TW200804983A - Chemically amplifying positive photoresist composition - Google Patents

Abstract

Disclosed is a positive amplifying positive photoresist composition, which is characterized by containing (A) a resin obtained from reaction among linear phenol resin, a compound of which the molecule contains at least two vinyl ether structures, and poly(hydroxystyrene) of which the molecule having hydroxkl groups that are partly protected by substituted 1-alkoxyalkyl or 2-oxocycloaklyl, and (B) acid generation agent.

Description

200804983

V (1) Description of the Invention [Technical Field of the Invention] The present invention relates to a chemically enhanced positive-type photoresist composition. [Prior Art] A chemically-enhanced positive-type photoresist composition for thick film, which is one of chemically-enhanced positive-type photoresist compositions, can be used for the formation of bumps φ (batteries) in the manufacture of semiconductor devices, and in the manufacture of circuit boards. In the formation of circuit patterns or thick film photoresist layers, the formation of thick film photoresist patterns in the manufacture of semiconductor devices. The chemically enhanced positive-type photoresist composition for thick film, for example, disclosed in the specification of U.S. Patent Publication No. 2004/03 8 1 48, which discloses a P-hydroxystyrene containing styrene and 2-benzyl- A copolymer of 2-propyl acrylate and a composition of an acid generator, which is disclosed in Japanese Laid-Open Patent Publication No. 2004-309775, discloses a 1-ethylcyclohexyl methacrylate and 2-ethoxyethyl acrylate. A composition of a copolymer, a novolac resin, and an acid generator. In the manufacture of a semiconductor device, in the formation of bumps, in particular, cracks are likely to occur in the formed thick film, so that it is generally difficult to form one. A chemically-enhanced positive-type photoresist composition in which a thick film of a crack occurs is formed. In other words, it is extremely desired to develop a chemically-enhanced positive-type photoresist composition having excellent crack resistance. SUMMARY OF THE INVENTION - 5 - 200804983 Λ (2) An object of the present invention is to provide a chemically-enhanced positive resist composition which can form a thick film which is less prone to cracking. That is, the present invention provides a chemically amplified positive-type resist composition characterized by comprising (A) a phenol novolac resin and a compound having at least two structures of an ene ether in a molecule. a resin obtained by reacting a part of a hydroxyl group in the molecule with a poly(hydroxyphenylethylidene) φ protected by a 1-alkoxyalkyl group or a 2-oxocycloalkyl group, and (B) an acid A chemically amplified positive-type photoresist composition according to <1>, wherein the 1-alkoxyalkyl group which may be substituted may be an alkoxy group or a decyloxy group. Taking a 1-alkoxyalkyl group of #1 -3 &lt; 3 &gt; a chemically enhanced positive-type photoresist composition according to &lt;1> or &lt; 2 &gt; wherein poly(hydroxystyrene) is a poly The chemically amplified positive-type photoresist composition according to any one of <1>, wherein a part of the intramolecular hydroxyl group may be substituted. Poly(hydroxystyrene) protected by φ alkoxyalkyl or 2-oxocycloalkyl is of formula (la)

(wherein, R1 is an alkyl group having 1 to 4 carbon atoms, and R2 is a group having a carbon number of 1 to 7; further, R 1 and R 2 may be bonded to form a propyl group or a butyl group) Formula (lb) -6- 200804983 (3)

The chemically enhanced positive resist composition of the formula (la), wherein the structural unit represented by the formula (la) is Formula (lc)

(wherein, R1 and R2 have the same meanings as described above.) The structural unit shown by the formula (lb) is a formula (Id)

The chemically-enhanced positive-type photoresist composition of any one of the above-mentioned, wherein there are at least two in the molecule; The compound of the vinyl ether structure is 1,4-bis(vinyloxymethyl)cyclohexane or 1,2-bis(ethyleneoxy) ethene; &lt;7 &gt;&lt; 1 &gt;~&lt; 5 &gt Chemically enhanced positive type

200804983 (4) A photoresist composition in which at least a compound in the molecule is a 15-4 bis(vinyloxymethyl) ring &lt;8&gt; as in &lt;1&gt;~&lt;7&gt; The generator is h3c 1 with 2 vinyl ethers; the chemically enhanced positive (Ilia) (Ilia) compound or formula (IIIb)

(Illb)

The compound shown in any one of <1> to <7>, wherein the acid generator is

a compound of the chemically enhanced positive type (IHb) (Illb); <1 0> such as a photoresist composition of <1> to <9>, the ruthenium containing a molecularly substituted 1 -oxyne group or 2-oxocyclic ring I: olefinic resin, novolac resin, poly(hydroxy hydroxy styrene) in which a part of the hydroxyl group in the chemically enhanced positive form of the hydroxy group is protected by a group Is at least one resin selected from the group consisting of a group of resins which are insoluble or poorly soluble in the aqueous alkali solution and which is soluble in the aqueous solution by the action of an acid. &lt;11&gt; The chemically-enhanced positive-type photoresist composition of any one of <1> to <9>, which contains a part of the intramolecular hydroxyl group which can be substituted a poly(hydroxystyrene) protected by a 2- or 2-oxocycloalkyl group and a novolac resin; # &lt; 1 2 &gt; a chemical enhancement according to any one of &lt;1 &gt;~&lt;9&gt; a positive-type photoresist composition, the ruthenium containing a 1-alkoxyalkyl group or a 2-oxocycloalkyl group having a part of a hydroxyl group in the molecule which may be substituted The protected poly(hydroxystyrene), the novolac resin and the base which is unstable to the acid, which are insoluble or poorly soluble in the aqueous alkali solution, and are soluble in the aqueous alkali solution via the action of the acid; &lt; The chemically amplified positive-type photoresist composition according to any one of <1>, wherein the acid generator is present in a total amount of the solid component of the photoresist composition. When the content is based on the content, it is 0.1 to 1% by weight; &lt; 1 4 &gt; A resin characterized by a novolac resin and a compound having at least two vinyl ether structures in the molecule, and a hydroxyl group in the molecule a part of a resin obtained by reacting a poly(hydroxystyrene) protected by a 1-alkoxyalkyl group or a 2-oxocycloalkyl group; &lt; 15 &gt; a resin such as &lt;14&gt; Wherein, the alkoxyalkyl group which may be substituted is a 1-alkoxyalkyl group which may be substituted by an alkoxy group or a decyloxy group; &lt; 16 6&gt; The resin of &lt;1 4 &gt; wherein poly( The hydroxystyrene) is a poly(P-hydroxystyrene); -9- 200804983 (6) &lt; 1 7 &gt; 1 &lt; 1 4 &gt; A hydroxyl group in the molecule of the points can be substituted alkoxyalkyl 1- or 2-oxo-cycloalkyl group of the poly (phenylethyl group by too) of formula (La) Protection

