KR101233382B1 - Positive type photosensitive resin composition - Google Patents

Abstract

The present invention relates to a positive photosensitive resin composition, comprising: (A) a polyimide-polybenzoxazole alternating co-polymer precursor having a repeating unit represented by the following formula (1) or (2): ; (B) a photosensitive diazoquinone compound; (C) a silane compound; (D) a phenol compound; And (E) relates to a positive photosensitive resin composition comprising a solvent.

[Formula 1]

[Formula 2]

(In the formulas (1) and ( ₂₎ , the definitions of X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , and Z ₂ are as described in the detailed description of the specification.)

The positive photosensitive resin composition of the present invention includes both a polyimide structure having excellent mechanical properties and a polybenzoxazole structure having excellent optical properties such as high sensitivity, high resolution, good pattern shape, excellent residue removal property, and low film reduction rate. It is possible to provide a post-curing film exhibiting excellent mechanical properties and heat resistance while maintaining photosensitivity.

Polyimide-Polybenzooxazole Alternating Copolymer Precursor, Positive Photosensitive Resin Composition, Semiconductor Device

Description

 Positive type photosensitive resin composition {POSITIVE TYPE PHOTOSENSITIVE RESIN COMPOSITION}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive resin composition, and to a positive photosensitive resin composition having high sensitivity, high resolution, good pattern shape, excellent residue removal property, low film reduction rate, and the like, and a final cured film having excellent mechanical properties and good heat resistance. will be.

Conventionally, polyimide resins having excellent heat resistance, electrical properties, mechanical properties, and the like have been used for surface protection films and interlayer insulating films of semiconductor devices. This polyimide resin is recently used in the form of a photosensitive polyimide precursor composition, and is easy to apply. After applying the polyimide precursor composition onto a semiconductor device, surface treatment is performed by patterning, developing, and thermal imidization with ultraviolet rays. A protective film, an interlayer insulating film, etc. can be formed easily. Therefore, it has a feature that a process can be significantly shortened compared with the conventional non-photosensitive polyimide precursor composition.

The photosensitive polyimide precursor composition has a positive type in which the exposed part is dissolved by development and a negative type in which the exposed part is cured. In the positive type, a non-toxic aqueous alkali solution can be used as a developer. The positive photosensitive polyimide precursor composition includes polyamic acid as a polyimide precursor, diazonaphthoquinone as a photosensitive material, and the like. However, the positive photosensitive polyimide precursor composition has a problem that a desired pattern can not be obtained because the solubility of the carboxylic acid of the polyamic acid used in the alkali is too high.

In order to solve this problem, a substance in which a phenolic hydroxyl group is introduced instead of carboxylic acid, such as a content of reacting an alcohol compound having one or more hydroxyl groups through an ester bond to polyamic acid (JP-A-10-307393), has been proposed. This material has insufficient developability and has a problem of reducing the film or peeling the resin from the substrate.

In another way, a material in which a diazonaptoquinone compound is mixed with a polybenzoxazole precursor (Japanese Patent Laid-Open No. 63-096162) has recently been attracting attention, but especially when a polybenzoxazole precursor composition is actually used, especially in developing. Since the film reduction amount of the miner is large, it is difficult to obtain a desired pattern after development. In order to improve this problem, if the molecular weight of the polybenzoxazole precursor is increased, the film reduction amount of the unexposed part becomes small, but developing residue (scum) occurs in the exposed part during development, resulting in poor resolution and longer developing time of the exposed part. there was.

In order to solve this problem, it is reported that the amount of film reduction of unexposed portions during development is suppressed by adding a specific phenol compound to the polybenzoxazole precursor composition (Japanese Patent Laid-Open No. 9-302221 and Japanese Patent Laid-Open No. 2000-). 292913). However, in this method, the effect of suppressing the reduction amount of the unexposed portion is insufficient, and there has been a continuous demand for research to increase the film reduction suppression effect without generating development residues (scum).

However, since the thermosetting film formed using such a polyimide or polybenzoxazole precursor composition continuously remains in the semiconductor device and acts as a surface protective film, mechanical properties such as tensile strength, elongation, and Young's modulus are particularly important factors. . In particular, with the rapid development of semiconductor packaging methods, the mechanical properties of polyimide or polybenzoxazole films used as surface protective films are very important in order to cope with their development. In the case of a general positive type photosensitive resin composition, such mechanical properties, more specifically, elongation and Young's modulus are often below an appropriate level. At the same time, further improvement is required in terms of heat resistance.

However, these studies can improve the mechanical properties represented by the elongation. However, they cannot reach practical levels in terms of optical properties such as sensitivity and resolution. Therefore, these mechanical properties can be improved and excellent mechanical properties and heat resistance can be achieved. There is an urgent need for research on how to do this.

One embodiment of the present invention has a high sensitivity, high resolution, good pattern shape and excellent residue removal properties, after curing, exhibits a low film reduction rate and excellent film properties, and the positive photosensitive property excellent in the mechanical properties and heat resistance of the film after curing It is to provide a resin composition.

Another embodiment of the present invention is to provide a photosensitive resin film prepared using the positive photosensitive resin composition.

Another embodiment of the present invention is to provide a semiconductor device including the photosensitive resin film.

The technical problems to be achieved by the present invention are not limited to the above-mentioned technical problems, and other technical problems not mentioned will be clearly understood by the average technician from the following description.

