TW201015224A - Positive photosensitive resin composition - Google Patents

Abstract

The present invention relates to a positive photosensitive resin composition that includes (A) a polyamide polymer, (B) an esterified quinonediazide compound, (C) a phenol group-included compound, and (D) a solvent. The positive photosensitive resin composition has excellent heat resistance and is capable of providing high sensitivity and high-resolution fine patterns.

Description

201015224 VI. Description of invention:

TECHNICAL FIELD OF THE INVENTION The 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. L Λ* Chair; 3 Related Technical Notes Recently, as semiconductors and liquid crystal display devices tend to have higher integration, higher reliability, and higher density, researchers have actively used organic materials with purity and workability. Research. 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 electrical mechanical properties, and to form a precise high-resolution pattern, which makes it possible to create an ultra-high-level integrated semiconductor. Conventional photosensitive resin compositions are prepared by co-adding photosensitive acetonitrile to a polyamine polymer or by covalently bonding a polyamine polymer to a acetonitrile diazonium. 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 into a carboxylic acid, and then the exposed layer is brought into contact with a specific _ (traditional ’ 崎 崎 developer aqueous solution) 20 201015224. The portion of the composition including the converted carboxylic acid increases the solubility to 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 patterning with 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 property. In particular, since the precision pattern properties of the conventional polyamines are negatively correlated with the layer properties after curing, the development of the 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 J SUMMARY OF THE INVENTION An exemplary embodiment of the present invention provides a positive photosensitive resin composition 201015224. Another exemplary embodiment of the present invention provides a positive photosensitive property which has excellent heat resistance and (4) a fine pattern having high (four) properties and high riding comfort. Resin. A further embodiment of the present invention provides a method of producing a photosensitive pattern using the photosensitive resin composition 5. 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.料 It is not limited to the above scientific and technological purposes, and those skilled in the art can understand other scientific and technological purposes. 1A According to a specific example of the present invention, there is provided a positive photosensitive resin group comprising: (A) a polystyrene polymer having the following formula 1, (8) (iv) a diazobenzene compound, and (C) a cut. a base compound, and (D) a solvent. , [Chemical Formula 1]

NH—XI--HNOC—Y1—C0NH—X1- Ink L 1 . R1 ml HNOC—Y2—c〇nh_X2. R2 In Equation 1, m2 NH—E2

Xl and X2 are the same or different and independently are divalent to tetravalent organic groups,

Yl is the same or different from the Υ2 system, and the site is a divalent to hexavalent organic group.