(wherein, R1 is an alkyl group having 1 to 4 carbon atoms, and R2 is an alkyl group having 1 to 7 carbon atoms: further, R1 and R2 may be bonded to form a propyl group or a butyl group). (lb)

A poly(hydroxyphenylene) formed by the structural unit shown; &lt;18&gt;&gt;&lt;1&gt;&gt;, wherein the structural unit represented by the formula (la) is a formula (Ϊ c )

(wherein, R1 and R2 have the same meanings as described above) the structural unit shown, and the structural unit represented by the formula (lb) is the formula (Id -10 - 200804983 V (7)

(10) The structural unit shown; &lt; 1 9 &gt; The resin according to any one of &lt; 1 4 &gt; to &lt; 1 8 &gt;, wherein the compound having at least two vinyl ether structures is 1,4 - bis-methyl)cyclohexane or 1,2-bis(ethyleneoxy)ethane; &lt;20&gt; The resin of any one of &lt;14&gt;~&lt;18&gt;, having at least 2 The compound of the vinyl ether structure is I,4-bismethyl)cyclohexane; the invention. The chemically amplified positive-type photoresist composition of the present invention is composed of a novolac resin and a molecule having at least two vinyl ether compounds in the molecule, and a part of the intramolecular hydroxyl group may be substituted with 1- or 2-oxygen. The poly(hydroxystyrene) reactive lipid protected by the cycloalkyl group, and the (B) acid generator are characteristic chemically enhanced positive constituents. First, the novolac resin will be described. The novolac resin is usually a novolac resin obtained by reacting a phenol compound with a hydroformylation catalyst. Bismuth compounds such as phenol, hydrazine-formamidine, m-cresol, p-cresol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, methyl Bismuth, 2-tert-butyl quinone, 3-terb butyl quinone, 4-tert· where, sub-(the sulphur oxygen is divided into (the ethylene-oxygen (A) structure of the chemical system Resistive composition to acid phenol, 2,3-2,3,5-tributylphenol, -11 - 200804983 (8) 2-tert-butyl-4-methylphenol, 2-tert-butyl-5 -methylphenol, 2-, methyl resorcinol, 4-methyl resorcinol, 5-methyl resorcinol, 2-methoxyphenol, 3-methoxyindole, 4-methyl Oxime, 2,3-methoxy oxime, 2,5-mono-methoxyphenol, 3,5-dimethoxyphenol, 2-methoxy resorcinol, 4-tert-butyl Glycol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 2,5-diethylphenol, 3.5-diethylphenol, 2,3,5-triethylphenol, Polyhydroxytriphenylmethane obtained by the reaction of 2-naphthol, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, dimethylphenol and hydroxybenzaldehyde. The phenolic compounds may be used alone or in combination of two or more It can also be used. Among them, bismuth-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, * 3.5- Cresol, 2,3,5-trimethylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2-tert-butyl-4-methylphenol 2-tert-butyl-5-methylphenol is preferred. Aldehyde compounds such as formaldehyde, acetaldehyde, propionaldehyde, η·butyl aldehyde, isoformyl aldehyde, acrolein, crotonaldehyde, cyclohexane aldehyde, Cyclopentanal, furfural, furanyl acrolein, benzaldehyde, hydrazine-methylbenzaldehyde, m-methylbenzaldehyde, ρ-methylbenzaldehyde, P-ethylbenzaldehyde, 2,4-di Methylbenzaldehyde, 2,5-dimethylbenzaldehyde, 3,4-dimethylbenzaldehyde, 3,5-dimethylbenzaldehyde, hydrazine-hydroxybenzaldehyde, m-hydroxybenzaldehyde, P•hydroxyl Benzaldehyde, phenylacetaldehyde, cinnamaldehyde, etc. These aldehyde compounds may be used singly or in combination of two or more kinds thereof. Among the aldehyde compounds, it is industrially easy to obtain, and formaldehyde is preferred. 'For aldehyde compounds, an excess of phenolic compounds is used. Acid catalysts such as hydrochloric acid, sulfuric acid, perchloric acid, phosphoric acid, etc., A , acetic acid, oxalic acid, trichloroacetic acid, ρ-toluenesulfonic acid and other organic acids, acetic acid-12-200804983 i Ο) zinc, zinc chloride, magnesium acetate and other divalent metal salts, etc. The aforementioned acid touch alone, or will be two The above-mentioned amount of the acid may be usually a reaction of a 0.01 to 1 molybdenum phenol compound with an aldehyde compound for the aldehyde compound 1 molar, and it can be carried out according to a known method for producing a linear grease. The reaction temperature is usually from 60 to 120 ° C and is usually from about 2 to 30 hours. The reaction is usually carried out in a solvent for the reaction. After the completion of the φ reaction, for example, an organic solvent insoluble in water may be added to the reaction, and the reaction mixture may be subjected to water shrinkage to take out the novolac resin. Hereinafter, at least two vinyl ether structures (hereinafter, simply referred to as vinyl ether compounds) in the molecule will be described. The vinyl ether compound may have two or more ethyl ether compounds in the molecule, and preferably has two vinyl ether structures in the molecule. • A compound having two vinyl ether structures in the molecule with 1,4-bis(vinyloxymethyl)cyclohexane, iota, 2-bis (ethylene oxide, etc., again with 1,4·bis (vinyloxymethyl) Cyclohexane is preferred. The above vinyl ether compound may be used in the following commercially available articles, and one of the hydroxyl groups in the molecule may be taken as an oxyalkyl group or a 2-oxocycloalkyl group (hereinafter, referred to as The protective group) poly(hydroxystyrene) (hereinafter, simply referred to as a styrene containing a protective group) will be described. The poly(hydroxystyrene) containing a protective group is a poly(phenolic phenolic tree which is separately catalyzed by a medium), and is a mixture of an inactive mixture and a concentrated compound ether structure. A compound in which a part of the hydroxyl group in the molecule of the poly(hydroxystyrene-13-200804983 (10)) protected by the 1-ethane of the ethane is protected by a protecting group. As the poly(hydroxystyrene), any of poly(0-hydroxystyrene), poly(m-hydroxystyrene) and poly(p-hydroxystyrene) can be used, and poly(P-hydroxystyrene) is preferably used. ). The poly(hydroxystyrene) may be a commercially available article or an article manufactured by a known method. Specific examples of the commercially available poly(P-hydroxystyrene) are Marja-Μ (trade name) manufactured by Jiushan Petrochemical Co., Ltd., and VP polymer (trade name) manufactured by Japan Saoda Co., Ltd. The 1-alkoxy group which may be substituted in the protecting group, for example, a 1-oxo hospital group which may be substituted by an alkoxy group or a methoxy group. Alkoxy groups such as methoxy, ethoxy, η-propoxy, isopropoxy, η-butoxy, tert-butoxy, η-hexyloxy, cyclohexyloxy, 1-golden a straight-chain, branched chain or cyclic alkoxy group having a carbon number of 1 to 12, such as an ethyloxy group, an η-propenyloxy group, a 1-adamantyloxy group, or the like. A decyloxy group having a carbon number of 2 to 12 or the like. Specific examples of the alkyloxyalkyl group which may be substituted are, for example, 1-ethoxyethyl, b(2.methylpropoxy)ethyl, 1-cyclohexyloxyethyl, 1-(2-methoxyB Oxy)ethyl, 1-(2-ethoxyethoxyethoxy)ethyl, ι·[2-(ι·金垸垸-oxy)ethoxy]ethyl, 1-[2-(1- King Kong Institute mine oxygen) ethoxy] ethyl and the like. The protecting group is, for example, a 2-oxocycloalkyl group such as a 2-oxo ring group having a carbon number of 4 to 6 such as a tetrahydro-2-pyranyl group or a tetrahydro-2-furanyl group. The protective group-containing poly(hydroxystyrene) has an acetal structure. The protective group-containing poly(hydroxystyrene) is, for example, the formula (Ia) -14- 200804983 % (11)

