it.

This requires an etching process for processing holes using a separate photoresist for wire bonding and metal interconnects using conventional non-photosensitive polyimide, but using photosensitive polyimide, lithography with photoresist Since the lithography process can be omitted, the buffer coating process can be shortened by about 50%, thereby improving productivity and reducing manufacturing costs. In addition, this is because there is an advantage such as shortening the process at the end of the semiconductor device assembly process (assembly process) to greatly improve the production yield.

U.S. Patent No. 3,957,512 discloses a practical photosensitive polyimide, first developed by Siemens, Rubner et al. The polyimide precursor used is a form in which a photosensitive group is ester-bonded to polyamic acid. to be. According to the patent, when the photosensitive polyimide precursor solution is coated on a substrate to form a film and exposed to ultraviolet light, photopolymerization occurs at the exposed portion to form crosslinks between precursor molecules. In this state, development with an organic solvent removes the non-exposed part, and the final heat treatment results in the imidization reaction, and at the same time, the ester-bonded photosensitive group is decomposed and removed to obtain a desired pattern consisting of polyimide only.

On the other hand, U.S. Patent No. 4,243,743 discloses a photosensitive polyimide in which a compound having a photosensitive group and an amino component in a polyamic acid is ion-bonded, developed by Toray, Japan. Such photosensitive polyimide has advantages in that it is easy to manufacture and generates less harmful by-products than conventional photosensitive polyimide.

Recently, however, studies on positive photosensitive polyimides have been actively conducted, rather than such negative photosensitive polyimides.

The reason is that, firstly, it has better resolution than negative photosensitive polyimide, and secondly, since the light irradiation area is relatively smaller than that of negative photosensitive polyimide, third, defects are less likely to occur. In the negative method, since organic solvents such as N-methyl-2-pyrrolidone (NMP) or dimethylacetamide (DMAc) are used as the developer, there are problems in terms of costs and environmental aspects such as wastewater treatment. The positive method using an alkaline aqueous solution is cost-saving and environmentally friendly.

However, the positive type photosensitive polyimide has not been commercialized in earnest to date due to technical problems to be overcome, as described below, despite these many advantages.

The prior art related to the positive type photosensitive polyimide resin is a method of manufacturing a pattern by mixing the polyamic acid and the naphtoquinonediazide compound, which is a dissolution inhibitor, as a polyimide precursor, by the dissolution rate of the exposed portion and the non-exposed portion. (Japanese Patent Laid-Open Nos. 52-13315 and 62-135824), a method of using a mixture of a soluble polyimide having a hydroxy group and a naphthoquinone diazide compound (Japanese Patent Laid-Open No. 64-60630), and a photosensitive material to a polyimide precursor Prepared by ester-bonding the o-nitrobenzylester group (JP-A-60-37550) and the resin obtained by substituting the carboxyl group of a polyamic acid with an acetal group dissociable with an acid, and mixing with a photoacid generator. One chemically amplified composition (Japanese Patent Laid-Open Nos. 7-33874 and 7-134414) and the like have been proposed.

However, these conventional techniques do not have a large difference in the dissolution rate between the exposed portion and the non-exposed portion so as to form a high-resolution pattern, respectively (Japanese Patent Laid-Open Nos. 52-13315 and 62-135824), and a large amount of photosensitizer is added and polyimide The structure of the precursor is limited, the physical properties are weak (Japanese Patent Laid-Open No. 60-37550), and the low strength makes it difficult to improve the film thickness (Japanese Patent Laid-Open No. 60-37550). There are problems such as high and weak physical properties (Japanese Patent Laid-Open Nos. 7-33874 and 7-134414).

The present invention is to solve the problems of the prior art as described above, (A) one or more repeating units, represented by the following formula (1), one or both ends of the molecular chain terminal is a reactive terminal block monomer (end soluble polyimide terminated with -capping monomer); (B) a polyamic acid comprising one or more repeating units represented by the following formula (5), wherein one or both ends of the molecular chain ends are terminated with a reactive end-capping monomer; (C) a dissolution inhibitor in which a functional group dissociable with an acid is introduced into a part of hydrogen of a carboxy group or a hydroxy group of a compound having a carboxylic acid or phenolic hydroxy group soluble in an aqueous solution; (D) photoacid generator; And (E) a polar solvent, which is capable of expressing excellent pattern formation, having a transparent film color after curing, and having a low film reduction rate.

1 is a cross-sectional view of a semiconductor device in which a polyimide resin is applied to a buffer coating film.

2 is a pattern photograph of a 5 μm line width formed on a 10 μm thick film made of the polyimide composition of the present invention.

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

The present invention relates to a photosensitive polyimide precursor composition comprising (A) soluble polyimide, (B) polyamic acid, (C) dissolution inhibitor, (D) photoacid generator and (E) polar solvent.

(A) Soluble Polyimide

The soluble polyimide of the present invention is a soluble polyimide containing one or more repeating units represented by the following general formula (1) and whose at least one end is terminated with a reactive terminal block monomer.

Where

X is a tetravalent aromatic or aliphatic organic group;

Y is a divalent aromatic or aliphatic organic group;

m is an integer of 1 or more.

In the present invention, the soluble polyimide has a low film shrinkage and maintains stable membrane properties because the polymer chain is imidized, and has a hydroxyl group, so that the soluble polyimide is uniformly mixed with the polyamic acid and the polyamic acid ester. It plays a role in controlling the dissolution rate of polyamic acid.

In Formula 1, X is a tetravalent aromatic or aliphatic organic group, and particularly, the aromatic organic group is preferably selected from functional groups represented by the following Formula (2).

[Formula 2]

Such tetravalent aromatic organic groups are derived from tetracarboxylic dianhydrides having the general structure of the following general formula (3).

[Formula 3]

Wherein X is as defined in formula (I).