R1 and R2 are the same or different and are independently hydrogen or cue5 organic groups, and the coffee 2 is the same or different and independently hydrogen, or is derived from a group selected from the group consisting of monospores and active derivatives thereof, The premise is that both 仏 and e2 are non-hydrogen, and the genus is called 13⁄4 or different and independently 〇 to 1〇〇, and 11^+1112 is between 5 and 100. 5 20 201015224 According to another embodiment of the present invention, there is provided a method of producing a photosensitive pattern comprising: coating the above positive photosensitive resin composition on a support substrate and drying it into a resin composition layer, The resin composition layer is exposed to develop the exposed resin composition layer with an organic developing solution, and heats the 5-developed resin composition layer. 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, specific examples of the present invention will be described in detail. According to one embodiment of the present invention, the positive photosensitive resin composition includes one or both ends of polyamine which are derived from an alkyl group, an aryl group, an alicyclic ring selected from the group consisting of a monocarboxylic acid and an activated derivative. The base or heterocyclic group is capped to maximize the solubility difference between the unexposed portion and the exposed portion. Therefore, when the photosensitive resin composition is patterned, the development rate of the exposed portion is increased so that it is possible to form a high-resolution pattern. After the curing process, the degree of ring closure and the degree of crosslinking are enhanced to provide a photosensitive resin layer having excellent film properties. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a process diagram for producing a pattern using a positive photosensitive resin composition. [Embodiment] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, specific examples of the present invention will be described in detail. However, these specific examples are merely illustrative and are not intended to limit the invention. According to the present invention, the green grease reading system includes (4) 201015224, a polyamine polymer represented by the following formula 1, (B) an esterified diazonium compound, (c) a compound containing a group, and (D) Solvent. As used in this context, the term "substituted" when used in the absence of a specific definition means that one is substituted with at least one substituent including a halogen, an alkyl group, an aryl group, an alkoxy group, an amine group, or an alkenyl group 5. In the present case, the term "alkyl" means that C1 to C30 alkyl group is preferably C1 to C15 alkyl, and the term "aryl" means C30 aryl, preferably. The term "alkenyl" refers to 匸2 to C30 alkenyl, preferably C2 to C15 alkenyl, and the term "alkoxy" refers to oxime to 10 C30 alkoxy, preferably. It is ci to C15, and the term "alicyclic" is used for the C3 to C40 cycloalkyl or C3 to C40 cycloalkenyl group, preferably C3 to C24 cyclodecyl or C3 to C24 cycloalkenyl. In the case of this case, the term "divalent to tetravalent organic group" and "divalent to hexavalent organic group" are used to refer to an organic group including 2 to 15 functional groups, respectively, when no specific definition is provided. And an organic group comprising 2 to 6 functional groups. A functional group refers to a substituent other than chlorine. In the case of this case, the term "heterocyclic" is used in the sense of "heteroaryl", "heterocycloalkyl", "heterocycloalkenyl", and "heterocycloalkynyl". One of the groups formed. In the present case, the term "hetero-compound" means a compound including at least one atom selected from the group consisting of N, 〇, p, and Si in place of carbon, when no specific definition is provided. Each component will be described in detail hereinafter. (A) Polymerization of polyamines 7 201015224 The polyamine polymer is represented by the following formula 1. E1—NH—X1-—HN0C ～Y1 — CONH —X1 — L 丨- ml —HNOC—Y2 —CONH X2 R1 1 ” Q0 NH-E2 In the above formula 1, 5 Xl is the same as & Or different and independently divalent to tetravalent organic groups, γ#γ2 (4) or different and independently divalent to hexavalent organic groups, 2 are the same or different and independently hydrogen or 01 to An organic group, "e#e2# is the same or different and independently hydrogen, or is derived from - a moiety selected from the group consisting of monocarboxylic acids and their heterozygous rides, provided that both & E2 and Preferably, El and E2 are a leukoyl group, an aryl group, an alicyclic group, or a heterocyclic group, which is the same or different from the calling system and independently from 〇 to 1〇〇, and 1^+13⁄4 is between 5 and 1〇〇. 15

The polyamidamide polymer represented by the above formula 1 is prepared by reacting a diamine mono- and a group of acid monomers selected from the group consisting of four New Zealand liver, two, two tests, and active derivatives thereof, with _reduction The product is reacted with the capping monomer to convert the amine group of the reaction product into a brewing group. A method of preparing a polyamine polymer is described in more detail. The diamine monomer can be represented by X(NH2)2, and the lanthanide in the oxime is the same as the chemical formula... Xl or X2. The oxi and X2 of Chemical Formula 1 are derived from a diamine monomer. The following formulas 2 to 7 are shown, but are not limited to those. [Chemical Formula 2] 20 201015224 [Chemical Formula 3]

[Chemical Formula 4]

5 [Chemical Formula 5]

[Chemical Formula 6]

[Chemical Formula 7]

