KR20100110580A - Positive type photosensitive resin composition - Google Patents

Abstract

PURPOSE: A positive photosensitive resin composition, a photosensitive resin film, and a semiconductor device using thereof are provided to secure the excellent sensitivity, resolution, and a residue elimination property of the composition. CONSTITUTION: A positive photosensitive resin composition includes a recurring unit marked with chemical formula 1, a polybenzoxazole precursor including a functional group induced from a substituted or non-substituted monoamine compound, a photosensitive diazoquinone compound, a silane compound, a phenolic compound, and a solvent. In the chemical formula 1, X is either an aromatic organo group or a tetravalent~hexavalent aliphatic organic group.

Description

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

The present substrate relates to a positive 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 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, 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 so soluble in alkali that the desired pattern is not obtained.

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 attracted attention, but when it is actually used, the amount of film reduction in unexposed portions during development is large. Therefore, it is difficult to obtain a desired pattern after development. In order to improve this problem, if the molecular weight of the polybenzoxazole precursor is increased, the film reduction amount of the unexposed part becomes small, but developing residue (scum) occurs in the exposed part during development, resulting in poor resolution and longer developing time of the exposed part. there was.

In order to solve this problem, it is reported that the amount of film reduction of unexposed portions during development is suppressed by adding a specific phenol compound to the polybenzoxazole precursor composition (Japanese Patent Laid-Open No. 9-302221 and Japanese Patent Laid-Open No. 2000). -292913). However, with 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.

In addition, the photosensitive polyimide / polybenzoxazole composition has a problem that the sensitivity is lower than that of the existing non-photosensitive polyimide / polybenzoxazole process, resulting in a long time required in the patterning process and inevitably decreases productivity. .

Since the sensitivity and the good patternability are in conflict, the methods for improving the sensitivity and the excellent residue removal property often have a decrease in the patternability, adversely affecting the reliability of the semiconductor device, and improving the patternability. Silver is accompanied by a decrease in sensitivity and generation of residues, and thus, there is a shortcoming in practical use as the productivity is lowered. Therefore, there is an urgent need for research on a photosensitive polyimide / polybenzoxazole composition capable of improving productivity by improving sensitivity and securing high reliability with good patternability.

One embodiment of the present invention is to provide a positive type photosensitive resin composition excellent in sensitivity, resolution, pattern shape and residue removal.

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

Yet another embodiment of the present invention is to provide a semiconductor device manufactured using the positive photosensitive resin composition.

One embodiment of the present invention (A) polybenzoxazole precursor (polybenzoxazole comprising a repeating unit represented by the formula (1), and having a functional group derived from a substituted or unsubstituted monoamine compound in at least one terminal portion The positive photosensitive resin composition containing precursor), (B) photosensitive diazoquinone compound, (C) silane compound, (D) phenolic compound, and (E) solvent is provided.

[Formula 1]

In Chemical Formula 1,

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

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

n ₁ is an integer indicating the number of repeating units.

Specific examples of the substituted or unsubstituted monoamine compound include compounds represented by the following formula (7) and compounds represented by the following formula (8).

[Formula 7]

In Chemical Formula 7,

R ₈ may be a substituted or unsubstituted arylene group,

D ₁ may be OH or SH.

[Formula 8]

In Chemical Formula 8,

R ₁₄ may be a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted alicyclic organic group,

D ₂ may be COOH or SO ₃ H.

More specific examples of the substituted or unsubstituted monoamine compound include 4-amino-m-cresol represented by the following Formula 9, 4-aminobenzoic acid represented by the following Formula 10, and 3-aminobenzoic acid represented by the following Formula 11 , 2-aminobenzoic acid represented by the following formula (12), alpha amino acid represented by the following formula (13), and a combination thereof.

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

In Chemical Formula 13,

R may be hydrogen, an alkyl group or an aryl group.

The polybenzoxazole precursor may be one having a weight average molecular weight (Mw) of 3,000 to 300,000.

The positive type photosensitive resin composition is 5 to 100 parts by weight of the (B) photosensitive diazoquinone compound, 0.1 to 30 parts by weight of the (C) silane compound, relative to 100 parts by weight of the (A) polybenzoxazole precursor. (D) may include 1 to 30 parts by weight of the phenol compound and 200 to 900 parts by weight of the solvent (E).

Another embodiment of the present invention provides a photosensitive resin film prepared using the positive photosensitive resin composition.

Another embodiment of the present invention provides a semiconductor device manufactured 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 can promote the image development by alkaline developing solution, and can obtain the outstanding sensitivity, resolution, pattern shape and residue removal property, and low film shrinkage rate.

