TWI376574B - Positive photosensitive resin composition - Google Patents

Description

1376574 VI. OBJECTS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a positive photosensitive resin composition. More particularly, the present invention relates to a positive photosensitive resin composition which has excellent heat resistance and can provide a high sensitivity and high resolution fine pattern. I: Prior Art 3 Related Technical Description

Recently, as semiconductors and liquid crystal display devices have tended to require higher integration, more reliance on, and more research, organic materials that have been actively used by researchers and have high purity and workability. Therefore, the surface protective layer and the interlayer insulating layer of the semiconductor device require a resin composition having excellent heat resistance and excellent electrical and mechanical properties. Further, in order to meet the demand for a surface protective layer and an interlayer insulating layer which are required to be more integrated, a resin composition capable of forming a high-resolution fine pattern has attracted attention. It is a core technology to form a surface protective layer and an interlayer insulating layer pattern with a resin composition having excellent heat resistance and excellent electromechanical properties, and to form a precise high-resolution pattern, which makes it possible to create ultra-high integrated semiconductors. . The conventional positive photosensitive resin composition is covalently bonded by adding the photosensitive g to the polyamine polymer or by binding the polyamine polymer to the brewing gas. preparation. The general pattern forming process using the composition includes patterning the photomask to expose the photosensitive resin composition to light of a specific wavelength. In the exposed portion, the diazonium compound is chemically denatured to convert it to a slow acid. Thereafter, the exposed layer was brought into contact with a specific material (conventional 'alkaline developing aqueous solution) 3 1376574. The portion including the converted carboxylic acid is added to the solubility of the alkaline developing solution, thereby being selectively developed. The patterned layer is then heated to provide a cured pattern. In the case of a technique using a surface protective layer or an interlayer insulating layer, it is necessary to develop a composition material having high heat resistance and excellent mechanical properties after a curing process, and a pattern having high resolution and high sensitivity light properties. Material. However, in order to enhance the protective layer, it should be designed to provide a large amount of aromatic compounds, a higher polymer molecular weight, a higher degree of crosslinking, and a lower fluidity, but in order to enhance optical properties, It is designed to provide a smaller amount of aromatic compound, a lower polymer molecular weight, a lower degree of crosslinking, and a higher fluidity, so that it is not easy to develop a material that satisfies the divergence performance. In particular, since the precise pattern properties of the conventional polyamines are negatively correlated with the layer properties after curing, the development of the improved photosensitive resin composition is limited. Further, although the soluble polyimine enhances the mechanical layer properties, the transmittance of the exposure wavelength is deteriorated due to the closed-loop structure, so that the final resolution and sensitivity are lowered, and the performance for forming a precise pattern is deteriorated. As described above, the conventional photosensitive resin composition still has a problem that it cannot satisfy the demand for a more precise pattern and improved mechanical properties 20 required for improvement of a highly integrated semiconductor device. Therefore, there is a need to develop new photosensitive resin materials required to overcome the limitations of conventional materials. I. SUMMARY OF THE INVENTION 3 SUMMARY OF THE INVENTION An exemplary embodiment of the present invention provides a positive photosensitive resin composition. The present invention (4) - exemplifying a specific example provides a positive photosensitive resin which has excellent properties and can form a fine with high sensitivity Wei and high (four) degrees. Still another embodiment of the present invention provides a method of producing a photosensitive pattern using the photosensitive resin composition. Another specific example of the present invention provides a photosensitive resin layer and a semiconductor electronic member produced by using the positive photosensitive resin composition. The specific examples of the present invention are not limited to the above scientific and technical purposes. Those who are familiar with this art can understand other scientific and technological purposes. According to the present invention - a specific example, a positive photosensitive resin composition is provided, which comprises a polyamine polymer having the following formula 1, a (meth) esterified diazo moth compound, Base compound, and (d) solvent [Chemical Formula 1] Towel 1 E1~~-NH-X1--HN0C-Y1-CONH-X1-L I R1 In the above formula 1, HNOC-Y2-c〇nh_X2 _ Nh —E2 I ”m2 R2 X] is the same or different from x2 and independently is a divalent to tetravalent organic group, and Υ#Υ2 is the same or different and independently a divalent to hexavalent organic group, the ground is Hydrogen or C1C5 organic group, El_2 is the same or different and independently hydrogen, or derived from a moiety selected from the group consisting of acid and its active derivatives, provided that both ruthenium and osmium are non-hydrogen, mi and M2 is the same or different and independently is 〇-excited, and mi+m2 is between 5 and 100. According to another embodiment of the present invention, there is provided a method of producing a photosensitive pattern comprising the above-mentioned positive photosensitive resin The composition is coated on the support substrate and dried to form a resin composition layer, and the resin composition layer is exposed to an exponentially developed solution to expose the exposed tree. The composition layer is developed and the developed resin composition layer is heated. According to still another embodiment of the present invention, there is provided a semiconductor electronic component for a semiconductor comprising a photosensitive resin layer produced using the positive photosensitive resin composition Hereinafter, a specific example of the present invention will be described in detail. According to an embodiment of the present invention, the positive photosensitive resin composition comprising one or both ends of the polystyrene is derived from a group selected from the group consisting of a monocarboxylic acid and an activated derivative. The alkyl group, the aryl group, the alicyclic group, or the heterocyclic group of the group is blocked to maximize the difference in solubility between the unexposed portion and the exposed portion. Therefore, when the photosensitive resin composition is patterned, the exposed portion is Since the development rate is increased, it is possible to form a high-resolution pattern. After the curing process, the degree of ring closure and the degree of crosslinking increase the 'providing a photosensitive resin layer having excellent film characteristics. FIG. Process diagram for producing a pattern of a positive photosensitive resin composition. [Implementation] Formula Description of Preferred Embodiments Hereinafter, the present invention will be described in detail. Specific examples are exemplified. However, the specific examples are merely illustrative and are not intended to limit the present invention. According to the present invention, the H-form photosensitive (tetra) lipid composition includes (4) 1376574 polyamine polymer represented by the following formula 1, (B) esterification A diazonium compound, (c) a phenol-based compound, and 1) a solvent. When used in the present case, "substituted" _ word means that one is substituted with at least one substituent including a halogen, an alkyl group, an aryl group, an alkoxy 'amine group, or an alkenyl group. In the present case, the term "alkyl" means that the C1 to C30 alkyl group is preferably a C1 to C15 alkyl group, and the term "aryl" means (6 to C30 aryl group). Preferably, it is a C^C18 aryl group, and the term "dilute base" means that the C30 dilute group is preferably (^ to (3) a dilute group, and the term "alkyloxy group" means a hydrazine to 10 C3G alkoxy group. Preferably, it is a C1 to (1) alkoxy group, and the term "alicyclic group" means a C3 to (10) cycloalkyl or a (10) cycloaliphatic group, preferably a ca(3) cycloalkyl or a C3 to C24 cycloalkenyl group. In the present case, when no specific definition is provided, the terms "bivalent to tetravalent organic group" and "bivalent to hexavalent organic group" refer to organic groups including 2 to 15 functional groups, respectively. An organic group comprising 2 to 6 functional groups. The functional group means a substituent other than hydrogen. In the present case, the term "heterocyclic" means selected from "heteroaryl" or "in the absence of a specific definition." One of the groups consisting of a heterocyclic group, a "heterocyclic group", and a "heterocyclic group". 2" In this case, when a specific definition is not provided, "hetero-compound" - word system Means included 1 ντ Free Ν, 0, Ρ, and a compound composed of at least one atom of Si in place of carbon. The components will be described in detail later. (A) Polyamine Poly 7 1376574 Polyamine polymer is the following formula 1 Said. [Chemical Formula 1]

