KR20100039183A - Positive type photosensitive resin composition - Google Patents

Abstract

PURPOSE: A positive photosensitive resin composition is provided to obtain excellent heat resistance and to form a minute pattern of high definition and high-sensitivity. CONSTITUTION: A positive photosensitive resin composition comprises: a polyamide polymer marked as a chemical formula 1; esterified quinonediazide compound; a compound containing phenolic group; and a solvent. In the chemical formula 1, X1 and X2 are similar or different and are independently divalent ~ tetravalent organic group. Y1 and Y2 are similar or different and are independently divalent ~ hexavalent organic group. R1 and R2 are the organic group of hydrogen or carbon number 1 ~ 5.

Description

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

The present invention relates to a positive photosensitive resin composition, and more particularly, to a positive photosensitive resin composition which is excellent in heat resistance and capable of forming a fine pattern with high sensitivity and high resolution.

BACKGROUND ART In recent years, as semiconductors and liquid crystal display devices have been increasingly integrated, high reliability, and high density, research has been actively conducted to use high purity organic materials having excellent workability as materials for electronic devices. Accordingly, there is a demand for a resin composition having excellent heat resistance and excellent electrical and mechanical properties for the surface protective film and the interlayer insulating film of a semiconductor device. In addition, in order to serve as surface protection films and interlayer insulating films of devices that are becoming increasingly integrated, a resin composition having high resolution and easy fine pattern shapes is required. The pattern forming technology of the surface protective film and the resin composition for an interlayer insulating film, which is excellent in heat resistance, excellent in electrical and mechanical properties, and capable of forming a high-resolution fine pattern, becomes a core and serves as a driving force for ultra-high integration of semiconductors.

Existing positive type photosensitive resin composition adds esterified quinone diazide which shows photosensitivity to a polyamide polymer, or connects quinone diazide by covalent bond to a polyamide polymer. In the usual pattern formation process using this composition, the photosensitive resin composition is first exposed to light of a specific wavelength in a pattern manner to be exposed. At this time, at the exposed site, the quinonediazide compound undergoes chemical change and is converted into the carboxylic acid form. The exposed film is then contacted with any material (typically an aqueous alkaline developer). The portion of the composition containing the converted carboxylic acid is selectively developed in alkaline solution due to increased solubility in the developer. The temperature of the patterned layer is then increased to form a cured pattern.

The technique of the surface protective film or the interlayer insulating film requires development of both a composition material having high heat resistance and excellent mechanical properties after curing and a patterning material having high resolution and high sensitivity optical properties. However, to function as a protective film, the design of high aromatic compound content, high molecular weight molecular weight, high crosslinking degree and low fluidity is required. However, in order to improve optical properties, the content of aromatic compound is low or high molecular weight is high. It is not easy to develop a material that is small, has a low crosslinking degree, and has good fluidity, thereby satisfying conflicting physical properties.

In particular, in the existing polyamide, there is a limit to the development of a high characteristic photosensitive resin composition due to the inverse relationship between the pattern refining properties and the film properties after curing.

In addition, in the case of soluble polyimide, it is possible to achieve the improvement of the mechanical film properties, while the already closed ring structure lowers the transmittance of the exposure wavelength, which in turn lowers the resolution and sensitivity, which hinders the characteristics in the formation of fine patterns.

As described above, the conventional photosensitive resin composition also has a problem in that it still fails to meet the required physical properties due to the refinement of the semiconductor device and the demand for high characteristics having excellent mechanical properties. Therefore, there is a need for development of a new type of photosensitive resin material that overcomes the limitations of existing materials.

The present invention is to provide a positive photosensitive resin composition which is excellent in heat resistance and capable of forming a fine pattern with high sensitivity and high resolution.

The present invention also provides a method for producing a photosensitive pattern using the photosensitive resin composition.

The present invention also provides a photosensitive resin film prepared using the photosensitive resin composition and an electronic component for semiconductor including the same.

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 for achieving the above object, (A) a polyamide polymer represented by the following formula (1), (B) esterified quinonediazide compound, (C) phenol group-containing compound, and (D Provided is a positive photosensitive resin composition comprising a solvent.

[Formula 1]

(In Formula 1,

X ₁ and X ₂ are the same or different from each other, and each independently a divalent to tetravalent organic group,

Y ₁ and Y ₂ are the same or different from each other, and each independently a divalent to hexavalent organic group,

R ₁ and R ₂ are the same or different from each other, and each independently hydrogen or an organic group having 1 to 5 carbon atoms,

E ₁ and E ₂ are the same or different from each other, and each independently hydrogen; Or a residue of one selected from the group consisting of a single carboxylic acid and active derivatives thereof, wherein E ₁ and E ₂ may not be hydrogen at the same time,

m ₁ and m ₂ are the same or different from each other, each independently 0 to 100,

m ₁ + m ₂ is 5 to 100.)