Specific examples of the compound having the structure of Formula 3 include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride (3,3,4, 4 -biphenyl tetracarboxylic dianhydride), 4,4-oxydiphthalic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (3,3 ', 4,4'-benzophenone tetracarboxylic dianhy-dride), 2,2-bis (3,4-benzenedicarboxylic anhydride) perfulopropane (2,2-bis (3,4-benzenedicarboxylic anhydride) perfluoropropane), 4,4-sulfonyldiphthalic dianhydride, and the like, and preferably pyromellitic dianhydride, 3,3 ', 4,4'-biphenyl tetra Carboxylic dianhydride or 4,4'- oxydiphthalic dianhydride is used individually or two or more types are used simultaneously.

In Formula 1, Y is a divalent aromatic or aliphatic organic group derived from diamines represented by the following Formula 13.

Specific examples of the compound having the structure of Formula 4, in particular, for example, a compound having an aromatic ring, 1,3-diamino-4,6-dihydroxybenzene (1,3-diamino-4,6-dihydroxybenzene ), 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'- Dihydroxybiphenyl (4,4'-diamino-3,3'-dihydroxybiphenyl), 2,2-bis (3-amino-4-hydroxyphenyl) propane (2,2-bis (3-amino-4 -hydroxyphenyl) propane), 2,2-bis (4-amino-3-hydroxyphenyl) propane (2,2-bis (4-amino-3-hydroxyphenyl) propane), bis (3-amino-4-hydroxy Bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (3-amino 4-hydroxyphenyl) ether (bis (3-amino-4-hydroxyphenyl) ether), bis (4-amino-3-hydroxyphenyl) ether (bis (4-amino-3-hydroxyphenyl) ether), 2 , 2-bis (3-amino-4-hydroxype Hexafluoropropane (2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane), 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane (2,2-bis ( 4-amino-3-hydroxyphenyl) hexafluoropropane) and the like, preferably 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3- Hydroxyphenyl) hexafluoropropane and the like are used alone or in combination of two or more thereof.

Soluble polyimides of the present invention are prepared by first synthesizing the polyamic acid and then thermosetting it in solution.

(B) polyamic acid

The polyamic acid of the present invention is a polyamic acid including one or more repeating units represented by the following formula (5) and at least one terminal terminated with a reactive terminal block monomer.

[Formula 5]

Where

X is a tetravalent aromatic or aliphatic organic group;

Y is a divalent aromatic or aliphatic organic group;

n is an integer of 1 or more.

In Formula 5, X is a tetravalent aromatic or aliphatic organic group, and particularly, the aromatic organic group is preferably selected from functional groups represented by the following Formula (2).

[Formula 2]

Such tetravalent aromatic organic groups are derived from tetracarboxylic dianhydrides having the general structure of the following general formula (3).

[Formula 3]

Wherein X is as defined in formula (I).

Specific examples of the compound having the structure of Formula 3 include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyl tetracarboxylic dianhydride (3,3,4, 4 -biphenyl tetracarboxylic dianhydride), 4,4-oxydiphthalic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride (3,3 ', 4,4'-benzophenone tetracarboxylic dianhy-dride), 2,2-bis (3,4-benzenedicarboxylic anhydride) perfuluoropropane (2,2-bis (3,4-benzenedicarboxylic anhydride perfluoropropane), 4,4-sulfonyldiphthalic dianhydride, and the like, and preferably pyromellitic dianhydride, 3,3 ', 4,4'-biphenyl tetra Carboxylic dianhydride or 4,4'- oxydiphthalic dianhydride is used individually or two or more types are used simultaneously.

In Formula 5, Y is a divalent aromatic or aliphatic organic group, derived from diamines represented by the following Formula 6.

Specific examples of the compound having the structure of Chemical Formula 6, for example, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4 ' -Diaminodiphenyl ether, 2,2-bis (4-aminophenyl) propane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 1,4-bis (3- Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (p-aminophenylsulfonyl) benzene, 1,4-bis (m-aminophenylsulfonyl) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] methane, bis [3,5-dimethyl-4- (4-aminophenoxy ) Menyl] methane, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] perfuluropropane, and the like, and preferably 4, 4'-diaminodiphenylether, 4,4'-diaminodiphenylsulfone, 2,2-bis (4-aminophenyl) propane, or the like can be used alone or two or more Used.

In the present invention, the polyamic acid has a higher permeability and a higher dissolution rate in the aqueous alkali solution than the polyimide, and is easy to be modified in various ways, thereby introducing the siloxane component into the polyamic acid molecular chain, thereby adhering the resin composition to the substrate. You can also improve your sex.

In order to improve the adhesion, 1 to 50% of the Y constituting the polyamic acid has a repeating unit having a siloxane structure represented by the following formula (7).

Where

R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each an alkyl group, an aryl group, an alkoxy group, or a hydroxy group;

R ₁₅ and R ₁₆ are each a divalent alkyl group or an aryl group;

k is an integer of 1 or more.

The polyamic acid including the siloxane units as described above may be obtained by using polysiloxane diamine represented by the following formula (8) as a comonomer during polyamic acid polymerization.

In the above formula,

R ₁₁ to R ₁₆ and k are the same as defined in Chemical Formula 7.

On the other hand, the soluble polyimide and the polyamic acid of the present invention each contain a reactive terminal block monomer at either or both of the molecular chain ends.

When the reactive endblocking monomer is introduced, the molecular weight of the resin can be reduced to lower the viscosity of the final resin composition, thereby facilitating processing, and in the curing step after the patterning step, crosslinking is formed between the endblocking groups to increase the molecular weight of the film. Can improve. In particular, when end-blocking monomers are introduced into the sock end of each of the molecular chains of the soluble polyimide and the polyamic acid, the soluble polyimide and the polyamic acid have their own unique properties until the patterning process. Low viscosity and the like are maintained, and uniform crosslinking is formed between the soluble polyimide and the reactive end-blocking group of the polyamic acid in the final curing process, thereby increasing the molecular weight, thereby maximizing the mixing effect of the compositions.