El—NH—XI—HNOC—Y1—CONH—X1--- _ | Jml - R1 HNOC—Y2 —CONH—X2 —NH —E2 I ”m2 R2 5 In Equation 1, 乂丨 and 乂] The same or different and independently divalent to tetravalent organic groups, 丫1 and 丫2 are the same or different and independently divalent to hexavalent organic groups, 1^ and 尺2 are the same or different and independent The ground is hydrogen or a C1 to C5 organic group, and E1 and E2 are the same or different and independently hydrogen, or are derived from a selected one.

10 15 Part of a group consisting of a monocarboxylic acid and a reactive derivative thereof, provided that both E1 and E2 are not hydrogen. Preferably, E1 and E2 are alkyl, aryl, alicyclic or heterocyclic groups. 〇11 and 〇12 are the same or different and independently 0 to 100, and between 5 and 100. The polyamidamide polymer represented by the above formula 1 is prepared by reacting a diamine monomer and an acid monomer selected from the group consisting of tetracarboxylic dianhydride, dicarboxylic anhydride, dicarboxylic acid, and reactive derivatives thereof. The reaction is carried out to obtain a reaction product, and the reaction product and the terminal blocking monomer are reacted to convert the amine group of the reaction product into a mercaptoamine group. A method of preparing a polyamine polymer is described in more detail. The diamine monomer may be represented by X(NH2)2, wherein the X system is the same as 乂1 or 乂2 of Chemical Formula 1. The ruthenium and osmium of Chemical Formula 1 are derived from a diamine monomer. X can be represented by the following formulas 2 to 7, but is not limited to them. [Chemical Formula 2]

8 20 1376574 [Chemical Formula 3]

[Chemical Formula 4]

5 [Chemical Formula 5]

