KR20110069467A - Ortho-nitrobenzyl ester compound and positive type photosensitive resin composition including the same - Google Patents

Abstract

PURPOSE: A positive type photosensitive resin composition including an ortho-nitrobenzyl ester compound is provided to ensure excellent sensitivity, resolution, pattern formation capablity and residue removal proeprty. CONSTITUTION: An ortho-nitrobenzyl ester compound includes a compound represented by chemical formula 1, a compound represented by chemical formula 2, or combination thereof. In chemical formulas 1 and 2, R1, R2, R5 and R6 are the same and different and represent substituted or unsubstituted aliphatic organic group or substituted or unsubstituted alicyclic organic group; R3 and R7 are the same and different and represent a single bond, or substituted or unsubstituted divalent organic group; R4, R8 and R9 are the same and different and represent substituted or unsubstituted aliphatic organic group or substituted or unsubstituted alicyclic organic group; n1 is an integer of 1-5; n2 is an integer of 0-3; n3 is an integer of 0-4; and n2+n3 is an integer of 1 or greater.

Description

ORTHO-NITROBENZYL ESTER COMPOUND AND POSITIVE TYPE PHOTOSENSITIVE RESIN COMPOSITION INCLUDING THE SAME}

The present disclosure relates to an ortho-nitrobenzyl ester compound and a positive photosensitive resin composition comprising the same.

The conventional positive photosensitive resin composition generally suppresses the dissolution of the resin having a phenolic hydroxyl group which is easily dissolved in an aqueous alkali solution, and during the non-exposure, and promotes the development of the resin during exposure or at least stops the inhibition of dissolution. It was prepared by mixing a photosensitive agent to enable the patterning. As such a resin, a novolak resin obtained by polycondensation of a phenol compound and formaldehyde, a poly (4-hydroxy) styrene resin, and a polyhydroxy amide, which is a polybenzoxazole precursor, were used. As a photosensitizer, 4-, or Diazonaptoquinone compounds having the form of sulfonic acid esters and amides in the 5-position are mainly used.

The performance of this type of dissolution inhibiting positive type photosensitive resin composition is characterized by the ability of the photosensitive agent to inhibit dissolution of the non-exposed portion, the ability of the photosensitive agent to readily decompose after exposure, and the ability of the dissolution rate of the resin to recover or promote due to the decomposition. Determined by In the case of diazonaptoquinone compounds used in the past, the photolysis rate and absorbing ability were excellent, but the ability to suppress the dissolution of non-exposed parts was not good, so that a relatively large amount of diazonaphtho was obtained in order to obtain an appropriate residual film ratio for patterning. Quinone compounds had to be used. Accordingly, the patterning of the exposed portion required the decomposition of a relatively large amount of diazonaptoquinone compound, and as a result, a higher exposure amount was required, which caused a relatively low sensitivity.

Therefore, research on the photosensitizer excellent in the ability to suppress the dissolution of a non-exposed part is made.

Provided is an ortho-nitrobenzyl ester compound having excellent ability to inhibit dissolution of non-exposed parts.

Provided is a positive photosensitive resin composition comprising the ortho-nitrobenzyl ester compound and excellent in sensitivity, resolution, pattern shape, and residue removal property.

It provides the photosensitive resin film manufactured using the said positive photosensitive resin composition.

Provided is a semiconductor device comprising the photosensitive resin film.

An aspect of the present invention provides an ortho-nitrobenzyl ester compound including a compound represented by the following Chemical Formula 1, a compound represented by the following Chemical Formula 2, or a combination thereof.

[Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2,

R ₁ , R ₂ , R ₅ and R ₆ are the same or different from each other, and each independently represent a substituted or unsubstituted aliphatic organic group, or a substituted or unsubstituted alicyclic organic group,

R ₃ and R ₇ are the same or different from each other, each independently represent a single bond or a substituted or unsubstituted divalent aliphatic organic group,

R ₄ , R ₈ and R ₉ are the same or different from each other, and each independently a substituted or unsubstituted aliphatic organic group, or a substituted or unsubstituted alicyclic organic group,

n ₁ is an integer of 1 to 5,

n ₂ is an integer of 0 to 3,

n ₃ is an integer of 0 to 4,

n ₂ + n ₃ is an integer of 1 or more.

Another aspect of the invention (A) a hydroxyl group-containing alkali-soluble resin; (B) the ortho-nitrobenzyl ester compound; (C) photosensitive diazoquinone compound; (D) silane compound; (E) phenolic compounds; And (F) to provide a positive photosensitive resin composition comprising a solvent.

The hydroxyl group-containing alkali-soluble resin is a polybenzoxazole precursor containing a repeating unit represented by the following formula (9), a novolak resin comprising a repeating unit represented by the following formula (10), a repeating unit represented by the following formula (11) It may include a poly-4-hydroxy styrene resin or a combination thereof.