(la) (wherein, R1 is an alkyl group having 1 to 4 carbon atoms; R2 is an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 5 to 7 carbon atoms; further, R1 and R2 may be bonded to form a C. Base or butyl) • The structural unit and formula (lb) shown

(lb) The poly(hydroxystyrene) formed by the structural unit shown is preferred; formula (Ic)

(wherein, R1 and R2 have the same meaning as described above), and the structural unit, and formula (Id)

The poly(hydroxystyrene) formed by the structural unit shown by (Id) is more preferable; -15- 200804983 (12) The alkyl group having 1 to 4 carbon atoms represented by R1, such as methyl group, ethyl group, η- A linear or branched chain alkyl group having a carbon number of 1 to 4 such as a propyl group, an isopropyl group or a η-butyl group is preferably a methyl group. a linear group having a carbon number of 1 to 6 represented by R2, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an η-butyl group, an η-pentyl group, an η-hexyl group, or the like a cycloalkyl group having a carbon number of 5 to 7 such as a cyclopentyl group, a cyclohexyl group or a cycloheptyl group, and preferably an ethyl group, an η-propyl group or a cyclohexyl group. Cyclohexyl is preferred. Φ Poly(hydroxystyrene) containing a protecting group, preferably 10 to 90% of the hydroxyl groups of the poly(hydroxystyrene) are protected by a protecting group (polyhydroxysilane), and protected by 20 to 60% The poly(hydroxystyrene) protected by the base is more preferred. In the case where the proportion of the hydroxyl group protected by the protecting group is less than 1%, or more than 90%, the resin having a crosslinked structure (A) and the poly(hydroxystyrene) having the protective group are not easily obtained. Poly(hydroxystyrene) and a substituted 1-alkoxyalkene can be obtained by a method such as reverse reaction. The ratio of the hydroxyl group protected by the protecting group in the obtained protective group-containing poly(hydroxystyrene) can be adjusted by adjusting the amount of the alkoxy olefin to be substituted. For example, in the case of producing poly(hydroxystyrene) in which 10 to 90% of the hydroxyl groups of the poly(hydroxystyrene) are protected by a protecting group, the total molar of the hydroxyl group in the poly(hydroxystyrene) can be used. 0.1 to 0.9 moles of 1-alkoxy alkene phthalic acid catalyst, such as hydrochloric acid, sulfuric acid, perchloric acid, phosphoric acid, etc., formic acid, acetic acid, oxalic acid, trichloroacetic acid, P·toluenesulfonic acid Such as organic acids and so on. -16 - 200804983 % (13) The acid catalysts may be used singly or in combination of two or more. The amount of the acid catalyst used is usually 0.00 0 1 to 1% by weight for poly(hydroxystyrene). The reaction mode of poly(hydroxystyrene) with a 1-alkoxy alkene which may be substituted, usually a way of mixing poly(hydroxystyrene) with a replaceable 1-alkoxy alkene and an acid catalyst in a solvent Implementation. The solvent is not particularly limited as long as it is a solvent which is reactive to the reaction. The reaction temperature is usually 〇~^ 1 〇 〇 °C, and the reaction time is usually about 0.5 to 4 8 hours. After the completion of the reaction, for example, if necessary, a water-insoluble organic solvent may be added to the reaction mixture, and if necessary, an alkaline substance such as triethylamine may be added to the reaction mixture, and then washed with water and concentrated. The poly(hydroxystyrene) containing the protective group was taken out. Further, the poly(hydroxystyrene) containing a protective group may not be taken out, and the reaction mixture containing the protective group-containing poly(hydroxystyrene) may be used in the production of the resin (A) described later. The resin (A) will be described. The resin (A) can be produced by reacting a linear acid awakening resin with an ethoxylated ether compound and a poly(hydroxystyrene) having a protective group in the presence of an acid catalyst. This reaction can be carried out usually by mixing a novolac resin with a vinyl ether compound and a poly(hydroxystyrene) containing a protecting group with an acid catalyst in a solvent. The order of mixing is not particularly limited, and it is preferred to add an ethyl ether compound to a mixture of a linear phenol resin and a poly(hydroxystyrene) containing a protective group and an acid catalyst. As the acid catalyst, for example, the above-mentioned acid catalyst may be used in the production method of the poly(hydroxystyrene) having a protective group as described in -17-200804983 (14). Further, the poly(hydroxystyrene) having a protective group is linear when a reaction mixture containing a protective group-containing poly(hydroxystyrene) obtained by the above-mentioned method for producing a poly(hydroxystyrene) containing a protective group is used. In the reaction of the phenolic resin with the vinyl ether compound and the protective group-containing poly(hydroxystyrene), it is not necessary to add a new acid catalyst. The solvent is not particularly limited as long as it is a solvent which is inactive, and φ can be, for example, methyl isobutyl ketone or the like, and the amount thereof is not particularly limited. The amount of the poly(hydroxystyrene) containing a protective group is preferably from 20 to 80% by weight, based on the total of the novolac resin and the poly(hydroxyphenylene)-containing protective group. It is 30 to 70% by weight. When the amount of the vinyl ether compound used is too large, the molecular weight of the obtained resin (A) is too large, and the solubility of the obtained resin in the solvent is deteriorated. When the amount of the vinyl ether compound used is too small, the crosslinked structure is not easily formed. The amount of the vinyl ether compound to be used is preferably 2 to 20% by weight based on the total of the novolac resin and the vinyl ether compound and the protective group-containing poly(hydroxystyrene). After completion of the reaction, for example, a basic substance such as triethylamine is added to the reaction mixture, and then the resin (A) can be taken out by washing with water. The resin (A) taken out may be re-refined using an ion exchange resin or the like if necessary. The resin (A) obtained by the above method has a crosslinked structure and has a weight average molecular weight of usually 30,000 to 300,000, preferably -18 to 200804983 (15) 50,000 to 200,000 Å, followed by a (acid) acid generator. Be explained. The acid generator is not particularly limited as long as it can be decomposed by irradiation with light or radiation to form an acid compound. When the acid generated by the acid generator acts on the resin (A), the protective group present in the resin (A) may be subjected to a dissociation reaction or a cracking reaction of a crosslinked structure to change the resin (A). Soluble in aqueous alkali solution.