According to one embodiment of the present invention, (A) a polyimide-polybenzoxazole alternating co-polymer precursor having a repeating unit represented by the following formula (1) or (2); (B) a photosensitive diazoquinone compound; (C) a silane compound; (D) a phenol compound; And (E) provides a positive photosensitive resin composition comprising a solvent.

[Formula 1]

(In Formula 1, X ₁ is an aromatic organic group, Y ₁ is an aromatic organic group or a 2 to 6-valent aliphatic organic group, and Z ₁ is an aromatic organic group.)

[Formula 2]

(In Chemical Formula 2, X ₂ is an aromatic organic group, Y ₂ is an aromatic organic group, and Z ₂ is an organic group selected from the group consisting of an aromatic organic group, a 2-6 valent aliphatic organic group, and a 2-6 hexavalent alicyclic organic group.)

According to another embodiment of the present invention, to provide a photosensitive resin film prepared using the positive photosensitive resin composition.

Another embodiment of the present invention to provide a semiconductor device comprising the photosensitive resin film.

The positive photosensitive resin composition of the present invention includes both a polyimide structure having excellent mechanical properties and a polybenzoxazole structure having excellent optical properties, thereby providing photosensitivity such as high sensitivity, high resolution, good pattern shape, and excellent residue removal property. While maintaining, it is possible to provide a post-curing film exhibiting excellent mechanical properties and heat resistance.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Unless otherwise specified in the present specification, "alkyl group" means an alkyl group having 1 to 20 carbon atoms, "alkoxy group" means an alkoxy group having 1 to 8 carbon atoms, and "aryl group" means an aryl group having 6 to 30 carbon atoms. And a halogen atom means F, Cl, Br, or I.

In addition, in this specification, "substituted" means that one or more hydrogen atoms of the functional group of the present invention is halogen atom (F, Cl, Br, or I), hydroxy group, nitro group, cyano group, amino group (-NH ₂ , -NH (R ), -N (R "') (R""),R"' and R "" are independently of each other an alkyl group having 1 to 10 carbon atoms), amidino group, hydrazine or hydrazone group, carboxyl group, substituted or unsubstituted Substituted with one or more substituents selected from the group consisting of an alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted heterocycloalkyl group. it means.

Specific examples of the alkyl group in the present invention include methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl and the like as the linear or branched.

In addition, in the present specification, hetero means that the carbon atom is substituted with any one atom selected from the group consisting of N, O, S, and P unless otherwise specified.

Examples of the unsubstituted alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. In addition, examples of the substituted alkyl group include hydroxymethyl, methoxymethyl, ethoxymethyl, hydroxyethyl, methoxyethyl or ethoxyethyl.

Positive type photosensitive resin composition according to an embodiment of the present invention (A) a polyimide-polybenzoxazole alternating copolymer precursor having a repeating unit represented by the following formula (1) or (2); (B) a photosensitive diazoquinone compound; (C) a silane compound; (D) a phenol compound; And (E) a solvent.

Moreover, the said positive photosensitive resin composition of this invention may further contain other (F) other additives.

[Formula 1]

(In the formula 1,

X ₁ is an aromatic organic group,

Y ₁ is an aromatic organic group or a 2 to 6-valent aliphatic organic group,

Z ₁ is an aromatic organic group.)

[Formula 2]

(In Formula 2,

X ₂ is an aromatic organic group,

Y ₂ is an aromatic organic group,

Z ₂ is an organic group selected from the group consisting of an aromatic organic group, a 2-6 valent aliphatic organic group, and a 2-6 hexavalent alicyclic organic group.)

Hereinafter, each component will be described in detail.

(A) polyimide-polybenzoxazole alternating copolymer precursor

The polyimide-polybenzoxazole alternating copolymer precursor of this invention has the repeating unit of the said Formula (1) or (2), and has a thermopolymerizable functional group in at least one terminal part.

In Formula 1 or Formula 2, X ₁ and X ₂ are aromatic organic groups, for example, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino -3,3'-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxy Phenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoro Compounds selected from the group consisting of propane, 2,2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane and combinations thereof It is not limited to this.

In addition, X ₁ and X ₂ may preferably be a compound represented by the following formula (3) or (4).

(3)

[Formula 4]

(In Chemical Formulas 3 and 4,

A ₁ is O, CO, CR ₈ R ₉ (wherein R ₈ , and R ₉ are the same or different from each other, and each independently may be selected from the group consisting of hydrogen, and a substituted or unsubstituted alkyl group, preferably Preferably a fluoroalkyl group), SO ₂ , S, and a single bond.

R ₁ to R ₂ are the same or different from each other, and each independently hydrogen, a substituted or unsubstituted alkyl group, It may be selected from the group consisting of a hydroxyl group, a carboxylic acid group, and a thiol group,

n ₁ may be an integer from 1 to 2,

n ₂ and n ₃ are the same or different from each other, and each independently may be an integer of 1 to 3.)

More specifically, the examples of X ₁ and X ₂ are the same as the following Chemical Formulas 5 to 10.

[Chemical Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Chemical Formula 9]

[Formula 10]

In Formula 1, Y ₁ is an aromatic organic group or a divalent hexavalent aliphatic organic group, and is derived from a compound having both an amine group and a carboxylic acid. Specific examples of these compounds include 4-amino benzoic acid, 3-amino benzoic acid, 2-amino benzoic acid, amino acids such as glycine, betaglycine, and the like. Specific structures thereof may be represented by the following Chemical Formulas 11 to 14, but are not limited thereto.