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, "substituted" to "substituted" means that at least one hydrogen atom of the functional group of the present invention is a halogen atom (F, Br, Cl, or I), a hydroxy group, a nitro group, a cyano group, an amino group (NH ₂ , NH (R ') or N (R'')(R'''), wherein R ', R''andR''' are the same or different from each other, each independently having 1 to 10 carbon atoms Amidino group, hydrazine group or hydrazine group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or It means substituted with one or more substituents selected from the group consisting of an unsubstituted heteroaryl group and a substituted or unsubstituted heterocyclic group.

Unless stated otherwise in the present specification, "alkyl group" means an alkyl group having 1 to 30 carbon atoms, more specifically, 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 specifically, a cycloalkyl group having 3 to 18 carbon atoms, "alkoxy group" means an alkoxy group having 1 to 30 carbon atoms, more specifically means an alkoxy group having 1 to 18 carbon atoms, "aryl group Means an aryl group having 6 to 30 carbon atoms, more specifically, an aryl group having 6 to 18 carbon atoms, and an "alkenyl group" means an alkenyl group having 2 to 30 carbon atoms, and more specifically 2 to 18 carbon atoms. Means an alkenyl group, and "alkylene group" means an alkylene group having 1 to 30 carbon atoms, more specifically, an alkylene group having 1 to 18 carbon atoms, and "arylene group" Means an arylene group having 6 to 30 carbon atoms.

In addition, the term "aliphatic organic group" used herein means an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an alkynyl group having 2 to 30 carbon atoms, and an "alicyclic organic group" means a cycloalkyl group having 3 to 30 carbon atoms. , A cycloalkenyl group having 3 to 30 carbon atoms or a cycloalkynyl group having 3 to 30 carbon atoms, and "aromatic organic group" means an aryl group having 6 to 30 carbon atoms or a heteroaryl group having 2 to 30 carbon atoms.

In addition, in this specification, "*" means the part connected with the same or different atom or formula.

According to one embodiment of the present invention, the positive photosensitive resin composition includes (A) a repeating unit represented by the following Formula 1, and has a functional group derived from a substituted or unsubstituted monoamine compound in at least one terminal portion. Polybenzoxazole precursors, (B) photosensitive diazoquinone compounds, (C) silane compounds, (D) phenolic compounds, and (E) solvents.

The positive photosensitive resin composition may further include (F) other additives.

[Formula 1]

In Chemical Formula 1,

X may be an aromatic organic group or a 4-6 valent aliphatic organic group,

Y may be an aromatic organic group or a 2 to 6-valent aliphatic organic group,

n ₁ is an integer indicating the number of repeating units.

The positive photosensitive resin composition may further include (F) other additives.

Hereinafter, each component will be described in detail.

(A) Polybenzoxazole  Precursor

The polybenzoxazole precursor includes a repeating unit represented by Chemical Formula 1 and has a functional group derived from a substituted or unsubstituted monoamine compound in at least one terminal portion.

In Formula 1, X may be an aromatic organic group or a 4 to 6-valent aliphatic organic group, but is not limited thereto.

Specific examples of X include compounds represented by the following formula (2) and (3).

[Formula 2]

(3)

In Chemical Formulas 2 and 3,

A ₁ may be O, CO, CR ₁₀₀ R ₁₀₁ , SO ₂ , S or a single bond, and R ₁₀₀ and R ₁₀₁ may be the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group. In particular, it may be a fluoroalkyl group,

R ₁ to R ₃ are the same or different from each other, and each independently may be hydrogen or a substituted or unsubstituted alkyl group,

n ₂ is an integer of 1 to 2,

n ₃ and n ₄ are the same or different from each other, and each independently an integer of 1 to 3.

X may be, for example, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-amino- 4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-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, 2,2-bis (3-amino-4-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2- Bis (3-amino-4-hydroxy-6-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxy-2-triflumethylphenyl) hexafluoropropane, 2 , 2-bis (4-amino-3-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxy-6-trifluoromethylphenyl) hexafluoro Rolopane, 2,2-bis 4-amino-3-hydroxy-2-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxy-5-pentafluoroethylphenyl) hexafluoropropane, 2 -(3-amino-4-hydroxy-5-trifluoromethylphenyl) -2- (3-amino-4-hydroxy-5-pentafluoroethylphenyl) hexafluoropropane, 2- (3-amino -4-hydroxy-5-trifluoromethylphenyl) -2- (3-hydroxy-4-amino-5-trifluoromethylphenyl) hexafluoropropane, 2- (3-amino-4-hydroxy- 5-trifluoromethylphenyl) -2- (3-hydroxy-4-amino-6-trifluoromethylphenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-5-trifluoromethylphenyl ) -2- (3-hydroxy-4-amino-2-trifluoromethylphenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-2-trifluoromethylphenyl) -2- (3 -Hydroxy-4-amino-5-trifluoromethylphenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-6 -Trifluoromethylphenyl) -2- (3-hydroxy-4-amino-5-trifluoromethylphenyl) hexafluoropropane and a combination thereof.