According to another embodiment of the present invention, applying the positive photosensitive resin composition on a support substrate and drying to form a resin composition layer, exposing the resin composition layer, the exposed resin composition layer with an alkaline developer It provides a method for producing a photosensitive pattern comprising the step of developing, and heating the developed resin composition layer.

According to another embodiment of the present invention, there is provided an electronic component for a semiconductor including a photosensitive resin film made of the positive photosensitive resin composition.

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

The positive type photosensitive resin composition of the present invention is an alkyl group, an aryl group, an alicyclic group derived from a compound selected from the group consisting of a single carboxylic acid and an active derivative thereof at one or both ends of the polyamide, Or sealed with a heterocyclic group, etc., the dissolution rate of the exposed portion and the non-exposed portion can be maximized. Therefore, when the pattern is formed with the photosensitive resin composition, the development speed of the exposed portion may be increased to form a high resolution pattern, and the ring closure degree and crosslinking degree after curing may be improved to form a photosensitive resin film having excellent film properties. have.

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.

Photosensitive resin composition according to an embodiment of the present invention, (A) the polyamide polymer represented by the formula (1), (B) esterified quinone diazide compound, (C) phenol group containing compound, and (D) solvent It includes.

Unless stated otherwise in the present specification, "substituted" means that at least one hydrogen of the compound is substituted with a substituent selected from the group consisting of halogen, alkyl group, alkoxy group, aryl group, amino group, and alkenyl group.

Unless stated otherwise in the present specification, "alkyl group" means an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 15 carbon atoms, and "aryl group" means an aryl group having 6 to 30 carbon atoms. More preferably, an aryl group having 6 to 18 carbon atoms, and an "alkenyl group" means an alkenyl group having 2 to 30 carbon atoms, more preferably an alkenyl group having 2 to 15 carbon atoms, and an "alkoxy group "Means an alkoxy group having 1 to 30 carbon atoms, more preferably an alkoxy group having 1 to 15 carbon atoms.

Unless stated otherwise in the present specification, "2- to 4-valent organic group" or "2- to 6-valent organic group" are each an organic group having 2 to 4 functional groups and an organic group having 2 to 6 functional groups, and hydrogen Combine with functional groups except.

Unless otherwise specified herein, "hetero cycle" means a compound selected from the group consisting of "hetero aryl group", "hetero cycloalkyl group", "hetero cycloalkenyl group", and "hetero cycloalkynyl group". .

Unless otherwise specified in this specification, "hetero compound" means that at least one of the carbons constituting the compound is substituted with an atom selected from the group consisting of N, O, P, and Si.

Hereinafter, each component will be described in detail.

(A) polyamide polymer

The polyamide polymer is preferably represented by the following formula (1).

[Formula 1]

In Chemical Formula 1

X ₁ and X ₂ are the same or different from each other, and each independently a divalent to tetravalent organic group,

Y ₁ and Y ₂ are the same or different from each other, and each independently a divalent to hexavalent organic group,

R ₁ and R ₂ are the same or different from each other, and each independently hydrogen or an organic group having 1 to 5 carbon atoms,

E ₁ and E ₂ are the same or different from each other, and each independently hydrogen; Or a residue of one selected from the group consisting of a single carboxylic acid and active derivatives thereof, wherein E ₁ and E ₂ may not be hydrogen at the same time, preferably E ₁ and E ₂ are alkyl, aryl, alici It may be a click group, or a heterocyclic group,

m ₁ and m ₂ are the same or different from each other, each independently 0 to 100,

m ₁ + m ₂ is 5 to 100.

The polyamide polymer represented by Chemical Formula 1 is a reaction product by reacting a diamine monomer with an acid monomer selected from the group consisting of tetracarboxylic dianhydride, dicarboxylic anhydride, dicarboxylic acid, and active derivatives thereof. After the preparation, the reaction product may be prepared by reacting the terminal block monomer with the amine group at the end of the reaction product, thereby preparing a description thereof.

The diamine monomer may be represented by X (NH ₂ ) ₂ (wherein X is the same as X ₁ or X ₂ of Formula 1), and X ₁ and X ₂ of Formula 1 are derived from the diamine monomer. .

X may be representatively represented by the following Chemical Formulas 2 to 7, but is not limited thereto.

[Formula 2]

[Formula 3]

[Formula 4]

[Chemical Formula 5]

[Formula 6]

[Formula 7]

In Chemical Formulas 2 to 7,

Z ₁ to Z ₁₅ are the same or different from each other, and each independently may be selected from the group consisting of hydrogen, substituted or unsubstituted alkyl group, hydroxy group, carboxylic acid group, and thiol group,

A ₁ to A ₆ are the same or different from each other, and each independently may be selected from the group consisting of CR ₃ R ₄ , S, O, SO ₂ , CO, CONH, and a single bond, the R ₃ and R ₄ Are the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group, preferably a fluoroalkyl group or a methyl group.