[Formula 9]

In Chemical Formula 9,

X ₁ is the same or different in each repeating unit, and each independently an aromatic organic group,

Y ₁ is the same or different from each other in each repeating unit, and each independently an aromatic organic group or a divalent to hexavalent alicyclic organic group,

[Formula 10]

In Chemical Formula 10,

R ₁₀ are the same or different from each other, and each independently hydrogen or a C1 to C10 alkyl group,

n ₄ is an integer of 0 to 3,

[Formula 11]

In Chemical Formula 11,

R ₁₁ are the same or different from each other, and each independently hydrogen or a C1 to C10 alkyl group,

n ₅ is an integer of 0-4.

The hydroxyl group-containing alkali-soluble resin may have a weight average molecular weight (Mw) of 3,000 to 300,000.

The positive photosensitive resin composition may include (A) 0.1 to 20 parts by weight of (B) the ortho-nitrobenzyl ester compound based on 100 parts by weight of the hydroxy group-containing alkali-soluble resin; (C) 5 to 100 parts by weight of the photosensitive diazoquinone compound; (D) 0.1 to 30 parts by weight of the silane compound; (E) 1 to 30 parts by weight of the phenol compound; And (F) 200 to 900 parts by weight of the solvent.

According to still another aspect of the present invention, there is provided a photosensitive resin film manufactured using the positive photosensitive resin composition.

According to still another aspect of the present invention, a semiconductor device including the photosensitive resin film is provided.

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

Ortho-nitrobenzyl ester compound according to an aspect of the present invention has the ability to inhibit the dissolution of the hydroxy group-containing alkali-soluble resin in the non-exposed portion, and the photo-degradation in the exposed portion to stop the dissolution or contain a hydroxyl group Dissolution of alkali-soluble resin can be promoted. The positive photosensitive resin composition including the ortho-nitrobenzyl ester compound may have excellent sensitivity, resolution, pattern shape, and residue removal property.

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 specification, "substituted" to "substituted" means that at least one hydrogen of the functional group of the present invention is halogen (F, Br, Cl or I), hydroxy group, nitro group, cyano group, amino group (NH ₂ , NH (R ₁₀₀ ) or N (R ₁₀₁ ) (R ₁₀₂ ), wherein R ₁₀₀ , R ₁₀₁ and R ₁₀₂ are the same or different from each other, and are each independently C 1 to C 10 alkyl groups, amidino groups , Hydrazine group, hydrazone group, carboxyl group, substituted or unsubstituted alkyl group, substituted or unsubstituted haloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alicyclic organic group, substituted or unsubstituted aryl group , Substituted or unsubstituted alkenyl group, substituted or unsubstituted alkynyl group, substituted or unsubstituted heteroaryl group, and substituted or unsubstituted heterocycloalkyl group means one substituted with one or more substituents selected from the group do.

Unless stated otherwise in the present specification, "alkyl group" means a C1 to C30 alkyl group, specifically, a C1 to C15 alkyl group, and a "cycloalkyl group" means a C3 to C30 cycloalkyl group, specifically C3 To C18 cycloalkyl group, "heterocycloalkyl group" means C2 to C30 heterocycloalkyl group, specifically C2 to C18 heterocycloalkyl group, "alkenyl group" means C2 to C30 alkenyl group , Specifically, a C2 to C18 alkenyl group, "alkylene group" means a C1 to C30 alkylene group, specifically, a C1 to C18 alkylene group, and "alkoxy group" means a C1 to C30 alkoxy group In particular, it means a C1 to C18 alkoxy group, "cycloalkylene group" means a C3 to C30 cycloalkylene group, specifically, between C3 to C18 Refers to a roalkylene group, "heterocycloalkylene group" means a C2 to C30 heterocycloalkylene group, specifically means a C2 to C18 heterocycloalkylene group, "aryl group" means a C6 to C30 aryl group , Specifically, a C6 to C18 aryl group, "heteroaryl group" refers to a C2 to C30 heteroaryl group, specifically a C2 to C18 heteroaryl group, "arylene" group refers to a C6 to C30 arylene group It means, specifically, C6 to C18 arylene group, "heteroarylene group" means C2 to C30 heteroarylene group, specifically means C2 to C18 heteroarylene group, "alkylaryl group" Means a C7 to C30 alkylaryl group, specifically means a C7 to C20 alkylaryl group, "halogen" means F, Cl, Br or I.

Also, unless stated otherwise in the present specification, a heterocycloalkyl group, a heterocycloalkylene group, a heteroaryl group, and a heteroarylene group each independently represent one or more heteroatoms of N, O, S, Si, or P in one ring. It contains three, and the rest means a cycloalkylene group, an aryl group, and an arylene group which are carbon.