In Chemical Formula 1, Y may be an aromatic organic group or a 2 to 6-valent aliphatic organic group, but is not limited thereto.

Y may be a residue of a dicarboxylic acid or dicarboxylic acid derivative.

Examples of the dicarboxylic acid may include Y (COOH) ₂ (where Y is the same as Y in Formula 1).

Examples of the dicarboxylic acid derivatives include active compounds that are carboxylic acid halide derivatives or active ester derivatives obtained by reacting Y (COOH) ₂ with 1-hydroxy-1,2,3-benzotriazole and the like. . Specific examples thereof include 4,4'-oxydibenzoyl chloride, diphenyloxydicarbonyldichloride, bis (phenylcarbonyl chloride) sulfone, bis (phenylcarbonyl chloride) ether, bis (phenylcarbonyl chloride) phenone, And a compound selected from the group consisting of taloyldichloride, terephthaloyldichloride, isophthaloyldichloride, dicarbonyldichloride, diphenyloxydicarboxylate dibenzotriazole and combinations thereof.

In addition, Y may be a compound represented by Formula 4 to Formula 6.

[Formula 4]

[Chemical Formula 5]

[Formula 6]

In Chemical Formulas 4 to 6,

R ₄ to R ₇ may be the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

n ₅ , n ₇ and n ₈ are integers from 1 to 4,

n ₆ is an integer of 1 to 3,

A ₂ may be O, CR ₁₀₂ R ₁₀₃ , CO, CONH, S or SO ₂ , wherein R ₁₀₂ and R ₁₀₃ may be the same or different from each other, and each independently hydrogen, a substituted or unsubstituted alkyl group, Specifically, it may be a fluoroalkyl group.

In addition, the polybenzoxazole precursor includes a functional group derived from a substituted or unsubstituted monoamine compound at either or both ends of the molecular chain. The functional group derived from the substituted or unsubstituted monoamine compound may be a functional group which is ionized by an alkaline developer to promote development, and thus a positive photosensitive resin according to an embodiment of the present invention including the functional group. The composition can exhibit good sensitivity, resolution, pattern shape and residue removal.

The functional group may be derived from a substituted or unsubstituted monoamine compound which is a functional terminal encapsulant. Specific examples of the substituted or unsubstituted monoamine compound include, but are not limited to, compounds represented by the following Chemical Formulas 7 and 8.

[Formula 7]

In Chemical Formula 7,

R ₈ may be a substituted or unsubstituted arylene group, specifically, a substituted or unsubstituted phenylene group, or may be a substituted or unsubstituted naphthalene group,

D ₁ may be OH or SH.

Specific examples of the R ₈ may be a compound represented by the following formula (7a) to formula (7c).

[Formula 7a]

[Formula 7b]

[Formula 7c]

In Chemical Formulas 7a to 7c,

R ₉ to R ₁₃ are the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

n ₉ , n ₁₂ and n ₁₃ are integers from 1 to 4,

n ₁₀ And n ₁₁ is an integer of 1 to 3,

A ₃ may be O, CO, CR ₁₀₄ R ₁₀₅ , SO ₂ , S or a single bond, and R ₁₀₄ and R ₁₀₅ may be the same or different from each other, and each independently hydrogen, a substituted or unsubstituted alkyl group, and Specifically, it may be a fluoroalkyl group.

[Formula 8]

In Chemical Formula 8,

R ₁₄ may be a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted alicyclic organic group, and specifically, the alkylene group may be an alkyl group substituted with an alkyl group or an aryl group, The arylene group may be a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthalene group,

D ₂ may be COOH or SO ₃ H.

Specific examples of the R ₁₄ is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, for example, a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, a compound represented by the following Chemical Formulas 8a to 8c, and 3 to 18 substituted or unsubstituted cycloalkylene group, for example, a substituted or unsubstituted cycloalkylene group having 5 to 10 carbon atoms.

