KR100965549B1 - Positive photosensitive resin composition - Google Patents

Abstract

The present invention relates to a positive type photosensitive resin composition, wherein the positive type photosensitive resin composition (A) has a repeating unit represented by the following general formula (1), and has a polybenzoxazole precursor having a thermopolymerizable functional group on at least one end portion thereof. (polybenzoxazole precursor); (B) photosensitive diazoquinone compound; (C) silane compound; (D) phenolic compounds; (E) cardo-based resin comprising a repeating unit represented by the following formula (3); And (F) a solvent.

[Formula 1]

(3)

(In Formulas 1 and 3, the definition of each substituent is the same as defined in the specification.)

 Positive type, photosensitive polybenzoxazole precursor composition, dissolution regulator, thermal polymerization crosslinking agent, aqueous alkali solution, semiconductor device

Description

Positive photosensitive resin composition {POSITIVE PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a positive type photosensitive resin composition, and more particularly, has a high sensitivity and high resolution, a good pattern shape, a high residue removal property, a low film shrinkage rate, in particular a positive mechanical property after thermal curing It relates to a type photosensitive resin composition.

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 are recently used in the form of a photosensitive polyimide precursor composition 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. The surface protective film, the interlayer insulating film and the like can be easily formed. Therefore, compared with the conventional non-photosensitive polyimide precursor composition, it has the characteristic that the process shortening is large.

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 is 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, 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 often fall below an appropriate level, and 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 degradation, foaming during coating, and the like, the level of practical use has not been reached.

In addition, due to the properties of these compositions that must remain as a surface protective film on the surface of the semiconductor, these thermosetting films should be particularly excellent in hygroscopicity and chemical resistance. The polyimide and polybenzoxazole thermosets used generally show some degree of hygroscopicity and chemical resistance, but are still of practical value for polybenzoxazole and polyimide precursors made using terminal block monomers. Are not obtained.

The present invention prevents the deterioration of optical properties, in particular the deterioration of sensitivity, resolution, and pattern shape due to the problem of fine step occurring when coating polyimide or polybenzoxazole precursor on a substrate, and also the mechanical properties of the film after curing. To provide a photosensitive resin composition that can be further improved.

This invention also provides the produced photosensitive resin film using the said positive photosensitive resin composition.

This invention also provides the semiconductor element containing the photosensitive resin film manufactured using the said 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) a polybenzoxazole precursor having a repeating unit represented by the following formula (1) and having a thermopolymerizable functional group in at least one terminal portion (B) photosensitive diazoquinone compound; (C) silane compound; (D) phenolic compounds; (E) cardo-based resin having a repeating unit represented by the following formula (3); And (F) it provides a positive photosensitive resin composition containing 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, 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 the molar ratios of

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.)

(3)

(In Chemical Formula 3,

R ₂₄ to R ₂₇ are the same or different from each other, and each independently selected from the group consisting of a hydrogen atom, a halogen atom, and a substituted or unsubstituted alkyl group,

R ₂₈ and R ₂₉ are the same or different from each other, and are each independently selected from the group consisting of a hydrogen atom and CH ₂ OR _a (R _a is a vinyl group, an acryl group, or a methacryl group),

R ₃₀ are the same or different from each other, and each independently selected from the group consisting of a hydrogen atom, an alkyl group, an acryl group, a vinyl group, and a methacryl group,

Z ₁ is the same or different from each other, and each independently CO, SO ₂ , CR _b R _c , SiR _d R _e (wherein R _b to R _e are the same or different from each other, and each independently hydrogen, fluoroalkyl group And, it is selected from the group consisting of an alkyl group), O, a single bond, and selected from the group consisting of compounds represented by the following formula 39 to 49,

Z ₂ is the same or different from each other, and each independently a residue of an acid anhydride or acid dianhydride.)