Also, unless stated otherwise in the specification, an "aliphatic organic group" means a C1 to C30 alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group, a C1 to C30 alkylene group, a C2 to C30 alkenylene group, or a C2 to C30 group. An alkynylene group, specifically, a C1 to C15 alkyl group, a C2 to C15 alkenyl group, a C2 to C15 alkynyl group, a C1 to C15 alkylene group, a C2 to C15 alkenylene group, or a C2 to C15 alkynylene group, and Alicyclic organic group "means a C3 to C30 cycloalkyl group, a C3 to C30 cycloalkenyl group, a C3 to C30 cycloalkynyl group, a C3 to C30 cycloalkylene group, a C3 to C30 cycloalkenylene group, or a C3 to C30 cycloalkynylene group Specifically, C3 to C15 cycloalkyl group, C3 to C15 cycloalkenyl group, C3 to C15 cycloalkynyl group, C3 to C15 cycloalkylene group, C3 to C15 cycloalkenylene group, Or C3 to C15 cycloalkynylene group, and "aromatic organic group" means C6 to C30 aryl group, C2 to C30 heteroaryl group, C6 to C30 arylene group, or C2 to C30 heteroarylene group, specifically C6 To C16 aryl group, C2 to C16 heteroaryl group, C6 to C16 arylene group or C2 to C16 heteroarylene group.

Unless otherwise defined herein, “combination” means mixed or copolymerized. In addition, "copolymerization" means block copolymerization to random copolymerization, and "copolymer" means block copolymer to random copolymerization.

In addition, in the present specification, "*" means a part connected with the same or different atoms or formulas.

According to one embodiment of the present invention, an ortho-nitrobenzyl ester compound including a compound represented by the following Chemical Formula 1, a compound represented by the following Chemical Formula 2, or a combination thereof is provided.

[Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2,

R ₁ , R ₂ , R ₅ and R ₆ are the same or different from each other, and each independently represent a substituted or unsubstituted aliphatic organic group, or a substituted or unsubstituted alicyclic organic group, and specifically, a substituted or unsubstituted group. It may be a C1 to C10 aliphatic organic group, or a substituted or unsubstituted C3 to C10 alicyclic organic group.

R ₃ and R ₇ are the same or different from each other, and each independently represent a single bond or a substituted or unsubstituted divalent aliphatic organic group, and specifically, may be a substituted or unsubstituted C1 to C5 aliphatic organic group. When R ₃ and R ₇ are substituted or unsubstituted C1 to C5 aliphatic organic groups, excellent sensitivity can be obtained, and also excellent thermal stability and optical stability can be effectively maintained.

R ₄ , R ₈ and R ₉ are the same or different from each other, and each independently represent a substituted or unsubstituted aliphatic organic group or a substituted or unsubstituted alicyclic organic group, and specifically, a substituted or unsubstituted C1 to C15 It may be an aliphatic organic group, or a substituted or unsubstituted C3 to C15 alicyclic organic group, more specifically, a substituted or unsubstituted C1 to C10 aliphatic organic group, or a substituted or unsubstituted C3 to C10 alicyclic organic group There is,

n ₁ is an integer of 1 to 5,

n ₂ is an integer of 0 to 3,

n ₃ is an integer of 0 to 4,

n ₂ + n ₃ is an integer of 1 or more.

In this case, n ₁ is the case of 2 or more integer, R each ₄ can, if the same or may be different from each other, n ₂ is 2 or more integer, each of R ₈ are the same or be different from each other, n ₃ In this case, two or more integer, R Each of ₉ may be the same or different from each other.

The ortho-nitrobenzyl ester compound represented by the above formulas (1) and (2) has an effect of inhibiting the dissolution of the hydroxyl group-containing alkali-soluble resin in the aqueous alkali solution due to the polarity difference.

In addition, ortho-nitrobenzyl ester compounds represented by Chemical Formulas 1 and 2 have ether groups in 5- and 6-positions, such as -OR ₁ , -OR ₂ , -OR _5, and -OR ₆ . The ether group exhibits an electron donating effect, which induces an absorption wavelength into a long wavelength region, thereby causing light having a wavelength of 300 nm to 450 nm, specifically, an i-line (365 nm) light. Can be easily absorbed. When the ortho-nitrobenzyl ester compound represented by Formulas 1 and 2 absorbs light and decomposes, the hydroxy group-containing alkali-soluble resin can be easily dissolved in an aqueous alkali solution.

Therefore, the ortho-nitrobenzyl ester compound represented by Chemical Formulas 1 and 2 may be used as a photosensitive assistant to dissolution regulator in the positive photosensitive resin composition.

Specific examples of the ortho-nitrobenzyl ester compound represented by Chemical Formulas 1 and 2 include, but are not limited to, compounds represented by Chemical Formulas 3 to 8.