Z13 10 In the above formulas 2 to 7, B1 to 215 are the same or different and are independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, hydroxyl, carboxylic acid, and thiol. 'And eight! Up to 8 6 are the same or different, and are independently selected from the group consisting of CR3R4, S, Ο, S〇2, CO, CONH, and a single bond, wherein R^R4 are the same or different and independently selected from ammonia Or a substituted or unsubstituted alkyl group 15 201015224 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 phenylamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxy)-linked Benzene, bis-5 [4-(4-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenoxy)benzene, 4'-diamino-3,3'-di Hydroxybiphenyl, 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'- Diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-10 diaminodiphenylmethane, 3,4'-diaminodiphenyl hydrazine, 4,4'-di Aminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, p-phenylenediamine, m-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, cyclohexanediamine, methylenebiscyclohexylamine, 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)methane, 2,2-bis-( 3-amino-4-hydroxyphenyl)propane, 2,2-bis-(3- 4-hydroxyphenyl)hexafluoropropane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxy Benzophenone, 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'-diaminodiphenylmethane, 2,2-bis-(3-amino-4-hydroxybenzene Group of hexafluoropropane, 3,3'-diamino-4,4'-dihydroxy sulfone, and mixtures thereof. The guanidine-containing diamine monomer can be used in conjunction with the diamine monomer. The ruthenium containing diamine monomer increases the adhesion to the substrate. 201015224 5

10 15

Examples of the fluorene-containing diamine monomer include bis(4-aminophenyl)dimethyl decane, bis(4-aminophenyl)tetramethyl decane, bis(p-aminophenyl)tetramethyl Dioxazane, bis(gamma-aminopropyl)tetradecyldioxane, 1,4-bis-(gamma-aminopropyldimethylguanidinyl)benzene, 1,3-double -(Aminopropyl)tetramethyldioxane, and the like, but not limited to them. Preferred geminal diamine-containing monomers include bis(4-aminophenyl)tetradecyl decane, bis(p-aminophenyl)tetradecyldioxane, or a mixture 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. [Chemical Formula 8]

In the above formula 8, the Y system is the same as the 丫1 or 丫2 of the chemical formula 1. The dicarboxylic acid monomer may be represented by Y(COOH)2, wherein the Y system is the same as ¥! or Y2 of the chemical formula 120. The reactive derivative of the dicarboxylic acid monomer can be represented by Y(COK')2, wherein the lanthanide is the same as YiSYz of Chemical Formula 1, and K' is such that Y(COOH)2 and a halide, 11 201015224 or Y(COOH)2* The fraction obtained by the reaction of 1-hydroxy-1,2,3-benzotriazole. The following formulas 9 to 16 can be derived from an acid monomer. [Chemical Formula 9]

5 [Chemical Formula 10]

[Chemical Formula 11]

[Chemical Formula 12]

[Chemical Formula 13]

Κ9 K10

* * [Chemical Formula 14] K11 K12

12 201015224 [Chemical Formula 15]

[Chemical Formula 16]

5 In the above formulas 9 to 16, 1^1 to 1^21 are the same or different 'and independently selected from the group consisting of hydrogen, substituted or unsubstituted, thiol, thiol, thiol, and C a group consisting of 〇〇r5, wherein R5 is hydrogen or a C1 to C5 alkyl group, and the group consisting of or not, -S〇2- 10 15 _C〇-, -CONH-, and a single bond a group wherein 6 and 7 are the same or different and are independently selected from the group consisting of a hydrogen acid monomer which may be a tetracarboxylic acid diphenyltetracarboxylic dianhydride, 2" such as pyromellitic dianhydride, 3, 3, 4, 4, Jiayi four ships two Xuan, double heart 4, stupid four mM, - diphenyl thiophene 仏 two ^ double Bu ^ Ben Chong two liver - double - like two body can be two m acid activity derivative 7 The base of the two needles, and the like. The acid monoacid monomer and 1-hydroxy 12 - such as a carbonyl dentate derivative and a derivative. The active occupational lin (four) vinegar derived] includes 4,4 oxy Benzoquinone gas, o-benzene 13 20 201015224 dimethyl hydrazine gas, diphenoxy dimethyl hydrazine gas, climbing # χ 本 本 基 ) ) ) ) ) 、 、 双 双 双 双 双 双 双 双 、 、 、 Helium), abundance - ^, phthalic acid, diphenyloxybenzotrimethane And the like. Preferred acid monomers include 3,3',4,4'-di-poor alpha-tetracarboxylic acid two-needle, bis(3,4-disyl)ether dianhydride, diphenoxy A material, a sterilible gas, and the like, but not limited to the same. The polyamine polymer represented by the chemical formula may be a copolymer in which two or more single systems are not damaged by the guanamine bond unit. Homopolymer or poly