Η匕6 6 In the above formulas 2 to 7, /, to the same or different, and independently selected from hydrogen, substituted or unsubstituted alkyl, hydroxyl, carboxylic acid, and thiol The group formed, and the gossip to the 6 series are the same or different, and are independently selected from the group consisting of CR3R4, S, 0, 15 S02, CO, CONH, and a single bond, the center of which is the same as the 114 series Or different and independently selected from the group consisting of hydrogen, or a substituted or unsubstituted alkyl group 9 1376574 and preferably a fluoroalkyl group. The diamine monomer may include an aromatic diamine, an alicyclic diamine, and an aliphatic diamine. Examples of the diamine monomer include benzidine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenyloxy)phosphonium, bis(4-aminophenoxy)biphenyl , bis 5 [4-(4-Aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenoxy)benzene, 4'-diamino-3,3'-dihydroxy Biphenyl, 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'-diaminodiphenyl ether, 4,4'-di Aminodiphenyl ether, 3,4'-diaminodiphenyl decane, 4,4'-10 diaminodiphenylmethane, 3,4'-diaminodiphenyl, 4,4'-di Aminodiphenyl, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, p-phenylenediamine, m-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, cyclohexanediamine, fluorenylenedicyclohexylamine, 3,3'-diamino-4,4'-dihydroxybiphenyl, 3,3'-diamino-4, 4'-dihydroxy sulfone, 4,4'-diamino-3,3'-dihydroxyphenyl sulfone, bis(3-amino-4-15 hydroxyphenyl)decane, 2,2-dual- (3-amino-4-hydroxyphenyl)propane, 2,2- -(3-Amino-4-hydroxyphenyl)hexafluoropropane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4 '-Dihydroxybenzophenone' 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, and 1,3- Diamino-2,4-dihydroxybenzene, but not limited to them. These diamine monomers may be used singly or in combination. The diamine monomer may preferably be selected from the group consisting of 4,4'-diaminodiphenyl ether, 4,4'-diaminodimethane, 2,2-bis-(3-amino-4-hydroxybenzene Group of hexafluoropropane, 3,3'-diamino-4,4'-dihydroxy sulfone, and mixtures thereof. The ruthenium containing diamine monomer can be used in conjunction with the diamine monomer to increase the adhesion to the substrate. 10 1376574

-10 15

Examples of the fluorene-containing diamine monomer include bis(4-aminophenyl)dicon0-decane, bis(4-aminophenyl)tetradecyloxyne, bis(p-aminophenyl)tetraindole. Dioxazane, bis(gamma-aminopropyl)tetradecyldioxane, 1,4-bis-(gamma-aminopropyldimethylguanidinyl)benzene, 1,3-double -(Aminopropyl)tetradecyldioxane, and the like, but not limited to them. Preferred guanidine-containing diamine monomers include bis(4-aminophenyl)tetradecyloxyne, bis(p-aminophenyl)tetradecyldioxane, or mixtures thereof. In order to increase the adhesion of the upper and lower layers, it is advantageous to use a copolymer containing a nonammonium diamine monomer in a ratio of from 0.1 to 10 wt%. When the amount of the fluorene-containing diamine monomer falls within the range, the optical properties and the layer properties are not deteriorated and the adhesion is excellent. The acid monomer which is reacted with the diamine monomer may be selected from the group consisting of tetracarboxylic dianhydride, dicarboxylic anhydride, dicarboxylic acid, and reactive derivatives thereof. The oxime 1 and oxime 2 of Chemical Formula 1 are derived from an acid monomer. The tetracarboxylic dianhydride can be represented by the following formula 8, but is not limited thereto. In the above formula 8, the Y system is the same as 丫1 or 丫2 of Chemical Formula 1. The dicarboxylic acid monomer may be represented by Y(COOH)2, wherein the Y system is the same as YiSYz of Chemical Formula 1. The reactive derivative of the dicarboxylic acid monomer can be represented by Y(COK')2, wherein the Y system is the same as the oxime of Chemical Formula 1, or 丫2, and the κ' is such that Y(COOH)2 and the halide, 11 20 1376574 or Y The fraction obtained by the reaction of (COOH) 2 with 1-hydroxy-1,2,3-benzotriazole. The following formulas 9 to 16 can be derived from an acid monomer. [Chemical Formula 9]

[Chemical Formula 11]

[Chemical Formula 13]

Κ9 K10

Ben * [Chemical Formula 14]

12 1376574 dropout 15]

[Chemical Formula 16]