[Formula 11]

[Chemical Formula 12]

[Chemical Formula 13]

[Formula 14]

(In Formula 14, n ₄ is an integer between 1 and 12.)

In Formula 1 of the present invention, Z ₁ is a residue derived from tetracarboxylic dianhydride as an aromatic organic group. Specifically, Z ₁ is benzene, naphthalene, biphenyl, dimethylbiphenyl, diphenyl ether, diphenylthioether, diphenylsulfone, diphenylpropane, diphenyl-1,1,1,3,3,3-hexa Fluoropropane, benzophenone and the like. Examples of the specific tetracarboxylic dianhydride which may form this residue may be represented by the following Chemical Formulas 15 to 19, but are not limited thereto.

[Formula 15]

[Chemical Formula 16]

[Chemical Formula 17]

[Chemical Formula 18]

[Formula 19]

In the general formula (2) of the present invention, Y ₂ is an aromatic organic group, and examples thereof include those derived from trimellitic acid represented by the following Chemical Formula 20, but are not limited thereto, and cyclic dicarboxylic anhydrides and carboxylic acids present independently of them. It can be derived from any compound having a functional group.

[Chemical Formula 20]

Z ₂ in the general formula (2) is the residue derived from the diamine, as an organic group selected from the group of aromatic organic group, divalent aliphatic organic group of 2 to 6 and 2 to 6-valent aliphatic organic group consisting of a. Although there is no restriction | limiting in the kind of diamine which can comprise this Z <_2> , For example, benzene, naphthalene, biphenyl, dimethyl biphenyl, diphenyl ether, diphenylthio ether, diphenyl sulfone, diphenyl propane, diphenyl- Aromatic diamines including 1,1,1,3,3,3-hexafluoropropane, benzophenone, etc., and aliphatic diamines having a structure such as propyl, butyl, pentyl, hexyl, or cyclohexyl, adamantyl, etc. Alicyclic diamine which has a is mentioned. Most preferred examples include the structures of the following Chemical Formulas 21 to 24, but the present invention is not limited thereto.

[Chemical Formula 21]

[Formula 22]

(23)

&Lt; EMI ID =

In the present invention, the weight average molecular weight (Mw) of the polyimide-polybenzoxazole alternating copolymer precursor is in the range of 3,000 to 300,000, and when the weight average molecular weight is less than 3,000, sufficient physical properties are not obtained, which is not preferable. If it exceeds 300,000, the solubility in organic solvents becomes low and handling becomes very difficult, which is not preferable.

(B) photosensitive diazoquinone compound

As the photosensitive diazoquinone compound used in the present invention, a compound having a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure can be preferably used, which is described in US Patent Nos. 2,772,975, 2,797,213 and A material known from US Pat. No. 3,669,658, which patent is incorporated herein by reference.

Examples of the photosensitive diazoquinone compound include, but are not limited to, compounds represented by the following Chemical Formulas 23 to 28.

(25)

(In the formula (25)

R ₄ to R ₆ may be the same or different from each other, and may each independently be a substituted or unsubstituted alkyl group, preferably CH ₃ ,

D ₁ to D ₃ may be each independently OQ, wherein Q may be hydrogen, and the following Chemical Formula 25-1 or 25-2, wherein Q may not be hydrogen at the same time,

n ₅ to n ₇ are the same or different from each other, and each independently an integer of 1 to 3.)

[Formula 25-1]

[Formula 25-2]

(26)

(In the above formula (26)

R ₇ is hydrogen or substituted or unsubstituted alkyl,

D ₄ to D ₆ may be each independently OQ, wherein Q is the same as defined in Formula 25,

n ₈ to n ₁₀ are the same or different from each other, and each independently an integer of 1 to 3.)

(27)

(In the above formula (27)

A ₂ may be CO or CRR ′,

R and R 'are the same or different from each other, and each independently may be a substituted or unsubstituted alkyl group,

D ₇ to D ₁₃ are the same or different from each other, and each independently may be hydrogen, a substituted or unsubstituted alkyl group, OQ, or NHQ, wherein Q is the same as defined in Formula 25,

n ₁₀ to n ₁₇ are the same or different from each other,

n ₁₀ + n ₁₀ + n ₁₀ + n ₁₀ and n ₁₀ + n ₁₀ + n ₁₀ may each independently be an integer of 5 or less.

However, at least one of D ₁₁ to D ₁₃ may be OQ, one aromatic ring may include 1 to 3 OQs, and the other aromatic ring may include 1 to 4 OQs.)

(28)

(In Chemical Formula 28,

R ₈ to R ₁₅ are the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group, Q is the same as defined in Formula 25,

n ₁₈ to n ₁₉ are the same or different from each other, and each independently may be an integer of 1 to 5, more preferably an integer of 2 to 4).

In the positive photosensitive resin composition of the present invention, the content of the photosensitive diazoquinone compound is preferably included in an amount of 5 to 100 parts by weight based on 100 parts by weight of the polyimide-polybenzoxazole alternating copolymer precursor. When the content of the photosensitive diazoquinone compound is included in the amount of 5 to 100 parts by weight, there is little residue (scum) due to exposure to excellent pattern shape, it is possible to obtain a good pattern without loss of film thickness during development.

(C) silane compound

The positive photosensitive resin composition of the present invention contains a silane compound, whereby the adhesion to the substrate can be improved.

The silane compound represented by the following formula (31) can be used.