Copolymerization of the light properties, layer properties, and water solubility of the article. The copolymer 10 may include various types, for example, a random copolymer, a copolymer, or a graft copolymer, 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 monodecanoic acid and a reactive derivative thereof. 15 The monocarboxylic acid may be any carboxylic acid, especially an alicyclic monocarboxylic acid such as cyclohexylcarboxylic acid 'norbornic acid formic acid, adamantyl formate, isobornyl formate,

And norbornene-based formic acid, or a reactive derivative thereof. The monocarboxylic acids can be used singly or in combination. Reactive derivatives of carboxylic acids include cyclohexylformamidine, norbornane methyl hydrazide, norbornene methyl hydrazine, adamantyl carbene, isobornyl helium, 4 borne norbornene , cyclohexylbenzotriazol ester, norbornene benzotriazole methyl ester, and the like. The molecular weight of the polystyrene polymer can be selected within the range not impairing the advantages of the present invention, but in a specific example, the weight average molecular weight (Mw) is between 14 201015224 500 and 500, OOO, in another specific example, It is between 1000 and 50,000 to ensure effective solubility and coating characteristics and to maximize patterning 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. "B1 vinegar heavy gas hydrazine compound The esterified diazonium compound acts as a photoactive compound (PAC), preferably including 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 201015224 [Chemical Formula 18-1] 〇

S02 [Chemical Formula 18-2] 〇

5 [Chemical Formula 19]

In the above formulas 17 to 19, 01 to 04 are the same or different and are independently selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group, and the alkyl group is preferably a methyl group, 10 or the like. Is the same or different, and independently is 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 above formula 18- 1 or 18-2 is indicated. 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 201015224 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) A compound containing a phenol The compound containing a precursor is used as a dissolution inhibitor to control the difference in dissolution rate between the exposed portion and the unexposed portion. The group-containing compound includes 2,6-dimethoxymethyl-4+butanol, 2,6-dimethoxymethyl-P-cresol, or 2,6-diethoxyindolyl-p _ cresol, but not limited to them. The age-containing compound can be represented by the following formulas 20 to 25, but is not limited thereto. [Chemical Formula 20]

15 20 In the above formula 20, 'Rg to R10 are the same or different, and are independently an atmosphere, or a substituted or unsubstituted alkyl group, the scales 11 to 15 are the same or different, and are independently selected from H, The group consisting of QH and a substituted or unsubstituted alkyl group is preferably CH3, and n10 is an integer of from 1 to 5. 17 201015224 [Chemical Formula 21]

In the above formula 21, R!6 to Rai are the same or different and are independently selected from the group consisting of H, 〇H, and 5 substituted or unsubstituted alkyl groups, A* is 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, the alkyl group is preferably CH3, and is called + squeaking and calling ten! !!5.!!!6 is the same or different and is independently an integer of $10 or less. [Chemical Formula 22]

In the above formula 22, R22 to R24 are the same or different 'and independently hydrogen' or a substituted alkyl group which is not substituted by 15, ηπ, !8, which is the same as or different from the postal system, and is independently 丨To an integer of 5, η!9 is the same as or different from the nso, and is independently an integer from 0 to 4. 201015224 [Chemical Formula 23]

R25 to R27 are the same or different and are independently selected from the group consisting of hydrogen, hydrazine H, and 5 substituted or unsubstituted alkyl groups, and 〃