In addition, as the diamine monomer, an aromatic diamine, an alicyclic diamine, an aliphatic diamine, or the like may be used.

Examples of the diamine monomers include benzidine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4- (4-amino Phenoxy) phenyl] ether, 1,4-bis (4-aminophenoxy) benzene, 4'-diamino-3,3'-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) Propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, 2,2-bis (4-amino-3-hydroxyphenyl) -1,1 , 1,3,3,3-hexafluoropropane, 3,4'-diaminodiphenylether, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenyl methane, 4,4 '-Diaminodiphenyl methane, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodi Phenyl sulfide, para-phenylenediamine, meta-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine cyclohexyldiamine, methylenebissi Rohexylamine, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxysulfone, 4,4'-diamino- 3,3'-dihydroxyphenylsulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis -(3-amino-4-hydroxyphenyl) hexafluoropropane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-di Hydroxybenzophenone, 4,4'-diamino-3,3'-dihydroxydiphenylether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2, 4-dihydroxybenzene, and the like, but is not limited thereto. The said diamine monomer can be used individually or in mixture of 2 or more types.

More preferably the diamine monomer is 4,4'-diaminodiphenylether, 4,4'-diaminodiphenyl methane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane , 3,3'-diamino-4,4'-dihydroxysulfone, and mixtures thereof.

Moreover, a silicone containing diamine monomer can be used with the said diamine monomer. The silicone-containing diamine monomer is preferable because it can improve the adhesion to the substrate.

Representative examples of the silicon-containing diamine monomers include bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (p-aminophenyl) tetramethyldisiloxane, and bis- (gamma-amino Propyl) tetramethyldisiloxane, 1,4-bis (gamma-aminopropyldimethylsilyl) benzene, 1,3-bis (aminopropyl) tetramethyldisiloxane, and the like, but are not limited thereto. More preferably, as the silicone-containing diamine monomer, bis (4-aminophenyl) tetramethylsiloxane, bis (p-aminophenyl) tetramethyldisiloxane or a mixture thereof may be used.

In order to increase the adhesion to the upper and lower membranes, it is preferable to use a copolymer having a ratio of the silicone-containing diamine monomer to the silicone-containing diamine monomer in the range of 0.1 to 10% by weight. When the content of the silicone-containing diamine monomer is in the above range, the optical properties and the film properties are not deteriorated, and excellent adhesion is preferable.

The acid monomer is selected from the group consisting of tetracarboxylic dianhydride, dicarboxylic acid anhydride, dicarboxylic acid, and active derivatives thereof, and Y ₁ and Y ₂ of Formula 1 are derived from the acid monomer. .

Examples of the tetracarboxylic dianhydride include, but are not limited to, those represented by the following formula (8).

[Formula 8]

(In Formula 8, Y is the same as Y ₁ or Y ₂ of Formula 1)

Examples of the dicarboxylic acid monomers include those represented by Y (COOH) ₂ (wherein Y is the same as Y ₁ or Y ₂ in Formula 1).

In addition, examples of the active derivative of the dicarboxylic acid monomer is Y (COK ') ₂ (wherein Y is the same as Y ₁ or Y ₂ of Formula 1, K' is Y (COOH) ₂ and And a residue obtained by reacting a halide or 1-hydroxy-1,2,3-benzotriazole or the like.

In addition, compounds represented by the following Chemical Formulas 9 to 16 may be derived from acid monomers.

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

(In Chemical Formulas 9 to 16

K ₁ to K ₂₁ are the same or different from each other, and are each independently selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, a hydroxy group, a carboxylic acid group, a thiol group, and COOR ₅ , wherein R ₅ is hydrogen or An alkyl group having 1 to 5 carbon atoms,

B ₁ to B ₆ are the same or different from each other, and each independently -CR ₆ R _7- , -S-, -O-, -SO _2- , -CO-, -CONH-, and in the group consisting of a single bond It may be selected, wherein R ₆ and R ₇ 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, wherein the substituted alkyl group is a fluoroalkyl group Is preferable, and an unsubstituted alkyl group is preferably a methyl group.)

When the acid monomer is tetracarboxylic dianhydride, specific examples thereof include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4- Biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, bis (3, 4- dicarboxy phenyl) ether dianhydride, etc. are mentioned. In addition, when the acid monomer is a dicarboxylic acid active derivative, examples thereof include active compounds such as carbonyl halide derivatives, active ester derivatives reacted with 1-hydroxy-1,2,3-benzotriazole, and the like. Specific examples include 4,4-oxydibenzoyl chloride, phthalic dichloride, Diphenyloxydicarboxylic acid chloride, bis (phenylcarboxylic acid chloride) sulfone, bis (phenylcarboxylic acid chloride) ether, bis (phenylcarboxylic acid chloride) phenone, phthalic carboxylic acid dichloride, or diphenyloxy Dicarboxylate benzotriazole etc. are mentioned.