[Formula 8a]

[Formula 8b]

[Formula 8c]

In Chemical Formulas 8a to 8c,

R ₁₅ to R ₁₉ are the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

n ₁₄ , n ₁₇ and n ₁₈ are integers from 1 to 4,

n ₁₅ And n ₁₆ is an integer from 1 to 3,

A ₄ may be O, CO, CR ₁₀₆ R ₁₀₇ , SO ₂ , S or a single bond, R ₁₀₆ and R ₁₀₇ may be the same or different from each other, and each independently hydrogen, a substituted or unsubstituted alkyl group, and Specifically, it may be a fluoroalkyl group.

More specific examples of the substituted or unsubstituted monoamine compound include 4-amino-m-cresol represented by the following Formula 9, 4-aminobenzoic acid represented by the following Formula 10, and 3-aminobenzoic acid represented by the following Formula 11 , 2-aminobenzoic acid represented by the following formula (12), alpha amino acid represented by the following formula (13), and a combination thereof.

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

In Chemical Formula 13,

R may be hydrogen, an alkyl group or an aryl group.

The weight average molecular weight (Mw) of the polybenzoxazole precursor may be in the range of 3,000 to 300,000. When the weight average molecular weight of the polybenzoxazole precursor is within the above range, sufficient physical properties may be obtained, and at the same time, sufficient solubility in an organic solvent may be obtained.

(B) photosensitive Diazoquinone  compound

The photosensitive diazoquinone compound may be a compound having a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure, which is known from US Patent Nos. 2,772,975, 2,797,213 and 3,669,658. Substance. Specific examples of the photosensitive diazoquinone compound may include compounds represented by the following Chemical Formula 14 and Chemical Formulas 16 to 18, but are not limited thereto.

[Formula 14]

In Chemical Formula 14,

R ₂₀ to R ₂₂ may be the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group, specifically CH ₃ ,

R ₂₃ to R ₂₅ may be the same or different from each other, and may each independently be OQ, wherein Q may be hydrogen, Formula 15a or Formula 15b, wherein Q may not be hydrogen at the same time,

n ₁₉ to n ₂₁ are the same or different from each other, and each independently an integer of 1 to 3.

[Formula 15a]

[Formula 15b]

[Formula 16]

In Chemical Formula 16,

R ₂₆ may be hydrogen or a substituted or unsubstituted alkyl group,

R ₂₇ to R ₂₉ may be OQ, wherein Q is the same as defined in Formula 14,

n ₂₂ to n ₂₄ are the same or different from each other, and each independently an integer of 1 to 3.

[Formula 17]

In Chemical Formula 17,

A ₅ may be CO or CR ₁₀₈ R ₁₀₉ , wherein R ₁₀₈ and R ₁₀₉ may be the same or different from each other, and each independently a substituted or unsubstituted alkyl group,

R ₃₀ to R ₃₃ are the same or different from each other, and each independently hydrogen, a substituted or unsubstituted alkyl group, OQ or NHQ, wherein Q is the same as defined in Formula 14,

n ₂₅ to n ₂₈ are the same or different from each other, and each independently an integer of 1 to 4,

n ₂₅ + n ₂₆ and n ₂₇ + n ₂₈ are each independently an integer of 5 or less,

However, at least one of R ₃₂ and R ₃₃ may be OQ, one aromatic ring may include 1 to 3 OQs, and the other aromatic ring may include 1 to 4 OQs.

[Formula 18]

In Chemical Formula 18,

R ₃₄ to R ₄₁ are the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

n ₂₉ and n ₃₀ are the same or different from each other, and each independently may be an integer of 1 to 5,

Q is the same as defined in the formula (14).

The content of the photosensitive diazoquinone compound in the photosensitive resin composition may be 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 with a board | substrate. Specific examples of the silane compound include compounds represented by the following Chemical Formulas 19 to 21; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane; Or 3-Macryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryl 스티 trimethoxysilane, # 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldie Oxysilane; Carbon-carbon unsaturated bond containing silane compounds, such as trimethoxy [3- (phenylamino) propyl] silane, are mentioned, but it is not limited to these.

[Formula 19]

In Chemical Formula 19,

R ₄₂ may be a vinyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and specifically, may be 3- (meth) acryloxypropyl, p-styryl or 3- (phenylamino) propyl. And

R ₄₃ to R ₄₅ are the same or different from each other, and each independently may be a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkyl group, or halogen, wherein at least one of R ₄₃ to R ₄₅ is an alkoxy group or halogen In detail, the alkoxy group may be an alkoxy group having 1 to 8 carbon atoms, and the alkyl group may be an alkyl group having 1 to 20 carbon atoms.