Hu to η% are the same or different, and are independently an integer from 丨 to 4, and n22+n24 and n23+n26 are independently an integer of 5 or less. [Chemical Formula 24]

(〇H)n29 (^3〇)η3〇10 In the above formula 24, Κ·28 is a substituted or unsubstituted alkyl group, preferably CH3, R29 is the same or different, and independently hydrogen, Or a substituted or unsubstituted alkyl group, ηπ29, which is the same or different from, and independently from 丨 to 5, and n28, ho, and 叱2 are the same or different, and independently from 〇 to 4 The integer is η27+η28, η29+η3. It is an integer of 5 or less independently of n31+rl32. 19 201015224 [Chemical Formula 25]

(〇Η)Π33 识35)|134-一(§H^$> R34 焱(' (ΟΗ)π35 ^ώη36 in the above formula 25' · I2, R33, and R34 are the same or different and independent Is a substituted or unsubstituted alkyl group, preferably CH3, R35 to R38 are the same or different 'and independently hydrogen, or substituted or unsubstituted alkyl, 3, η%, and 9 is the same or different 'and independently' to an integer of 5, η34, η%, and 叱8 are the same or different, and are independently an integer from 〇 to 4, and 1137 is an integer from 1 to 4, provided that Η33+η34, η35+η36, and η38+η39 are independently _ integers of 5 or less. According to a specific example, the phenol-based compound is 0.1 to 3 in terms of 1 part by weight of the polyamidamide polymer. The 〇 part by weight is included. When the amount of the compound containing the base group falls within the range of the imaginary range, the sensitivity does not deteriorate during development' and the dissolution rate of the unexposed portion is appropriately increased to provide a good pattern. Huishen's showcases excellent stability. 20 201015224 The solvent can be an organic solvent, preferably \_methyl_2_pyrrolidone, gamma-butyrolactone, N,N- Methyl acetate, dimethyl hydrazine 'diethylene glycol dimethyl bond, diethyl ether diethyl ether, methyl lactate, ethyl lactate, methyl-1,3-butanediol acetate, 1, 3-butanediol·3_monodecyl ether, diethylene glycol dibutyl ether, propylene glycol 5 monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monoterpene ether acetate, methyl lactate, ethyl lactate, Butyl lactate, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, and the like, but not limited to them. Solvents may be used singly or in combination. Solvents and polyamine polymers It can be used in a weight ratio of 2 〇:8 〇 to 90:10. Within this range, a sufficiently thick film can be obtained and a good solubility and coating can be provided. According to another specific example, a positive type is provided. A method of producing a photosensitive pattern by using a photosensitive resin composition. A method of producing a photosensitive pattern 15 using the positive photosensitive resin composition of the present invention comprises: coating the above positive photosensitive resin composition on a support substrate and Drying into a resin composition layer; exposing the resin composition layer to an exposed developing tree with an alkali developing solution The composition layer is developed; and the developed resin composition layer is heated. Fig. 1 is a 20-process diagram for producing a pattern using a positive photosensitive resin composition. Thereafter, the method is explained in more detail with reference to Fig. 1. 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 (51). Then 'exposure the photosensitive resin composition layer (S2) The resin composition is chemically changed, and the dissolution rate of the exposed portion is increased. Subsequently, it is developed (S3) with the test solution 21 201015224 to provide a pattern. During the exposure process (S2), when a mask (not shown) is used for irradiation, When the line or the like UV light exposes the photosensitive resin composition layer 2, the photosensitive agent of the exposed portion 3 undergoes a chemical change, but the unexposed portion 4 does not undergo 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, and the patterned photosensitive resin composition layer 5 is provided. 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 positive patterns 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. <Synthesis Example 1>: Synthesis of polyamine-polymerized sodium. At the same time as nitrogen flow, 18.3 g of 2,2-bis-(3-amino-4-cyclophenyl)hexafluoropropane was added thereto. In a four-necked flask of a stirrer, a temperature control device, a nitrogen gas injector, and a condenser 20, 'N-methyl-2-d than cyprofenone (nmp) was placed and dissolved. The solid was completely dissolved. 9.9 g of the bite was placed in the solution. While the temperature of the solution was maintained at 5 ° C, 14.8 g of 4,4, oxybenzophenone was dissolved in 142 g of N-methyl-2-pyrrolidone (NMP) to provide a solution. The solution was slowly dropped into it at thirty minutes 22, 2010,152,224. One hour after the dropwise addition, the reaction was carried out at 5 ° C. Then, the temperature was raised to temperature and shaken for one hour. Thereafter, 1.5 g of cyclohexylmethyl chloride was placed and shaken for one hour to complete the reaction. The reaction mixture was placed in a water/methanol = 1 Torr / 1 (volume ratio) solution to give a 5 precipitate. The precipitate was filtered, washed thoroughly with water, and then dried at 8 (TC for 24 hours or longer) to synthesize a polyamine polymer represented by the following chemical formula. From the GPC results of the synthesized polymer, the weight average was confirmed. The molecular weight is 11K. (Chemical Formula 1-1)