(3)

[Formula 4]

[Chemical Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

According to another embodiment of the present invention (A) a hydroxyl group-containing alkali-soluble resin; (B) the ortho-nitrobenzyl ester compound; 　 (C) photosensitive diazoquinone compound; (D) silane compound; (E) phenolic compounds; And (F) it provides a positive photosensitive resin composition containing a solvent.

In addition, the positive photosensitive resin composition may further include (G) other additives.

Hereinafter, each component will be described in detail.

(A) Hydroxyl group  Alkali-soluble resin

The hydroxyl group-containing alkali-soluble resin is a polybenzoxazole precursor containing a repeating unit represented by the following formula (9), a novolak resin comprising a repeating unit represented by the following formula (10), a repeating unit represented by the following formula (11) It may include a poly-4-hydroxy styrene resin or a combination thereof.

[Formula 9]

In Chemical Formula 9,

X ₁ is the same or different in each repeating unit, and each independently an aromatic organic group,

Y ₁ is the same as or different from each other in each repeating unit, and each independently an aromatic organic group or a divalent to hexavalent alicyclic organic group.

[Formula 10]

In Chemical Formula 10,

R ₁₀ are the same or different from each other, and each independently hydrogen or a C1 to C10 alkyl group,

n ₄ is an integer of 0 to 3.

R ₁₀ may be the same or different in each repeating unit, and when n ₄ is an integer of 2 or more, each of R ₁₀ may be the same or different in one repeating unit.

[Formula 11]

In Chemical Formula 11,

R ₁₁ are the same or different from each other, and each independently hydrogen or a C1 to C10 alkyl group,

n ₅ is an integer of 0-4.

R ₁₁ may be the same or different in each repeating unit, and when n ₅ is an integer of 2 or more, each of R ₁₁ may be the same or different in one repeating unit.

In Formula 9, X ₁ may be a residue derived from an aromatic diamine as an aromatic organic group.

Examples of the aromatic diamine include 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-trifluoromethylphenyl) hexafluoropropane, 2 , 2-bis (4-amino-3-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxy-6-triflu Oromethylphenyl) hexafluoropropane, 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-pentafluoro Ethylphenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-5-trifluoromethylphenyl) -2- (3-hydroxy-4-amino-5-trifluoromethylphenyl) hexafluoro Propane, 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 Hydroxy-2-trifluoromethylphenyl) -2- (3-hydroxy-4-amimi -5-trifluoromethylphenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-6-trifluoromethylphenyl) -2- (3-hydroxy-4-amino-5-trifluoro Methylphenyl) hexafluoropropane, or a combination thereof, but is not limited thereto.

Examples of the X ₁ may be a functional group represented by the following Chemical Formulas 12 and 13, but is not limited thereto.

[Chemical Formula 12]

[Formula 13]

In Chemical Formulas 12 and 13,

A ₁ is O, CO, CR ₁₀₃ R ₁₀₄ , SO ₂ , S or a single bond, wherein R ₁₀₃ and R ₁₀₄ are the same or different from each other and are each independently hydrogen or a substituted or unsubstituted alkyl group, specifically, fluorine It may be a roalkyl group,

R ₁₂ to R ₁₄ are the same or different from each other, and each independently hydrogen, a substituted or unsubstituted alkyl group, 　 It is selected from the group consisting of a hydroxyl group, a carboxyl group and a thiol group,

n ₆ is an integer of 1 to 2,

n ₇ and n ₈ are the same or different from each other, and each independently an integer of 1 to 3.

In Formula 9, Y ₁ may be an aromatic organic group or a divalent to hexavalent alicyclic organic group, and may be a residue of dicarboxylic acid or a residue of dicarboxylic acid derivative.

Examples of the dicarboxylic acid may include Y ₁ (COOH) ₂ (wherein Y ₁ is the same as Y ₁ of Formula 9).

Examples of the di-carboxylic acid derivatives is Y ₁ (COOH) ₂ of the carbonyl halide derivative, or Y ₁ (COOH) ₂ and 1-hydroxy-1,2,3-benzotriazole-active ester derivative by reacting a sol such as And an active compound (wherein Y ₁ is the same as Y _{1 in} Formula 9). Specific examples of the dicarboxylic acid derivatives include 4,4'-oxydibenzoyl chloride, diphenyloxydicarbonyldichloride, bis (phenylcarbonyl chloride) sulfone, bis (phenylcarbonyl chloride) ether, bis (phenylcarbonyl chloride). ) Phenone, phthaloyldichloride, terephthaloyldichloride, isophthaloyldichloride, dicarbonyldichloride, diphenyloxydicarboxylate dibenzotriazole or combinations thereof, but is not limited thereto.

Examples of the Y ₁ may be a functional group represented by the following Chemical Formulas 14 to 16, but are not limited thereto.