[Formula 20]

In Chemical Formula 20,

R ₄₆ may be NH ₂ or CH ₃ CONH,

R ₄₇ to R ₄₉ are the same or different from each other, and each independently represent a substituted or unsubstituted alkoxy group, specifically, the alkoxy group may be OCH ₃ or OCH ₂ CH ₃ ,

n ₃₁ is an integer of 1 to 5;

[Formula 21]

In Chemical Formula 21,

R ₅₀ to R ₅₃ may be the same or different from each other, and may each independently be a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkoxy group, specifically CH ₃ or OCH ₃ ,

R ₅₄ and R ₅₅ are the same or different from each other, and may each independently be a substituted or unsubstituted amino group, specifically NH ₂ or CH ₃ CONH,

n ₃₂ and n ₃₃ are the same or different from each other, and each independently an integer of 1 to 5.

The content of the silane compound may be 0.1 to 30 parts by weight with respect to 100 parts by weight of the polybenzoxazole precursor. When the content of the silane compound is within the above range, the adhesion with the upper and lower membrane layers is excellent, and no residual film is left after development, and optical properties (transmittance) and mechanical properties of the membrane such as tensile strength, elongation, and Young's modulus can be improved.

(D) phenolic compounds

The phenolic compound may increase the dissolution rate and sensitivity of the exposed portion during development with an aqueous alkali solution to form a pattern with the photosensitive resin composition, and may serve as a high resolution pattern without developing residues during development.

In addition, the phenolic compound has a functional group capable of thermal polymerization, so that it is capable of crosslinking with the polybenzoxazole precursor of the above item (A) at the time of thermosetting.

Specific examples of the phenol compound may include compounds represented by the following Chemical Formulas 22 to 27, but are not limited thereto.

[Formula 22]

In Chemical Formula 22,

R ₅₆ to R ₅₈ are the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

R ₅₉ to R ₆₃ are the same or different from each other, and each independently may be H, OH, or a substituted or unsubstituted alkyl group, specifically, the alkyl group may be CH ₃ ,

n ₃₄ is an integer of 1 to 5.

[Formula 23]

In Chemical Formula 23,

R ₆₄ to R ₆₉ may be the same or different from each other, and may each independently be H, OH, or a substituted or unsubstituted alkyl group,

A ₆ may be CR ₁₁₀ R ₁₁₁ or a single bond, R ₁₁₀ and R ₁₁₁ may be the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group, and specifically, the alkyl group is CH Can be ₃ ,

n ₃₅ + n ₃₆ + n ₃₇ and n ₃₈ + n ₃₉ + n ₄₀ are the same or different from each other, and each independently an integer of 5 or less.

[Formula 24]

In Chemical Formula 24,

R ₇₀ to R ₇₂ are the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

n ₄₁ , n ₄₂ and n ₄₅ are the same or different from each other, and each independently an integer of 1 to 5,

n ₄₃ and n ₄₄ are the same or different from each other, and each independently an integer of 0 to 4;

[Formula 25]

In Chemical Formula 25,

R ₇₃ to R ₇₈ are the same or different from each other, and each independently hydrogen, OH, or a substituted or unsubstituted alkyl group,

n ₄₆ to n ₄₉ are the same or different from each other, and each independently may be an integer of 1 to 4,

Provided that n ₄₆ + n ₄₈ and n ₄₇ + n ₄₉ are each independently an integer of 5 or less.

[Formula 26]

In Chemical Formula 26,

R ₇₉ may be a substituted or unsubstituted alkyl group, specifically CH ₃ ,

R ₈₀ to R ₈₂ are the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

n ₅₀ , n ₅₂ and n ₅₄ are the same or different from each other, and each independently an integer of 1 to 5,

n ₅₁ , n ₅₃ and n ₅₅ are the same or different from each other, and each independently an integer of 0 to 4,

Provided that n ₅₀ + n ₅₁ , n ₅₂ + n _53, and n ₅₄ + n ₅₅ are each independently an integer of 5 or less.

[Formula 27]

In Chemical Formula 27,

R ₈₃ to R ₈₅ may be the same or different from each other, and may each independently be a substituted or unsubstituted alkyl group, specifically CH ₃ ,

R ₈₆ to R ₈₉ are the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

n ₅₆ , n ₅₈ and n ₆₀ are the same or different from each other, and each independently an integer of 1 to 5,

n ₅₇ , n ₅₉ and n ₆₁ are the same or different from each other, and each independently an integer of 0 to 4,

n ₆₂ is an integer from 1 to 4,

Provided that n ₅₆ + n ₅₇ , n ₅₈ + n ₅₉ and n ₆₀ + n ₆₁ are each independently an integer of 5 or less.