The acid generator is, for example, at least one compound selected from the group consisting of an iron salt, a halogen-containing compound, a diazoketone compound, a compound, and a sulfonic acid compound, and a key salt or a sulfonic acid compound is preferred. When the wavelength of the light source used in the exposure of the photoresist composition of the present invention is near 4 3 6 nm (g line) to 3 6 5 nm (i line), it is 4 3 6 nm (g line) and 3 6 5 A formula with large absorption near nm (i line) (IΠ a )

(Ilia) (wherein R3 is a substituent containing an oxygen atom or a nitrogen atom, or a hydrocarbon group which may be substituted by a halogen atom) or a sulfonic acid compound represented by the formula (Illb)

(In the formula, R3 has the same meaning as described above) -19-200804983 The sulfonic acid compound shown is preferably used as an acid generator, and the sulfonic acid compound represented by the formula (Illb) is more preferably used. Specific examples of the nicotine group not represented by R3 are, for example, 'methyl, ethyl, η-propyl, n-butyl, η-octyl, and the like, an alkyl group having 1 to 12 carbon atoms, a phenyl group, a tolyl group, 254, 6- a aryl group having a carbon number of 6 to 18 such as a trimethylphenyl group, a 2,4,6-triisopropylphenyl group, a 4-dodecylphenyl group or a 2-naphthyl group, and a benzyl group having a carbon number of 7 to 30 Aralkyl group and the like. The substituent containing an oxygen atom or a nitrogen atom, for example, an alkoxycarbonyl group, a hydroxyl group, an alkoxy group, a carbonyl group, a nitro group or the like, a halogen atom such as fluorine, chlorine, bromine or the like. Specific examples of the hydrocarbon group substituted with a substituent of an oxygen atom or a nitrogen atom or a halogen atom, for example, 4-methoxyphenyl group, the following formula

The base shown, etc. For the sulfonic acid compound, a commercially available compound may be used. For example, a compound produced by a known method described in International Publication No. 99/0 1 429 or the like can be used. Also, the key salt is, for example, the formula (V a )

(wherein P1, P2 and P3 are independent hydroxyl groups, alkyl groups having 1 to 6 carbon atoms or -20-200804983 (17) are alkoxy groups having 1 to 6 carbon atoms; a, b and c are independent 〇~ An integer of 3; when a is 2 or 3, most of P1 may be the same or different from each other. When b is 2 or 3, most of P2 may be the same or different from each other. When c is 2 or 3, most P3 may be the same or different from each other. Z - is an organic counter ion) compound, formula (Vb)

(wherein P4 and P5 are independently a hydroxyl group, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and d and e are independently 0 or 1; Z is an organic counter ion) The compound shown, formula (V c ) P6, + 〇7/S-CH-S-P9 Z-(Vc) P7 Hong (wherein P6 and P7 are independent alkyl groups having 1 to 6 carbon atoms, carbon number a cycloalkyl group of 3 to 10, or a divalent aliphatic hydrocarbon group bonded to P7 and having a carbon number of 3 to 7 and a contiguous S + simultaneously form a ring; wherein at least one of the aliphatic hydrocarbon groups is -CH2- It may be substituted by a carbonyl group, an oxygen atom or a sulfur atom. ρ8 is a hydrogen atom, P is a hospital group having a carbon number of 1 to 6, a ring group having a carbon number of 3 to 10 or a substituted aromatic ring group, or P8 and P9. The bond is a compound represented by a divalent aliphatic hydrocarbon group and a neighboring -CHCO- simultaneously forming a ring, which is an organic counter ion. Specific examples of the alkyl group having a carbon number of 1 to 6 in P1, P2, P3, P4 and p5 - 200804983 (18) such as methyl, ethyl, n-propyl, isopropyl, n-butyl, Tert-butyl, n-pentyl 'n-hexyl, etc., alkoxy having 1 to 6 carbon atoms such as methoxy, ethoxy, II-propoxy, isopropoxy, η-butoxy and the like. In ρ6, ρ7 and Ρ9, specific examples of the alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, η-propyl group, isopropyl group, η-butyl group, tert-butyl group, η-pentyl group, η- A cyclyl group having a carbon number of 3 to 10, such as a fluorenyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group or the like. a divalent aliphatic hydrocarbon group having a carbon number of 3 to 7 formed by φ Ρ6 and Ρ7 bonding, such as a propyl group, a butyl group, a pentyl group, etc., and the ρ6 and ρ7 bonds are bonded to the adjacent S + Specific examples of the ring include, for example, a sulfonio group, a sulfonio group, an oxoethylene sulfonyl group, and the like. In P9, an aromatic ring group which may be substituted by carbon, such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group or the like. a divalent aliphatic hydrocarbon group formed by bonding P8 and P9, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, etc., and a P8 and P9 bond with the adjacent -CHCO- The ring is formed, for example, 2-oxocyclohexyl, 2-oxocyclopentyl, and the like. Specific examples of the cation of the compound represented by the formula (Va), the formula (Vb) and the formula (ν〇) are as follows, for example, -22- 200804983 (19)

-23- 200804983 (20)

-24- 200804983 (21)