Reactive end-blocking monomers suitable for this purpose are monoamines or monoanhydrides having carbon-carbon double bonds, which have a single functional group to terminate condensation polymerization and form terminal groups of the polymer, Crosslinks are formed between the carbon-carbon double bonds.

Reactive endblocking monomers useful in the present invention include ethynylaniline (EA), 5-norbornene-2,3-dicarboxylic anhydride (NDA), 3,4,5,6-tetrahydrophthalic anhydride (3,4,5,6-tetrahydrophthalicanhydride), cis-1,2,3,6, -tetrahydrophthalic anhydride (cis-1, 2,3,6-tetrahydrophthalicanhydride, maleicanhydride (MA), itaconicanhydride (IA), citraconicanhydride (CA), 2,3-dimethylmaleic Unhydride (2,3-dimethylmaleicanhydride (DMMA)) and the like, preferably 5-norbornene-2,3-dicarboxylic anhydride (NDA) represented by the following Chemical Formula 9, represented by the following Chemical Formula 10 Itaconic anhydride (IA) or 2,3-dimethylmaleic anhydride (DMMA) represented by the following formula (11) is used.

[Formula 9]

[Formula 10]

[Formula 11]

The ratio of (A) soluble polyimide and (B) polyamic acid in the polyimide precursor mixture of the present invention is from 0.005 to A / (A + B) when A is the weight of soluble polyimide and B is the weight of polyamic acid. It is preferable to be in the range of 0.95, and the ratio can control the transmittance, viscosity, dissolution rate of the exposed portion, the residual film ratio of the non-exposed portion, and physical properties.

(C) Dissolution Inhibitor

In the present invention, the dissolution inhibitor is a compound in which a dissociable functional group is introduced by an acid into a hydrogen portion of a carboxy group or a hydroxy group of a compound having a carboxylic acid or phenolic hydroxy group soluble in an aqueous solution.

First, since the non-polar group is substituted by the ester bond or the ether bond, it maintains the stable residual film ratio of the non-exposed part. Second, when the functional group is dissociated by the acid generated during exposure, the polar group is a carboxyl group or a phenolic hydroxy group. Increase the rate of dissolution of the wealth.

Since the present invention is chemically amplified to the dissolution inhibitor, a small amount of a photosensitizer may be used. Since the content of the dissolution inhibitor having an ester-bonded substituent is not high, the film shrinkage rate is low and the physical properties are excellent.

The dissolution inhibitor may include a structure of Formula 12 or Formula 13 below, and may have a structure of Formula 14 below.

Where

R ₁ and R ₂ are each a functional group dissociable by hydrogen or an acid;

X is a tetravalent aromatic or aliphatic organic group;

Y is a divalent aromatic or aliphatic organic group;

v is an integer of 1 or more.

Where

R ₃ and R ₄ are each a functional group dissociable by hydrogen or an acid;

X is a tetravalent aromatic or aliphatic organic group;

Y is a divalent aromatic or aliphatic organic group;

w is an integer of 1 or more.

Where

R ₅ , R ₆ , R ₇ , and R ₈ are functional groups dissociable by hydrogen or acid, respectively;

X is a divalent group comprising an aromatic or aliphatic organic group and a hetero element;

Z is a trivalent group comprising an aromatic or aliphatic organic group and a hetero element;

Y is a tetravalent group containing an aromatic or aliphatic organic group and a hetero element.

Examples of functional groups dissociable by acids in Chemical Formulas 12, 13 and 14 include -CHR ₉ -OR ₁₀ groups (R ₉ and R ₁₀ are each hydrogen or a saturated hydrocarbon, unsaturated hydrocarbon or aromatic organic group having 1 to 20 carbon atoms, respectively). R ₉ and R ₁₀ may be connected to each other to form a cyclic compound) and trimethylsilyl group, t-butyl group, menthyl group, isobornyl group, 2-methyl-2-adama 2-methyl-2-adamantyl group, dicyclopropylmethyl (Dcpm) group, dimethylcyclopropylmethyl (Dmcp) group, and the like.

The number of functional groups dissociable by the acid introduced into the dissolution inhibitor is the number of hydrogen atoms of the carboxyl or phenolic hydroxyl group which is a developable functional group in the aqueous solution present in the dissolution inhibitor, a, of the functional group dissociable by acid. When number is b, it is preferable that b / (a + b) has a value of 0.1 or more and 1 or less. If b / (a + b) is less than 0.1, the dissolution inhibiting effect in the aqueous alkali solution is too low, and an excellent pattern is not formed.

When the dissolution inhibitor includes a repeating unit represented by Formula 12 or Formula 13, one or both ends of the molecular chain terminal may be terminated with a reactive end-capping monomer.

Suitable reactive end-blocking monomers are monoamines or monoanhydrides having carbon-carbon double bonds, which have a single functional group to terminate condensation polymerization and form end groups of the polymer, and upon radical reaction the carbon-carbon Crosslinks are formed between the double bonds.

Reactive endblocking monomers useful in the present invention include ethynylaniline (EA), 5-norbornene-2,3-dicarboxylic anhydride (NDA), 3,4,5,6-tetrahydrophthalic anhydride (3,4,5,6-tetrahydrophthalicanhydride), cis-1,2,3,6,-tetrahydrophthalic anhydride (cis-1, 2,3,6-tetrahydrophthalicanhydride, maleicanhydride (MA), itaconic hydride (IA), citraconicanhydride (CA), 2,3-dimethylmaleic Unhydride (2,3-dimethylmaleicanhydride (DMMA)) and the like, preferably 5-norbornene-2,3-dicarboxylic anhydride (NDA) represented by the following Chemical Formula 9, represented by the following Chemical Formula 10 Itaconic anhydride (IA) or 2,3-dimethylmaleic anhydride (DMMA) represented by the following formula (11) is used.