The amount of the phenol compound may be 1 to 30 parts by weight based on 100 parts by weight of the polybenzoxazole precursor. When the content of the phenolic compound is within the above range, it does not cause a decrease in sensitivity during development, and moderately increases the dissolution rate of the non-exposed part, thereby obtaining a good pattern, and may not exhibit precipitation during freezing storage, and thus may exhibit excellent storage stability. .

(E) solvent

Specific examples of the solvent include 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, and combinations thereof may be selected, but is not limited thereto. These solvents can be used alone or in combination of two or more thereof.

The amount of the solvent may be 200 to 900 parts by weight based on 100 parts by weight of the polybenzoxazole precursor. When the amount of the solvent used is within the above range, it is possible to coat a film of sufficient thickness, and may have excellent solubility and coating property.

(F) other additives

The positive photosensitive resin composition according to the embodiment of the present invention may further include a heat latent acid generator as an additive. Specific examples of the heat latent acid generator include p-toluenesulfonic acid, arylsulfonic acid such as benzenesulfonic acid, trifluoromethanesulfonic acid, perfluoroalkyl sulfonic acids such as perfluorobutanesulfonic acid, methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid and the like. The same alkylsulfonic acid may be mentioned, but is not limited thereto. The heat latent acid generator can smoothly proceed the cyclization reaction even if the curing temperature is lowered as a catalyst for the dehydration reaction of the polyphenol benzoxazole precursor-containing polyamide and the cyclization reaction.

In addition, in order to prevent staining of the film thickness or to improve the developability, a suitable surfactant or reveling agent may be further used as an additive.

The process of forming a pattern using the positive photosensitive resin composition includes the steps of: (b) applying a positive photosensitive resin composition on a support substrate, drying the applied positive photosensitive resin composition to form a positive photosensitive resin composition film, Exposing the positive photosensitive resin composition film, developing the exposed positive photosensitive resin composition film with an aqueous alkali solution, and preparing a photosensitive resin film; and heating the photosensitive resin film. Process conditions for forming the pattern, etc. are well known in the art, so detailed description thereof will be omitted.

According to another embodiment of the present invention to provide a photosensitive resin film prepared using the positive photosensitive resin composition. The photosensitive resin film may be an insulating film or a protective film.

According to another embodiment of the present invention provides a semiconductor device manufactured using the positive photosensitive resin composition. The positive photosensitive resin composition may be usefully used to form an insulating film, a passivation layer or a butter coating layer in a semiconductor device. That is, the positive photosensitive resin composition may be usefully used to form 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 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  One] Polybenzoxazole  Precursor ( PBO1 ) Synthesis

Four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injector and a cooler was passed through the Ethnitrogen 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3, 14.7 g of 3-hexafluuropropane and 2.74 g of 4-aminobenzoic acid were added, and 152 g of N-methyl-2-pyrrolidone (NMP) was added to dissolve it. In the solution obtained at this time, solid content was 15 weight%.

When the solid was completely dissolved, 9.5 g of pyridine was added, 14.8 g of 4,4'-oxydibenzoyl chloride was added while maintaining the temperature at 0 to 5 ° C, and 84 g of N-methyl-2-pyrrolidone (NMP) was added to dissolve it. 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, the temperature was raised to room temperature, followed by stirring for 1 hour, and then the reaction was terminated. The reaction mixture was poured into a solution of water / methanol = 10/1 (volume ratio) to form a precipitate, and the precipitate was filtered and washed sufficiently with water, and then dried under vacuum at a temperature of 80 ° C. for at least 24 hours to produce polybenzoxazole. Precursor (PBO1) was prepared.

[ Synthetic example  2] Polybenzoxazole  Precursor ( PBO2 ) Synthesis

2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane 14.7 g, 4-37 benzoic acid 1.37 g, 4,4'-oxydi A polybenzoxazole precursor (PBO2) was prepared in the same manner as in Synthesis example 1, except that 13.3 g of benzoyl chloride was used.

Synthesis Example 3 Polybenzoxazole Precursor ( PBO3 ) Synthesis

A polybenzoxazole precursor (PBO3) was prepared in the same manner as in Synthesis example 1, except that 2.74 g of 3-aminobenzoic acid was used instead of 4-aminobenzoic acid.