[Formula 29]

(In Chemical Formula 29,

R ₁₆ may be selected from the group consisting of a vinyl group, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group, and preferably 3- (meth) acryloxypropyl, p-styryl, or 3- (Phenylamino) propyl,

R ₁₇ to R ₁₉ are the same or different from each other, and each independently selected from the group consisting of a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkyl group, and halogen, wherein at least one of R ₁₇ to R ₁₉ is An alkoxy group or a halogen, preferably the alkoxy group is an alkoxy group having 1 to 8 carbon atoms, and the alkyl group may be an alkyl group having 1 to 20 carbon atoms.)

Representative examples of the silane compound include compounds represented by the following Chemical Formulas 30 and 31; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyl trichlorosilane, vinyltris (β-methoxyethoxy) silane; Or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryl trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldie Oxysilane; Silane compounds containing carbon-carbon unsaturated bonds, such as trimethoxy [3- (phenylamino) propyl] silane, are mentioned, Most preferably, vinyl trimethoxysilane or vinyl triethoxysilane is mentioned.

(30)

(In Chemical Formula 30,

R ₂₀ is NH ₂ or CH ₃ CONH,

R ₂₁ to R ₂₃ are the same or different from each other, each independently represent a substituted or unsubstituted alkoxy group, preferably the alkoxy group may be OCH ₃ or OCH ₂ CH ₃ ,

n ₂₀ may be an integer from 1 to 5.

(31)

(In Chemical Formula 31,

R ₂₄ to R ₂₇ are the same or different from each other, and each independently may be selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted alkoxy group, preferably CH ₃ or OCH ₃ ,

R ₂₈ and R ₂₉ are the same or different from each other, each independently represent a substituted or unsubstituted amino group, preferably NH ₂ or CH ₃ CONH,

n ₂₁ and n ₂₂ are the same or different from each other, and each independently may be an integer of 1 to 5.)

The silane compound may be used in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the polyimide-polybenzoxazole alternating copolymer precursor. When the content of the silane compound is in the above range, the adhesion to the upper and lower membrane layers is excellent, and no residue is left after development, and the optical properties such as transmittance, tensile strength, elongation, and Young's modulus can be improved. Do.

(D) Phenol compound

The phenolic compound included in the positive photosensitive resin of the present invention can increase the dissolution rate and sensitivity of the exposed portion during development with an aqueous alkali solution, and also allows for patterning at high resolution due to less residue during development.

Moreover, the said phenolic compound has a functional group which can be thermally polymerized, and can crosslink with the said (A) polyimide polybenzoxazole alternating-polymer precursor at the time of thermosetting.

Specific examples of the phenolic compound include those represented by the following Chemical Formulas 32 to 37, but are not limited thereto.

(32)

(In Chemical Formula 32,

R ₃₀ to R ₃₂ are the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

R ₃₃ to R ₃₇ are the same or different from each other, and each independently may be selected from the group consisting of H, OH, and a substituted or unsubstituted alkyl group, preferably the alkyl group may be CH ₃ ,

n ₂₃ may be an integer from 1 to 5.

(33)

(In Chemical Formula 33,

R ₃₈ to R ₄₃ are the same or different from each other, and each independently may be selected from the group consisting of H, OH, and a substituted or unsubstituted alkyl group,

A ₃ may be CR′R ″ or a single bond, and R ′ and R ″ may be the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

Preferably the alkyl group may be CH ₃ ,

n ₂₄ + n ₂₅ + n ₂₆ and n ₂₇ + n ₂₈ + n ₂₉ may be the same or different from each other and may each independently be an integer of 5 or less.)

[Formula 34]

(In Chemical Formula 34,

R ₄₄ to R ₄₆ may be the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

n ₃₀ , n ₃₁ , and n ₃₄ are the same or different from each other, and each independently may be an integer of 1 to 5,

n ₃₂ and n ₃₃ are the same or different from each other, and may each independently be an integer of 0 to 4).

(35)

(In Chemical Formula 35,

R ₄₇ to R ₅₂ are the same or different from each other, and each independently may be selected from the group consisting of hydrogen, OH, and a substituted or unsubstituted alkyl group,

n ₃₅ to n ₃₈ are the same or different from each other, and each independently may be an integer of 1 to 4,

Provided that n ₃₅ + n ₃₇ and n ₃₆ + n ₃₈ are each independently an integer of 5 or less)

(36)

(In Formula 36,

R ₅₃ may be a substituted or unsubstituted alkyl group, preferably CH ₃ ,

R ₅₄ to R ₅₆ are the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

n ₃₉ , n ₄₁ , and n ₄₃ are the same or different from each other, and each independently may be an integer of 1 to 5,

n ₄₀ , n ₄₂ , and n ₄₄ are the same or different from each other, and each independently may be an integer of 0 to 4,

Provided that n ₃₉ + n ₄₀ , n ₄₁ + n ₄₂₈ , and n ₄₃ + n ₄₄ are each independently an integer of 5 or less.)

[Formula 37]

(In Chemical Formula 37,

R ₆₁ , R ₆₂ , and R ₆₃ are the same or different from each other, and may each independently be a substituted or unsubstituted alkyl group, preferably CH ₃ ,

R ₅₇ to R ₆₀ are the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

n _45, n ₄₇ , and n ₅₁ are the same or different from each other, and each independently may be an integer of 1 to 5,

n ₄₆ , n ₄₈ , n ₄₉ , and n ₅₀ are the same or different from each other, and each independently may be an integer of 0 to 4,

Provided that n ₄₅ + n ₄₆ , n ₄₇ + n ₄₈ , and n ₅₀ + n ₅₁ are each independently an integer of 5 or less.)