[Formula 9]

[Formula 10]

[Formula 11]

In the present invention, the dissolution inhibitor may be used alone or two or more kinds at the same time. The content of the preferred dissolution inhibitor is 0.01 to 50 parts by weight, more preferably 0.1 to 30 parts by weight based on 100 parts by weight of the soluble polyimide and polyamic acid. If the addition amount of the dissolution inhibitor is less than 0.01 part by weight, the remaining film ratio of the non-exposed part is lowered, and if it exceeds 50 parts by weight, the film color after the final curing becomes poor.

(D) Mine generator

The photoacid generator means a compound capable of generating an acid upon receiving light. Examples of the photoacid generator may include nonionic photoacid generators such as halides for generating HX and sulfones for generating sulfonic acid; There are ionic photoacid generators such as ammonium salt compounds, diazonium salt compounds, iodonium salt compounds, sulfonium salt compounds, phosphonium salt compounds, onium salt polymer compounds, selenium salt compounds and azenium salt compounds.

More specific examples include nonionic photoacid generators such as diazonaphthoquinones (DNQ) represented by the following general formula (15) and nitrobenzyl sulfonates represented by the following general formula (16); _{^{Ph 3 S + SbF 6 -,}} Ph 3 S + TosO -, Ph 3 S + TfO - such as the sulfonium _{^{salt-based, Ph 2 I + AsF 6 -}} , Ph 2 I + PF 6 - , such as iodonium salts to, of formula an ionic photo-acid generators such as iodonium salt-based, such as ^azo-aromatic sulfonic acid represented by 17-diphenyl-iodonium (diphenyl iodonium) salt-based, and _{RO-C 6 H 4 -N 2} + SbF 6. In addition, polymer type photoacid generators can be used in the present invention.

Where

Q ₁ and Q ₂ are each a monovalent alkyl or aryl group;

h and g are each an integer of 1 or more.

Where

R ₁₇ may be an alkyl group or an aryl group, or a group in which carbon or hydrogen is substituted with a heteroatom in the alkyl or aryl group;

j is an integer of 1-3.

Where

R ₁₈ , R ₁₉ and R ₂₀ are each an alkyl group, an aryl group, an alkoxy group, or a hydroxy group;

Ar ₁ is a phenyl group, a naphthalene group, or an anthracene group;

i is an integer of 1 to 5, and when i is 2 or more, R ₁₈ may be one or more functional groups.

In the present invention, the photoacid generator may be used alone or in combination of two or more thereof. The amount of the photoacid generator added is 0.01 to 50 parts by weight, more preferably 0.05 to 30 parts by weight, relative to 100 parts by weight of the polyimide precursor mixture composed of (A) soluble polyimide, (B) polyamic acid and (C) dissolution inhibitor. . When the amount of the photoacid generator is less than 0.01 part by weight, the light sensitivity of the composition is lowered. When the amount of the photoacid generator is exceeded by 50 parts by weight, the transmittance of the entire composition decreases and the film thickness cannot be increased, and the film color and physical properties after the final curing are not good.

(E) polar solvent

Examples of polar solvents usable in the present invention include N- methyl-2-pyrrolidone, N, N - dimethyl-acetic agent, dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), acetonitrile, di Klim, γ Butyrolactone, phenol, cyclohexanone and the like, among which N-methyl-2-pyrrolidone (NMP) and γ-butyrolactone are particularly preferred.

The photosensitive polyimide precursor composition of the present invention may further contain other additives such as dissolution rate regulators, sensitizers, and adhesion aids in addition to the components mentioned above.

As an example of an additive, the alcohol type which has a hydroxyl group, the benzyl alcohol type, the phenol type compound like bisphenol A, or the aromatic compound which does not have a hydroxyl group like diphenyl sulfone is mentioned.

The sum of the solids content in the total composition, that is, the content of (A) soluble polyimide, (B) polyamic acid, (C) solubilizer and (D) photoacid generator and other additives, depends on the thickness of the film to be formed. In general, it is preferably 5 to 60% by weight of the total photosensitive polyimide precursor composition. If the solid content is less than 5% by weight, the film shrinkage is too high, and if it exceeds 60% by weight, it is difficult to process such as spin coating due to the high viscosity.

The photosensitive polyimide precursor composition of this invention is positive type, and uses aqueous alkali solution as a developing solution. It is more environmentally friendly and economical than organic solvents. Examples of the alkali developer include aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide or amine aqueous solutions such as ammonia, ethylamine, propylamine, diethylamine and triethylamine. Can be. Among them, tetramethylammonium hydroxide (TMAH) aqueous solution is most commonly used.

By using the photosensitive resin composition of this invention, the heat resistant polyimide film patterned on the board | substrates, such as glass and a silicon wafer, can be formed easily. In this case, as a method of coating the resin composition, spin coating, bar coating, screen printing, or the like may be used.

It is preferable that the thickness of the film to be coated is about 0.5 to 20 μm, and the thicker the film, the lower the resolution. After coating, the solvent is evaporated by prebaking at 50 to 150 ° C. for 4 to 15 minutes to form a prebaked film. Next, ultraviolet rays are irradiated using a photomask on which a pattern to be processed is formed. The amount of exposure during irradiation is preferably 100-4,000 mJ / cm 2, and a post exposure baking (PEB) process is performed for 10 to 600 seconds at a temperature of 50 to 150 ° C. after exposure. By this series of processes, the photoacid generator present in the exposed portion generates an acid upon exposure, and the acid desorbs the protecting group from the dissolution inhibitor. As a result, when developing in the above alkaline developing solution, since the dissolution rate of the exposed part is significantly increased compared to the non-exposed part, it is easily removed by the developer to form a desired pattern. When the thus formed pattern is washed with distilled water or alcohol and dried, only the pattern of the polyimide precursor remains on the substrate.