[Formula 39]

[Formula 40]

[Formula 41]

[Formula 42]

[Formula 43]

(In Chemical Formula 43,

R _f is selected from the group consisting of a hydrogen atom, an ethyl group, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH═CH ₂ , and a phenyl group)

[Formula 44]

[Formula 45]

[Formula 46]

[Formula 47]

[Formula 48]

[Formula 49]

According to another embodiment of the present invention, there is provided a photosensitive resin film formed using the positive photosensitive resin composition.

According to another embodiment of the invention provides 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 the terminal blockade monomer which has a suitable reactivity and structure in the molecular chain terminal, and coats a polyimide or polybenzoxazole precursor on a board | substrate using the cardo resin which has a suitable structure as an additive. It is possible to prevent the degradation of optical characteristics, in particular the deterioration of sensitivity, resolution, and pattern shape, due to the problem of fine step that occurs. In addition, after curing, the film can obtain improved mechanical properties, good residue removal properties and low film shrinkage.

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.

Positive type photosensitive resin composition according to an embodiment of the present invention (A) a polybenzoxazole precursor having a repeating unit represented by the following formula (1), having a thermopolymerizable functional group in at least one terminal portion; (B) photosensitive diazoquinone compound; (C) silane compound; (D) phenolic compounds; (E) cardo-based resin having a repeating unit represented by the following formula (3); And (F) 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, 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 the molar ratios of

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.)

(3)

(In Chemical Formula 3,

R ₂₄ to R ₂₇ are the same or different from each other, and each independently selected from the group consisting of a hydrogen atom, a halogen atom, and a substituted or unsubstituted alkyl group,

R ₂₈ and R ₂₉ are the same or different from each other, and are each independently selected from the group consisting of a hydrogen atom and CH ₂ OR _a (R _a is a vinyl group, an acryl group, or a methacryl group),

R ₃₀ are the same or different from each other, and each independently selected from the group consisting of a hydrogen atom, an alkyl group, an acryl group, a vinyl group, and a methacryl group,

Z ₁ is the same or different from each other, and each independently CO, SO ₂ , CR _b R _c , SiR _d R _e (wherein R _b to R _e are the same or different from each other, and each independently hydrogen, fluoroalkyl group , And an alkyl group), O, a single bond, and a compound represented by the following Chemical Formulas 39 to 49,

Z ₂ is the same or different from each other, and each independently an acid anhydride or a residue of an acid dianhydride.)

[Formula 39]

[Formula 40]

[Formula 41]

[Formula 42]

[Formula 43]

(In Chemical Formula 43,

R _f is selected from the group consisting of a hydrogen atom, an ethyl group, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH═CH ₂ , and a phenyl group)

[Formula 44]

[Formula 45]

[Formula 46]

[Formula 47]

[Formula 48]

[Formula 49]

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

In the present specification, unless otherwise specified, "alkyl group" means an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and "cycloalkyl group" means a cycloalkyl group having 3 to 30 carbon atoms. It means more preferably a cycloalkyl group having 3 to 18 carbon atoms, "alkoxy group" means an alkoxy group having 1 to 30 carbon atoms, more preferably means an alkoxy group having 1 to 18 carbon atoms, "aryl Group ”means an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 18 carbon atoms, and“ alkenyl group ”means an alkenyl group having 2 to 30 carbon atoms, and more preferably 2 to 30 carbon atoms. Mean an alkenyl group of 18, "alkylene group" means an alkylene group having 1 to 30 carbon atoms, more preferably means an alkylene group having 1 to 18 carbon atoms, "arylene Means an arylene group having 6 to 30 carbon atoms, more preferably an arylene group having 6 to 18 carbon atoms, and an "alicyclic group" means an alicyclic group having 3 to 40 carbon atoms, more preferably Means an alicyclic group having 3 to 24 carbon atoms.

Hereinafter, each component of the photosensitive resin composition according to one embodiment of the present invention will be described in detail.

( A) polybenzoxazole precursor

The polybenzoxazole precursor has a repeating unit represented by the following formula (1) and has a thermopolymerizable functional group at at least one end thereof.

[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, 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 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.)

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.

In addition, preferably X ₁ may be a compound represented by the following formula (4) or (5).

