KR100995079B1 - Positive photosensitive resin composition - Google Patents

Abstract

The present invention relates to a positive photosensitive resin composition, wherein the positive photosensitive resin composition (A) has a repeating unit represented by the following general formula (1), and exhibits hydrophilicity at least on one end thereof before heat curing to increase developability. Polybenzoxazole precursor which has a terminal functional group which changes into a thermopolymerizable functional group at the time of thermosetting; (B) photosensitive diazoquinone compound; (C) silane compound; (D) phenolic compounds; And (E) a solvent.

[Formula 1]

(In the general formula 1, as defined in the specification of each substituent.)

Positive type photosensitive resin composition of this invention can raise the developability of an exposure site | part very much, can acquire a sensitivity improvement effect, a pattern shape is favorable and can exhibit the outstanding resolution. In addition, crosslinking can be efficiently formed during thermosetting, thereby lowering the molecular weight of the polymer before curing, thereby obtaining excellent mechanical properties, excellent residue removal property, and low hygroscopicity of the membrane after curing.

Positive type, photosensitive polybenzoxazole precursor composition, dissolution controller, thermal polymerization crosslinker, aqueous alkali solution, semiconductor device

Description

Positive photosensitive resin composition {POSITIVE PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a positive photosensitive resin composition, and more particularly, to a positive photosensitive resin composition exhibiting high sensitivity and high resolution, good pattern shape, high residue removal property, and excellent mechanical properties after thermal curing. .

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. Such polyimide resins have recently been used in the form of photosensitive polyimide precursor compositions, and are easy to apply. After applying the polyimide precursor composition onto a semiconductor device, patterning by ultraviolet rays, development, thermal imidization treatment, and the like are performed. Thus, the surface protective film, the interlayer insulating film and the like can be easily formed. Therefore, there is a feature that the process can be significantly shortened as 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 in that the carboxylic acid of the polyamic acid used is too soluble in alkali to obtain a desired pattern.

In order to solve this problem, a substance in which a phenolic hydroxyl group is introduced instead of carboxylic acid, such as reacting an alcohol compound having at least one hydroxyl group through an ester bond with polyamic acid (see Japanese Patent Application Laid-Open No. 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. 63-96162) has recently been attracting attention, but especially when the polybenzoxazole precursor composition is actually used, Since the film reduction amount of the unexposed part 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 phenolic 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). In addition, the phenol used to control the solubility causes problems such as decomposition or side reactions at high temperatures during thermal curing, which causes great damage to the mechanical properties of the resulting cured film. Research is also continuing.

In addition, such photosensitive polyimide or polybenzoxazole precursor composition should form a pattern for a thick film compared to a general photoresist. Due to this thick thickness, there was a side where sensitivity was much lowered, and at the same time, this thick film also causes residues during development. In order to solve this problem, a method of improving developability by using a more hydrophilic polyimide or polybenzoxazole precursor can be considered, but in this case, even if the sensitivity and developability can be improved, the hygroscopic and chemical resistance of the film after thermosetting Because of this problem, practical applications are limited.

In addition, since the thermosetting film formed using such a polyimide or polybenzoxazole precursor composition continuously remains in the semiconductor device and functions as a surface protective film, mechanical properties of the film 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. However, in the case of polyimide or polybenzoxazole precursors that are generally used, such mechanical properties, more specifically, elongation are often below an appropriate level. In order to solve this problem, various additives are used or crosslinking during thermal curing. Examples have been reported of using precursor compounds and the like of which structures can occur.

However, in the case of these studies, the mechanical properties represented by elongation can be improved, but the optical properties such as sensitivity and resolution do not reach practical levels, and thus excellent mechanical properties are achieved without bringing down such optical properties. There is an urgent need for research on how to do this. This lack of optical properties is due to the high viscosity and high surface tension of the polyimide or polybenzoxazole precursor when the photosensitive polyimide or polybenzoxazole precursor is introduced to the substrate surface by spin coating. There is a big cause for what happens. In order to solve this problem, the use of various planarizers can be considered, but due to problems such as substrate adhesion, mechanical property deterioration, and foaming during coating, coating has not reached a practically usable level.

The present invention prevents the problem of deterioration of optical properties in thick films generated when patterning polyimide or polybenzoxazole precursors, in particular, deterioration of sensitivity and resolution and deterioration of pattern shape, and at the same time, mechanical properties of the film after curing. It is for providing the photosensitive resin composition which can improve the performance.

The present invention also provides a photosensitive resin film produced by using the positive photosensitive resin composition.

The present invention also provides a semiconductor device comprising a photosensitive resin film produced using the positive photosensitive resin composition.

Technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

According to one embodiment of the present invention, (A) has a repeating unit represented by the following formula (1), at least one of the end portion of the hydrophilic properties before heat curing to increase the developability, and change the thermopolymerizable functional group at the time of thermal curing Polybenzoxazole precursors having a terminal functional group; (B) photosensitive diazoquinone compound; (C) silane compound; (D) phenolic compounds; And (E) provides a positive photosensitive resin composition comprising a solvent.

[Formula 1]

(In the formula 1,

X ₁ is an aromatic organic group or a 4-6 valent aliphatic organic group,

X ₂ is an aromatic organic group or a 2 to 6-valent aliphatic organic group, or a functional group having a structure represented by the following formula (2),

Y ₁ and Y ₂ are the same or different from each other, and each independently an aromatic organic group or a 2 to 6-valent aliphatic organic group,

m ₁ and m ₂ are each molar ratio m ₁ + m ₂ = 100 mol%,

m ₁ is 60-100 mol%,

m ₂ is 0-40 mol%,

[Formula 2]

In Chemical Formula 2,

R ₁ and R ₂ are the same or different from each other, and each independently selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, and a hydroxy group,

R ₃ and R ₄ are the same or different from each other, and each independently a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group,

k is an integer from 1 to 50.)

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

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

Other specific details of embodiments of the present invention are included in the following detailed description.

Positive type photosensitive resin composition of this invention introduce | transduces terminal functional group derived from the terminal blockade monomer which has the appropriate reactivity and structure in the molecular chain terminal, and the light in the thick film | membrane which arises when patterning a polyimide or polybenzoxazole precursor is provided. It is possible to prevent the problem of deterioration of properties, in particular, deterioration of sensitivity and resolution, and deterioration of pattern shape, and at the same time, improve mechanical properties of the film after curing.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Unless stated otherwise in the present specification, “4 to 6-valent organic group” or “2 to 6-valent organic group” is an organic group having 4 to 6 functional groups and an organic group having 2 to 6 functional groups. Combines with the functional groups except

In this specification, unless specified otherwise, "substituted" means that at least one hydrogen of the compound is substituted with a substituent selected from the group consisting of halogen, alkyl group, aryl group, alkoxy group, amino group, and alkenyl group.

In the present specification, unless otherwise specified, an "alkyl group" is an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and an "alkoxy group" is an alkoxy group having 1 to 30 carbon atoms. Preferably, an alkoxy group having 1 to 18 carbon atoms, an aryl group having 6 to 30 carbon atoms as "aryl group", more preferably an aryl group having 6 to 18 carbon atoms, and an alkenyl group having 2 to 30 carbon atoms as "alkenyl group" Preferably an alkenyl group having 2 to 18 carbon atoms is an alkylene group having 1 to 30 carbon atoms as "alkylene group", more preferably an alkylene group having 1 to 18 carbon atoms, and an aryl having 6 to 30 carbon atoms as "arylene group". A rene group means more preferably an arylene group having 6 to 18 carbon atoms.

Photosensitive resin composition according to an embodiment of the present invention (A) has a repeating unit represented by the formula (1), exhibits hydrophilicity before heat curing at least one end portion to increase the developability, and thermal polymerization at the time of thermal curing Polybenzoxazole precursors having terminal functional groups which change into functional groups; (B) photosensitive diazoquinone compound; (C) silane compound; (D) phenolic compounds; And (E) a solvent.

In addition, the photosensitive resin composition of the present invention may further include (F) other additives.

Hereinafter, each component will be described in detail.

(A) Polybenzoxazole  Precursor

The polybenzoxazole precursor has a repeating unit represented by the following formula (1), and at least one terminal portion exhibits hydrophilicity before thermosetting to increase developability, and has a terminal functional group that is changed to a thermopolymerizable functional group upon thermal curing.

[Formula 1]

In Chemical Formula 1,

X ₁ is an aromatic organic group or a 4 to 6-valent aliphatic organic group,

X ₂ is an aromatic organic group or a 2 to 6-valent aliphatic organic group, or a functional group having a structure represented by the following Chemical Formula 2,

Y ₁ and Y ₂ are the same or different from each other, and each independently an aromatic organic group or a 2 to 6-valent aliphatic organic group,

M ₁ and m ₂ are molar ratios, m ₁ + m ₂ is 100 mol%,

M ₁ is 60 to 100 mol%,

M ₂ may be 0 to 40 mol%,

[Formula 2]

In Chemical Formula 2,

R ₁ to R ₂ are the same or different from each other, and each independently selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, and a hydroxy group,

R ₃ and R ₄ are the same or different from each other, and each independently a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group,

k is an integer of 1-50.

Specifically, X ₁ is 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-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone , 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl ) -1,1,1,3,3,3-hexafluoropropane, and combinations thereof, but is not limited thereto.

Also, preferably, X ₁ may be a compound represented by the following Chemical Formula 3 or 4.