10 <will be piped Example 2>: Polycarbamide polymer was replaced by 1.5 g of norbornane methyl hydrazine instead of 1.5 g of cyclohexylformamidine. Polymerization of polyamine represented by the following chemical formula 1-2 The system was synthesized according to the same procedure as in Synthesis Example 1. The polymer has a weight average molecular weight (Mw) of 10 K ° 15 (Chemical Formula 1-2)

<Synthesis Example: Synthetic polyamine loading polymerization, while nitrogen flow, 17·4 § 2,2-bis-(3-amino-4-yl-phenylphenyl)hexafluoropropane and ruthenium.86 g 1 , 3-bis-(aminopropyl)tetramethyldioxane was added to a 23-necked flask with a stirrer, temperature control, nitrogen injector and condenser, and 280 g of N-methyl- 2-Pyrrolidone (NMP) was placed and dissolved. After the solid was completely dissolved, 9.9 g of pyridine was introduced into the solution, and 13,4'4'-oxybenzophenone was introduced and dissolved in 142 g of N-methyl-2-pyrrolidinium 5 (NMP) solution. Slowly drip in for 30 minutes while maintaining the solution temperature at 0 to. C. 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 - hour. 15 g of cyclohexylmethylguanidine 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 = 1 Torr / 1 (volume ratio) solution to give a solution. The precipitate was then filtered, washed thoroughly, and taken at 8 Torr. (: drying in a vacuum for 24 hours or more to synthesize a polyamine polymer represented by the following Chemical Formula 13. The polymer has a weight average molecular weight of 11 K. (Chemical Formula 1-3)

15 5. Synthesis Example 4 > ^ Polyamide polymer

The polyamidamide polymer represented by the following Chemical Formulas 1-4 was synthesized according to the same procedure as in Synthesis Example 3 except that L5g of norbornane helium gas was used instead of 1.5 g of cyclohexylmethane. The polymer has a weight average molecular weight of 10K. (Chemical Formula 1-4)

Or [>>Ho_5>1^ into a polyamine polymer while the atmosphere is flowing, adding 18.3 g of 2,2-bis-(3-amino-4-hydroxyphenyl) 24 201015224 hexafluoropropane to A four-necked flask equipped with a stirrer, a thermostat, a nitrogen gas injector and a condenser was placed and 280 g of N-mercapto-2-pyrrolidone (NMP) was placed and dissolved. To completely dissolve the solid, 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-methyl-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 cyclohexylformamidine chloride was introduced and shaken for one hour, and then the reaction was completed. 10 The reaction mixture was placed in a water/methanol = 1 (V1 (volume ratio) solution to form a precipitate. The precipitate was then filtered, thoroughly washed, 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 11 K. (Chemical Formula 1-5)