[Formula 4]

[Chemical Formula 5]

(In Chemical Formulas 4 and 5,

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 substituted or unsubstituted alkyl group, preferably R ₈ and R ₉ is a fluoroalkyl group,

R ₅ to R ₇ 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 of 1 or 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 may also be derived from aromatic diamines, silicone diamines, and cycloaliphatic 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- Naphthalenediamine, 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, but is not limited thereto.

Specific examples of the alicyclic diamine include, but are not limited to, cyclohexyldiamine, methylenebiscyclohexylamine, and the like.

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

Specific examples of the dicarboxylic acid derivative include an active compound which is a carbonyl halide derivative or an active ester derivative obtained by reacting dicarboxylic acid with 1-hydroxy-1,2,3-benzotriazole. 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 Compounds and the like.

In addition, it is preferable that Y ₁ and Y ₂ are compounds selected from the group consisting of the following Chemical Formulas 6 to 8.

[Formula 6]

[Formula 7]

[Formula 8]

(In Chemical Formulas 6 to 8,

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, CR ₁₄ R ₁₅ , CO, CONH, S, SO ₂ , And it may be selected from the group consisting of a single bond, the R ₁₄ and R ₁₅ may be selected from the same or independently selected from the group consisting of a substituted or unsubstituted alkyl group, hydrogen, and fluoroalkyl group.)

The polybenzoxazole precursor has a thermopolymerizable functional group derived from the terminal block monomer at either or both ends of the molecular chain terminal.

As the terminal blocking monomer, monoanhydrides or monocarboxylic acid halides may be used.

Specific examples of the monoanhydrides include 5-norbornene-2,3-dicarboxylic hydride represented by the following Chemical Formula 9, 3,6-epoxy-1,2, represented by the following Chemical Formula 10, 3,6-tetrahydrophthalic hydride or isobutenyl succinic hydride, maleic hydride, aconitic anhydride represented by the following formula (11), 3,4,5,6-tetra Hydrophthalic hydride (3,4,5,6-tetrahydrophthalic anhydride), cis-1,2,3,6, -tetrahydrophthalic anhydride (cis-1,2,3,6-tetrahydrophthalic anhydride ), Itaconic anhydride (IA), citraconicanhydride (CA), 2,3-dimethylmaleic anhydride (DMMA) And the like.

[Formula 9]

[Formula 10]

[Formula 11]

In addition, Chemical Formulas 12 to 16 are representative examples of the thermopolymerizable functional group bonded to the terminal of the polybenzoxazole precursor, and the thermopolymerizable functional group may be crosslinked in the heating process.

 [Formula 12]

(In Chemical Formula 12,

R ₁₆ is H, CH ₂ COOH, or CH ₂ CHCHCH ₃

[Formula 13]

(In Chemical Formula 13,

R ₁₇ and R ₁₈ are the same or different from each other, and each independently H or CH _3. )

[Formula 14]

[Formula 15]

(In Chemical Formula 15,

R ₁₉ is H or CH ₃ and R ₂₀ is CH ₂ or O.

[Formula 16]

(In Chemical Formula 16,

R ₂₁ and R ₂₂ are the same or independently of each other, H, CH ₃ or OCOCH _3. )

As the mono carboxylic acid halides, those represented by the following formula (17) can be used.

[Formula 17]

(In Formula 17,

R ₂₃ may be selected from a group consisting of a substituted or unsubstituted alicyclic group, and a substituted or unsubstituted aryl group,

The substituted alicyclic group or substituted aryl group is selected from the group consisting of a substituted or unsubstituted namidido group, a substituted or unsubstituted alicyclic group, a substituted or unsubstituted alicyclic group and an aryl group fused ring. It may be substituted with a substituent, wherein the alicyclic group is most preferably a maleimide group,

Z ₁ is F, Cl, Br, or I)

Specific examples of the monocarboxylic acid halides include 5-norbornene-2-carboxylic acid chloride represented by the following 18, 4-namidido benzoyl chloride represented by the following formula 19, and 4- (4-phenyl represented by the following formula 20: Ethynylphthalimido) benzoyl chloride, 4- (2-phenylmaleicimido) benzoyl chloride represented by the following formula 21, benzoyl chloride represented by the following formula 22, cyclo benzoyl chloride represented by the following formula 23, 4- (3-phenylethynylphthalimido) benzoyl chloride and 4-maleimido benzoyl chloride can be preferably used. These can also be used individually or in mixture with each other.