5 In the above formulas 9 to 16, 1 to 1 <:21 are the same or different, and are independently selected from hydrogen, substituted or unsubstituted alkyl group, hydroxyl group, carboxylic acid group, mercaptan, and COOR5. a group wherein r5 is hydrogen or a C1 to C5 alkyl group, and 81 to the lanthanide are the same or different, and are independently selected from -CR6R7-, -S-, 10-Ο-, -S02-, -CO- ' a group consisting of -CONH-, and a single bond, wherein R6 and R7 are the same or different and are independently selected from the group consisting of hydrogen and substituted or unsubstituted alkyl. The substituted alkyl group is preferably a fluoroalkyl group, and the unsubstituted alkyl group is preferably a fluorenyl group. The acid monomer may be a tetracarboxylic dianhydride such as pyromellitic dianhydride, 3,3',4,4'-15 biphenyltetracarboxylic dianhydride, 2,3,3',4-biphenyltetra Carboxylic dianhydride, 3,3',4,4'-dibenzophenone tetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 1,1-bis-(2,3 -Dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, and the like. The acid monomer may be a dicarboxylic acid reactive derivative such as a carbonyl halide derivative and an active ester derivative obtained by reacting an acid monomer with 1-hydroxy-1,2,3-benzotriazole. Specific examples of the reactive derivative include 4,4-oxybenzophenone gas, o-benzene 13 1376574 dioxane, diphenoxy difluorene gas, bis(phenylphosphonium chloride)sulfone, bis(benzene) Base helium) ether, bis(phenylformamidine)benzophenone, phthalic acid, diphenoxybenzotriazole diacetic acid vinegar, and the like. Preferred acid monomers include 3,3',4,4'-benzophenone tetracarboxylic dianhydride, bis 5 (3,4-dicarboxyphenyl) ether dianhydride, diphenoxy dioxime , phthalic acid, and the like, but not limited to them. The polyamidamide polymer represented by Chemical Formula 1 may be a copolymer in which two or more single systems are used to impair the light properties, layer properties, and water solubility of a homopolymer or polymer composed of a guanamine bond unit. The range of copolymerization. The copolymer may include various types, such as random copolymers, block copolymers, or graft copolymers, but in a specific example, it includes a random copolymer. Further, the blocked monomer which reacts with the reaction product obtained by reacting the acid monomer with the diamine monomer may include a compound selected from the group consisting of monocarboxylic acids and reactive derivatives thereof. The monocarboxylic acid may be any carboxylic acid, especially an alicyclic monocarboxylic acid such as cyclohexyl decanoic acid, norbornane citric acid, adamantyl citric acid, isobornyl formic acid, and norbornene based acid, or Active derivative. The monocarboxylic acids can be used singly or in combination. The reactive derivatives of carboxylic acids include cyclohexyl helium, norbornane 20 chlorine, norbornene formazan chloride, adamantylmethyl chloride, isobornyl formazan chloride, 4-norbornene benzoquinone Gas, cyclohexylbenzotriazol ester, norbornene benzotriene. Sitting on oxime esters, and the like. The molecular weight of the polyamine polymer can be selected within a range that does not impair the advantages of the present invention, but in a specific example, the weight average molecular weight (Mw) is between 14 1376574 500 and 500,000, and in another specific example, It is from 1000 to 50,000 to ensure effective solubility and coating characteristics and to maximize the patterning effect after patterning. When the weight average molecular weight falls within this range, it is possible to provide sufficient physical properties and excellent solubility of the organic solvent to make it easy to handle. fBl esterified diazonium compound The esterified diazonium compound acts as a photoactive compound (PAC), preferably comprising a 1,2-diazonium benzoquinone or a 1,2-diazonaphthoquinone structure. Such compounds are described in U.S. Patent Nos. 2,772,975, 2,797,213, and 3,669,658. The esterified -10 diazonium compound may include the compounds represented by the following formulas 17 to 19, but is not limited thereto. [Chemical Formula 17]

[Chemical Formula 18]

15 1376574 [Chemical Formula 18-1] 〇

S〇2

5 [Chemical Formula 19]

In the above formulas 17 to 19,

0| to 04 are the same or different and are independently selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group, preferably an alkyl group, 10 ... to the same or different, and Independently an integer between 1 and 3, m3 is an integer from 0 to 3, 0, to 09 are the same or different, and are independently OQ, and Q is hydrogen, or the above formula 18-1 or 18-2 . Q is a ratio of hydrogen, that is, the ratio of OH substitution in the aromatic ring is from 0 to 90 mol%, preferably from 30 to 15 80 mol%. Within this range, suitable photosensitivity and suitable light absorbance can be provided to advantageously form a pattern. 16 1376574

According to a specific example, the esterified diazonium compound may be included in an amount of from 1 to 50 parts by weight based on 100 parts by weight of the polyamide polymer, and in another specific example, from 5 to 30 parts by weight. When the amount of the esterified diazonium compound falls within the range, no residue is exposed, a pattern is suitably formed, and it is possible to avoid film thickness loss during development and to provide a good pattern. (C) Phenolic group-containing compound The phenol group-containing compound acts as a dissolution inhibitor to control the difference in dissolution rate between the exposed portion and the unexposed portion. The phenol-containing compound includes 2,6-dimethoxymethyl-4-t-butanol, 2,6-dimethoxymethyl-P-cresol, or 2,6-diethoxyanthracene. Base-P-cresol, but not limited to them. The phenol group-containing compound can be represented by the following formulas 20 to 25, but is not limited thereto. [Chemical Formula 20]

In the above formula 20, R8 to R10 are the same or different and are independently hydrogen, or a substituted or unsubstituted alkyl group,

Rn to Rl5 are the same or different and are independently selected from the group consisting of hydrazine, OH, and a substituted or unsubstituted alkyl group, preferably an alkyl group, and n10 is an integer of from 1 to 5. 17 1376574 [Rl6)mi (Rl9) nu

In the above formula 21, R16 to R2i are the same or different and are independently selected from the group consisting of hydrazine, OH, and a substituted or unsubstituted alkyl group, and A4 is a CR'R" or a single bond, wherein R' and R" are the same or different and are independently hydrogen, or a substituted or unsubstituted alkyl group, and the alkyl group is preferably CH3' and 10 ni l+n!2+ni3 and Πΐ4+Πΐ5+ Πΐ6 is the same or different 'and independently 5 or less integers. [〇Η22] (〇Η)π,7 (〇Η)ηιβ