\A&gt;0 \AjO ocO

^A&gt;CC ^&gt;0 3/csO ^°cs〇°

-25 200804983 (22)

Φ In the compounds of the formulas (Va), (Vb) and (Vc), the organic counter ion Z is, for example, represented by the formula (VI)

[wherein, Q1, Q2, Q3, Q4 and Q5 are independently a hydrogen atom, a halogen atom-aldehyde group, a linear or branched chain alkyl group having a carbon number of 1 to 16 and a carbon number of 1 to 16 Chain or branched chain alkoxy group, carbon number 1 to 8 halogenated alkyl group, carbon number 6 to 12 aryl group, carbon number 7 to 12 aralkyl group, cyano group, carbon number 1 to 4 An alkylthio group, an alkanesulfonyl group having 1 to 4 carbon atoms, a hydroxyl group, a nitro group or a formula (VII)-COO-X-Cy1 (VII) (wherein X is a linear chain which may contain an oxygen atom or a sulfur atom) The alkyl group Cy1 is an anion represented by the alicyclic hydrocarbon group having 3 to 20 carbon atoms. -26- (23) 200804983 4 A linear or branched chain alkyl group having a carbon number of 1 to 16 in the formula (VI), such as methyl, ethyl, n-propyl, isopropyl, butyl Base, tert-butyl, η-pentyl, η-hexyl, η-octyl, η-fluorenyl, n-dodecyl, η-hexadecyl, and the like. a linear or branched chain alkoxy group having 1 to 16 carbon atoms, such as methoxy, ethoxy, η-propoxy, isopropoxy, η-butoxy, tert-butoxy , η-pentyloxy, η-hexyloxy, isopentyloxy, n-decyloxy, n-tertiaryoxy, η-hexadecanyloxy and the like. A halogenated alkyl group having 1 to 8 carbon atoms, such as a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group or the like. A halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, a ruthenium: an atom or the like. An aryl group having 6 to 12 carbon atoms, such as a phenyl group, a tolyl group, a methoxyphenyl group, a naphthyl group or the like. A aryl group having 7 to 12 carbon atoms, such as a benzyl group, a chloro group, a methoxybenzyl group, or the like. An alkylthio group having 1 to 4 carbon atoms, such as a methylthio group, an ethylenethio group, a propylthio group, an isopropylthio group, a butylthio group or the like. The sulfonyl group having a carbon number of 1 to 4 ® is, for example, a methylsulfonyl group, an ethylsulfonyl group, a η-propylsulfonyl group, an isopropylsulfonyl group, an η-butylsulfonyl group or the like. In the case where two or more of Q1, Q2, q3, q4 and q5 of the formula (VI) are a group represented by the formula (VI), the enthalpy and the cyi of the group may be independently selected. X, for example, the following linkage, -27- 200804983 (24) -GH2- (a ^1) -CH2-CH2~ (a -2) -CHrCH2-CH2» (a -3) (a-7) -CHrCH2- CHrCH2-(a -4) -CHrCH2*CHrCH2-CHr (a -5) -CHrCH2-CHrCH2CHrCH2- (a -6) -CHrCH2-CHrC:H2CHrCHrC:HrCH2-_CH2-0-(s -8)

_CH2-G-CH. · (a -9) _CH2-O—CH2~CH2&quot; (a ·10) —CH2-CH2*〇—〇Η2ΌΗ2- (a-11) —CH2-S_ (a,12) One CH2^S—CH2* ^3) A CHrS-CH2-CH2-(a Ί4)-CHrCH2-S-CH2-CH2- (a-15) a linear alkylene of 1 to 7 which is again (a-1)~(a -7) The 51 base is better. 9 Cy1, such as the substituents described below. -28- (25)200804983 羲 1(W) -〇 (b_2) —(b-3)

(b-12) t〇(b-21) (b-22) (b-4) (b-13) TU (b-23) (b-5) XD (b-14) (b-24) ( B-6) Me ^C〇(b-15) ID (b-25) Et &lt;φ (b-16) IQ (b-26) with cyclohexyl (b-4), 2-pyro-alkyl ( B- 2 1), 23), 1-adamantyl (b-24) is preferred. For the specific example of the ion Ζ, as described below, the base. 2-gold -29- 200804983 (26)

CH3S〇2

F

CN CH3SO2 CH〇 -|-〇-s〇; CF3 h3cs

-30- 200804983 (27)

-31 - 200804983 (28)

-32- 200804983 &lt; (29) C12H25

SO3

CN

CH3SO2 CH〇

Ci2H25-&lt;3~S03 Ct2H25-HfVs〇3

-33- 200804983 (30)

O3s—

C〇 °^b

〇3s

Br-&lt;〇^C〇0,〇&gt; ^S〇3

-34- 200804983 i (31)

Further, 'organic counter ion Z—for example, the following formula (VIII a) -35- 200804983 (32) eS03-Q6 (coffee) (wherein Q6 is a perfluoroalkyl group having 1 to 20 carbon atoms, a substitutable naphthyl group or An anion which can be substituted for the thiol group. Specific examples of the anion represented by the formula (Villa), for example, the following

O3s-cf3 o3s-cf:~~cf3 o3s-cf2gf2~cf3 o3s-cf-CF3 one-3 O3S-CF2—CF2—CF2-CF3 〇aS-QF —CF2—CF3 03S-CF2—CF—CF3 CFs CF3 o3s -c^ , cf3 cf3 cf3 03S - CF^—*CF2~CF 2~CF2—CF3 o3s-cf2—cf2—cf3 o3s-gf2—cf2—cf2—cf2—cf2—cf3 cf3 o3s-cf2—cf2—cf2 -cf2—cf2-cf2-cf2-cf3

O3S-/7-C10F21 O3S -/&gt;C12F25 03S-/7-C16F33 03S-/7-C2〇F41

36 200804983 (33)

Also, the organic counter ion z_ is, for example, the following formula (Vlllb)

Q7—S02-N—S02—Q8 (VHIb) (wherein Q7 and Q8 are independently a perfluoroalkyl group having 1 to 20 carbon atoms or an aromatic ring group having a carbon number of 6 to 20 which may be substituted) . Specific examples of the anion represented by the formula (Vlllb), for example, the following

F3C, s, N, s, CF3 C2F5, sA, sX2F5 F3C, s/N, sX2F5 〇2 〇2 〇2 〇2 〇2 〇2 C4F9, s, n, 3, C4F9 C8F17, sJM, sX: 8F17 c10f21 ,&gt;c10f21 〇2 〇2 〇2 〇2 〇2 〇2 25C16F33^g&gt;Nvg.C16F 33 C2〇F41x^K^C2〇F41 〇2〇2 〇2〇2 〇2〇2 -37- 200804983