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

In the present invention, the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably in the range of 3,000 to 300,000. When the weight average molecular weight is in the above range, sufficient physical properties are obtained, solubility in organic solvents is high, and handling is preferable.

(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. It is a material known by US Pat. Nos. 2,772,975, 2,797,213, or 3,669,658, the contents of which are incorporated herein by reference.

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

[Formula 24]

(In Chemical Formula 24,

R ₃₁ to R ₃₃ may be the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group, preferably CH ₃ ,

D ₁ to D ₃ may be each independently OQ,

Q may be represented by hydrogen, Chemical Formula 25-1, or Chemical Formula 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 25-1]

[Formula 25-2]

[Formula 26]

(In Formula 26,

R ₃₄ is hydrogen or a substituted or unsubstituted alkyl group, and D ₄ to D ₆ may be each independently 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 loss of film thickness 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; Silane compounds having an aryl group such as trimethoxy [3- (phenylamino) propyl] silane; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyl trichlorosilane, vinyltris (β-methoxyethoxy) silane; Or 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryl trimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldi Silane compounds containing carbon-carbon unsaturated bonds, such as ethoxysilane, 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 polybenzoxazole precursor. When the content of the silane compound is in the above range, the adhesion with the upper and lower membrane layers is excellent, and since the residual film does not remain after development, the optical properties (transmittance) and mechanical properties such as tensile strength, elongation, and Young's modulus can be improved. .

(D) phenolic compounds

The phenol group-containing compound can increase the dissolution rate and sensitivity of the exposed portion during development with an aqueous alkali solution, and also serves to pattern at high resolution without a residue during development.

Specific examples of the phenolic compound may be represented by the following Chemical Formulas 32 to 38: Although these etc. are mentioned, It is not limited to these.

[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 may each independently 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 ₁₀₀ and n ₁₀₁ 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 to R ₁₁₃ 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 ₁₀₃ to n ₁₀₆ are the same or different from each other, and each independently may be an integer of 1 to 4,

Provided that 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 ₁₀₇ , n ₁₀₉ , and n ₁₁₁ are the same or different from each other, and each independently may be an integer of 1 to 5,

n ₁₀₈ , n ₁₁₀ , and n ₁₁₂ are the same or different from each other, and each independently may be an integer of 0 to 4,

Provided that n ₁₀₇ + n ₁₀₈ , n ₁₀₉ + n ₁₁₀ , and n ₁₁₁ + n ₁₁₂ 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 ₁₁₃ , n ₁₁₅ , and n ₁₁₈ are the same or different from each other, and each independently may be an integer of 1 to 5,

n ₁₁₄ , n ₁₁₆ , and n ₁₁₇ are the same or different from each other, and each independently may be an integer of 0 to 4,

n ₁₁₉ may be an integer from 1 to 4,

Provided that n ₁₁₃ + n ₁₁₄ , n ₁₁₅₊ n ₁₁₆ , and n ₁₁₇ + n ₁₁₈ 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 the polybenzoxazole precursor. When the content of the phenolic 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, thus showing excellent storage stability. It is preferable.

(E) cardo resin

The cardo-based resin is a polymer having a repeating unit represented by the following formula (3).