(Μη2ι In the above formula 22, R22 to R24 are the same or different, and are independently hydrogen, or a substituted or unsubstituted alkyl group, n17, n18, which are the same or different from the n21 system, and independently 1 to An integer of 5, n19 and n20 are the same or different, and are independently an integer from 0 to 4. 1376574 [Chemical Formula 23]

尔彳日丨0J attack

Site selected from hydrogen, 〇H

The term is selected from the group consisting of substituted or unsubstituted alkyl groups, and η22 to h are the same or different, and are intended to be an integer from 1 to 4, and the extract is n22+n24 and n23+ N26 is independently 5 or less [Chemical Formula 24]

(〇H)n (Ra^ In the above formula 24, R28 is a substituted or unsubstituted alkyl group, preferably CH3, R·29 to the same or different ', and independently hydrogen or substituted Or unsubstituted alkyl, nr, 叱9, the same or different 'and is independently an integer from 1 to 5, and n28, ho, and Π32 are the same or different' and are independently an integer from 0 to 4. , provided that η27+η28, kiss+(10), and called +~2 are independently an integer of 5 or less. 15 1376574 [Chemical Formula 25]

In the above formula 25, R32, R33, and R34 are the same or different and are independently a substituted or 5 unsubstituted alkyl group, preferably CH3, and R35 to R38 are the same or different and independently hydrogen. Or substituted or unsubstituted alkyl group,

N33, n35, and n39 are the same or different, and are independently an integer of 1 to 5, n34, n36, and n38 are the same or different, and are independently an integer of 0 to 4, and 10 n37 is 1 to 4 An integer, provided that n33 + n34, n35+n36, and n38+n39 are independently an integer of 5 or less. According to a specific example, the phenol group-containing compound is included in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the polyamidamide polymer. When the proportion of the phenol-based compound falls within the range, the sensitivity does not deteriorate during development, and the dissolution rate of the unexposed portion is suitably increased to provide a good pattern. In addition, it does not precipitate when frozen, demonstrating excellent storage stability. (D) Solvent 20 1376574 5 / The agent may be an organic solvent, preferably ν·methyl_2_.毕洛炫 嗣 嗣 嗣 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , -1,3-butanediol acetate, 1,3-succinic acid qs%-3- early methyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl mystery-propanol monomethyl bond, propylene glycol single Acrylic vinegar, methacetin, butyl citrate, butyl lactate, decyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionic acid, and the like, but not limited to them. Solvents may be used singly or in combination. • The agent and the polyamide polymer can be used in a ratio of 2〇:8〇 to 9〇: 1〇 by weight. Within this range, a sufficiently thick film can be obtained and a good solubility and coating can be provided. According to another specific example, there is provided a method of producing a photosensitive pattern using the positive photosensitive resin composition. The method for producing a photosensitive pattern using the positive photosensitive resin composition of the present invention comprises: applying the above positive photosensitive resin composition onto a support substrate and drying it into a resin composition layer; The layer is exposed; the exposed resin composition layer is developed with an alkali developing solution; and the developed resin composition layer is heated. 20 Fig. 1 is a process diagram for producing a pattern using a positive photosensitive resin composition. Thereafter, the method is explained in more detail with reference to Figure i. As shown in Fig. 1, an object to be manipulated, for example, a semiconductor substrate, is coated with a photosensitive resin composition to provide a photosensitive resin composition layer 2 (S1). Then, the photosensitive resin composition layer is exposed (S2), and the resin composition produces a chemical change, and the dissolution rate of the exposed portion increases. It is then developed (S3) with an alkaline solution 21 1376574 to provide a pattern. During the exposure process (S2), when a photosensitive resin composition layer 2 is exposed by irradiating an i-ray or the like with UV light (not shown), the photosensitive agent of the exposed portion 3 undergoes a chemical change, but is not exposed. Part 4 did not produce a chemical change. During the subsequent process, when the exposed photosensitive resin composition layer is developed with an alkaline aqueous solution (S3), the chemically changed exposed portion 3 is removed 'k for patterning the photosensitive resin composition layer 5 . When the patterned photosensitive resin composition layer is heated, the pattern layer of the resin composition is cured to provide the photosensitive resin composition layer 6. According to another embodiment of the present invention, there is provided a semiconductor electronic member comprising a photosensitive resin layer obtained using a positive photosensitive resin composition. The photosensitive resin layer 6 can be applied to a surface protective layer or an interlayer insulating layer. In addition, it can be widely applied to various fields requiring a positive pattern with high sensitivity and high resolution. The following examples illustrate the invention in more detail. However, it is to be understood that the invention is not limited to the embodiments. <Combination_Example 1>: Synthesis of polyamine polymer While adding nitrogen, 18.3 g of 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropene was added thereto. A four-necked flask of the temperature control device, the nitrogen gas injector and the condenser 20 was dispensed, and 280 g of N-methyl-2-° ratio slightly burned-(NMP) was placed and dissolved. After the solid was completely dissolved, 9.9 g of pyridine was placed in the solution. While the temperature of the solution was maintained at 5 ° C, 14.8 g of 4,4'-oxydibenzocarbazone was dissolved in I42 g of N-methyl-2-° ratio of each ketone (NMP) to provide a solution. The solution was slowly dropped into it at thirty-one 22 1376574. One hour after the dropwise addition, the reaction was carried out at 5 ° C, then the temperature was raised to room temperature and shaken for one hour. Thereafter, 1.5 g of cyclohexylformamidine chloride was placed and shaken for one hour to complete the reaction. The reaction mixture was placed in a water/sterol = 10/1 (volume ratio) solution to form a 5 precipitate. The precipitate was filtered, washed thoroughly with water, and then dried at 80 ° C for 24 hours or longer to synthesize a polyamine polymer represented by the following Chemical Formula 1-1. From the GPC results of the synthesized polymer, it was confirmed that the weight average molecular weight was 11K. (Chemical Formula 1-1)