[ Synthetic example  4] Polybenzoxazole  Precursor ( PBO4 ) Synthesis

A polybenzoxazole precursor (PBO4) was prepared in the same manner as in Synthesis example 1, except that 2.5 g of 4-amino- m -cresol was used instead of 4-aminobenzoic acid.

[ Synthetic example  5] Polybenzoxazole  Precursor ( PBO5 ) Synthesis

2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3, while passing nitrogen through a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injection device and a cooler 18.3 g of 3-hexafluuropropane was added, and 164 g of N-methyl-2-pyrrolidone (NMP) was added to dissolve it. In the solution obtained at this time, solid content was 15 weight%.

When the solid is completely dissolved, 8.3 g of pyridine is added, 13.3 g of 4,4'-oxydibenzoyl chloride is added while maintaining the temperature at 0 to 5 ° C, and 75 g of N-methyl-2-pyrrolidone (NMP) is added to dissolve it. 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, the temperature was raised to room temperature, followed by stirring for 1 hour, and then the reaction was terminated. The reaction mixture was poured into a solution of water / methanol = 10/1 (volume ratio) to form a precipitate, and the precipitate was filtered and washed sufficiently with water, and then dried under vacuum at a temperature of 80 ° C. for at least 24 hours to produce polybenzoxazole. Precursor (PBO5) was prepared.

[ Example  One]

15 g of prepared polybenzoxazole precursor (PBO1) and 35.0 g of γ-butyrolactone (GBL) were added to dissolve it, and then 3 g of a photosensitive diazoquinone having a structure of Formula 14a and a silane coupling agent were used. 0.75 g of methoxy [3- (phenylamino) propyl] silane (C) and 0.75 g of a phenolic compound (D) of the following Chemical Formula 23a were added, dissolved, and filtered through a 0.45 μm fluorine resin filter to obtain a positive photosensitive resin composition. .

[Formula 14a]

In Chemical Formula 14a,

Q is the same as defined in Chemical Formula 14, and 67% of the Q is substituted with the chemical formula 15a.

[Formula 28]

[Formula 23a]

In Chemical Formula 23a,

R ₉₀ , R ₉₂ , R ₉₃ and R ₉₅ are H,

R ₉₁ and R ₉₄ are OH,

R ₉₆ is CH ₃ ,

R ₉₇ is H.

[ Example  2]

A positive photosensitive resin composition was obtained in the same manner as in Example 1, except that 15 g of polybenzoxazole precursor (PBO2) was used instead of 15 g of polybenzoxazole precursor (PBO1).

[ Example  3]

A positive photosensitive resin composition was obtained in the same manner as in Example 1, except that 15 g of polybenzoxazole precursor (PBO3) was used instead of 15 g of polybenzoxazole precursor (PBO1).

[ Example  4]

A positive photosensitive resin composition was obtained in the same manner as in Example 1, except that 15 g of polybenzoxazole precursor (PBO4) was used instead of 15 g of polybenzoxazole precursor (PBO1).

[ Comparative example One]

A positive photosensitive resin composition was obtained in the same manner as in Example 1, except that 15 g of polybenzoxazole precursor (PBO5) was used instead of 15 g of polybenzoxazole precursor (PBO1).

The structures of the positive photosensitive resin compositions of Examples 1 to 4 and Comparative Example 1 are shown in Table 1 below.

TABLE 1

Polybenzoxazole precursors menstruum Photosensitivity
Diazoquinone Compound Silane
compound phenol
compound Resin type Encapsulant Type Mw Example 1 PBO1

12.1K GBL With With With Example 2 PBO2

10.9K GBL With With With Example 3 PBO3

11.2K GBL With With With Example 4 PBO4

11.3K GBL With With With Comparative Example 1 PBO5 - 11.5K GBL With With With

<Property evaluation>

The positive photosensitive resin composition prepared according to Examples 1 to 4 and Comparative Example 1 was coated on an 8-inch wafer using a Mikasa (1H-DX2) spin coater, and then coated on a hot plate at 120 ° C., 4 Heating for minutes gave a photosensitive polyimide precursor film.

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

The sensitivity is obtained by obtaining an exposure time in which a 10 μm L / S pattern is formed with a line width of 1 to 1 after exposure and development, and is determined as an optimal exposure time, and the resolution is measured by using the minimum pattern dimension at the optimum exposure time as the resolution. It was. The results are shown in Table 2 below. The resolution could be confirmed through an optical microscope.