[Formula 14]

[Formula 15]

[Formula 16]

In Chemical Formulas 14 to 16,

R ₁₅ to R ₁₈ are the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

n ₉ , n ₁₇ and n ₁₈ are integers from 1 to 4,

n ₁₀ is an integer of 1 to 3,

A ₂ is O, CR ₁₀₅ R ₁₀₆ , CO, CONH, S, SO ₂ ,  Or a single bond, R ₁₀₅ and R ₁₀₆ are the same or different from each other, and each independently hydrogen, a substituted or unsubstituted alkyl group, and specifically, a fluoroalkyl group.

The hydroxyl group-containing alkali-soluble resin may have a weight average molecular weight (Mw) of 3,000 to 300,000. When the weight average molecular weight of the hydroxyl group-containing alkali-soluble resin is within the above range, a sufficient residual film ratio can be obtained in the non-exposed part during development with an aqueous alkali solution, and patterning can be efficiently performed.

(B) Ortho - Nitrobenzyl  Ester compound

The ortho-nitrobenzyl ester compound may include a compound represented by Formula 1, a compound represented by Formula 2, or a combination thereof. Specific examples of the ortho-nitrobenzyl ester compound may include a compound represented by Formula 3 to 8, but is not limited thereto.

The ortho-nitrobenzyl ester compound can suppress dissolution of the hydroxy group-containing alkali-soluble resin in the non-exposed part. Meanwhile, in the exposed portion, the ortho-nitrobenzyl ester compound may be decomposed to easily dissolve the hydroxy group-containing alkali-soluble resin. This may allow efficient and selective patterning when the ortho-nitrobenzyl ester compound is used as a photosensitive aid or dissolution modifier.

In the positive photosensitive resin composition, the content of the ortho-nitrobenzyl ester compound is 0.1 to 20 parts by weight, specifically 0.5 to 10 parts by weight, more specifically, based on 100 parts by weight of the hydroxy group-containing alkali-soluble resin. May be 1 to 2 parts by weight. When the content of the ortho-nitrobenzyl ester compound is within the above range, the dissolution inhibiting effect of the non-exposed part can be maintained excellent. In addition, in the exposed portion, the ortho-nitrobenzyl ester compound is effectively absorbed and decomposed together with the following photosensitive diazoquinone compound, so that the hydroxyl group-containing alkali-soluble resin can be easily dissolved. As a result, the pattern is well formed without the residue by exposure, there is no loss of the film thickness during development, and a good pattern can be obtained. As a result, the ortho-nitrobenzyl ester compound can function as a photosensitizer to a dissolution regulator, specifically a dissolution inhibitor.

(C) photosensitive diazoquinone compound

As the photosensitive diazoquinone compound, a compound having a 1,2-benzoquinone diazide structure or a 1,2-naphthoquinone diazide structure may be preferably used, which is described in US Patent Nos. 2,772,975, 2,797,213, and Material known from US Pat. No. 3,669,658.

Examples of the photosensitive diazoquinone compound include compounds represented by the following Chemical Formula 17 and Chemical Formulas 19 to 21, but are not limited thereto.

[Formula 17]

In Chemical Formula 17,

R ₁₉ to R ₂₁ are the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group, and specifically may be CH ₃ ,

R ₂₂ to R ₂₄ are the same or different from each other, and each independently OQ, wherein Q is hydrogen, a functional group represented by Formula 18a, or a functional group represented by Formula 18b, wherein Q may not be hydrogen at the same time,

n ₁₃ to n ₁₅ are each independently an integer of 1 to 3;

[Formula 18a]

[Formula 18b]

[Formula 19]

In Chemical Formula 19,

R ₂₅ is hydrogen or a substituted or unsubstituted alkyl group,

R ₂₆ to R ₂₈ are the same or different from each other, and each independently OQ, wherein Q is the same as defined in Formula 17,

n ₁₆ To n ₁₈ are each independently an integer of 1 to 3;

[Formula 20]

In Chemical Formula 20,

A ₃ is CO or CR ₁₀₇ R ₁₀₈ , wherein R ₁₀₇ And R ₁₀₈ are the same or different from each other, and each independently a substituted or unsubstituted alkyl group,

R ₂₉ to R ₃₂ 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 17,

n ₁₉ to n ₂₂ are each independently an integer of 1 to 4,

n ₁₉ + n ₂₀ and n ₂₁ + n ₂₂ are each independently an integer of 5 or less,

However, at least one of the R ₂₉ and R ₃₀ is OQ, one aromatic ring may contain one to three OQ, the other aromatic ring may contain one to four OQ.

[Formula 21]

In Chemical Formula 21,

R ₃₃ to R ₄₀ are the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

n ₂₃ and n ₂₄ are each independently an integer of 1 to 5,

Q is the same as defined in Formula 17 above.

In the positive photosensitive resin composition, the content of the photosensitive diazoquinone compound may be 5 to 100 parts by weight based on 100 parts by weight of the hydroxy group-containing alkali-soluble resin. 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.