Even more preferably, the acid monomer is 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, diphenyloxydicarboxylic acid Chloride, phthalic carboxylic acid dichloride, and the like, but is not limited thereto.

The polyamide polymer represented by Chemical Formula 1 may be a copolymer in which two or more monomers are copolymerized within the range of not impairing the optical properties, the film properties, and the water solubility of the homopolymer or polymer composed of the amide bond unit. As the copolymer, various patterns are possible. For example, a random copolymer, a block copolymer, or a graft copolymer may be used, but a random copolymer is most preferred.

In addition, the terminal blocking monomer reacting with the reaction product obtained by reacting the acid monomer with the diamine monomer may include a compound selected from the group consisting of a single carboxylic acid and an active derivative thereof.

The single carboxylic acid may be any carboxylic acid, but particularly cyclohexyl carboxylic acid, norbornane carboxylic acid, adamantyl carboxylic acid, and isolic in alicyclic form. Carbonyl carboxylic acid, norbornene carboxylic acid, and the like are preferred, and active derivatives thereof can also be used. These can be used individually or in mixture of 2 or more types.

In addition, as the active derivative of the carboxylic acid, cyclohexyl carboxyl chloride, norbornane carboxyl chloride, norbornene carboxyl chloride, adamantyl carboxylic acid chloride, isobornyl carboxylic acid chloride, 4-namidido benzoyl chloride , Cyclohexyl carboxylate benzotriazole, norbornene carboxylate benzotriazole and the like can be used.

Although the molecular weight of the polyamide polymer may be arbitrarily selected within a range that does not impair the effects of the present invention, while ensuring effective solubility and applicability, the weight average molecular weight (Mw) is 500 to maximize the effect of post-exposure pattern generation. It is preferably from 500,000 to 500,000, more preferably from 1,000 to 50,000. When the weight average molecular weight is in the above range, sufficient physical properties can be obtained, and since the solubility in organic solvents is excellent, the handling is easy and preferable.

[B] Esterized Quinonediazide Compounds

The esterified quinonediazide compound is a compound serving as a photo active compound (PAC), and preferably has a compound having a 1,2-benzoquinonediazide structure or a 1,2-naphthoquinonediazide structure. Can be used. This is a material known from US Pat. Nos. 2,772,972, 2,797,213, 3,669,658 and the like. Representative examples of the esterified quinonediazide compound include compounds represented by the following Chemical Formulas 17 to 19, but are not limited thereto.

[Formula 17]

[Formula 18]

[Formula 18-1]

[Formula 18-2]

[Formula 19]

In Chemical Formulas 17 to 19,

G ₁ to G ₄ are the same or different from each other, and each independently may be selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group, preferably the alkyl group may be a methyl group,

n ₁ to n ₉ are the same or different from each other, and each independently an integer of 1 to 3,

m ₃ may be an integer from 0 to 3,

D ₁ to D ₉ may be the same or different from each other, and may each independently be OQ,

Q may be hydrogen, or Chemical Formula 18-1 or 18-2, wherein Q is hydrogen (the ratio of OH substituted in an aromatic ring) may be 0 to 90 mol%, more preferably 30 To 80 mole%. In the above range, appropriate photosensitivity can be imparted, and appropriate light absorption is exhibited, which is beneficial for pattern formation.

The esterified quinonediazide compound may be used in an amount of 1 to 50 parts by weight, and more preferably 5 to 30 parts by weight, based on 100 parts by weight of the polyamide polymer. When the content of the esterified quinonediazide compound is in the above range, the pattern is well formed without residue by exposure, and it is preferable because there is no loss of film thickness during development and a good pattern can be obtained.

(C) phenol group containing compound

The said phenol group containing compound functions as a dissolution inhibitor which controls the difference in the dissolution rate of an exposed part and a non-exposed part.

Representative examples of such phenol group-containing compounds include 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, and the like. It may include, but is not limited thereto.

Typical examples of the phenol group-containing compound include, but are not limited to, those represented by the following Chemical Formulas 20 to 25.

[Formula 20]

In Formula 20, R ₈ to R ₁₀ may be the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

R ₁₁ to R ₁₅ 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 ₁₀ may be an integer from 1 to 5.

[Formula 21]

(In Chemical Formula 21,

R ₁₆ to R ₂₁ 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 ₁₁ + n ₁₂ + n ₁₃ and n ₁₄ + n ₁₅ + n ₁₆ may be the same or different from each other, and may each independently be an integer of 5 or less.)