10 <Synthesis Example 2>: Synthesis of polyamine polymer In addition to 1.5 g of norbornane methyl hydrazine instead of 1.5 g of cyclohexylmethane gas, the polyamine polymer represented by the following chemical formula 1-2 is based on The same procedure as in Synthesis Example 1 was carried out. The polymer had a weight average molecular weight (Mw) of 10K. 15 (Chemical Formula 1-2)

<Synthesis Example 3>: Synthetic polyamine polymer 17.7 g of 2,2-bis-(3-amino-4-hydroxyphenyl)hexafluoropropane and 〇.86 g 1, while flowing nitrogen 3-bis-(aminopropyl)tetramethyldioxane was added to a four-necked flask equipped with a stirrer, a temperature control device, a nitrogen gas injector and a condenser, and 280 g of N-mercapto-2 was added. Pyrrolidone (NMP) is placed and dissolved. After the solid was completely dissolved, 9.9 g of pyridine was introduced into the solution, and 13.3 g of 4,4'-oxydiphenylfluorene chloride was introduced and dissolved in a solution of 142 g of N-mercapto-2-pyrrolidone 5 (NMP) to three. Slowly drip in for ten minutes while maintaining the temperature of the solution at 0 to ° (:. After the completion of the dropwise addition, the reaction was carried out at a temperature of 5 ° C for one hour, and after the temperature was raised to room temperature, the reaction was allowed to proceed for one hour. 1.5 g of the ring was placed. Hexyl helium was introduced and shaken at room temperature for two hours, and then the reaction was completed. The reaction mixture was placed in a water/methanol = 10/1 (volume ratio) solution to form a 10 precipitate. The precipitate was then filtered and thoroughly washed. And drying in a vacuum at 80 ° C for 24 hours or more to synthesize a polyamide polymer represented by the following Chemical Formula 1-3. The polymer has a weight average molecular weight of 11 K. (Chemical Formula 1-3)

The polyamine polymer represented by the following Chemical Formulas 1-4 was synthesized according to the same procedure as in Synthesis Example 3 except that 1.5 g of norbornane helium gas was used instead of 1.5 g of cyclohexylcarbazide. The polymer has a weight average molecular weight of 10K. (Chemical Formula 1-4)

<Synthesis Example 5>: Synthesis of polyamine polymer While adding nitrogen, 18.3 g of 2,2-bis-(3-amino-4-hydroxyphenyl) 24 1376574 hexafluoropropane was added thereto. A four-necked flask of a stirrer, a thermostat 'nitrogen injector and a condenser, and 280 g of N-mercapto-2-pyrrolidone (NMP) was placed and dissolved. After the solid was completely dissolved, 9.9 g of pyridine was introduced into the solution, and 11.8 g of 5 4,4'-oxybenzhydryl chloride was introduced and dissolved in a solution of 142 g of N-mercapto-2-pyrrolidone (NMP) to 30. The solution was slowly dropped into the solution while maintaining the temperature at 5 °C. After the completion of the dropwise addition, the mixture was reacted at a temperature of 5 ° C for one hour and heated to room temperature. After shaking for one hour, 1.5 g of cyclohexylmethylguanidine was introduced and shaken for one hour, and then the reaction was completed. -10 The reaction mixture was placed in a water/methanol = 10/1 (volume ratio) solution to form a precipitate. The precipitate was then filtered, washed thoroughly, and dried in vacuum at 80 ° C for 24 hours or longer to synthesize a polyamine polymer represented by the following Chemical Formula 1-5. The polymer has a weight average molecular weight of 11K. (Chemical Formula 1-5)

<Synthesis Example 6>: Synthesis of polyamine polymer In addition to 1.5 g of norbornanemethyl hydrazine gas instead of 1.5 g of cyclohexylmethane gas, the polyamine polymer represented by the following Chemical Formula 1-6 is based on Synthesis Example 5 was synthesized in the same manner. The polymer has a weight average molecular weight of 10K. 20 (Chemical Formula 1-6)