In addition, since the reduction rate of the film thickness after development affects the developability and the final film thickness, the film thickness reduction should be small at the time of development, and a 2.38 wt% tetramethylammonium hydroxide (TMAH) Development was carried out by immersing in an aqueous solution by time and rinsing with water, and the residual film ratio (thickness after development / thickness before development, unit%) was measured by measuring the change in film thickness over time, and is shown in Table 2 below. The film thickness change after preliminary baking, image development, and hardening was measured using the KMAC (ST4000-DLX) apparatus.

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.

While storing the positive photosensitive resin compositions prepared in Examples 1 to 4 and Comparative Example 1 at room temperature, the same coating thickness and exposure time were exhibited, that is, the coating thickness coated using the positive photosensitive resin composition. And the number of days that elapsed until the exposure performance showed abnormal behavior was calculated in the storage stability shown in Table 2 below.

TABLE 2

Thickness
(Μm) Sensitivity
(mJ / cm ² ) resolution
(Μm) Residual rate
(%) keep
stability
(Work) Resin type Preliminary firing After phenomenon Example 1 PBO1 11.90 10.00 385 3.5 84 8 Example 2 PBO2 11.72 9.84 380 3 84 8 Example 3 PBO3 11.94 10.09 375 3.5 84.5 8 Example 4 PBO4 11.65 9.79 390 3 84 10 Comparative Example 1 PBO5 11.61 9.73 420 4.0 83.8 3

As shown in Table 2, when the photosensitive resin composition of Examples 1 to 4 is used, since the residual film ratio value with time is higher than that of Comparative Example 1, a pattern during development with an aqueous alkali solution may be better formed. It can be seen that.

Since Examples 1 to 4 show better sensitivity and resolution than Comparative Example 1, it can be seen that they are superior in all aspects (sensitivity, resolution, residual film ratio during development) with respect to pattern formation.

When storage stability was evaluated through the patterning characteristics, Examples 1 to 4 show better storage stability than Comparative Example 1.

On the cured film side through thermal curing after development, in the films obtained using all the positive photosensitive resin compositions of Examples and Comparative Examples, a cured film is formed with a thickness reduction of about 20% of the thickness after development, and each positive type There is no significant difference in physical properties between the photosensitive resin compositions.

Therefore, the positive photosensitive resin composition according to the embodiment of the present invention can form a semiconductor insulating film or a protective film having excellent performance through more efficient patterning than a resin composition using a conventional positive photosensitive polybenzoxazole precursor. You can check it.

While the 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. Naturally, it belongs to the scope of the invention.

Claims (7)

(A) a polybenzoxazole precursor comprising a repeating unit represented by the following formula (1) and having a functional group derived from a substituted or unsubstituted monoamine compound in at least one terminal portion; (B) photosensitive diazoquinone compound; (C) silane compound; (D) phenolic compounds; And (E) solvent Positive photosensitive resin composition comprising: [Formula 1]

In Chemical Formula 1, X is an aromatic organic group or a 4-6 valent aliphatic organic group, Y is an aromatic organic group or a 2 to 6-valent aliphatic organic group, n ₁ is an integer indicating the number of repeating units. The method of claim 1, The substituted or unsubstituted monoamine compound is a positive photosensitive resin composition which is a compound represented by the following formula (7) or (8): [Formula 7]

In Chemical Formula 7, R ₈ is a substituted or unsubstituted arylene group, D ₁ is OH or SH, [Formula 8]

In Chemical Formula 8, R ₁₄ is a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted alicyclic organic group, D ₂ is COOH or SO ₃ H. The method of claim 2, The substituted or unsubstituted monoamine compound is 4-amino-m-cresol represented by the following formula (9), 4-aminobenzoic acid represented by the following formula (10), 3-aminobenzoic acid represented by the following formula 11, formula 12 A positive type photosensitive resin composition selected from the group consisting of 2-aminobenzoic acid represented by the following, alpha amino acid represented by the following Chemical Formula 13 and combinations thereof: [Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

In Chemical Formula 13, R is hydrogen, an alkyl group or an aryl group. 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 resin composition is Based on 100 parts by weight of the (A) polybenzoxazole precursor, 5 to 100 parts by weight of the (B) photosensitive diazoquinone compound; 0.1 to 30 parts by weight of the (C) silane compound; 1 to 30 parts by weight of the (D) phenol compound; And 200 to 900 parts by weight of the solvent (E) Positive photosensitive resin composition comprising a. The photosensitive resin film manufactured using the positive photosensitive resin composition of any one of Claims 1-5. The semiconductor device manufactured using the positive photosensitive resin composition of any one of Claims 1-5.