[Formula 22]

(In Chemical Formula 22,

R ₂₂ to R ₂₄ may be the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

N ₁₇ , n ₁₈ , and n ₂₁ may be the same or different from each other, and may be each independently an integer of 1 to 5, and n ₁₉ and n ₂₀ may be the same or different from each other, and may each independently be an integer of 0 to 4; have.)

[Formula 23]

(In Formula 23,

R ₂₅ to R ₂₇ 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 ₂₂ to n ₂₆ are the same or different from each other, and each independently may be an integer of 1 to 4, provided that n ₂₂ + n ₂₄ and n ₂₃ + n ₂₆ are each independently an integer of 5 or less.)

[Formula 24]

(In Chemical Formula 24,

R ₂₈ may be a substituted or unsubstituted alkyl group, preferably CH ₃ ,

R ₂₉ to R ₃₁ are the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

n ₂₇ , n ₂₉ , and n ₃₁ are the same or different from each other, and each independently may be an integer of 1 to 5,

n ₂₈ , n ₃₀ , and n ₃₂ are the same or different from each other, and each independently may be an integer of 0 to 4,

Provided that n ₂₇ + n ₂₈ , n ₂₉ + n ₃₀ , and n ₃₁ + n ₃₂ are each independently an integer of 5 or less.)

[Formula 25]

(In Chemical Formula 25,

R ₃₂ , R ₃₃ , and R ₃₄ are the same or different from each other, and may each independently be a substituted or unsubstituted alkyl group, preferably CH ₃ ,

R ₃₅ to R ₃₈ are the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkoxy group,

n _33, n ₃₅ , and n ₃₉ are the same or different from each other, and each independently may be an integer of 1 to 5,

n ₃₄ , n ₃₆ , and n ₃₈ are the same or different from each other, and each independently may be an integer of 0 to 4,

n ₃₇ may be an integer from 1 to 4,

Provided that n ₃₃ + n ₃₄ , n ₃₅₊ n ₃₆ , and n ₃₈ + n ₃₉ are each independently an integer of 5 or less.)

The phenol group-containing compound is preferably used in 0.1 to 30 parts by weight based on 100 parts by weight of the polyamide polymer. When the content of the phenol group-containing compound is in the above range, it does not cause a decrease in sensitivity during development, and moderately increases the dissolution rate of the non-exposed part to obtain a good pattern, and does not cause precipitation during freezing storage, and thus excellent storage stability It is preferable because it can show.

(D) 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, methyl lactate, ethyl lactate, methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol mono Methyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl pyruvate, ethyl pyruvate, or 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 and the polyamide polymer may be used in a weight ratio of 20:80 to 90:10. 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.

According to another embodiment of the present invention, a method of manufacturing a photosensitive pattern using a positive photosensitive resin composition may be provided.

Said process of manufacturing 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, and drying it to form a resin composition layer; Exposing the resin composition layer; Developing the exposed resin composition layer with an alkaline developer; And heating the developed resin composition layer.

FIG. 1 is a view illustrating a process of manufacturing a pattern using the positive photosensitive resin composition. Hereinafter, each process will be described in detail with reference to FIG. 1.

As shown in FIG. 1, first, a photosensitive resin composition may be applied onto a workpiece 1 such as a semiconductor substrate to form a photosensitive resin composition layer 2 (S1).

Then, the photosensitive resin composition layer is exposed (S2) to cause a chemical change in the resin composition to increase the dissolution rate of the exposed portion, and develop in an alkaline solution (S3) to form a pattern.

When the photosensitive resin composition layer 2 is exposed by irradiating UV light such as i-line using a photomask (not shown) or the like in the exposure step S2, the exposure part 3 chemically changes the photosensitive agent. Occurs, and no chemical change occurs in the non-exposed part 4. In a subsequent process, when the exposed photosensitive resin composition layer is developed with an aqueous alkali solution (S3), the exposed portion 3 having a chemical change is removed to form a photosensitive resin composition layer 5 having a pattern.

When the photosensitive resin composition layer on which the pattern is formed is heated, the pattern layer of the resin composition may be cured to form the photosensitive resin composition film layer 6.

According to another embodiment of the present invention, an electronic component for a semiconductor including a photosensitive resin film manufactured using the positive photosensitive resin composition may be provided, and the photosensitive resin film 6 may be a surface protective film or an interlayer insulating film. Can be used. In addition, it can be widely used in various fields requiring a positive high sensitivity and a high resolution pattern.

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 the purpose of explanation and are not intended to limit the present invention.

Synthesis Example 1 Synthesis of Polyamide Polymer

18.3 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added while passing nitrogen through a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injection device, and a cooler. 280 g of methyl-2-pyrrolidone (NMP) was added and dissolved.