<Synthesis Example 6>: Synthesis of polyamine polymer ❿ In addition to 1.5 g of norbornane methyl hydrazine instead of 1.5 g of cyclohexyl fluorene chloride, the polyamine polymer represented by the following Chemical Formula 1-6 is based on The same procedure as in Synthesis Example 5 was carried out. The polymer has a weight average molecular weight of 10K. 20 (Chemical Formula 1-6)

<Synthesis Example 7>: Synthesis of Polyamine Polymer 25 201015224 In addition to 1.5 g of maleic anhydride in place of L5S cyclohexylformamidine chloride, the polyamine polymer represented by the following Chemical Formula 1-7 was subjected to synthesis and synthesis. Example 1 was synthesized in the same procedure. The polymer has a weight average molecular weight of 10K. (Chemical Formula 1-7)

The polyamidamide polymer represented by the following chemical formula 8 was synthesized according to the same procedure as in Synthesis Example 1, except that 1.5 g of 5-norbornene-2,3-phthalic anhydride was substituted for 1.5 g of cyclohexylmethane chloride. . The polymer has a weight average molecular weight of 11K. 10 (Chemical Formula 1-8)

<Examples 1 to 12>: Synthetic optical resin group_成物

The composition ratios shown in the following Table 1 will synthesize the respective polyamine polymers synthesized in Examples 1 to 8 and the esterified diazonium compound, and the phenol-containing compound 2,6-diethyl 15-oxymethyl-oxime-A The phenol and the solvent γ-butyrolactone (GBL) are mixed to provide a positive photosensitive resin composition. "26a" in Table 1 means Qi to Q3 of Chemical Formula 26, two of which are represented by Chemical Formula 26-1 and the remainder one is a compound of nitrogen, and 26b means two of (^ to () 3 of Chemical Formula 26 A compound represented by Chemical Formula 26-2 and the other one being 20 hydrogen. 26 201015224 [Chemical Formula 26]

[Chemical Formula 26-1] 0

[Chemical Formula 26-2]