In general, the resolution of the photosensitive resin is expressed as an aspect ratio (d / w), which is a ratio of the thickness (d) to the line width (w) of the formed pattern, and using the photosensitive polyimide precursor composition of the present invention, the aspect ratio is 3.0. Achieve high levels of resolution. That is, it can manufacture from the film thickness of 15 micrometers to the pattern of the line width of 5 micrometers. The pattern of the polyimide precursor obtained by this process is converted into a polyimide pattern by heat treatment. The heat treatment is carried out stepwise or continuously for 0.5 to 5 hours under the vacuum or nitrogen stream with a maximum temperature between 100 ° C and 450 ° C.

In the heat treatment step, the substituents of the dissolution inhibitor are pyrolyzed and removed, and the polyamic acid is imidized, and at the same time, a crosslinking reaction occurs between the reactive terminal blockers at the molecular chain ends of each of the soluble polyimide and the polyamic acid. This is converted to a polyimide higher than the initial.

Hereinafter, the present invention will be described in detail with reference to Examples, but these Examples are for explaining the present invention and should not be construed as limiting the protection scope of the present invention.

Example 1

1) Synthesis of Soluble Polyimide Resin

11.0 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 80 g of γ-butyrolactone were sequentially added to a 1 L round bottom flask, followed by slow stirring to completely dissolve the flask. 13.3 g of 2,2-bis (3,4-benzenedicarboxylic anhydride) perfuluropropane was slowly added while maintaining in water at room temperature. After the mixture solution was stirred at room temperature for 16 hours, 16 g of toluene was added thereto, and the mixture solution was installed to remove water through a dean-stark distillation and refluxed at 140 ° C. for 3 hours. The solution was cooled to room temperature, poured slowly into a methanol: water = 1: 4 mixture to solidify, and dried in a 40 ° C. vacuum drying oven for one day to obtain 22 g of a soluble polyimide resin.

2) Synthesis of Polyamic Acid

40 g of ODA (4,4'-diaminodiphenylether) and 239 g of NMP (N-methyl-2-pyrrolidone) were sequentially added to a 1 L round bottom jacket reactor, and the mixture was slowly stirred to completely dissolve. 55.8 g of ODPA (4,4'-oxydiphthalic anhydride) was slowly added while stirring at room temperature. After the reaction mixture was stirred for 2 hours to fully react, 6.6 g of 5-norbornene-2,3-dicarboxylic anhydride (NDA) was slowly added thereto, and the mixture was further stirred at room temperature for 16 hours.

3) Synthesis of Dissolution Inhibitor

Into a 1 L round bottom flask, 3.44 g of BAPB (1,4-bis (4-aminophenyl) benzene), 9.42 g of ODA (oxydianiline), and 140 g of NMP (N-methyl-2-pyrrolidone) were sequentially added and stirred thoroughly. After dissolving, the flask was stirred with water by slowly adding 1.24 g of pyromellitic dianhydride (PMDA) and 15.92 g of ODPA (4,4'-oxydiphthalic anhydride) while maintaining the temperature at room temperature. After the reaction mixture was stirred for 2 hours to fully react, 0.25 g of NDA (5-norbornene-2,3-dicarboxylic anhydride) and 0.17 g of IA (itaconicanhydride) were added slowly, and the mixture was stirred at room temperature for 16 hours. Then, replace the water bath of the flask with ethylene glycol / dry ice bath to maintain the temperature of the solution at -25 ℃, 50ml of NMP (N-methyl-2-pyrrolidone) is added to dilute the concentration of the mixed solution And, while maintaining the low temperature, 7.26 g of TEA (triethylamine) was diluted in 30 ml of NMP (N-methyl-2-pyrrolidone) and slowly added with stirring. After the addition was completed, the mixture was sufficiently stirred for 10 minutes to allow the TEA (triethylamine) to be evenly mixed, and then 7.18 g of CME (chloromethylethyl ether) was diluted in 30 ml of NMP (N-methyl-2-pyrrolidone) and slowly added. After stirring was continued for 2 hours, the mixture was kept at low temperature and filtered to remove the triethylammonium chloride salt, and the filtrate was slowly poured into a mixture of 1 L of methanol and 2 L of distilled water, which was rapidly precipitated as a white fine solid. After filtration to separate only white solid, it was washed with about 5 L of distilled water. The solid was dried in a 40 ° C. vacuum oven for 36 hours to give 30 g of a white powder.

4) Preparation of Photosensitive Polyimide Precursor Composition

A polyimide precursor mixture was prepared by mixing 1.8 g of the soluble polyimide synthesized in 1) and 14 g of the polyamic acid synthesized in 2). Subsequently, 0.6 g of the polyamic acid ester synthesized in 3) as a dissolution inhibitor and 0.6 g of hydroxynaphthalene sulfonic acid diphenyliodonium salt as a photoacid generator were dissolved in the solution. This was filtered through a filter having a pore size of 0.1 μm to prepare a photosensitive polyimide precursor composition.

5) Resolution evaluation

The photosensitive polyimide precursor composition of 4) was spin coated on a 4 inch silicon wafer, and heated at 90 ° C. for 4 minutes on a hot plate to form a 15 μm thick photosensitive polyimide precursor film. After vacuum-coating the coated silicon wafer to the photomask, UV light having a wavelength of 365 nm was irradiated with an exposure dose of 1000 mJ / cm 2 using a high pressure mercury lamp. After exposure, a post exposure baking (PEB) process was performed for 3 minutes at 125 ° C. again on a hot plate, and developed for 3 minutes in a 2.38 wt% TMAH (tetramethylammoniumhydroxide) aqueous solution, followed by washing with distilled water to clear the non-exposed part. Left the pattern. The silicon wafer thus patterned was slowly heated for about 30 minutes under nitrogen stream, starting at room temperature on a hot plate until reaching 180 ° C, and then held at 180 ° C for 60 minutes, and then until 300 ° C. After slowly heating, the mixture was maintained at 300 ° C. for 60 minutes and heat treated. The completed film was 10 micrometers in thickness, and the minimum line width of the pattern was 5 micrometers.