When the solid is completely dissolved, 9.9 g of pyridine is added to the solution, and 14.8 g of 4,4'-oxydibenzoyl chloride is added to N-methyl-2-pyrrolidone (NMP) while maintaining the temperature of the solution at 5 ° C. The solution dissolved in 142 g was slowly added dropwise for 30 minutes. After dropping, the reaction was carried out at 5 ° C. for 1 hour, the temperature was raised to room temperature, followed by stirring for 1 hour, and cyclohexyl. 1.5 g of carboxychloride was added thereto, stirred 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. The precipitate was filtered and thoroughly washed with water. It dried at 80 degreeC or more for 24 hours, and synthesize | combined the polyamide polymer of following formula (1-1). The weight average molecular weight was 11K as a result of GPC measurement of the synthesized polymer.

(Formula 1-1)

Synthesis Example 2 Synthesis of Polyamide Polymer

A polyamide polymer of the following Chemical Formula 1-2 was synthesized in the same manner as in Synthesis Example 1, except that 1.5 g of cyclohexyl carboxychloride was changed to 1.5 g of norbornane carboxychloride. The weight average molecular weight (Mw) of this polymer was 10K.

(Formula 1-2)

Synthesis Example 3 Synthesis of Polyamide Polymer

17.4 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoro propane while passing nitrogen through a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injector, and a cooler 0.86 g of 3-bis (aminopropyl) tetramethyldisiloxane was added, and 280 g of N-methyl-2-pyrrolidone (NMP) was added thereto to dissolve it.

When the solid was completely dissolved, 9.9 g of pyridine was added, and 13.3 g of 4,4'-oxydibenzoyl chloride was added thereto while N-methyl-2-pyrrolidone ( NMP) was added dropwise into the solution of 142g and slowly dissolved for 30 minutes. After dropping, the reaction was carried out at a temperature of 5 ° C. for 1 hour, and the reaction was carried out for 1 hour by raising the temperature to room temperature. Here, 1.5 g of cyclohexyl carboxychloride was added thereto, and the reaction was terminated by stirring at room temperature for 2 hours.

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 thoroughly washed with water. The polyamide polymer of Formula 1-3 was synthesized by drying at a temperature of 80 ° C. under vacuum for at least 24 hours. The weight average molecular weight of this polymer was 11K.

(Formula 1-3)

Synthesis Example 4 Synthesis of Polyamide Polymer

A polyamide polymer of the following Chemical Formula 1-4 was synthesized in the same manner as in Synthesis Example 3, except that 1.5 g of cyclohexyl carboxychloride was changed to 1.5 g of norbornane carboxychloride. The weight average molecular weight of this polymer was 10K.

(Formula 1-4)

Synthesis Example 5>: Synthesis of polyamide polymer

18.3 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added while passing nitrogen through a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injection device, and a cooler. 280 g of methyl-2-pyrrolidone (NMP) was added and dissolved.

When the solid was completely dissolved, 9.9 g of pyridine was added, and 11.8 g of 4,4'-oxydibenzoyl chloride and 2.5 g of phthalic chloride were added N-methyl-2-pi while maintaining the temperature of the obtained solution at 5 ° C. The solution dissolved in 142 g of rollidone (NMP) was dissolved dropwise for 30 minutes. After dropping, the reaction was carried out at a temperature of 5 ° C. for 1 hour, the temperature was raised to room temperature, the mixture was stirred for 1 hour, 1.5 g of cyclohexyl carboxychloride was added thereto, and the reaction was terminated after further stirring for 1 hour.

The reaction mixture was poured into a solution of water / methanol = 10/1 (volume ratio) to form a precipitate, and the precipitate was filtered and washed sufficiently with water. The polyamide polymer of Formula 1-5 was synthesized by drying at a temperature of 80 ° C. under vacuum for at least 24 hours. The weight average molecular weight of this high molecule was 11K.

(Formula 1-5)

Synthesis Example 6 Synthesis of Polyamide Polymer

A polyamide polymer of the following Chemical Formula 1-6 was synthesized in the same manner as in Synthesis Example 5, except that 1.5 g of cyclohexyl carboxychloride was changed to 1.5 g of norbornane carboxychloride. The weight average molecular weight of this polymer was 10K.

(Formula 1-6)

Synthesis Example 7 Synthesis of Polyamide Polymer

A polyamide polymer of the following Chemical Formula 1-7 was synthesized in the same manner as in Synthesis Example 1, except that 1.5 g of cyclohexyl carboxychloride was changed to 1.5 g of maleic anhydride. The weight average molecular weight of this polymer was 10K.

(Formula 1-7)

Synthesis Example 8 Synthesis of Polyamide Polymer

1.5 g of cyclohexyl carboxychloride A polyamide polymer of the following Chemical Formula 1-8 was synthesized in the same manner as in Synthesis Example 1 except that 1.5 g of 5-norbornene-2,3-carboxylic anhydride was changed. The weight average molecular weight of this polymer was 11K.