(3)

[Formula 4]

(In Chemical Formulas 3 and 4,

The A ₁ may be selected from the group consisting of O, CO, CR ₈ R ₉ , SO ₂ , S, and a single bond,

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 R ₈ And R ₉ is a fluoroalkyl group,

R ₅ to R ₇ may be the same or different from each other, and may be each independently selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, a hydroxy group, a carboxylic acid group, and a thiol group,

N ₁ may be an integer of 1 to 2,

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

X ₂ can also be derived from aromatic diamines or silicone diamines.

Specific examples of the aromatic diamine include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane and 4,4'-diaminodiphenyl Methane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6- Aromatic amines such as naphthalenediamine; Or a compound in which the aromatic ring is substituted with an alkyl group or a halogen atom in the aromatic amine; Bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, 1, 4-bis (4-aminophenoxy) benzene and the like, but are not limited thereto. In addition, these aromatic diamine monomers can be used individually or in mixture.

Specific examples of the silicone diamine include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (p-aminophenyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetra Methyldisiloxane, 1,4-bis (γ-aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetraphenyldisiloxane, 1,3-bis (amino Propyl) tetramethyldisiloxane And the like.

Of course, the aromatic diamine and silicone diamine are not limited to the compounds.

In addition, the Y ₁ and Y ₂ may be derived from a derivative of dicarboxylic acid.

Specific examples of the dicarboxylic acid derivatives include carbonyl halide derivatives or The active compound which is an active ester type derivative which made dicarboxylic acid and 1-hydroxy-1,2,3-benzotriazole react etc. is mentioned. Examples thereof include 4,4'-oxydibenzoyl chloride, diphenyloxydicarboxylic acid chloride, bis (phenylcarboxylic acid chloride) sulfone, bis (phenylcarboxylic acid chloride) ether and bis (phenylcarboxylic acid Chloride) phenone, phthalic carboxylic acid dichloride, terephthalic acid dichloride, isophthalic carboxylic acid dichloride, carboxylic acid dichloride, diphenyloxydicarboxylate benzotriazole and combinations thereof Can be mentioned

In addition, it is preferable that Y ₁ and Y ₂ are compounds selected from the group consisting of the following Chemical Formulas 5 to 7.

[Chemical Formula 5]

[Formula 6]

[Formula 7]

(In Chemical Formulas 5 to 7,

R ₁₀ to R ₁₃ may be the same or different from each other, and may be each independently selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group,

N ₄ , n ₆ , and n ₇ may be an integer of 1 to 4, n ₅ may be an integer of 1 to 3,

A ₂ is O, CRR ′, CO, CONH, S, SO ₂ , And it may be selected from the group consisting of a single bond, the R And R ′ may be the same or independently selected from the group consisting of a substituted or unsubstituted alkyl group, hydrogen, and a fluoroalkyl group.)

It is located in at least one terminal portion of the polybenzoxazole precursor, the hydrophilic properties before heat curing to increase the developability, the terminal functional group is changed to a thermopolymerizable functional group during thermosetting aliphatic carboxylic acid derivative having one or more alkoxy groups Can be derived from. The alkoxy group of the aliphatic carboxylic acid is converted to a carbon-carbon double bond or triple bond through thermal curing to form a reactive functional group.

In addition, the aliphatic carboxylic acid derivative is preferably a carboxylic acid derivative in an activated form for efficiently reacting with the terminal of the polybenzoxazole precursor, and examples thereof include carboxylic acid halide derivatives.

Specific examples of the carboxylic acid halide derivative include a compound represented by the following Chemical Formula 8 including lactic aicd chloride substituted with an aliphatic ether, and tataric acid chloride substituted with an aliphatic or alicyclic ether. To the compounds of the formulas (9) and (10), and the compound of the formula (11) including glyceric acid chloride substituted with an alicyclic ether, and the like, and the like.

[Formula 8]

(In Formula 8,

R ₁₄ is an alkyl or alkoxy alkyl group having 1 to 5 carbon atoms,

n ₈ is 0 or 1)

[Formula 9]

(In Chemical Formula 9)

R ₁₅ , R ₁₆ , and R ₁₇ are the same or different from each other, each independently represent an alkyl group or alkoxy alkyl group having 1 to 5 carbon atoms,

n ₉ and n ₁₀ are each independently 0 or 1.)

[Formula 10]

(In Chemical Formula 10,

R ₁₈ to R ₂₀ are the same or different from each other, and each independently hydrogen or an alkyl group having 1 to 5 carbon atoms,

n ₁₁ and n ₁₂ are each independently 0 or 1.)

[Formula 11]

(In Chemical Formula 11,

R ₂₁ And R ₂₂ is hydrogen or an alkyl group having 1 to 5 carbon atoms.)