The phenolic compound is preferably used in an amount of 1 to 30 parts by weight based on 100 parts by weight of the polyimide-polybenzoxazole alternating copolymer precursor. When the content of the phenolic compound is in the above range, a satisfactory pattern can be obtained by appropriately increasing the dissolution rate of the non-exposed part without causing sensitivity deterioration during development. Precipitation does not occur during storage, and thus may exhibit excellent storage stability.

(E) Solvent

The solvent used in the present invention uses an organic solvent, preferably N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether , Diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3- Butylene glycol acetate, 1, 3- butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3- methoxy propionate Or the like may be used, but the present invention is not limited thereto. The said solvent can be used individually or in mixture of 2 or more types.

In the positive photosensitive resin composition of the present invention, the solvent is preferably used in an amount of 200 to 900 parts by weight based on 100 parts by weight of the polyimide-polybenzoxazole alternating copolymer precursor. When the content of the solvent is within the above range, a film of sufficient thickness can be applied, and it is preferable because of excellent solubility and applicability.

(F) Other additives

The photosensitive resin composition of the present invention may further include a heat latent acid generator and the like as an additive.

Examples of the heat latent acid generator include aryl sulfonic acids such as p-toluene sulfonic acid and benzene sulfonic acid; Perfluoroalkylsulfonic acids such as trifluoromethanesulfonic acid and fluorobutanesulfonic acid; Alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid and butanesulfonic acid; And mixtures thereof.

The heat latent acid generator is a catalyst for the dehydration reaction and the cyclization reaction of the structure of the phenolic hydroxyl group-containing polyamide of the polyimide-polybenzoxazole alternating copolymer precursor, and the reaction can proceed smoothly even if the curing temperature is lowered. .

In addition, the positive photosensitive resin composition of the present invention may further include a surfactant or a leveling agent as an additive for preventing staining of the film thickness or improving developability.

The process of forming a pattern using the positive photosensitive resin composition of this invention,

Applying a positive photosensitive resin composition on a supporting substrate;

Drying the applied composition to form a photosensitive polyimide-polybenzoxazole alternating copolymer precursor film;

Exposing the polyimide-polybenzoxazole alternating copolymer precursor film;

Developing the exposed polyimide-polybenzoxazole alternating copolymer precursor film with an aqueous alkali solution to produce a photosensitive resin film; And

And heat-treating the photosensitive resin film.

Process conditions for forming the pattern, etc. are well known in the art, so detailed description thereof will be omitted.

According to another embodiment of the present invention, there is provided a photosensitive resin film prepared using the positive photosensitive resin composition of the present invention. Preferable examples of the photosensitive resin film include a photosensitive insulating film or a photosensitive protective film.

In addition, according to another embodiment of the present invention, a semiconductor device including the photosensitive resin film of the present invention is provided.

The composition of the present invention can be usefully used for an insulating film, a passivation layer or a buffer coating layer in a semiconductor device. That is, the composition of the present invention can be usefully used as a surface protective film and an interlayer insulating film of a semiconductor device.

Hereinafter, preferred examples and comparative examples of the present invention are described. However, the following examples and comparative examples are for illustrative purposes and are not intended to limit the invention.

Synthesis Example 1 Synthesis of Polyimide-Polybenzooxazole Alternating Copolymer Precursor (PI-PBO-1)

27.43 g of 4-aminobenzoic acid and bis- (3,4-dicarboxylic acid anhydride phenyl) ethers while passing nitrogen through a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injector, and a cooler 31.02 g was added and 1500 ml of acetic acid was added. The mixture was stirred for 1 hour at room temperature and then heated up to reflux of the solvent, followed by further stirring for 12 hours. The temperature of this solution was lowered back to room temperature, and the precipitated white solid was filtered and washed three times with cold ethanol.

The solid obtained was dried for 12 h while heating to 100 ° C. under vacuum. The obtained solid was put into the four neck flask equipped with the stirrer, the thermostat, the nitrogen gas injection device, and the cooler, and 500 g of thionyl chloride was added while passing nitrogen. The solution was heated to reflux until thionyl chloride was refluxed, followed by further stirring for 12 hours. The temperature of this solution was lowered back to room temperature and then all thionyl chloride was removed under vacuum. The white solid obtained was washed five times with toluene and then dried for 12 hours while heating to 50 ° C. under vacuum.

Separately, 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3, while passing nitrogen through a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injection device and a cooler, 18.3 g of 3,3-hexafluoropropane was added, and 240 g of N-methyl-2-pyrrolidone (NMP) was added to dissolve it. Solid content was 9 weight% in the solution obtained at this time.

When the solid was completely dissolved, 5.6 g of pyridine was added, and 20.5 g of the solid obtained in the above experiment was added with 142 g of N-methyl-2-pyrrolidone (NMP) while maintaining the temperature at 0 to 5 ° C. It was dripped slowly for 30 minutes. After dropping, the reaction was carried out at a temperature of 0 to 5 ° C. for 1 hour, and the reaction was terminated by raising the temperature to room temperature and stirring for 1 hour. The reaction mixture was poured into a solution of water / methanol = 10/1 (volume ratio) to form a precipitate. The precipitate was filtered and washed sufficiently with water, and dried under vacuum at a temperature of 80 ° C. for at least 24 hours to obtain polyimide-polybenzooxa. Sol Sol Copolymer Precursor (PI-PBO-1) was prepared. ¹ H-NMR of the prepared PI-PBO-1 was measured and the results are shown in FIG. 1.