(34)

As the acid generator, commercially available articles or articles manufactured by a known method can be used. In the photoresist composition of the present invention, the content of the acid generator is usually 0.1 to 10% by weight based on the total solid content of the photoresist composition. In the present invention, the total solid content means the total amount after removal of the solvent. Further, the photoresist composition of the present invention may further contain other resins in addition to the resin (A) and the acid generator. Other resins, such as a resin which is soluble in an aqueous alkali solution or which has a rest on the acid-38-200804983 (35), and which are insoluble or poorly soluble in an aqueous alkali solution, can be made into an aqueous alkali solution by the action of an acid. Soluble resin is preferred. a resin soluble in an aqueous alkali solution, for example, the above-mentioned novolac resin, the above-mentioned protective group-containing poly(hydroxystyrene), poly(hydroxystyrene), etc., and the above-mentioned protective group-containing poly(hydroxystyrene) and linear novolac Resin is preferred. An unstable group having a base which is unstable to an acid and which is insoluble or poorly soluble in an alkali water φ solution and which is soluble in an aqueous alkali solution by the action of an acid, for example, a carbon atom adjacent to an oxygen atom is four An alkyl ester group of a carbon atom, an alicyclic ester group in which a carbon atom adjacent to the oxygen atom is a quaternary carbon atom, and an ester of a carboxylic acid such as a lactone ester group in which a carbon atom adjacent to the oxygen atom is a quaternary carbon atom. Further, the "ester group" in the present specification means the structure having an ester of a carboxylic acid. Specifically, &quot;t e r t -butyl ester group&quot; is intended to have the structure π of the carboxylic acid t e r t _ butyl ester, which can be described as &quot;-C Ο O C (C Η 3 ) 3 ”. Further, the "four-stage carbon atom" is meaning "a carbon atom bonded to four substituents other than a hydrogen atom". • The acid is an unstable group, such as a neighboring oxygen atom such as a tert-butyl ester group. The carbon atom is a quaternary aryl group of a quaternary carbon atom; methoxymethyl acetate, ethoxymethyl, 1-ethoxyethyl, 1-isobutoxyethyl, 1-isopropyloxy Ester group, 1-ethoxypropyl ester group, 1-(2. methoxyethoxy)ethyl ester group, 1-(2-ethoxycarbonylethoxy)ethyl ester group, i-[2-(1) -adamantyloxy)ethoxy]ethyl ester, 1-[2-(1-golden-glycoloxy)ethoxy]ethyl ester, tetrahydro-2-furanyl, tetrahydro-2 An acetal ester group such as a pyranoyl group; an isobornyl ester group, a 1-alkylcycloalkyl ester group, a 2-alkyl-2-adamantyl ester group, 1·(1-adamantyl)-1- The carbon atom adjacent to the oxygen atom such as an alkyl alkyl ester group is • 39- (36) 200804983 4 an alicyclic ester group of a quaternary carbon atom, etc. has an unstable group for an acid, and is insoluble or poorly soluble in itself. An aqueous alkali solution which is soluble in an aqueous alkali solution by the action of an acid, for example, having an acid-containing acid a resin having a structural unit derived from an ester of acrylic acid, and a structural unit having a structural unit induced by an ester containing methacrylic acid having an unstable group, and having an unstable group for acid, and Specific examples of the resin which is insoluble or poorly soluble in the alkaline water φ solution and which is soluble in the aqueous alkali solution by the action of an acid, for example, tert-butyl acrylate, tert-butyl methacrylate, methoxy methacrylate, Methoxymethyl methacrylate, ethoxy methacrylate, ethoxymethyl methacrylate, 1-ethoxyethyl, acrylate, 1-ethoxyethyl methacrylate, 1-iso Butoxyethyl acrylate, 1-isobutoxyethyl methacrylate, _ isopropyloxyethyl acrylate, 1-isopropyloxyethyl methacrylate, 丨 ethoxypropyl acrylate , 1-ethoxypropyl methacrylate, 1-(2-methoxyethoxy)ethyl acrylate, 1-(2-methoxyethoxy)ethyl methacrylate, -acetamidine Oxyethoxyethyl)ethyl acrylate, 1-(2-ethoxyethoxyethoxy)ethyl methacrylate, 1 _[ 2 - (1 -adamantyloxy)ethoxy]ethyl acrylate, 1-[2-(1-adamantyloxy)ethoxy]ethyl methacrylate, 1-[2- ( 1-adamantanylcarbonyloxy)ethoxy]ethyl acrylate, 1-[2·(1·adamantanylcarbonyloxy)ethoxy]ethylmethylpropanoic acid vinegar, tetrahydro-2-furan Acrylate, tetrahydro-2-furanyl methacrylate, tetrahydro-2-pyranosyl acrylate, tetrahydro-2-pyranyl methacrylate, isophorone acrylate, iso -40- 200804983 (37) Vorketone methacrylate, 1 ·alkylcycloalkyl acrylate, 1-alkylcycloalkyl methacrylate '2-alkyl-2-adamantyl acrylate '2-Alkyl-2.adamantyl methacrylate, 1-(1-adamantyl)-1-alkyl-based acrylate, 1-(1-adamantyl)-bualkylalkyl Methacrylate and the like. The photoresist composition of the present invention comprises, in addition to the resin (A) and the acid generator, a photoresist composition further comprising a protective group-containing poly(hydroxystyrene) and a linear phenolic resin φ lipid, in addition to the resin (A) and In addition to the acid generator, the poly(hydroxystyrene) containing a protective group, the novolac resin, and the acid are unstable, and the solution itself is insoluble or poorly soluble in the aqueous alkali solution, and is affected by the action of the acid. The aqueous alkali solution is preferably a photoresist composition of a soluble resin. The content of the other resin is preferably 0 to 90% by weight based on the total of the resin (A) and the other resin. In the chemically-enhanced positive-type photoresist composition of the present invention, the performance deterioration caused by the passivation of the acid accompanying the exposure after exposure, and the addition of an organic basic compound, particularly a nitrogen-containing basic organic compound, is used for cooling. When the agent (quencher) is added, it can be improved. Specific examples of the nitrogen-containing basic organic compound, for example, an amine compound represented by the following formula, -41 - 200804983 (38)