The terminal functional groups are crosslinked after being transformed into thermally polymerizable functional groups upon thermal curing.

The thermopolymerizable functional group derived from the compound of Formula 8 may be a compound of Formulas 12 and 13, and the thermosynthetic functional group derived from the compound of Formula 9 may be a compound of Formulas 14 and 15, The thermopolymerizable functional group derived from the compound of Formula 10 may be a compound of Formula 16 to 18, and the thermopolymerizable functional group derived from the compound of Formula 11 may be a compound of Formula 19.

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

In addition, the terminal functional group is a monocarboxylic acid halide capable of thermal polymerization From mixtures with terminal blockade monomers. Specific examples of the monocarboxylic acid halide include 5-norbornene-2-carboxylic acid halide of formula 20, 4-namidido benzoyl halide of formula 21, 4- (4-phenylethynylphthalimide of formula 22 Benzoyl halide, 4- (2-phenylmaleimido) benzoyl halide of formula (23), and the like. In addition, these can be used individually or in mixture with each other.

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

As described above, when an aliphatic carboxylic acid derivative having at least one alkoxy group is mixed with a carboxylic acid halide capable of thermal polymerization, the aliphatic carboxylic acid derivative is preferably used at 40 mol% or more. When the content of the aliphatic carboxylic acid derivative is in the above range, the addition effect can be properly expressed.

The polybenzoxazole precursor has a weight average molecular weight (Mw) in the range of 3,000 to 300,000, and sufficient physical properties are obtained within the above range, and excellent in solubility in an organic solvent is preferred for easy handling.

(B) photosensitive Diazoquinone  compound

As the photosensitive diazoquinone compound, a compound having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure can be preferably used. This is a material known from US Pat. Nos. 2,772,975, 2,797,213 and 3,669,658.

Representative examples of the photosensitive diazoquinone compound include, but are not limited to, a compound represented by the following Chemical Formulas 24 to 28.

[Formula 24]

(In Chemical Formula 24,

R ₃₁ to R ₃₃ 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,

Q may be hydrogen, Formula 25-1 or 25-2, wherein Q may not be hydrogen at the same time,

N ₃₁ To n ₃₃ are the same or different from each other, and each independently an integer of 1 to 3.)

[Formula 25a]

[Formula 25b]

[Formula 26]

(In Formula 26,

R ₃₄ is hydrogen or a substituted or unsubstituted alkyl group, D ₄ to D ₆ may be OQ,

Q is the same as defined in Formula 24,

N ₃₄ to n ₃₆ are the same or different from each other, and each independently an integer of 1 to 3.)

[Formula 27]

(In Chemical Formula 27,

A ₃ may be CO or CRR ′ and R is 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 ₁₀ are the same or different from each other, and each independently may be hydrogen, a substituted or unsubstituted alkyl group, OQ, or NHQ,

Q is the same as defined in Formula 24,

N ₃₇ , n ₃₈ , n ₃₉ , and n ₄₀ are the same or different from each other, and each independently an integer of 1 to 4,

n ₃₇ + n ₃₈ and n ₃₉ + n ₄₀ may be each independently an integer of 5 or less,

However, at least one of D ₇ to D ₈ may be OQ, one aromatic ring may include 1 to 3 OQs, and the other aromatic ring may include 1 to 4 OQs.)

[Formula 28]

(In Chemical Formula 28,

R ₃₅ to R ₄₂ may be the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

n ₄₁ and n ₄₂ 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, Q is the same as defined in formula (24).)

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 polybenzoxazole precursor. When the content of the photosensitive diazoquinone compound is within the above range, the pattern is well formed without residue by exposure, and there is no film thickness loss during development, and a good pattern can be obtained.

(C) Silane  compound

The said silane compound can improve the adhesive force of the photosensitive resin composition and a board | substrate.

As the silane compound, those represented by the following Chemical Formula 29 may be used.

[Formula 29]

In Chemical Formula 29,

R ₆₁ 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 ₆₂ to R ₆₄ 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 ₆₂ to R ₆₄ Is an alkoxy group or halogen, preferably the alkoxy group is an alkoxy group having 1 to 8 carbon atoms, 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-methacryloxypropylmethyldi Ethoxysilane; 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.

[Formula 30]

(In Chemical Formula 30,

R ₆₅ is NH ₂ or CH ₃ CONH, R ₆₆ to R ₆₈ are the same or different from each other, each independently represent a substituted or unsubstituted alkoxy group, preferably the alkoxy group is OCH ₃ or OCH ₂ CH ₃ And n ₆₁ may be an integer of 1 to 5.)