〇

Table 1 Example Polyamine S is a diazonium brewing compound 2,6-diethoxymethyl-p-shenling 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 9 2 g ig 20 g 6 10 g, Synthesis Example 3 26b, 2 g ig 20 g 27 201015224 7 Implementing your U 26a * 2 g lg 20 g 8 1 (Lg 'synthesis implementation 丨 4 26b, 2 g lg 20 g 9 1 (ij, synthetic implementation 丨 5 26a, 2 g lg 20 g 10 iO g: Synthesis Example 5 26b, 2 g lg 20 g 11 1 (Lg, synthesis...Example (S 26a, 2 g lg 20 g 12 I0 g: Synthesis Example 6 26b , 2 g lg 20 g _<Comparative IT application button compound 糸 糸 榭 榭 组成 composition The composition ratio shown in Table 2 below will be from Synthesis Example 7 8 obtained individual polyamine polymer and esterified diazonium compound, precursor compound, and reference solvent to provide a photosensitive resin composition. The esterified diazonium 5 compound system and table shown in Table 2 below 1 is the same as defined. Table 2 EXAMPLES WmM " Glyceride esterified diazonium compound 2,6-diethoxymercapto-p-cresol solvent (GBL) 1 mg, Synthesis Example 7 26a 5 2 g lg 20 g 2 il) g 'Synthesis Example 7 26b, 2 g 2g 20 g 3 ng, Synthesis Example 8 26a, 2 g lg lg 4 l〇g, Synthesis Example 8 26b, 2 g lg lg ^Examples 13 to 24>: The respective photosensitive resin compositions obtained in Examples 1 to 12 were subjected to lithography tests by the firing of the overnight bonds, and the results were shown in Examples 13 to 24 and shown in Table 3. The examples obtained from Examples 1 to 12 were obtained. Each positive photosensitive resin composition was coated on a tantalum wafer at 125. (: pre-baked for 120 seconds. A NikonilOc i-line stepper was used as an exposure apparatus to make a crystal of a photosensitive resin composition. It was rounded and developed for 2 minutes with 2.38 wt% aqueous solution of tetramethylammonium chloride (TMAH). It was dipped in steaming water for one minute, and 28 201015224 was measured by FE-SEM to determine CD (critical size). Further, the sensitivity was determined as the optimum exposure time by calculating the exposure time required to form a 1 μm L/S pattern at a line width of 1 to 1 after exposure development. The resolution is determined as the minimum pattern size at the optimum exposure time. After the pattern was formed, it was 15 Torr in a nitrogen atmosphere. The crucible was heated for 30 minutes 'to raise the temperature to 350 ° C - hour' to provide a cured film. Table 3 Exposure Energy (mJ/cm2) Resolution (μιη) 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, it was confirmed that all resolutions had excellent values of 3 μm or less. In addition, it was confirmed that the exposure energy value showed an excellent 10 optical performance of 4 〇〇 m J/cm 2 or less. That is, it is judged that the terminal group of the polystyrene polymer is not derived from an anhydride, but is substituted for a silk, a lipid, or an aryl group, so the transmittance is increased, and the difference in the dissolution rate between the unexposed portion and the exposed portion is maximized. Chemical. <Comparative Examples S to 8>: The same lithography test was carried out in accordance with the same procedure as in Example 13 except that the photosensitive resin composition was obtained from each of Comparative Examples to 4. The results were set to Comparative Examples 5 to 8 and shown in Table 4 below. 29 201015224 Table 4 Exposure Energy (mJ/cm2) Resolution (μπι) 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, but it is understood that the invention is not limited to the specific examples disclosed, but rather, Various modifications and equivalent configurations.

[Simplified description of the drawings; J Fig. 1 is a process diagram for producing a pattern using a positive photosensitive resin composition. 15 [Description of main component symbols] 1. Semiconductor device 2················· Patterned photosensitive resin composition layer 6···cured photosensitive resin composition layer 30

Claims (1)

201015224 VII. Patent application scope: 1. A positive photosensitive resin composition comprising: (A) a polyamidamide polymer represented by the following formula 1; (B) S is a heavy-weighting compound; 5 (C) a phenol-containing compound; and (D) a solvent: [Chemical Formula 1] E1—NH—XI--HN0C—Y1—CONH—XI--HNOC—Y2—CONH—X2-L 1 ” ml LI ” R1 R2 NH —E2 Wherein in the above formula 1, 10 乂丨 is the same or different and independently is a divalent to tetravalent organic group, and Y1 and Y2 are the same or different and independently a divalent to hexavalent organic group, Ri is the same or different from R2 and is independently hydrogen or a C1 to C5 organic 15 group, E1 and E2 are the same or different and independently hydrogen, or are derived from a monocarboxylic acid and a reactive derivative thereof. The portion of the group is premised that both E1 and E2 are non-hydrogen, 1^ and 1112 are the same or different and independently are 0 to 100, and 20 mi+1112 is between 5 and 100. 2. The photosensitive resin composition of claim 1, wherein the esterified diazonium compound is included in an amount of 1 31 201015224 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 polyamide polymer, and the solvent and the polyamine polymer are included in a weight ratio of 5:80 to 90:10. 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 oxime 1 of the chemical formula 1 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 is the same as Yi4Y2 of Chemical Formula 1. 7. The positive photosensitive resin composition of claim 3, wherein the acid single system is represented by Y(COK') 2, wherein Y is the same as 丫! or Y2 of Chemical Formula 1, K' is The fraction obtained by the reaction of Y(COOH)2* halide or Y(COOH)2 201015224 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] Ο Ο 5 ❹ 10 15 wherein, in the above formula 8, the Y system is the same as 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