25 Polyamide polymer represented by the following Chemical Formula 1-7 was synthesized by the same procedure as in Synthesis Example 1, except that 1.5 g of maleic anhydride was used instead of 1.5 g of cyclohexylcarbazide. The polymer has a weight average molecular weight of 10K" (Chemical Formula 1-7)

<Synthetic sinus application 8>: Synthesis of polyamine polymer divided by 1.5 g of 5-norbornene-2,3-phthalic anhydride instead of 1.5 g of cyclohexylmethane gas, the polymerization represented by the following chemical formula 1-8 The guanamine polymer was synthesized according to the same procedure as in Synthesis Example 1. The polymer has a weight average molecular weight of 11K. (Chemical Formula 1-8)

S Examples 1 to 12>: Synthesis of photosensitive blush group mash The composition ratios shown in Table 1 below will synthesize the respective polyamine polymers and esterified diazonium compounds synthesized in Examples 1 to 8, containing phenol The compound 2,6-diethoxymethyl-P-cresol and the solvent γ-butyrolactone (GBL) were mixed to provide a positive photosensitive resin composition. "26a" in Table 1 means a compound of Chemical Formula 26, wherein two of them are represented by Chemical Formula 26-1 and the other one is hydrogen; and "26b" means Chemical Formula 26 (^ to 仏 two of them) A compound represented by Chemical Formula 26-2 and the other one being hydrogen. 1376574 [Chemical Formula 26] 0

5 [Chemical Formula 26-2] 〇

Table 1 Example Polyamine Compound S Sodium Dihydrogen Brewing Compound 2,6-Diethoxymethyl-P-indole Solvent (GBL) 1 10 g, Synthesis Example 1 26a, 2 g Ig 20 g 2 10 g, Synthesis Example 1 26b, 2 g Ig 20 g 3 10 g, Synthesis Example 2 26a > 2 g ig 20 g 4 10 g, Synthesis Example 2 26b, 2 g ig 20 g 5 10 g Synthesis Example 3 26a 5 2 g ig 20 g 6 10 g, Synthesis Example 3 26b, 2 g Ig 20 g 27 A ' -- 7 ιυ g, synthetic Μ Μ 4 4 26a « 2 g !g 20 g 8 , Synthesis of 丨4 26b , 2 g 20 g 9 , Synthesis Example 5 26a , 2 g ig 20 g 10 , Synthesis of your 26b, 2 g !g 20 g 11 , Synthesis ~ 实施 Example 6 26a 5 2 g Lg 20 g 12 10-g 'Synthesis+Implementation 1A 26b * 2 g !g 20 g 丄Synthesis of sensitizing resin composition 组成The composition ratios shown in Table 2 below will be obtained from the respective synthesis examples 7 and 8. The guanamine polymer and the esterified diazonium compound, the phenol-containing compound, and the conjugated oxime to provide a photosensitive resin composition. The esterified diazonium compound shown in Table 2 below is the same as defined in Table 1. Table 2 Example of carbamide _ polymer esterified diazonium hydrazine compound 2,6-diethoxymethyl-p-methyl age · solvent (GBL) 1 Wg 'Synthesis Example 7 26a, 2 g ! g 20 g 2 , Synthesis Example 7 26b * 2 g 2g 20 g 3 I0_g, Synthesis_Example 8 26a, 2 g !g lg 4 Chuan g 'Synthesis Example 8 26b ' 2 g !g ig Examples 13 to 24&gt柃: The respective photosensitive resin compositions obtained in Examples 1 to 12 were subjected to a lithography test, and the results were shown in Examples 13 to 24 and shown in Table 3. The respective positive photosensitive resin compositions obtained in Examples 1 to 12 were coated on a ruthenium wafer and prebaked at 125 ° C for 120 seconds. A microwafer coated with a photosensitive resin composition was exposed by a Nikonil Inc i-line stepper as an exposure apparatus, and developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (TMAH) for two minutes. Dip for one minute in distilled water and measure 28 1376574 with FE-SEM to determine CD (critical size). Further, the sensitivity was measured as the optimum exposure time by calculating the exposure time required to form a 10 μm L/S pattern at a line width of 1 to 1 after exposure and development. The resolution is determined as the minimum pattern size at the optimum exposure time. 5 After patterning, it was heated at 150 ° C for 30 minutes in a nitrogen atmosphere to raise the temperature to 350 ° C - hour to provide a cured film. Table 3 Exposure Energy (mJ/cm2) Resolution (μηι) 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 Implementation Example 20 330 3 Example 21 380 2 Example 22 300 3 Example 23 480 3 Example 24 290 3