[Formula 31]

(In Chemical Formula 31,

R ₆₉ to R ₇₂ 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 ₇₃ and R ₇₄ 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 ₆₂ and n ₆₃ may be the same or different from each other, and may each independently 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 first polybenzoxazole precursor. When the content of the silane compound is included in the above range, the adhesion to the upper and lower membrane layers is excellent, and no residual film is left after development, and the optical properties (transmittance) and mechanical properties of the membrane such as tensile strength, elongation, and Young's modulus are improved. It is preferable to be able.

(D) phenolic compounds

The phenolic compound increases the dissolution rate and sensitivity of the exposed portion when developing with aqueous alkali solution, and also helps to pattern at high resolution without developing scum.

Representative examples of such phenolic compounds include 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, and the like. However, the present invention is not limited thereto.

Representative examples of the phenolic compound include those represented by the following Chemical Formulas 32 to 38 or Or combinations thereof, but is not limited thereto.

[Formula 32]

(In Chemical Formula 32,

R ₉₁ to R ₉₃ are the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

R ₉₄ to R ₉₈ 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 ₉₁ may be an integer from 1 to 5.

[Formula 33]

(In Chemical Formula 33,

R ₉₉ to R ₁₀₄ 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 ₄ 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 ₉₂ + n ₉₃ + n ₉₄ And n ₉₅ + n ₉₆ + n ₉₇ are the same or different from each other, and each independently may be an integer of 5 or less.)

[Formula 34]

(In Chemical Formula 34,

R ₁₀₅ to R ₁₀₇ may be the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

N ₉₈ , n ₉₉ , and n ₁₀₂ may be the same or different from each other, and each independently an integer of 1 to 5,

N ₁₀₁ and n ₁₀₂ may be the same or different from each other, and may each independently be an integer of 0 to 4.)

[Formula 35]

(In Chemical Formula 35,

R ₁₀₈ R ₁₁₃ to the same or different from each other, each independently may be selected from the group consisting of hydrogen, OH, and a substituted or unsubstituted alkyl group,

n ₁₀₃ to n ₁₀₆ are the same or different from each other, and each independently may be an integer of 1 to 4,

N ₁₀₃ + n ₁₀₅ and n ₁₀₄ + n ₁₀₆ are each independently an integer of 5 or less.)

[Formula 36]

(In Formula 36,

R ₁₁₄ may be a substituted or unsubstituted alkyl group, preferably CH ₃ ,

R ₁₁₅ to R ₁₁₇ are the same or different from each other, and may each independently be hydrogen or a substituted or unsubstituted alkyl group,

n ₁₀₅ , n ₁₀₇ , and n ₁₀₉ are the same or different from each other, and each independently may be an integer of 1 to 5,

n ₁₀₆ , n ₁₀₈ , and n ₁₁₀ are the same or different from each other, and each independently may be an integer of 0 to 4,

Provided that n ₁₀₅ + n ₁₀₆ , n ₁₀₇ + n ₁₀₈ , and n ₁₀₉ + n ₁₁₀ are each independently an integer of 5 or less.)

[Formula 37]

(In Chemical Formula 37,

R ₁₁₈ , R ₁₁₉ , and R ₁₂₀ are the same or different from each other, and may each independently be a substituted or unsubstituted alkyl group, preferably CH ₃ ,

R ₁₂₁ to R ₁₂₄ may be the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

n _{111 ,} n ₁₁₃ , and n ₁₁₇ are the same or different from each other, and each independently may be an integer from 1 to 5,

n ₁₁₂ , n ₁₁₄ , and n ₁₁₆ are the same or different from each other, and each independently may be an integer of 0 to 4,

n ₁₁₅ may be an integer from 1 to 5,

Provided that n ₁₁₁ + n ₁₁₂ , n _{113 +} n ₁₁₄ , and n ₁₁₆ + n ₁₁₇ are each independently an integer of 5 or less.)

[Formula 38]

(In Chemical Formula 38)

R ₁₂₅ may be selected from the group consisting of an alkyl group, an aryl group, and a vinyl group.)

The phenolic compound is preferably used in 1 to 30 parts by weight based on 100 parts by weight of polyamide polymer. When the content of the phenol group-containing compound is in the above range, it does not cause a decrease in sensitivity during development, and moderately increases the dissolution rate of the non-exposed part to obtain a good pattern, and does not cause precipitation during freezing storage, and thus excellent storage stability It is preferable because it can show.

(E) Solvent

As the solvent, 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, etc. are mentioned. The solvents may be used alone or in combination of two or more thereof.

The solvent may be used in an amount of 200 to 900 parts by weight based on 100 parts by weight of the (A) polybenzoxazole precursor. In the said range, the film | membrane of sufficient thickness can be formed and it is preferable because it is excellent in solubility and coating property.

(F) other additives

The photosensitive resin composition of this invention can further contain other additives (F) other than the component of (A)-(D).