(3)

(In Chemical Formula 3,

R ₂₄ to R ₂₇ are the same or different from each other, and each independently selected from the group consisting of a hydrogen atom, a halogen atom, and a substituted or unsubstituted alkyl group,

R ₂₈ and R ₂₉ are the same or different from each other, and are each independently selected from the group consisting of a hydrogen atom and CH ₂ OR _a (R _a is a vinyl group, an acryl group or a methacryl group),

R ₃₀ are the same or different from each other, and each independently selected from the group consisting of a hydrogen atom, an alkyl group, an acryl group, a vinyl group, and a methacryl group,

Z ₁ is the same or different from each other, and each independently CO, SO ₂ , CR _b R _c , SiR _d R _e (wherein R _b to R _e are the same or different from each other, and each independently hydrogen, fluoroalkyl group And, it is selected from the group consisting of an alkyl group), O, a single bond, and selected from the group consisting of compounds represented by the following formula 39 to 49,

Z ₂ is the same or different from each other, and each independently an acid anhydride or a residue of an acid dianhydride.)

[Formula 39]

[Formula 40]

[Formula 41]

[Formula 42]

[Formula 43]

(In Chemical Formula 43,

R _f is selected from the group consisting of a hydrogen atom, an ethyl group, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH═CH ₂ , and a phenyl group)

[Formula 44]

[Formula 45]

[Formula 46]

[Formula 47]

[Formula 48]

[Formula 49]

The cardo-based resin may be obtained by reacting a cardo-based compound represented by Formula 50 with tetracarboxylic dianhydride.

[Formula 50]

It is preferable that the said tetracarboxylic dianhydride is aromatic tetracarboxylic dianhydride. Examples include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3 '-Biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylethertetracarboxylic dianhydride, 3,3', 4 , 4'-diphenylsulfontetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalene Tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2, 2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride and the like, but are not limited thereto.

The cardo-based resin is preferably used 0.1 to 5 parts by weight based on 100 parts by weight of the polybenzoxazole precursor. When the content of the cardo-based resin is in the above range, it is possible to obtain a flattening effect, to obtain an optical characteristic improvement effect such as sensitivity and patternability, and excellent adhesion and heat resistance of the film after curing.

The cardo-based resin increases the uniformity of the photosensitive resin composition including a high viscosity polyimide or polybenzoxazole precursor and enables flattening of the film obtained by partially relieving the surface tension of the compound during spin coating. . Due to the planarization effect, it is possible to eliminate the micro step generated when the existing composition is used, thereby preventing harmful effects such as diffuse reflection or refraction generated on the surface of the film during exposure. Therefore, effects such as high sensitivity, resolution, and patternability can be obtained. In addition, the film produced after thermal curing is more uniform than when using the existing composition, the mechanical properties of the film can be improved, and the acrylic functional group contained in the monomer of the cardo resin, crosslinked with the thermopolymerizable functional group at the end of the polybenzoxazole To further improve the mechanical properties.

(F) solvent

The solvent is an organic solvent, preferably N-methyl-2-pyrrolidone, gamma-butyrolactone, N, N-dimethyl acetate, 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. may be used, but the present invention is not limited thereto. The solvent may be used alone or in combination.

The solvent is preferably used in an amount of 200 to 900 parts by weight based on 100 parts by weight of the polybenzoxazole precursor. When the content of the solvent is in the above range, it is possible to coat a film of sufficient thickness, it is preferable because of excellent solubility and coating properties.

(G) other additives

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

The other additives include heat latent acid generators. Examples of the heat latent acid generator include allyl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid; Perfluoroalkyl sulfonic acids such as trifluoromethanesulfonic acid and fluorobutanesulfonic acid; Alkyl sulfonic acids such as methane sulfonic acid, ethane sulfonic acid, butane sulfonic acid; And mixtures thereof.

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

Moreover, in order to prevent the film | membrane of a film thickness, or to improve developability, you may further use a suitable surfactant or reveling agent as an additive.

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, etc. are well known in the art, so detailed description thereof will be omitted herein.

According to another embodiment of the present invention, there is provided a photosensitive resin film prepared using the positive photosensitive resin composition. Preferable examples of the photosensitive resin film include an insulating film or a protective film. In addition, according to another embodiment of the present invention, there is provided a semiconductor device comprising a photosensitive resin film prepared using the photosensitive resin composition of the present invention. 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, the present invention will be described in more detail with reference to Examples, but the following Examples are only preferred examples of the present invention, and the present invention is not limited to the following Examples.