Synthesis Example 2 Synthesis of Polyimide-Polybenzooxazole Alternating Copolymer Precursor (PI-PBO-2)

Instead of 31.02 g of bis- (3,4-dicarboxylic acid anhydride) ether, 35.83 g of bis- (3,4-dicarboxylic acid anhydride phenyl) sulfone was used, and 2,2-bis was used using 22.17 g of the solid obtained using the same. Polyimide- Using the same method as in Synthesis Example 1, except that 18.3 g of (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane was reacted Polybenzoxazole alternating copolymer precursor (PI-PBO-2) was prepared.

Synthesis Example 3 Synthesis of Polyimide-Polybenzooxazole Alternating Copolymer Precursor (PI-PBO-3)

2,2-bis- (3,4-dicarboxylic acid anhydridephenyl) -1,1,1,3,3,3-hexafluoropropane in place of 31.02 g of bis- (3,4-dicarboxylic acid anhydride) ether 21.4 g of 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane using 33.63 g and 22.17 g of the solid obtained using the same A polyimide-polybenzoxazole alternating copolymer precursor (PI-PBO-3) was prepared in the same manner as in Synthesis Example 1, except that the reaction was conducted with.

Synthesis Example 4 Synthesis of Polyimide-Polybenzooxazole Alternating Copolymer Precursor (PI-PBO-4)

19.83 g of 4,4-diaminophenylmethane and 38.43 g of trimellitic acid were added to a four-necked flask equipped with a stirrer, a temperature controller, a nitrogen gas injection device, and a cooler, and 1500 ml of acetic acid was added thereto. The mixture was stirred at room temperature for 1 hour, then heated up to reflux of the solvent, followed by further stirring for 12 hours. The temperature of this solution was lowered back to room temperature, and the precipitated white solid was filtered and washed three times with cold ethanol. The solid obtained was dried for 12 h while heating to 100 ° C. under vacuum.

The obtained solid was put into the four neck flask equipped with the stirrer, the thermostat, the nitrogen gas injection device, and the cooler, and 500 g of thionyl chloride was added while passing nitrogen. The solution was heated to reflux until thionyl chloride was refluxed, followed by further stirring for 12 hours. The temperature of this solution was lowered back to room temperature and then all thionyl chloride was removed under vacuum. The white solid obtained was washed five times with toluene and then dried for 12 hours while heating to 50 ° C. under vacuum.

Separately, 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3, while passing nitrogen through a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injection device and a cooler, 18.3 g of 3,3-hexafluoropropane was added, and 240 g of N-methyl-2-pyrrolidone (NMP) was added to dissolve it. In the solution obtained at this time, solid content was 9 weight%.

When the solid was completely dissolved, 5.6 g of pyridine was added, and 20.42 g of the solid obtained in the above experiment was added with 142 g of N-methyl-2-pyrrolidone (NMP) while maintaining the temperature at 0 to 5 ° C. It was dripped slowly for 30 minutes. After dropping, the reaction was performed at a temperature of 0 to 5 ° C. for 1 hour, and the reaction was terminated by raising the temperature to room temperature and stirring for 1 hour. The reaction mixture was poured into a solution of water / methanol = 10/1 (volume ratio) to form a precipitate, and the precipitate was filtered and sufficiently washed with water. It dried at the temperature of 80 degreeC over 24 hours, and prepared the polyimide polybenzoxazole alternating copolymer precursor (PI-PBO-4). ¹ H-NMR of the prepared PI-PBO-4 was measured and the results are shown in FIG. 2.

Synthesis Example 5 Synthesis of Polyimide-Polybenzooxazole Alternating Copolymer Precursor (PI-PBO-5)

Instead of 19.83 g of 4,4-diaminophenylmethane, 20.03 g of 4,4-diaminophenyl ether was used, and 20.49 g of the solid obtained therefrom was used. The polyimide-polybenzoxazole alternating copolymer precursor was prepared in the same manner as in Synthesis Example 4 except that it was reacted with 18.3 g of oxyphenyl) -1,1,1,3,3,3-hexafluoropropane. PI-PBO-5) was prepared.

Synthesis Example 6 Synthesis of Polyimide-Polybenzooxazole Alternating Copolymer Precursor (PI-PBO-6)

Instead of 19.83 g of 4,4-diaminophenylmethane, 24.83 g of 4,4-diaminophenylsulfone was used, and 2,2-bis (3-amino-4-hydride was used using 22.17 g of the solid obtained using the same. The polyimide-polybenzoxazole alternating copolymer precursor was prepared in the same manner as in Synthesis Example 4 except that it was reacted with 18.3 g of oxyphenyl) -1,1,1,3,3,3-hexafluoropropane. PI-PBO-6) was prepared.

Synthesis Example 7 Synthesis of Polyimide-Polybenzooxazole Alternating Copolymer Precursor (PI-PBO-7)

Instead of 19.83 g of 4,4-diaminophenylmethane, 21.23 g of 4,4-diamino-2,2-dimethylbiphenyl was used, and 20.91 g of the solid obtained using the 2,2-bis (3 Polyimide-polybenzooxa using the same method as in Synthesis Example 4 except for reacting with 18.3 g of -amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane A sol shift copolymer precursor (PI-PBO-7) was prepared.