(wherein T1 and T2 are independently a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and the alkyl group, the cycloalkyl group and the aryl group may be derived from a hydroxyl group, an alkane having a carbon number of 1 to 4 The amine group substituted with a group and at least one selected from the group consisting of alkoxy groups having 1 to 6 carbon atoms which are substituted by an alkoxy group having 1 to 6 carbon atoms are substituted. Τ3 and Τ4 are a separate hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, the alkyl group, the cycloalkyl group, the aryl group and the alkoxy group, which may be a hydroxyl group and an alkane having a carbon number of 1 to 4 The at least one selected from the group consisting of an amine group substituted with a group and an alkoxy group having 1 to 6 carbon atoms is substituted. Further, Τ3 and Τ4 may be bonded and form an aromatic ring with the carbon atom bonded thereto. Τ5 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group or a nitro group, and the substituent group, the cycloalkyl group, the aryl group and the alkoxy group may be a base group and may be carbon number. The at least one selected from the group consisting of an amino group substituted with an alkyl group of 1 to 4 and an alkoxy group having 1 to 6 carbon atoms is substituted. Τ6 is an alkyl group or a cyclic k group 'the alkyl group and The cycloalkyl group can be used as a hydroxyl group and can be alkane having a carbon number of 1 to 4 At least one selected from the group consisting of an amine group substituted with a group and an alkoxy group having 1 to 6 carbon atoms which may be substituted by a carbon number of 1 to 6 to 42-200804983 (39) alkoxy group; Substituted. A1 is -CO.'-NH-, -S-, -SS., alkylene or alkenyl group, and at least one methyl group of the alkylene group and the alkenyl group may be - - substituted) and, the following formula T1 t2-n-t6 oh 士 7 (wherein, T1, T2 and T6 have the same meanings as described above, and T7 is a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, The alkyl group and the cycloalkyl group may be substituted by at least one selected from the group consisting of a hydroxyl group, an amine group which may be substituted by an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. The aryl group may be grouped in a group of a hydroxyl group, an amine group which may be substituted by an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a perfluoroalkyl group having 1 to 4 carbon atoms. The at least one selected one is substituted by the quaternary ammonium hydroxide or the like shown. The bases of T1, T2, T3, T4, T5, D6, and T7 are preferably those having a carbon number of ~1 〇, and preferably having a carbon number of 1 to 6. An amine group which may be substituted with an alkyl group having 1 to 4 carbon atoms, such as an amine group, a methylamino group, an ethylamino group, an η-butylamino group, a dimethylamino group, a diethylamino group or the like. Alkoxy groups having 1 to 6 carbon atoms which may be substituted by alkoxy groups having 1 to 6 carbon atoms, such as methoxy, ethoxy, η-propoxy, isopropoxy, butoxy, ter t -butoxy, η-pentyloxy, η-hexyloxy, 2-methoxyethoxy% -43 - 200804983 ' (40) The alkyl group which may be 1 to 4 carbon atoms A specific example of an alkyl group substituted with at least one selected from the group consisting of a substituted amino group and an alkoxy group having 1 to 6 carbon atoms substituted by an alkoxy group having 1 to 6 carbon atoms, Such as methyl, ethyl, η-propyl, isopropyl, η-butyl, tert-butyl, η-pentyl, η-hexyl, η-octyl, η-fluorenyl, η-fluorenyl, 2-(2-methoxyethoxy)ethyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-aminoethyl, 4-aminobutyl, 6-aminohexyl, and the like. The cycloalkyl groups in Τ1, τ2, Τ3, Τ4, Τ5, Τ6 and Τ7 are preferably about 5 to 10 carbon atoms. In the group of the hydroxyl group, an amine group which may be substituted by an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms which may be substituted by an alkoxy group having 1 to 6 carbon atoms; Specific examples of the cycloalkyl group substituted with at least one selected group are, for example, a cyclopentyl group, a cyclohexyl group, a cyclopentyl group, a cyclooctyl group and the like. The aryl groups in Τι, Τ2, τ3, Τ4, and Τ5 are preferably about 6 to 10 carbon atoms. It can be grouped in the group consisting of the hydroxyl group, an amine group which can be substituted by an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms which can be substituted by an alkoxy group having 1 to 6 carbon atoms. Specific examples of the aryl group substituted with at least one selected group include a phenyl group, a naphthyl group and the like. The aryl group in Τ7 is preferably about 6 to 10 carbon atoms. At least one selected from the group consisting of a hydroxyl group, an amine group which may be substituted by an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a perfluoroalkyl group having 1 to 4 carbon atoms Specific examples of the aryl group substituted by the group include, for example, a phenyl group such as a phenyl group, a naphthyl group or a 3-trifluoromethylphenyl group; and an alkoxy group in the oxime 4 and oxime 5 are preferably about 1 to 6 carbon atoms. The -44-200804983 (41) is specifically exemplified by methoxy, ethoxy, η-propoxy, isopropoxy, η-butoxy, tert-butoxy, II-pentyloxy, n-hexyl Oxyl and the like. The alkyl group and the alkenyl group in A1 are preferably a carbon number of 2 to 6. Specific examples of the alkylene group include an ethyl group, a propyl group, a butyl group, a methylenedioxy group, an ethylene 1,2-dioxy group, and the like, and specific examples of an alkenyl group, for example, ethylene-1,2 - Diyl, 1-propene-1,3-diyl, 2-butene-1,4-diyl, and the like. Specific examples of the amine compound, such as hexylamine, heptylamine, octylamine, φ mercaptoamine, mercaptoamine, aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4- Nitroaniline, 1-naphthylamine, 2-naphthylamine, ethylenediamine, tetramethyldiamine, hexamethyldiamine, 4,4'-diamino-1,2-diphenylethane , 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3, diethyldiphenylmethane, dibutylamine, two Amylamine, dihexylamine, diheptylamine, dioctylamine, didecylamine, didecylamine, N-methylaniline, piperidine, diphenylamine, triethylamine, trimethyl Amine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, tridecylamine, tridecylamine, methyldibutylamine, A Dipentylamine, methyldihexylamine, methyldicyclohexylamine, methyldiheptylamine, methyldioctylamine, methyldidecylamine,methyldidecylamine,ethyldi Butylamine, ethyldipentylamine, ethyldihexylamine, ethyldiheptylamine, ethyldioctylamine, ethyldidecylamine , ethyl decylamine, dicyclohexylmethylamine, tris[2-(2-methoxyethoxy)ethyl]amine, triisopropanolamine, N,N-dimethylaniline, 2, 6-isopropylaniline, imidazole, pyridine, 4-methylpyridine, 4-methylimidazole, bipyridine, 2,2'-dipyridylamine, di-2-pyridyl ketone, 1,2-di ( 2-(Piridinyl)ethane, 1,2-bis(4-pyridyl)ethane, 1,3-bis(4-py-45-200804983 (42) pyridine)propane, 1,2-double ( 2-pyridyl)ethylene~匕 bis-pyridyl)vinyl, 1,2-bis(4-pyridyloxy)ethane, 4,4,2-dipyridyl sulfide, 4,4 _-pyridine Isothioether,], 2 bis (4-pyridyl) ethylene, 2,2-monomethylamine, 3,3 '-diH, b, methylamine, and the like. Specific examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, tetra-hexylammonium hydroxide, and tetra-n-octylammonium hydroxide. And phenyltrimethylammonium hydroxide, 3-((3-methylmethyl) phenyldimethylammonium hydroxide, (2-hydroxyethyl)trimethylammonium hydroxide (ie, choline), and the like. Further, as disclosed in Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. The photoresist composition of the present invention is preferably a coolant containing G·0 〇 1 to 1% by weight based on the total solid content of the photoresist composition. The photoresist composition of the present invention may contain a small amount of various additives such as a sensitizer, a dissolution inhibitor, an interfacial activity agent, a stabilizer, and a dye, as long as the effect of the present invention is not impaired. In the photoresist composition of the present invention, a photoresist composition obtained by dissolving a solvent of each of the above components can be used, and a photoresist composition can be used for a substrate such as a tantalum wafer by a spin coating method or the like. The method is applied. The solvent to be used can be used as long as it can dissolve the above components and has a suitable drying rate, and the solvent can be evaporated to form a uniform and smooth coating film. It can use a solvent generally used in the art. The solvent, for example, ethyl cellosolve acetate, methyl cellosolve acetate-46 - 200804983 (43), glycol ether ester such as propylene glycol monomethyl ether acetate; ethyl lactate, butyl acetate An acyclic ester such as amyl acetate or ethyl pyruvate; a ketone such as acetone, methyl isobutyl ketone, 2-heptanone or cyclohexanone; or a cyclic ester such as 7-butyrolactone. These solvents may be used alone or in combination of two or more. The photoresist film which is applied to the substrate and then dried is subjected to exposure treatment for the purpose of pattern drawing or the like, followed by heat treatment for the purpose of promoting the deprotection reaction, and then developed with an alkali developer. As the alkali developer to be used, various alkaline aqueous solutions used in the art can be used. In general, most of them are aqueous solutions using oxidized tetramethyl hydrazine and ammonia oxidized (2-aminoethyl)trimethyl hydrazine (commonly known as biliary test). [Embodiment] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by the examples. In the examples, the "%" and "parts" indicating the content or the amount used are based on the weight basis unless otherwise noted. The weight average molecular weight of the obtained resin was measured by gel permeation chromatography using a polystyrene standard (device: HLC-8120GPC manufactured by Tosoh Corporation, pipe column: G4000HXL and G20 00HXL manufactured by Tosoh Corporation) Detector: RI detector, solvent: tetrahydrofuran). Resin Synthesis Example 1 &lt;Synthesis of Resin R1&gt; Jiushan Petrochemical Co., Ltd. which makes poly(P-hydroxystyrene)-47- (44) 200804983 i-Maljia-MS 2 P (trade name) 5 〇〇g is dissolved in methyl isobutyl ketone 2 0 0 0 g. The obtained solution was concentrated to obtain a solution of poly(p-hydroxystyrene) 1 6 6 7 g in a four-necked flask equipped with a stirrer, a reflux cooling tube and a thermometer, and the obtained poly(p-hydroxybenzene) was added. After the total amount of the solution of ethylene), methyl isobutylate 860 g and p-toluene bismuth ruthenium 〇 8 g, 165 g of cyclohexyl vinyl ether was added dropwise at room temperature over a period of 5 minutes. After the resulting mixture was stirred at room temperature for 3 hours, triethylamine hydrazine was added. Further, it was washed 5 times with 900 g of ion-exchanged water, and the obtained resin solution was concentrated to obtain a concentrated solution of 1400 g. Further, after adding propylene glycol monomethyl ether acetate 4 300 g, it was concentrated to obtain 108 Og of a resin solution having the following structural unit.