Synthesis Example 1 Synthesis of Polybenzoxazole Precursor (PBO-1)

While passing nitrogen through a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injector, and a cooler 17.4 g of 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3, -hexaflouropropane and 1,3-bis (aminopropyl) tetramethyldi 0.86 g of siloxane was added and 280 g of N-methyl-2-pyrrolidone (NMP) was added to dissolve it. Solid content in the solution obtained at this time 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 5-norbornene-2,3-dicarboxylic hydride was added thereto, followed by stirring at 70 ° C for 24 hours to complete 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. It dried under the vacuum of 80 degreeC for more than 24 hours, and produced the polybenzoxazole precursor (PBO-1) which has a weight average molecular weight of 11,000.

≪ Example 1 >

10 g of the polybenzoxazole precursor (PBO-1) obtained in Synthesis Example 1 was dissolved in 35.0 g of γ-butyrolactone (GBL), followed by melting 1 g of photosensitive diazoquinone having the structure of Formula 24a, and a tree of Formula 29a. 0.02 g of methoxy [3- (phenylamino) propyl] silane, 0.5 g of ethylresorcinol, and 0.1 g of cardo-based resin (NSCC, V-259ME) were added and dissolved in a 0.45 µm fluorine resin filter. Filtration gave a positive photosensitive polybenzoxazole precursor composition.

[Formula 24a]

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

[Formula 25-1]

[Formula 29a]

<Example 2>

Except having changed the content of cardo resin to 0.5g, it carried out similarly to Example 1, and obtained the photosensitive resin composition.

<Example 3>

The photosensitive resin composition was obtained in the same manner as in Example 1 except that the content of the cardo resin was changed to 0.05 g.

<Example 4>

Except having changed content of cardo resin to 0.01g, it carried out similarly to Example 1, and obtained the photosensitive resin composition.

Comparative Example 1

Except not using a cardo resin, it carried out similarly to Example 1 and obtained the positive photosensitive resin composition.

Property measurement

The photosensitive polybenzoxazole precursor composition prepared in Examples 1 to 4 and Comparative Example 1 was coated on an 8 inch wafer using a Mikasa (1H-DX2) spin coater, and then applied at 130 ° C. on a hot plate. Heating for minutes gave a photosensitive polybenzoxazole 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 polybenzoxazole precursor film, 40 seconds in an aqueous solution of tetramethylammonium hydroxide at room temperature of 2.38%, The exposed portion was dissolved and removed through two puddles and washed with pure water for 30 seconds. Subsequently, the obtained pattern was cured at 150 ° C./30 minutes at an oxygen concentration of 1000 ppm or less, followed by 320 ° C./30 minutes using an electric furnace to prepare a film with a pattern.

Sensitivity was determined to be the optimal exposure time by obtaining an 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 the resolution was measured using the minimum pattern dimension at the optimum exposure time as the resolution. . The resolution could be confirmed through an optical microscope.

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) ) The method of immersing in an aqueous solution and rinsing with water was developed, and the change in film thickness over time was measured and shown in Table 1 below.

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 prepare a cured film. Compared with before curing, the film after curing is considerably reduced in thickness. 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. .

In addition, in order to measure the mechanical properties of the film after curing, the film-cured silicon wafer was immersed in a 2% HF solution for 30 minutes to separate the film, and then cut into a ribbon piece of 6.0 cm × 1.0 cm. Specimens were prepared for measurement. The specimens were measured for mechanical properties such as tensile strength, elongation, and Young's modulus with an universal material tester (instron series IX), and the results are shown in Table 1 below.

TABLE 1

Thickness (um)
Sensitivity
(mJ / cm ² )

resolution
(um)

Development
Film thickness change
(um)

Shrinkage (%)

Preliminary firing
After phenomenon
After thermosetting
Example 1
9.3
8.1
6.64
360
4
1.2
18%
Example 2
9.5
8.1
6.80
320
3
1.4
16%
Example 3
9.3
8.1
6.48
380
3
1.2
20%
Example 4
9.3
8.2
6.48
390
3.5
1.1
20%
Comparative Example 1
9.1
7.7
6.01
450
5
1.4
22%

Referring to Table 1, it was confirmed that the photosensitive resin compositions of Examples 1 to 4 containing cardo-based resins are excellent in optical properties such as sensitivity, resolution, film thickness change, shrinkage ratio, etc. as compared with Comparative Example 1.