6) Film property evaluation

Spin-coated the photosensitive polyimide precursor composition prepared in 4) on a glass plate, and sequentially heat-treated at 180 ° C. for 60 minutes at 300 ° C. and 60 minutes at 300 ° C. under a nitrogen stream to form a polyimide film having a thickness of 10 μm. The film was peeled off from the glass plate by performing pressure cooking treatment (PCT) for 30 minutes under conditions of 125 ° C. and 2.3 atm in an autoclave. The peeled polyimide film was cut into a specimen size of 1 cm in width and 8 cm in length, and tensile properties were measured. The tensile strength was 150 MPa, modulus was 2.9 GPa, and elongation was 23%.

Example 2

1) Synthesis of Soluble Polyimide Resin

10.8 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 50 g of NMP (N-methyl-2-pyrrolidone) were sequentially added to a 1 L round bottom flask, followed by slow stirring to dissolve completely. Thereafter, 8.4 g of ODPA (4,4'-oxydiphthalic anhydride) was slowly added while maintaining the flask in water. After stirring for 2 hours, 1 g of NDA (5-norbornene-2,3-dicarboxylic anhydride) was added and further stirred at room temperature for 16 hours. 16 g of toluene was added to the solution to remove water through dean-stark distillation, and refluxed at 140 ° C. for 3 hours, and the solution was cooled to room temperature and methanol: water = 1: 4 was slowly poured into the mixture and solidified and dried in a 40 ° C vacuum drying oven for one day.

2) Synthesis of Polyamic Acid

2.4 g of SDA (siloxane diamine), 37.3 g of ODA (oxydianiline), and 235 g of NMP (N-methyl-2-pyrrolidone) were sequentially added to a 1L round bottom jacket reactor, and the mixture was slowly stirred to completely dissolve. 56 g of ODPA was added slowly while maintaining the temperature at 20 ° C. After the reaction mixture was stirred for 2 hours to fully react, 5.2 g of DMMA (2,3-dimethylmaleicanhydride) was slowly added thereto, and the mixture was further stirred at room temperature for 16 hours.

3) Preparation of Dissolution Inhibitor

Into a 1 L flask, 10.8 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 50 g of NMP (N-methyl-2-pyrrolidone) were sequentially added and slowly stirred to completely dissolve. 9.3 g of ODPA was slowly added while maintaining the flask in water. After the mixture solution was stirred at room temperature for 16 hours, 16 g of toluene was added thereto, and water was removed through a dean-stark distillation, and the mixture was refluxed at 140 ° C. for 3 hours. The solution was cooled to room temperature, poured slowly into a methanol: water = 1: 4 mixture to solidify, and dried in a vacuum drying oven at 40 ° C. for one day to obtain 18 g of a soluble polyimide resin. 10 g of the dried soluble polyimide resin was added to a 500 ml three-necked flask, and 100 ml of THF (Tetrahydrofuran) was added to completely dissolve. Then, 2.1 g of TEA (Triethylamine) was added and stirred for 20 minutes. 2.2 g of chloride (Me ₃ SiCl) were slowly added dropwise. After stirring for 2 hours while gradually raising the temperature from 0 ° C to room temperature, the resulting white triethylammonium chloride salt was filtered off, and the filtrate was slowly poured into a rapidly stirring methanol: water = 1: 4 mixture and white. After solidifying to a fine solid, and filtered to separate only the white solid, washed with about 5L of distilled water, which was dried for 36 hours in a 40 ℃ vacuum oven.

4) Preparation of Photosensitive Polyimide Precursor Composition

4 g of the soluble polyimide synthesized in 1) and 16 g of the polyamic acid synthesized in 2) were mixed to prepare a polyimide precursor mixture solution. To the solution was added 1.2 g of the dissolution inhibitor synthesized in 3), 0.6 g of bisphenol A (bisPA) as an additive, and a diethoxyanthracene sulfonic acid diphenyliodonium salt as a photoacid generator. After dissolving by adding 0.9 g, a filter having a pore size of 0.1 μm was filtered to prepare a photosensitive polyimide precursor composition.

5) Resolution evaluation

A 4 inch silicon wafer was spin coated with the photosensitive polyimide precursor composition of 4) and heated at 90 ° C. for 4 minutes on a hot plate to form a 15 μm thick photosensitive polyimide precursor film. After vacuum-coating the coated silicon wafer to the photomask, UV light having a wavelength of 365 nm was irradiated with an exposure dose of 1000 mJ / cm 2 using a high pressure mercury lamp. After exposure, a post exposure baking process was carried out for 3 minutes at 125 ° C. again on a hot plate, and developed for 3 minutes in a 2.38 wt% TMAH (tetramethylammoniumhydroxide) aqueous solution, followed by washing with distilled water to keep the non-exposed part clearly. I got a pattern. The silicon wafer thus patterned is gradually heated on a hot plate for about 30 minutes starting at room temperature until reaching 180 ° C., then held at 180 ° C. for 60 minutes, and then until 300 ° C. for 30 minutes. After slowly heating, the mixture was maintained at 300 ° C. for 60 minutes and heat treated. The completed film was 10 micrometers in thickness, and the minimum line width of the pattern was 8 micrometers.

6) Film property evaluation

Spin-coated the photosensitive polyimide precursor composition prepared in 4) on the wafer, and sequentially heat-treated at 180 ° C. for 60 minutes at 300 ° C. and 60 minutes at 300 ° C. under a nitrogen stream to form a polyimide film having a thickness of 10 μm. It was soaked for 30 minutes in a 2% hydrofluoric acid (HF) aqueous solution, and the cured polyimide film was peeled off from the wafer. The peeled polyimide film was cut into a width of 1 cm and a length of 8 cm to measure tensile properties with a tensile tester. The tensile strength was 160 MPa, modulus was 3.1 GPa, and elongation was 25%.