Synthesis Example 8 Synthesis of Polybenzoxazole Precursor (PA-1)

2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3, while passing nitrogen through a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injection device and a cooler 17.4 g of 3-hexaflouropropane and 0.86 g of 1,3-bis (aminopropyl) tetramethyldisiloxane were added, and 280 g of N-methyl-2-pyrrolidone (NMP) was added to dissolve it. At this time, the content of solids in the obtained solution was 9% by weight.

When the solid is completely dissolved, 9.9 g of pyridine is added, and 14.8 g of 4,4'-oxydibenzoyl chloride is added to 142 g of N-methyl-2-pyrrolidone (NMP) while maintaining the temperature at 0 to 5 ° C. The solution was slowly added dropwise for 30 minutes. After dropping, the reaction was performed at a temperature of 0 to 5 ° C. for 1 hour, and the reaction was terminated by raising the temperature to room temperature and stirring for 1 hour. The reaction mixture was poured into a solution of water / methanol = 10/1 (volume ratio) to form a precipitate, and the precipitate was filtered and washed sufficiently with water and dried under vacuum at a temperature of 80 ° C. for at least 24 hours to obtain a polybenzoxazole precursor (PA -1) was prepared.

Synthesis Example 9 Synthesis of Polybenzoxazole Precursor (PA-2)

2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3, while passing nitrogen through a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injection device and a cooler 17.4 g of 3-hexaflouropropane and 0.86 g of 1,3-bis (aminopropyl) tetramethyldisiloxane were added, and 280 g of N-methyl-2-pyrrolidone (NMP) was added to dissolve it. At this time, the content of solids in the obtained solution was 9% by weight.

When the solid is completely dissolved, 9.9 g of pyridine is added, and 14.8 g of 4,4'-oxydibenzoyl chloride is added to 142 g of N-methyl-2-pyrrolidone (NMP) while maintaining the temperature at 0 to 5 ° C. The solution was slowly added dropwise for 30 minutes. After dropping, the reaction was carried out at a temperature of 0 to 5 ° C. for 1 hour, and the temperature was raised to room temperature, followed by stirring for 1 hour. Then, 2.94 g of 4-namidido benzoyl chloride was added as an end-blocking agent, followed by stirring for 1 hour. Terminated. The reaction mixture was poured into a solution of water / methanol = 10/1 (volume ratio) to form a precipitate, and the precipitate was filtered and washed sufficiently with water and dried under vacuum at a temperature of 80 ° C. for at least 24 hours to obtain a polybenzoxazole precursor (PA -2) was prepared. ¹ H-NMR of the prepared PA-2 was measured and the results are shown in FIG. 3.

Synthesis Example 10 Synthesis of Polybenzoxazole Precursor (PA-3)

Polybenzoxazole precursor (PA-3) was polymerized in the same manner as in Synthesis Example 9 except that 5-norbornene-2,3-dicarboxylic acid anhydride was used instead of 4-namididobenzoyl chloride as an end-sealing agent. Prepared.

Example 1

After dissolving 15 g of the polyimide-polybenzoxazole alternate copolymer precursor (PI-PBO-1) synthesized in Synthesis Example 1 in 35.0 g of γ-butyrolactone (GBL), a photosensitive dia having a structure of Formula 38 3 g of quinquinone was used as a photosensitive diazoquinone compound, 0.75 g of trimethoxy [3- (phenylamino) propyl] silane represented by the following Chemical Formula 39 was used as a silane compound, and 0.75 g of ethylresosocinol represented by the following Chemical Formula 40 was used as a phenol compound. After melt | dissolution, it filtered with the fluororesin filter of 0.45 micrometer, and obtained the positive photosensitive polyimide polybenzoxazole alternating-copolymer precursor composition.

(38)

(In Formula 38,

로 치환되어 있다.)Two of the three Q's

Is replaced by.)

[Chemical Formula 39]

[Formula 40]

[Example 2]

A positive photosensitive polyimide-polybenzoxazole alternate copolymer precursor composition was obtained in the same manner as in Example 1 except that PI-PBO-2 was used instead of 15 g of PI-PBO-1.

[Example 3]

A positive photosensitive polyimide-polybenzoxazole alternating copolymer precursor composition was obtained in the same manner as in Example 1, except that PI-PBO-3 was used instead of 15 g of PI-PBO-1.

Example 4

A positive photosensitive polyimide-polybenzoxazole alternate copolymer precursor composition was obtained in the same manner as in Example 1 except that PI-PBO-4 was used instead of 15 g of PI-PBO-1.

[Example 5]

A positive photosensitive polyimide-polybenzoxazole alternate copolymer precursor composition was obtained in the same manner as in Example 1 except that PI-PBO-5 was used instead of 15 g of PI-PBO-1.

[Example 6]

A positive photosensitive polyimide-polybenzoxazole alternating copolymer precursor composition was obtained in the same manner as in Example 1 except that PI-PBO-6 was used instead of 15 g of PI-PBO-1.

[Example 7]

A positive photosensitive polyimide-polybenzoxazole alternate copolymer precursor composition was obtained in the same manner as in Example 1 except that PI-PBO-7 was used instead of 15 g of PI-PBO-1.

Comparative Example 1

A positive photosensitive polybenzoxazole precursor composition was obtained in the same manner as in Example 1 except that PA-1 was used instead of 15 g of PI-PBO-1.

Comparative Example 2

A positive photosensitive polybenzoxazole precursor composition was obtained in the same manner as in Example 1 except that PA-2 was used instead of 15 g of PI-PBO-1.

[Comparative Example 3]

A positive photosensitive polybenzoxazole precursor composition was obtained in the same manner as in Example 1 except that PA-3 was used instead of 15 g of PI-PBO-1.