(D) silane compound

The silane compound may improve the adhesion between the photosensitive resin composition and the substrate, and then improve the adhesion between the epoxy molding compound (EMC) and the photosensitive resin film which may come on top of the photosensitive resin film in the semiconductor manufacturing process. You can.

Examples of the silane compound include compounds represented by the following Chemical Formulas 22 to 24; Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane; Or 3-Macryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, # 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 22]

In Chemical Formula 22,

R ₄₁ is a vinyl group, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, and may specifically be 3- (meth) acryloxypropyl, p-styryl or 3- (phenylamino) propyl, ,

R ₄₂ To R ₄₄ are the same or different from each other, and each independently a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkyl group, or halogen, wherein R ₄₂ To R ₄₄ At least one is an alkoxy group or a halogen, specifically, the alkoxy group may be a C1 to C8 alkoxy group, the alkyl group may be a C1 to C20 alkyl group.

(23)

In Chemical Formula 23,

R ₄₅ are the same or different from each other, and each independently NH ₂ or CH ₃ CONH,

R ₄₆ to R ₄₈ are the same or different from each other, and each independently a substituted or unsubstituted alkoxy group, specifically the alkoxy group may be OCH ₃ or OCH ₂ CH ₃ ,

n ₂₅ is an integer of 1 to 5.

[Formula 24]

In Chemical Formula 24,

R ₄₉ R ₅₂ to the same or different from each other, each independently represent a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkoxy group, specifically CH ₃ or OCH ₃ ,

R ₅₃ and R ₅₄ are the same or different from each other, each independently represent a substituted or unsubstituted amino group, specifically NH ₂ or CH ₃ CONH,

n ₂₆ and n ₂₇ are each independently an integer of 1 to 5;

The content of the silane compound may be 0.1 to 30 parts by weight based on 100 parts by weight of the hydroxyl group-containing alkali-soluble resin. 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.

(E) 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.

Examples of the phenolic compound include compounds represented by the following Chemical Formulas 25 to 30, but are not limited thereto.

[Formula 25]

In Chemical Formula 25,

R ₅₅ to R ₅₇ are the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

R ₅₈ to R ₆₂ are the same or different from each other, and each independently H, OH, or a substituted or unsubstituted alkyl group, specifically, the alkyl group may be CH ₃ ,

n ₂₈ is an integer of 1 to 5;

[Formula 26]

In Chemical Formula 26,

R ₆₃ to R ₆₈ are the same or different from each other, and each independently H, OH, or a substituted or unsubstituted alkyl group,

A ₄ is CR ₁₀₉ R ₁₁₀ or a single bond, R ₁₀₉ and R ₁₁₀ are the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group, specifically, the alkyl group may be CH ₃ ,

n ₂₉ + n ₃₀ + n ₃₁ And n ₃₂ + n ₃₃ + n ₃₄ are each independently an integer of 5 or less.

[Formula 27]

In Chemical Formula 27,

R ₆₉ to R ₇₁ are the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

n ₃₅ , n ₃₆ and n ₃₉ are each independently an integer of 1 to 5,

n ₃₇ and n ₃₈ are each independently an integer of 0 to 4;

[Formula 28]

In Chemical Formula 28,

R ₇₂ To R ₇₇ are the same or different from each other, and each independently hydrogen, OH, or a substituted or unsubstituted alkyl group,

n ₄₀ To n ₄₃ are each independently an integer of 1 to 4,

Provided that n ₄₀ + n ₄₂ and n ₄₁ + n ₄₃ are each independently an integer of 5 or less.

[Formula 29]

In Chemical Formula 29,

R ₇₈ is a substituted or unsubstituted alkyl group, specifically CH ₃ ,

R ₇₉ to R ₈₁ are the same or different from each other, and each independently hydrogen or a substituted or unsubstituted alkyl group,

n ₄₄ , n ₄₆ and n ₄₈ are each independently an integer of 1 to 5,

n ₄₅ , n ₄₇ and n ₄₉ are each independently an integer of 0 to 4,

Provided that n ₄₄ + n ₄₅ , n ₄₆ + n _47, and n ₄₈ + n ₄₉ are each independently an integer of 5 or less.

[Formula 30]

In Chemical Formula 30,

R ₈₂ to R ₈₄ are the same or different from each other, and each independently represent a substituted or unsubstituted alkyl group, specifically, CH ₃ ,

R ₈₅ to R ₈₈ 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 each independently an integer from 1 to 5,

n ₅₁ , n ₅₃ and n ₅₅ are each independently an integer of 0 to 4,

n ₅₆ is an integer from 1 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.

Specific examples of the phenol compound include 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, and the like. However, the present invention is not limited thereto.

The amount of the phenol compound used may be 1 to 30 parts by weight based on 100 parts by weight of the hydroxy group-containing alkali-soluble resin. 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. .

(F) solvent

The said positive photosensitive resin composition contains the solvent which can melt | dissolve each component easily.