Example 3

1) Synthesis of Soluble Polyimide Resin

13.0 g of 3,3'-diamino-4,4'-dihydroxybiphenyl and NMP (N-methyl-2-pyrrolidone) in a 1 L round bottom flask ) 74.2 g were added sequentially and slowly stirred to dissolve completely. Then, 14.9 g of ODPA was slowly added while keeping the flask in water and keeping at room temperature. After stirring for 2 hours, 3.9 g of NDA were added and further stirred at room temperature for 16 hours. 16 g of toluene was added to the solution and the water was removed by dean-stark distillation. The mixture was refluxed at 140 ° C. for 3 hours, and the solution was cooled to room temperature and methanol: water = 1: 4 was slowly poured into the mixture and solidified and dried in a 40 ° C vacuum drying oven for one day.

2) Synthesis of Polyamic Acid

26.7 g of ODA (oxydianiline), and 158 g of NMP were sequentially added to the 1 L round bottom jacket reactor and slowly stirred to completely dissolve. Then, 33.1 g of ODPA was slowly added while stirring while maintaining the jacket temperature of the reactor at 20 ° C. After the reaction mixture was stirred for 2 hours to fully react, 4.4 g of NDA and 3.4 g of DMMA were added slowly, and the mixture was further stirred at room temperature for 16 hours.

3) Synthesis of Dissolution Inhibitor

7.7 g of tris (hydroxyphenyl) ethane are added to a 500 ml three-necked flask, and 100 ml of THF (Tetrahydrofuran) is added to dissolve completely. 5.1 g of TEA (Triethylamine) is added thereto and stirred for 20 minutes. 10.9 g of trimethylsilyl chloride (Me ₃ SiCl) was slowly added dropwise when the solution was sufficiently cooled. After stirring for 2 hours while gradually raising the temperature from 0 ° C to room temperature, the resulting white triethylammonium chloride salt was filtered off, and the filtrate was slowly poured into a rapidly stirring methanol: water = 1: 4 mixture and white. It was solidified to a fine solid of which was filtered and separated only white solid, washed with distilled water and dried for 36 hours in a 40 ℃ vacuum oven.

4) Preparation of Photosensitive Polyimide Precursor Composition

4 g of the soluble polyimide synthesized in 1) and 14 g of the polyamic acid synthesized in 2) and 0.3 g of the dissolution inhibitor synthesized in 3) and 0.3 g of diphenylsulfone as an additive were mixed to prepare a polyimide precursor solution. . As a photo-acid generating agent to the solution triphenyl sulfonium p-toluene sulphonic Acid Salt (triarylsufonium p-toluenesufonic acid salt: Ph 3 S + TosO -) were dissolved by the addition of 0.6g, the pore size is filtered through a filter 0.1㎛ To prepare a photosensitive polyimide precursor composition.

5) Resolution evaluation

A 4 inch silicon wafer was spin coated with the photosensitive polyimide precursor composition of 4) and heated at 90 ° C. for 4 minutes on a hot plate to form a 15 μm thick photosensitive polyimide precursor film. After vacuum-coating the coated silicon wafer to the photomask, a broadband band light of 300 nm to 400 nm wavelength was irradiated with an exposure dose of 1000 mJ / cm 2 without using a filter in a high pressure mercury lamp. After exposure, a post exposure baking process was performed for 3 minutes at 125 ° C. again on a hot plate, and developed for 3 minutes in a 2.74 wt% TMAH (tetramethylammoniumhydroxide) aqueous solution, followed by washing with distilled water to leave a clear unexposed portion. I got a pattern. The silicon wafer thus patterned is gradually heated on a hot plate for about 30 minutes starting at room temperature until reaching 180 ° C., then held at 180 ° C. for 60 minutes, and then until 300 ° C. for 30 minutes. After slowly heating, the mixture was maintained at 300 ° C. for 60 minutes and heat treated. The finished film had a thickness of 10 μm and the minimum line width of the pattern was 8 μm.

6) Film property evaluation

Spin-coated the photosensitive polyimide precursor composition prepared in 4) on the wafer, and sequentially heat-treated at 180 ° C. for 60 minutes at 300 ° C. for 60 minutes under a stream of nitrogen to form a polyimide film having a thickness of 10 μm. This was soaked in a 2% aqueous hydrofluoric acid (HF) solution for 30 minutes to release the cured polyimide film from the wafer. The peeled polyimide film was cut to a size of 1 cm in width and 8 cm in length, and tensile properties were measured with a tensile tester. The tensile strength was 155 MPa, modulus was 3.0 GPa, and elongation was 21%.

As described in detail above, when the precursor composition according to the present invention is used, it is excellent in dissolution rate, transmittance, strength, modulus, elongation, coefficient of thermal expansion, insulation, moisture absorption, etc. And the photosensitive polyimide precursor composition excellent in the adhesiveness to a board | substrate can be provided.

Therefore, when the polyimide film formed from the photosensitive polyimide precursor composition of the present invention is applied as an insulating film or protective film of various electronic devices such as an interlayer insulating film of a semiconductor device, an insulating film of a multilayer PCB, a buffer coating film, a passivation film, and the like, thermal, electrical, and mechanical It has excellent characteristics and can be applied to highly integrated semiconductors and packaging because it is possible to manufacture patterns of high resolution even in thick films of 10 μm or more.