(Formula 1-8)

<Examples 1-12>: Preparation of the photosensitive resin composition

The polyamide polymer synthesized in Synthesis Examples 1 to 8, an esterified quinone diazide compound represented by the following formula Lolactone (GBL) was mixed in the composition ratios shown in Table 1 below to prepare a positive photosensitive resin composition.

In this case, 26a described in Table 1 means a compound in which two of Q ₁ to Q ₃ of Formula 26 are represented by Formula 26-1 and the other one is hydrogen, and 26b represents two compounds of Q ₁ to Q ₃ represented by Formula 26 to Formula 26- 2 and the other one is hydrogen.

[Formula 26]

[Formula 26-1]

[Formula 26-2]

TABLE 1

 Example  Polyamide polymer  Esterified quinonediazide compounds  2,6-diacetoxy methyl-p-cresol  Solvent (GBL)  One  10 g, Synthesis Example 1  26a, 2 g  1 g  20 g  2  10 g, Synthesis Example 1  26b, 2 g  1 g  20 g  3  10 g, Synthesis Example 2  26a, 2 g  1 g  20 g  4  10 g, Synthesis Example 2  26b, 2 g  1 g  20 g  5  10 g, Synthesis Example 3  26a, 2 g  1 g  20 g  6  10 g, Synthesis Example 3  26b, 2 g  1 g  20 g  7  10 g, Synthesis Example 4  26a, 2 g  1 g  20 g  8  10 g, Synthesis Example 4  26b, 2 g  1 g  20 g  9  10 g, Synthesis Example 5  26a, 2 g  1 g  20 g  10  10 g, Synthesis Example 5  26b, 2 g  1 g  20 g  11  10 g, Synthesis Example 6  26a, 2 g  1 g  20 g  12  10 g, Synthesis Example 6  26b, 2 g  1 g  20 g

<Comparative Examples 1-4>: Preparation of Photosensitive Resin Composition

The polyamide polymers, esterified quinonediazide compounds, phenol group-containing compounds, and solvents prepared in Synthesis Examples 7 and 8 were mixed in the compositions shown in Table 2 to prepare photosensitive resin compositions. The esterified quinonediazide compounds of Table 2 below are the same as defined in Table 1.

TABLE 2

 Comparative example  Polyamide polymer  Esterified quinonediazide compounds  2,6-diacetoxy methyl-p-cresol  Solvent (GBL)  One  10 g, Synthesis Example 7  26a, 2 g  1 g  20 g  2  10 g, Synthesis Example 7  26b, 2 g  1 g  20 g  3  10 g, Synthesis Example 8  26a, 2 g  1 g  1 g  4  10 g, Synthesis Example 8  26b, 2 g  1 g  1 g

<Examples 13 to 24>: Lithography experiments

Lithography experiments were carried out on the photosensitive resin compositions prepared in Examples 1 to 12 as follows, and the results are shown in Table 3 as Examples 13 to 24, respectively.

On the silicon wafer, each of the positive photosensitive resin compositions made in Examples 1 to 12 was coated and prebaked at 125 ° C. for 120 seconds.

The silicon wafer coated with the photosensitive resin composition was exposed with a Nikoni10c i-line stepper as an exposure apparatus, and developed for 2 minutes with a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution. Then, after dipping in distilled water for 1 minute and washed, the CD (critical dimension) was measured using FE-SEM.

In addition, the sensitivity was determined to be an optimum exposure time by obtaining an exposure time in which a 10 μm L / S pattern was formed with a line width of 1 to 1 after exposure and development. The resolution made resolution the minimum pattern dimension in the said optimal exposure time.

After the pattern was formed, the mixture was heated at 150 ° C. for 30 minutes in a nitrogen atmosphere, and then heated to 350 ° C. for 1 hour, and heated at 350 ° C. for 1 hour to prepare a cured film.

[Table 3]

Exposure energy (mJ / cm ² )  Resolution (μm)  Example 13  400  3  Example 14  300  3  Example 15  370  3  Example 16  280  3  Example 17  440  3  Example 18  350  3  Example 19  420  3  Example 20  330  3  Example 21  380  2  Example 22  300  3  Example 23  480  3  Example 24  290  3

Referring to Table 3, it was confirmed that the resolutions all show excellent values of 3 µm or less. In addition, it was confirmed that the exposure energy value is 400mJ / cm ² or less, showing very excellent optical properties. This is because the terminal of the polyamide polymer is substituted by an alkyl group, an alicyclic group, or an aryl group, not due to an unhydride, and thus the transmission rate is maximized while maximizing the dissolution rate difference between the non-exposed part and the exposed part. do.