The other additives include heat latent acid generators. As the heat latent acid generator, allyl sulfonic acid, perfluoroalkyl sulfonic acid, or alkyl sulfonic acid may be used. Preferably, the allyl sulfonic acid may include p-toluene sulfonic acid or benzene sulfonic acid, and the perfluoroalkyl sulfonic acid may include trifluoromethane sulfonic acid or fluorobutane sulfonic acid, and the alkyl sulfonic acid may be methane sulfonic acid, ethane sulfonic acid, or Butane sulfonic acid. The heat latent acid generator may prevent a phenomenon in which the structure of the phenolic hydroxyl group-containing polyamide of the polybenzoxazole precursor causes a dehydration reaction and decreases the degree of cyclization even when the curing temperature is lowered as a cyclization catalyst.

In addition, a suitable surfactant or leveling agent may be further used as an additive to prevent staining of the film thickness or to improve developability. Said other additive can be used individually or in mixture of 2 or more types.

The process of forming a pattern using the positive photosensitive resin composition of this invention is a process of apply | coating a positive photosensitive resin composition on a support substrate; Drying the applied composition to form a photosensitive polybenzoxazole precursor film; Exposing the polybenzoxazole precursor film; Developing the exposed polybenzoxazole precursor film with an aqueous alkali solution to produce a photosensitive resin film; And heating the photosensitive resin film. Process conditions for applying the photosensitive resin composition, exposing and developing the pattern, and the like are well known in the art, and thus detailed descriptions thereof will be omitted.

In addition, a photosensitive resin film such as a photosensitive insulating film or a protective film manufactured by using the photosensitive resin composition may be provided.

In addition, another embodiment of the present invention relates to a semiconductor device comprising a photosensitive resin film prepared using the photosensitive resin composition. The composition of the present invention can be usefully used for insulating films, protective layers, buffer coating layers, and the like of semiconductor devices. That is, the photosensitive resin composition of this invention can also be usefully used also as a surface protection film and an interlayer insulation film of a semiconductor device.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the following Examples and Comparative Examples are for illustrative purposes only and are not intended to limit the present invention.

< Synthetic example  1>: Polybenzoxazole  Precursor ( PA Synthesis of -1)

Passing nitrogen through a four-necked flask equipped with a stirrer, temperature controller, nitrogen gas injector and cooler 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3, -hexaflouropropane 17.4 g, 1,3-bis (aminopropyl) tetramethyldisiloxane 0.86 g was added, and 280 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 is completely dissolved, 9.9 g of pyridine is added and 13.3 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 reaction was carried out for 1 hour by raising the temperature to room temperature.

1.6 g of (2,2-dimethyl) -1,3-dioxolane-4-carbonyl chloride was added thereto, followed by stirring at 70 ° C for 24 hours to terminate the reaction. 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. A polybenzoxazole precursor (PA-1) having a weight average molecular weight (Mw) of 11,000 was prepared by drying at a temperature of 80 ° C. under vacuum for at least 24 hours.

< Synthetic example  2>: Polybenzoxazole  Precursor ( PA -2) synthesis

1.6 g of (2,2-dimethyl) -1,3-dioxolane-4-carbonyl chloride; 1.28 g of (2,2-dimethyl) -1,3-dioxolane-4-carbonyl chloride and 4-namidido A polybenzoxazole precursor (PA-2) was prepared in the same manner as in Synthesis example 1 except for changing to 0.59 g of benzoyl chloride.

< Synthetic example  3>: Polybenzoxazole  Precursor ( PA -3) synthesis

1.6 g of (2,2-dimethyl) -1,3-dioxolane-4-carbonyl chloride; 0.8 g of (2,2-dimethyl) -1,3-dioxolane-4-carbonyl chloride and 4-namidido A polybenzoxazole precursor (PA-3) was prepared in the same manner as in Synthesis example 1 except for changing to 1.47 g of benzoyl chloride.

< Synthetic example  4>; Polybenzoxazole  Precursor ( PA Synthesis of -4)

1.6 g of (2,2-dimethyl) -1,3-dioxolane-4-carbonyl chloride, 0.64 g of (2,2-dimethyl) -1,3-dioxolane-4-carbonyl chloride and 4-namidido A polybenzoxazole precursor (PA-4) was prepared in the same manner as in Synthesis example 1 except for changing to 1.76 g of benzoyl chloride.

< Synthetic example  5>: Polybenzoxazole  Precursor ( PA -5) synthesis

1.6 g of (2,2-dimethyl) -1,3-dioxolane-4-carbonyl chloride, 0.32 g of (2,2-dimethyl) -1,3-dioxolane-4-carbonyl chloride and 4-namidido A polybenzoxazole precursor (PA-5) was prepared in the same manner as in Synthesis example 1 except for changing to 2.35 g of benzoyl chloride.