Referring to Table 3, confirm that all resolutions have an excellent value of 3 μm or less. In addition, confirm that the exposure energy value shows excellent optical performance of 400 m J/cm2 or less. That is, it is judged that the terminal group of the polyamine polymer is not derived from an anhydride but is substituted with an alkyl group, an alicyclic group, or an aryl group, so that the transmittance is increased while the dissolution rate of the unexposed portion and the exposed portion is increased. Maximize the difference. <Comparative Examples 5 to 8>: lithography test The same lithography test was carried out in accordance with the same procedure as in Example 13 except that the photosensitive resin compositions were obtained from the respective Comparative Examples 1 to 4. The results were set to Comparative Examples 5 to 8 and shown in Table 4 below. 29 1376574 Table 4 Exposure Energy (mJ/cm2) Resolution (μιη) Comparative Example 5 670 5 Comparative Example 6 500 7 Comparative Example 7 680 7 Comparative Example 8 490 5 As shown in Table 4, use according to comparison Comparative Examples 5 to 8 of the positive photosensitive resin composition solution of Example 4 have low transmittance, so the exposure energy is relatively higher than that according to the examples, and since the carboxylic acid remains in the terminal group, 5 Therefore, the difference in dissolution rate between the unexposed portion and the exposed portion is 5 μm or more. Further, although illustrated in the embodiment in the L/S (line and space) pattern, the present invention is not limited thereto, and can be applied to all different patterns such as a hole pattern. The present invention has been described with reference to the specific embodiments of the present invention. It is to be understood that the invention is not limited to the specific examples disclosed. Various modifications and equivalent configurations. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a process diagram for producing a pattern without using a positive photosensitive resin composition. 15 [Description of main component symbols] 1: Semiconductor device 2: Photosensitive resin composition layer 3: Exposure portion 4 of photosensitive resin composition layer: Unexposed portion 5 of photosensitive resin composition layer... Patterned photosensitive after development Resin composition layer 6... Photosensitive resin composition layer 30 after curing

Claims (1)

1376574 Announcement VII. Patent Application Range: 1. A positive photosensitive resin composition comprising: (A) a polyamine polymer represented by the following formula 1; (B) an esterified diazonium compound; (C) ) a phenol-containing compound; and (D) a solvent: [Chemical Formula 1] El—NH—XI—HNOC—Y1—CONH—XI LI R1 HNOC—Y2—CONH—X2—INH—E2 | ”m2 R2 where in Equation 1, 10 X丨 is the same or different and independent of x2 a divalent to tetravalent organic group, Υι and γ2 are the same or different and independently a divalent to hexavalent organic group, and Ri and R2 are the same or different and independently hydrogen or a C1 to C5 organic 15 group EI and E2 are the same or different and independently hydrogen, or are derived from a moiety selected from the group consisting of monocarboxylic acids and active derivatives thereof, provided that both E1 and E2 are non-hydrogen, and 1111 and 1112 are the same. Or different and independently 0 to 100, and 20 ΓΏ|+Π12 is between 5 and 100. 2. The photosensitive resin composition of claim 1, wherein the esterified diazonium compound is included in an amount of from 1 31 1376574 to 50 parts by weight based on 100 parts by weight of the polyamide polymer, The phenolic compound is included in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the polyamidamide polymer, and the solvent and the polyamidamide polymer are in a weight ratio of 20:80 to 90:10. include. 3. The positive photosensitive resin composition of claim 1, wherein the polyamine is prepared by the method comprising: diamine monomer and selected from tetracarboxylic dianhydride, dicarboxylic anhydride, and The acid monomer of the group consisting of a carboxylic acid and a reactive derivative thereof is reacted to obtain 10 to a reaction product; and the reaction product and the blocked monomer are reacted to convert the amine group of the reaction product into a mercapto group. . 4. The positive photosensitive resin composition of claim 3, wherein the diamine monomer is represented by X(NH2)2, wherein the X system is the same as X, 15 or X2 of Chemical Formula 1. 5. The positive photosensitive resin composition of claim 3, wherein the diamine single system comprises a non-nonanediamine monomer and is represented by X(NH2)2, wherein the X system and the formula 1 are 乂| Or the same as 乂2, and containing a quinone diamine monomer. 6. The positive photosensitive resin composition of claim 3, wherein the acid monosystem is a dicarboxylic acid monomer represented by Y(COOH)2, wherein the Y system and the chemical formula 1 are 丫! or 丫2 is the same. 7. The positive photosensitive resin composition of claim 3, wherein the acid single system is represented by Y(COK') 2, wherein the Y system is the same as the formula 1 or Y2, and K' is The fraction obtained by the reaction of Y(COOH)2 with a halide or Y(COOH)2 32 1376574 and 1-hydroxy-1,2,3-benzotriazole. 8. The positive photosensitive resin composition of claim 3, wherein the acid monomer is a tetracarboxylic anhydride represented by the following formula 8: [Chemical Formula 8] 5 0 0〇aya 0 0 0 • 10 15 In the above formula 8, the Y system is the same as the 丫1 or 丫2 of the chemical formula 1. A method of producing a photosensitive pattern, comprising: coating a positive photosensitive resin composition according to any one of claims 1 to 8 on a support substrate and drying it into a resin composition layer Exposing the resin composition layer; developing the exposed resin composition layer with an alkali developing solution; and heating the developed resin composition layer. A photosensitive resin layer produced by using the positive photosensitive resin composition of any one of claims 1 to 8. A semiconductor electronic component comprising the photosensitive resin layer according to item 10 of the patent application. 33