<Comparative Examples 5 to 8>: Lithography experiment

Except for using the photosensitive resin composition prepared in Comparative Examples 1 to 4 after the lithography experiment in the same manner as in Example 13, the results are shown in Table 4 as Comparative Examples 5 to 8.

[Table 4]

Exposure energy (mJ / cm ² )  Resolution (μm)  Comparative Example 5  670  5  Comparative Example 6  500  7  Comparative Example 7  680  7  Comparative Example 8  490  5

Referring to Table 4, in Comparative Examples 5 to 8 using the positive photosensitive resin composition solution prepared in Comparative Examples 1 to 4, the transmittance was low, and the exposure energy was relatively higher than that of the examples. It was confirmed that the dissolution rate difference was resolution or 5 µm or more due to the carboxylic acid remaining at the terminal.

In addition, the above embodiment has been described with a line and space (L / S) pattern, but the present invention is not limited thereto and may be applied to miniaturization of various patterns such as hole patterns.

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

1 is a view showing a step of producing a pattern using the positive photosensitive resin composition.

<Explanation of symbols for the main parts of the drawings>

1: semiconductor device

2: photosensitive resin composition layer

3: exposed part of photosensitive resin composition layer

4: non-exposed part of photosensitive resin composition layer

5: the photosensitive resin composition layer in which the pattern after image development was formed

6: photosensitive resin composition film layer after hardening

Claims (11)

(A) a polyamide polymer represented by the following formula (1); (B) esterified quinonediazide compounds; (C) phenol group containing compound; And (D) solvent Positive photosensitive resin composition comprising a. [Formula 1]

(In Chemical Formula 1) X ₁ and X ₂ are the same or different from each other, and each independently a divalent to tetravalent organic group, Y ₁ and Y ₂ are the same or different from each other, and each independently a divalent to hexavalent organic group, R ₁ and R ₂ are the same or different from each other, and each independently hydrogen or an organic group having 1 to 5 carbon atoms, E ₁ and E ₂ are the same or different from each other, and each independently hydrogen; Or a residue of one selected from the group consisting of single carboxylic acids and active derivatives thereof, wherein E ₁ and E ₂ may not be hydrogen at the same time, m ₁ and m ₂ are the same or different from each other, each independently 0 to 100, m ₁ + m ₂ is 5 to 100.) The method of claim 1, The esterified quinonediazide compound may be included in an amount of 1 to 50 parts by weight based on 100 parts by weight of the polyamide polymer. The phenol group-containing compound is included in 0.1 to 30 parts by weight with respect to 100 parts by weight of polyamide polymer, The solvent and the polyamide polymer is a photosensitive resin composition which is included in a weight ratio of 20:80 to 90:10. The method of claim 1, The polyamide is, After reacting the diamine monomer with an acid monomer selected from the group consisting of tetracarboxylic dianhydride, dicarboxylic anhydride, dicarboxylic acid, and active derivatives thereof, a reaction product is prepared. A positive photosensitive resin composition prepared by reacting the reaction product with a compound selected from the group consisting of a single carboxylic acid and an activated derivative thereof. The method of claim 3, The polyamine monomer is a positive photosensitive resin composition is represented by X (NH ₂ ) ₂ (wherein X is the same as X ₁ or X ₂ of Formula 1). The method of claim 3, The diamine monomer is a positive photosensitive resin comprising a silicon-free diamine monomer and a silicon-containing diamine monomer represented by X (NH ₂ ) ₂ (wherein X is the same as X ₁ or X ₂ of Formula 1). Composition. The method of claim 3, The acid monomer is a positive photosensitive resin composition that is a dicarboxylic acid monomer represented by Y (COOH) ₂ (wherein Y is the same as Y ₁ or Y ₂ of Formula 1). The method of claim 3, The acid monomer is Y (COK ') ₂ , wherein Y is the same as Y ₁ or Y ₂ of Formula 1, and K' is Y (COOH) ₂ and a halide or 1-hydroxy-1,2,3-benzo Positive photosensitive resin composition which is represented by the residue obtained by making triazole react. The method of claim 3, The acidic monomer is a positive photosensitive resin composition which is tetracarboxylic anhydride represented by the following formula (8). [Formula 8]

(In Formula 8, Y is the same as Y ₁ or Y ₂ of Formula 1) Applying the positive photosensitive resin composition of any one of claims 1 to 8 on a support substrate and drying to form a resin composition layer; Exposing the resin composition layer; Developing the exposed resin composition layer with an alkaline developer; And Heating the developed resin composition layer Method for producing a photosensitive pattern comprising a. The photosensitive resin film manufactured using the positive photosensitive resin composition of any one of Claims 1-8. An electronic component for a semiconductor comprising the photosensitive resin film of claim 10.

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