< Synthetic example  6>: Polybenzoxazole  Precursor ( PA -6) synthesis

Polybenzoxazole was prepared in the same manner as in Synthesis Example 1 except that 1.6 g of (2,2-dimethyl) -1,3-dioxolane-4-carbonyl chloride was changed to 2.94 g of 4-namidido benzoyl chloride. Precursor (PA-6) was prepared.

< Example  1>

10 g of the polybenzoxazole precursor (PA-1) obtained in Synthesis Example 1 was dissolved in 35.0 g of γ-butyrolactone (GBL), followed by melting 1 g of photosensitive diazoquinone of formula 24a and trimethoxy [3] of formula 29a. A positive photosensitive polybenzoxazole precursor composition was prepared by dissolving 0.02 g of-(phenylamino) propyl] silane and 0.5 g of ethylresorcinol, followed by dissolving with a 0.45 μm fluorine resin filter.

[Formula 24a]

(In the above formula, two of Q ₁ , Q ₂ , and Q ₃ are substituted with the following Formula 25a, and the other is hydrogen.)

[Formula 25a]

[Formula 29a]

< Example  2>

A positive type was carried out in the same manner as in Example 1 except that 10 g of the polybenzoxazole precursor (PA-1) obtained in Synthesis Example 1 was changed to 10 g of the polybenzoxazole precursor (PA-2) obtained in Synthesis Example 2. A photosensitive polybenzoxazole precursor composition was prepared.

<Example 3>

Positive type in the same manner as in Example 1 except that 10 g of the polybenzoxazole precursor (PA-1) obtained in Synthesis Example 1 was changed to 10 g of the polybenzoxazole precursor (PA-3) obtained in Synthesis Example 3. A photosensitive polybenzoxazole precursor composition was prepared.

< Example  4>

Positive in the same manner as in Example 1 except that 10 g of the polybenzoxazole precursor (PA-1) obtained in Synthesis Example 1 was changed to 10 g of the polybenzoxazole precursor (PA-4) obtained in Synthesis Example 4. A type photosensitive polybenzoxazole precursor composition was prepared.

< Comparative example  1>

A positive type was carried out in the same manner as in Example 1 except that 10 g of the polybenzoxazole precursor (PA-1) obtained in Synthesis Example 1 was changed to 10 g of the polybenzoxazole precursor (PA-6) obtained in Synthesis Example 6. A photosensitive polybenzoxazole precursor composition was prepared.

<Measurement of properties>

(1) film thickness variation, sensitivity, resolution, shrinkage rate measurement

Each of the photosensitive polybenzoxazole precursor compositions prepared in Examples 1 to 4 and Comparative Example 1 was coated on an 8-inch wafer with a Mikasa spin coater and applied, followed by 130 ° C. on a hot plate. It heated for 2 minutes and formed the photosensitive polyimide precursor film.

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

The resolution of the finished film pattern could be confirmed through an optical microscope, and the film thickness change after preliminary firing, development, and curing was measured using a KMAC (ST4000-DLX) device.

On the other hand, the reduction rate of the film thickness after development has an effect on the developability and the final film thickness, and the film thickness reduction should be small even during development, and the prebaked film was measured to be 2.38% tetramethylammonium hydroxide ( TMAH) was immersed in an aqueous solution over time and washed with water, and the thickness change was measured and summarized in Table 1 below.

After exposure and development, the sensitivity was obtained by determining an exposure time in which a 10 um L / S pattern was formed with a line width of 1 to 1, which was the optimum exposure time, and the resolution was the minimum pattern dimension in the optimum exposure time as the resolution.

Further, 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. Compared with the film thickness before curing, the thickness of the film after curing is considerably reduced. At this time, the film thickness after curing is very important in order that the film after curing can act as a buffer coating layer, an interlayer insulating film, and a surface protective film. Therefore, the smaller the film thickness change before and after curing, the better. This degree is expressed as a percentage of shrinkage, which is a percentage of the difference between the film thickness before baking and the film thickness after baking, and the measurement of the film thickness was measured using a KMAC (ST4000-DLX) equipment, and the results are shown in Table 1 below. .

TABLE 1

Thickness (㎛)
Sensitivity
(mJ / cm ² )

resolution
(Μm)

Development
Change of film thickness
(Μm)

Shrinkage
(%)

Preliminary firing
After phenomenon
After thermosetting Example 1 9.3 8.0 6.24 240 3.5 1.3 22 Example 2 9.5 8.2 6.48 250 3 1.3 21 Example 3 9.3 8.1 6.32 270 3 1.2 22 Example 4 9.3 8.1 6.32 250 3.5 1.2 22 Comparative Example 1 9.1 7.7 5.93 340 5 1.4 23

Referring to Table 1 above, the photosensitive resin compositions of Examples 1 to 4 including polybenzoxazole precursors containing terminal functional groups which are hydrophilic before thermosetting and hydrophilic, but which change into thermopolymerizable functional groups after thermal curing are compared. As compared with the photosensitive resin composition of Example 1, it was confirmed that the sensitivity, the resolution, and the shrinkage ratio were excellent.