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, methylpyruvate, ethylpyruvate, methyl-3-methoxy propionate, and combinations thereof, 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 hydroxy group-containing alkali-soluble resin. 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.

(G) other additives

The positive photosensitive resin composition according to the embodiment of the present invention may further include (G) other additives.

The other additives include heat latent acid generators. Examples of the heat latent acid generator include arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid; Perfluoroalkylsulfonic acids such as trifluoromethanesulfonic acid and trifluorobutanesulfonic acid; Alkyl sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid; Or combinations thereof, 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 phenolic hydroxyl group-containing polyamide of the polybenzoxazole precursor and the cyclization reaction.

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

The process of forming a pattern using the said positive photosensitive resin composition is a process of apply | coating 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 to produce a photosensitive resin film; And heat-treating the photosensitive resin film. Process conditions for forming the pattern, etc. are well known in the art, so detailed descriptions 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 used as an insulating film or a protective film.

According to another embodiment of the present invention, a semiconductor device including the photosensitive resin film is provided. The positive photosensitive resin composition may be usefully used to form an insulating film, a passivation layer or a buffer 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.

Example

[ Synthetic example  One] Ortho - Nitrobenzyl  Synthesis of Ester Compound

150 ml of acetic acid was added to 20 g of 5,6-dimethoxy-2-nitrobenzyl bromide and 12 g of 4-ethyl benzoic acid while passing nitrogen through a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injector, and a cooler. Was added to prepare a mixed solution. The mixed solution was blocked with ultraviolet rays and stirred at 3 ° C. for 24 hours, and then acetic acid was removed using a pressure reducing device to obtain a high viscosity yellow liquid. The yellow liquid was purified by column separation with a mixed solution of hexane and diethyl ether, and then the solvent was removed to obtain 12.4 g of a compound represented by the following Chemical Formula 3 as a yellow solid.

(3)

[ Synthetic example  2] Ortho - Nitrobenzyl  Synthesis of Ester Compound

150 ml of acetic acid was added to 20 g of 5,6-dimethoxy-2-nitrobenzyl bromide and 10 g of 4-hexyl benzoic acid while passing nitrogen through a four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injector, and a cooler. Was added to prepare a mixed solution. The mixed solution was blocked with UV light, stirred at 3 ° C. for 24 hours, and then precipitated in methanol. Subsequently, the resultant was filtered using a pressure reduction apparatus, washed several times with methanol at 0 ° C., and then dried at 40 ° C. for 17 hours under vacuum to obtain 18.4 g of a compound represented by the following Chemical Formula 5 as a yellow solid.

[Chemical Formula 5]

[ Example  1] Preparation of Positive Photosensitive Resin Composition

18.3 g of 2,2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3,3, -hexafluoropropane and 13.3 g of 4,4'-oxydibenzoyl chloride Pyridine was used as a catalyst in -methyl-2-pyrrolidone (NMP) solvent to obtain an alkali-soluble resin for the positive photosensitive resin composition. 15 g of the obtained alkali-soluble resin is dissolved in γ-butyrolactone (GBL) 35.0 g, and 3 g of the photosensitive diazoquinone compound represented by the following formula (31), 1 g of the phenol compound represented by the following formula (32), and represented by the formula (33) 0.4 g of the silane compound and 0.15 g of the compound represented by Chemical Formula 3 were added to dissolve it, and then filtered through a 0.45 μm fluorine resin filter to obtain a positive photosensitive resin composition.

[Formula 31]

In Chemical Formula 31,

Q is the same as defined in Chemical Formula 17, and 67% of the Q is substituted with the chemical formula 18a.

[Formula 32]

[Formula 33]

[ Example  2] Preparation of Positive Photosensitive Resin Composition

A positive photosensitive resin composition was obtained in the same manner as in Example 1, except that 0.15 g of the compound represented by Chemical Formula 5 was used instead of the compound represented by Chemical Formula 3.

[ Example  3] Preparation of Positive Photosensitive Resin Composition

A positive photosensitive resin composition was obtained in the same manner as in Example 1, except that 0.3 g of the compound represented by Chemical Formula 3 was used.

[ Example  4] Preparation of Positive Photosensitive Resin Composition

A positive photosensitive resin composition was obtained in the same manner as in Example 1, except that 0.3 g of the compound represented by Chemical Formula 5 was used instead of the compound represented by Chemical Formula 3.

Comparative Example 1 Preparation of Positive Photosensitive Resin Composition

A positive photosensitive resin composition was obtained in the same manner as in Example 1, except that the compound represented by Chemical Formula 3 and the compound represented by Chemical Formula 5 were not used.

<Property evaluation>

Sensitivity, resolution and Residual rate  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 polybenzoxazole precursor film.