Claims (21)

(A) a soluble polyimide comprising at least one repeating unit represented by Formula 1, wherein at least one end is terminated with a reactive terminal block monomer; (B) a polyamic acid including one or more repeating units represented by the following Chemical Formula 5, and at least one terminal terminated with a reactive terminal block monomer; (C) a dissolution inhibitor in which a part of the carboxyl group and a phenolic hydroxy group in the dissolution inhibitor is substituted with an acid dissociable with an acid; (D) photoacid generator; And (E) a polar solvent comprising: [Formula 1] Where X is a tetravalent aromatic or aliphatic organic group; Y is a divalent aromatic or aliphatic organic group; m is an integer of 1 or more. [Formula 5] Where X is a tetravalent aromatic or aliphatic organic group; Y is a divalent aromatic or aliphatic organic group; n is an integer of 1 or more. The polyimide precursor composition according to claim 1, wherein the reactive end-blocking monomers are monoamines or monoanhydrides having carbon-carbon double bonds. The polyimide precursor according to claim 2, wherein the monoanhydrides having a carbon-carbon double bond are 5-norbornene-2,3-dicarboxylic anhydride represented by the following formula (9). Composition: [Formula 9] The polyimide precursor composition according to claim 2, wherein the monoanhydrides having carbon-carbon double bonds are itaconic anhydrides (IA) represented by the following general formula (10): [Formula 10] According to claim 2, wherein the monoanhydrides having a carbon-carbon double bond is 2,3-dimethylmaleic anhydride represented by the following formula (11) Polyimide precursor composition [Formula 11] The polyimide precursor composition of claim 1, wherein 1 to 50% of the Y of the polyamic acid (B) is a repeating unit having a siloxane structure represented by the following Formula 7. [Formula 7] Where R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are each an alkyl group, an aryl group, an alkoxy group, or a hydroxy group; R ₁₅ and R ₁₆ are each a divalent alkyl group or an aryl group; k is an integer of 1 or more. The polyimide precursor composition of claim 1, wherein the (C) dissolution inhibitor comprises a polyamic acid ester represented by the following general formula (12): [Formula 12] Where R ₁ and R ₂ are each a group dissociable with hydrogen or an acid; X is a tetravalent aromatic or aliphatic organic group; Y is a divalent aromatic or aliphatic organic group; v is an integer of 1 or more. The polyimide precursor composition according to claim 1, wherein the (C) dissolution inhibitor comprises a soluble polyimide represented by the following formula (13): [Formula 13] Where R ₃ and R ₄ are each a group dissociable with hydrogen or an acid; X is a tetravalent aromatic or aliphatic organic group; Y is a divalent aromatic or aliphatic organic group; w is an integer of 1 or more. The polyimide precursor composition according to claim 1, wherein the (C) dissolution inhibitor is a compound represented by the following Formula (14): [Formula 14] Where R ₅ , R ₆ , R ₇ , and R ₈ are each functional groups dissociable by hydrogen or acid; X is a divalent group comprising an aromatic or aliphatic organic group and a hetero element; Z is a trivalent group comprising an aromatic or aliphatic organic group and a hetero element; Y is a tetravalent group containing an aromatic or aliphatic organic group and a hetero element. The method according to any one of claims 1 to 7, wherein the functional group capable of dissociation by an acid is -CHR ₉ -OR ₁₀ group, trimethylsilyl group, t-butyl group, menthyl group, Isobornyl group, 2-methyl-2-adamantyl group, dicyclopropylmethyl (Dcpm) group or dimethylcyclopropylmethyl (Dmcp) group Wherein R ₉ is hydrogen or a saturated hydrocarbon, unsaturated hydrocarbon or aromatic organic group having 1 to 20 carbon atoms, R ₁₀ is hydrogen or a saturated hydrocarbon, unsaturated hydrocarbon or aromatic organic group having 1 to 20 carbon atoms, R ₉ and R ₁₀ are connected to each other to form a cyclic compound, or a polyimide precursor composition characterized in that it does not form. The method according to claim 1, wherein (C) when the number of hydrogen atoms present at the carboxyl or phenolic hydroxy position in the dissolution inhibitor molecule is a and the number of functional groups dissociable by acid is b / (a + b ) Is 0.1 to 1 polyimide precursor composition. The polyimide according to claim 1, wherein A / (A + B) is 0.005 to 0.95 when the weight of the (A) soluble polyimide is A and the weight of the (B) polyamic acid is B. Precursor composition. The polyimide precursor composition according to claim 1, wherein the content of the (C) dissolution inhibitor is 0.01 to 50 parts by weight based on 100 parts by weight of the mixture of (A) soluble polyimide and (B) polyamic acid. The polyimide precursor composition according to claim 1, wherein the content of the (D) photoacid generator in the composition is 0.1 to 50 parts by weight based on 100 parts by weight of the (A + B + C) polyimide precursor mixture. The polyimide precursor composition according to claim 1, further comprising an alcohol, benzyl alcohol or phenol compound having a hydroxyl group as an additive. The polyimide precursor composition according to claim 1, further comprising an aromatic compound having no hydroxyl group as an additive. The solid content of the polyimide precursor composition, i.e., (A) soluble polyimide, (B) polyamic acid, (C) solubilizing agent, and (D) photoacid generator and other additives in a content of 5 to 60% by weight. Polyimide precursor composition characterized in that. The method of claim 1, wherein the photoacid generator (D) is a halide, sulfone compound, ammonium salt compound, diazonium salt compound, iodonium salt compound, sulfonium salt compound, phosphonium salt compound, onium salt compound, selenium salt compound and azenium salt Polyimide precursor composition, characterized in that at least one compound selected from the group consisting of compounds. The method of claim 1, wherein the (E) polar solvent is N-methyl-2-pyrrolidone, N, N-dimethylacetamide, dimethylformamide, dimethyl sulfoxide, acetonitrile, diclim, γ-butyrolactone And at least one compound selected from the group consisting of phenols. The photosensitive insulating film or the photosensitive protective film formed using the photosensitive polyimide precursor composition of Claim 1. A semiconductor device wherein the photosensitive polyimide precursor composition of claim 1 is applied to an insulating film, a passivation layer, or a buffer coating layer thereof.