(2) mechanical strength measurement

In order to measure the mechanical strength of the film after curing, the silicon wafer covered with the curing film was soaked in 2% HF solution for 30 minutes to separate the film, and then cut into a ribbon piece of 6.0 cm × 1.0 cm to measure mechanical properties. Specimen was prepared. The specimens were measured for mechanical properties such as tensile strength, elongation, and Young's modulus using a universal testing machine (instrom series IX), and the results are shown in Table 2 below.

TABLE 2

Tensile Strength (kgf / mm ² )
Elongation (%)

Young's modulus (kgf / mm ² ) Example 1 12.0 71 230 Example 2 11.7 74 220 Example 3 12.5 70 225 Example 4 12.1 71 235 Comparative Example 1 12.1 72 230

Referring to Table 2 above, the film obtained by thermosetting the photosensitive resin compositions of Examples 1 to 4 has the same mechanical level as compared with the comparative example using the polybenzoxazole precursor having a terminal functional group known to have excellent mechanical properties. It could be confirmed that the physical properties.

Therefore, the photosensitive resin composition of the present invention is excellent in mechanical properties, and particularly excellent in optical properties such as sensitivity, resolution, patternability, and the like, and thus can be manufactured as a photosensitive resin film having excellent mechanical strength and good patternability.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited thereto, and various modifications and changes can be made within the scope of the claims and the detailed description of the invention and the accompanying drawings. Naturally, it belongs to the scope of the invention.

Claims (9)

delete delete delete (A) A polybenzoxazole precursor having a repeating unit represented by the following formula (1), which has hydrophilicity at least on one end portion thereof before hydrosetting to improve developability, and has a terminal functional group which is changed into a thermopolymerizable functional group during thermosetting. (Polybenzoxazole precursor); (B) photosensitive diazoquinone compound; (C) silane compound; (D) phenolic compounds; And (E) solvent Including, Positive terminal photosensitive resin composition wherein the terminal functional group is derived from an aliphatic carboxylic acid derivative represented by the following formulas (8) to (11): [Formula 1]

In Chemical Formula 1, X ₁ is an aromatic organic group or a 4 to 6-valent aliphatic organic group, X ₂ is an aromatic organic group or a 2 to 6-valent aliphatic organic group, or a functional group having a structure represented by the following Chemical Formula 2, Y ₁ and Y ₂ are the same or different from each other, and each independently an aromatic organic group or a 2 to 6-valent aliphatic organic group, M ₁ and m ₂ are molar ratios, m ₁ + m ₂ is 100 mol%, M ₁ is 60 to 100 mol%, M ₂ may be 0 to 40 mol%, [Formula 2]

In Chemical Formula 2, R ₁ to R ₂ are the same or different from each other, and each independently selected from the group consisting of a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, and a hydroxy group, R ₃ and R ₄ are the same or different from each other, and each independently a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group, k is an integer from 1 to 50, [Formula 8]

In Chemical Formula 8, R ₁₄ is an alkyl or alkoxy alkyl group having 1 to 5 carbon atoms, n ₈ is 0 or 1, [Formula 9]

In Chemical Formula 9 R ₁₅ , R ₁₆ , and R ₁₇ are the same or different from each other, each independently represent an alkyl group or an alkoxy alkyl group having 1 to 5 carbon atoms, n ₉ and n ₁₀ are each independently 0 or 1, [Formula 10]

In Chemical Formula 10, R ₁₈ to R ₂₀ are the same or different from each other, and each independently hydrogen or an alkyl group having 1 to 5 carbon atoms, n ₁₁ and n ₁₂ are each independently 0 or 1, [Formula 11]

In Chemical Formula 11, R ₂₁ and R ₂₂ are hydrogen or an alkyl group having 1 to 5 carbon atoms. The method of claim 4, wherein The polybenzoxazole precursor has a weight average molecular weight (Mw) of 3,000 to 300,000 positive type photosensitive resin composition. The method of claim 4, wherein 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-methoxy propionate and combinations thereof. The method of claim 4, wherein The resin composition, Based on 100 parts by weight of the (A) polybenzoxazole precursor 5 to 100 parts by weight of the (B) photosensitive dizoquinone compound; Always (C) 0.1 to 30 parts by weight of the silane compound; 1 to 30 parts by weight of the (D) phenol compound; And 200 to 900 parts by weight of the solvent (F) Positive photosensitive resin composition comprising a. The photosensitive resin film formed using the positive photosensitive resin composition of any one of Claims 4-7. The semiconductor element containing the photosensitive resin film of Claim 8.