After exposing the photosensitive polybenzoxazole precursor film to the photosensitive polybenzoxazole precursor film by varying the exposure time using an I-line stepper (NSR i10C) manufactured by Nikon, Japan at 2.38 wt% tetramethylammonium hydroxide at room temperature After dissolving and exposing the exposed portion through a two puddle for 60 seconds in a side aqueous solution, the pattern was washed by pure water for 30 seconds.

The pattern of the completed film was able to confirm the resolution through an optical microscope.

The film thickness change after preliminary baking and development was measured using a KMAC (ST4000-DLX) equipment, and the residual film rate (thickness after development / thickness before development, unit%) was calculated by measuring the change in film thickness.

Sensitivity was determined 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, and measuring the exposure time as an optimum exposure time. The optimum exposure time was defined as the sensitivity of the photosensitive resin composition.

The physical property evaluation results are shown in Table 1 below.

TABLE 1

Ortho-nitrobenzyl ester compound Ortho-nitrobenzyl
Ester compound content
(Parts by weight relative to 100 parts by weight of alkali-soluble resin) Film thickness (㎛) Sensitivity
(mJ / cm ² ) Residual rate
(%) Preliminary firing After phenomenon Example 1 Formula 3 One 10.188 9.23 340 90.55 Example 2 Formula 5 One 10.377 9.36 300 90.24 Example 3 Formula 3 2 10.27 9.32 400 90.74 Example 4 Formula 5 2 10.40 9.42 350 90.59 Comparative Example 1 - - 9.984 8.861 400 88.44

As shown in Table 1, when the positive photosensitive resin composition of Examples 1 to 4 was used, the residual film ratio value was higher than that of Comparative Example 1 using only a conventional diazonaptoquinone compound, It can be seen that the pattern can be better formed during development with an aqueous solution.

In addition, in the case of using the positive photosensitive resin composition of Examples 1 to 4, it can be confirmed that the sensitivity is superior to or corresponding to that of Comparative Example 1.

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

Claims (7)

Ortho-nitrobenzyl ester compound comprising a compound represented by the formula (1), a compound represented by the formula (2) or a combination thereof: [Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2, R ₁ , R ₂ , R ₅ and R ₆ are the same or different from each other, and each independently represent a substituted or unsubstituted aliphatic organic group, or a substituted or unsubstituted alicyclic organic group, R ₃ and R ₇ are the same or different from each other, each independently represent a single bond or a substituted or unsubstituted divalent aliphatic organic group, R ₄ , R ₈ and R ₉ are the same or different from each other, and each independently a substituted or unsubstituted aliphatic organic group, or a substituted or unsubstituted alicyclic organic group, n ₁ is an integer of 1 to 5, n ₂ is an integer of 0 to 3, n ₃ is an integer of 0 to 4, n ₂ + n ₃ is an integer of 1 or more. (A) hydroxy group containing alkali-soluble resin; (B) the ortho-nitrobenzyl ester compound according to claim 1; (C) photosensitive diazoquinone compound; (D) silane compound; (E) phenolic compounds; And (F) solvent Positive photosensitive resin composition comprising a. The method of claim 2, The hydroxyl group-containing alkali-soluble resin is a polybenzoxazole precursor containing a repeating unit represented by the following formula (9), a novolak resin comprising a repeating unit represented by the following formula (10), a repeating unit represented by the following formula (11) A positive photosensitive resin composition comprising a poly-4-hydroxy styrene resin or a combination thereof comprising: [Formula 9]

In Chemical Formula 9, X ₁ is the same or different in each repeating unit, and each independently an aromatic organic group, Y ₁ is the same or different from each other in each repeating unit, and each independently an aromatic organic group or a divalent to hexavalent alicyclic organic group, [Formula 10]

In Chemical Formula 10, R ₁₀ are the same or different from each other, and each independently hydrogen or a C1 to C10 alkyl group, n ₄ is an integer of 0 to 3, [Formula 11]

In Chemical Formula 11, R ₁₁ are the same or different from each other, and each independently hydrogen or a C1 to C10 alkyl group, n ₅ is an integer of 0-4. The method of claim 2, The hydroxyl group-containing alkali-soluble resin is a positive photosensitive resin composition having a weight average molecular weight (Mw) of 3,000 to 300,000. The method of claim 2, The resin composition is (A) To 100 parts by weight of the hydroxyl group-containing alkali-soluble resin, (B) 0.1 to 20 parts by weight of the ortho-nitrobenzyl ester compound according to claim 1; (C) 5 to 100 parts by weight of the photosensitive diazoquinone compound; (D) 0.1 to 30 parts by weight of the silane compound; (E) 1 to 30 parts by weight of the phenol compound; And (F) 200 to 900 parts by weight of solvent Positive photosensitive resin composition comprising a. The photosensitive resin film manufactured using the positive photosensitive resin composition of any one of Claims 2-5. The semiconductor element containing the photosensitive resin film of Claim 6.