[Property evaluation]

The polyimide-polybenzoxazole alternating copolymer precursor composition prepared according to Examples 1 to 7 and the polybenzoxazole precursor composition prepared according to Comparative Examples 1 to 3 were prepared by Mikasa (1H-DX2) on an 8-inch wafer. After coating using a spin coater, the film was heated for 4 minutes on a 120 ° C. hot plate to form a photosensitive polyimide precursor film.

After exposing at 250ms with a Nikon I-line stepper (NSR i10C) using a mask engraved with patterns of various sizes on the polyimide precursor film, 60 seconds (2 seconds) in a 2.38% aqueous tetramethylammonium hydroxide solution at room temperature After exposing and removing the exposed portion through a puddle), it was washed with pure water for 30 seconds. Subsequently, the obtained pattern was dried at 150 ° C for 30 minutes at an oxygen concentration of 1000 ppm or less using an electric furnace, and further cured at 320 ° C for 30 minutes to prepare a film with a pattern.

The pattern of the finished film was confirmed by the optical microscope, the film thickness after preliminary firing, development, and curing was measured using a KMAC (ST4000-DLX) equipment.

In addition, the reduction rate of the film thickness after development has an effect on the developability and the final film thickness, which also requires a small decrease in the film thickness during development, which is 2.38% tetramethylammonium hydroxide (TMAH) It was immersed in the aqueous solution by time and washed with water, and the residual film ratio (thickness after development / thickness before development, unit%) was calculated by measuring the film thickness change with time. The thicknesses of all the films obtained through the examples were in the range of 11.1 to 11.6 um, and the residual film rates were calculated for each example and are shown in Table 2 below.

The sensitivity was obtained by determining the exposure time in which a 10 um L / S pattern was formed with a line width of 1 to 1 after exposure and development, and was used as the optimum exposure time. The resolution set the minimum pattern size at which the line width of one to one is formed in the optimum exposure time as the resolution.

After the pattern was formed, the mixture was heated at 120 ° C. for 30 minutes in a nitrogen atmosphere, and then heated up to 320 ° C. for 1 hour, and heated at 320 ° C. for 1 hour to produce a cured film.

In order to measure the mechanical properties of the film after curing, the film-covered silicon wafer was soaked in 2% HF solution for 30 minutes to separate the film, and then cut into 6.0 cm * 1.0 cm ribbon pieces to measure mechanical properties. A specimen was prepared for. The specimens were measured for mechanical properties such as tensile strength, elongation, and Young's modulus by the instrom series IX Universal Testing Machine. The results are shown in Table 1 below.

[Table 1]

As shown in Table 1, in the case of using the photosensitive polyimide-polybenzoxazole alternating copolymer composition of Examples 1 to 7 compared to Comparative Examples 1 to 3, the sensitivity, resolution and mechanical properties are superior, and the elongation is excellent. Young's modulus is shown. In particular, compared with the case of Comparative Example 1, which does not contain a thermal crosslinkable terminal encapsulant, it can be seen that it shows superior mechanical properties, and 4-namididobenzoyl chloride or 5-norbornene- having thermal crosslinkability due to double bonds. It can be seen that the mechanical properties are relatively superior to those of Comparative Examples 2 and 3 using 2,3-dicarboxylic anhydride as the terminal sealing agent.

Based on the above results, when the polyimide-polybenzoxazole alternating copolymer composition according to the preferred embodiment of the present invention is used, a thick film having optical properties and mechanical properties significantly superior to the existing ones can be made. In addition, since the preferred embodiment of the present invention exhibits the same optical characteristics as compared with the methods of the comparative example, it is possible to easily form a semiconductor interlayer insulating film or surface protective film having good patternability and at the same time excellent mechanical properties through the present invention. have.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, And it goes without saying that the invention belongs to the scope of the invention.

Claims (6)

(A) Polyimide-Polybenzoxazole alternating co-polymer precursor having a repeating unit represented by the following formula (1) or (2); (B) a photosensitive diazoquinone compound; (C) a silane compound; (D) a phenol compound; And (E) Solvent Positive photosensitive resin composition comprising a. [Formula 1]

(In the formula 1, X ₁ is an aromatic organic group, Y ₁ is an aromatic organic group or a 2 to 6-valent aliphatic organic group, Z ₁ is an aromatic organic group.) [Formula 2]

(In Formula 2, X ₂ is an aromatic organic group, Y ₂ is an aromatic organic group, Z ₂ is an organic group selected from the group consisting of an aromatic organic group, a 2-6 valent aliphatic organic group, and a 2-6 hexavalent alicyclic organic group.) The method of claim 1, The polyimide-polybenzoxazole alternating copolymer precursor has a weight average molecular weight (Mw) of 3,000 to 300,000. The method of claim 1, The solvent is N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether , Propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3 A positive photosensitive resin composition selected from the group consisting of monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, and combinations thereof. The method of claim 1, The resin composition is To 100 parts by weight of the (A) polyimide-polybenzoxazole alternating copolymer precursor, 5 to 100 parts by weight of the (B) photosensitive dizoquinone compound; 0.1 to 30 parts by weight of the (C) silane compound; 1 to 30 parts by weight of the (D) phenol compound; And 200 to 900 parts by weight of the solvent (E) Positive photosensitive resin composition comprising a. The photosensitive resin film manufactured using the positive photosensitive resin composition of any one of Claims 1-4. A semiconductor device comprising the photosensitive resin film of claim 5.