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
10.9
42
209

Referring to Table 2, it was confirmed that the photosensitive resin composition of Examples 1 to 4 including cardo-based resin exhibits excellent mechanical properties compared to Comparative Example 1. In particular, it was confirmed that the very excellent elongation.

Therefore, it was confirmed that the photosensitive resin composition of the present invention is excellent in optical properties such as sensitivity, resolution, patternability, and the like, and can form a thick film having mechanical properties. That is, when the photosensitive resin composition of this invention was used, it was confirmed that the photosensitive resin film, such as a semiconductor interlayer insulation film or a surface protective film, which has a favorable pattern property and was excellent in mechanical property, can be formed.

The present invention has been described in detail with reference to preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications can be made by those skilled in the art within the scope of the technical idea of the present invention. Do.

Claims (6)

(A) a polybenzoxazole precursor having a repeating unit represented by the following formula (1) and having a thermopolymerizable functional group at at least one end thereof; (B) photosensitive diazoquinone compound; (C) silane compound; (D) phenolic compounds (E) cardo-based resin having a repeating unit represented by the following formula (3); And (F) solvent Positive photosensitive resin composition comprising a. [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, 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.) (3)

(In Chemical Formula 3, R ₂₄ to R ₂₇ are the same or different from each other, and each independently selected from the group consisting of a hydrogen atom, a halogen atom, and a substituted or unsubstituted alkyl group, R ₂₈ and R ₂₉ are the same or different from each other, and are each independently selected from the group consisting of a hydrogen atom and CH ₂ OR _a (R _a is a vinyl group, an acryl group or a methacryl group), R ₃₀ are the same or different from each other, and each independently selected from the group consisting of a hydrogen atom, an alkyl group, an acryl group, a vinyl group, and a methacryl group, Z ₁ is the same or different from each other, and each independently CO, SO ₂ , CR _b R _c , SiR _d R _e (wherein R _b to R _e are the same or different from each other, and each independently hydrogen, fluoroalkyl group And, it is selected from the group consisting of an alkyl group), O, a single bond, and selected from the group consisting of compounds represented by the following formula 39 to 49, Z ₂ is the same or different from each other, and each independently a residue of an acid anhydride or acid dianhydride.) [Formula 39]

[Formula 40]

[Formula 41]

[Formula 42]

[Formula 43]

(In Chemical Formula 43, R _f is selected from the group consisting of a hydrogen atom, an ethyl group, C ₂ H ₄ Cl, C ₂ H ₄ OH, CH ₂ CH═CH ₂ , and a phenyl group) [Formula 44]

[Formula 45]

[Formula 46]

[Formula 47]

[Formula 48]

[Formula 49]

The method of claim 1, The polybenzoxazole precursor is a positive photosensitive resin composition having 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-methoxy propionate and combinations thereof. The method of claim 1, The photosensitive diazoquinone compound is included in an amount of 5 to 100 parts by weight based on 100 parts by weight of the polybenzoxazole precursor, The silane compound is included in 0.1 to 30 parts by weight based on 100 parts by weight of the polybenzoxazole precursor, The phenolic compound is included in 1 to 30 parts by weight based on 100 parts by weight of the polybenzoxazole precursor, The cardo-based resin is included in 0.1 to 5 parts by weight based on 100 parts by weight of the polybenzoxazole precursor, The solvent is a positive photosensitive resin composition which is included in 200 to 900 parts by weight based on 100 parts by weight of the polybenzoxazole precursor. The photosensitive resin film formed using the positive photosensitive resin composition of any one of Claims 1-4. A semiconductor device comprising the photosensitive resin film of claim 5.