The weight average molecular weight of the obtained resin was 5,200. The obtained resin is abbreviated as resin R1. Resin Synthesis Example 2 &lt;Synthesis of Resin R2&gt; In a four-necked flask equipped with a stirrer, a reflux cooling tube, and a thermometer, 1200 g of m-cresol, 56 g of oxalic acid dihydrate, and 90 wt% of acetic acid were introduced. After 78g and methyl isobutyl ketone, 2〇g, the temperature was raised to 8〇〇c. In the resulting mixture, '37% of formalin water was adjusted to 875 °C at the end of the dropwise addition. -48-200804983 (45) The formula was immersed in hourly time and then kept at 8 71 for 12 hours. After adding 1,2 2 0 g of methyl isobutyl ketone to the reaction mixture, it was washed 6 times with ion-exchanged water. After adding 500 mg of methyl isobutyl ketone to the obtained resin solution, it was concentrated to obtain a concentrated solution of 3 3 64 g. Methyl isobutyl ketone 6 1 5 2 g and η-heptane 6 7 7 4 g were added to the obtained concentrated solution at 60. (: stirring for 1 hour. After standing, the resin layer of the lower layer was separated. The resin-containing layer was diluted with 3,800 g of propylene glycol monomethyl ether acetate, and concentrated to obtain a solution containing a linear phenolic resin. 0 g. The weight average molecular weight of the obtained novolac resin is 7 7 50. The obtained novolac resin is abbreviated as resin R2. Resin Synthesis Example 3 &lt;Synthesis of Resin R3&gt; In a four-necked flask of a thermometer, 2,5-xylenol 413.5 g, o-hydroxybenzaldehyde 103·4 g, p-toluenesulfonic acid 20 μg, and methanol 826·9 g were added, and the resulting mixture was refluxed for 4 hours. After cooling the reaction mixture, methyl isobutyl ketone 1 32 2 g was added, and the resulting mixture was concentrated under normal φ pressure, and methyl isobutyl ketone 1 075 g was distilled off. 762.7 g of m-cresol and 29.0 g of 2-tert-butyl-5-methylphenol were added, and the temperature was raised to 65 ° C. In the obtained mixture, 3 7 % of formaldehyde water 6 7 8 g was adjusted until the end of the dropwise addition. 8 7 ° C method after dripping for 1.5 hours, and then kept at 8 7 t for 10 hours. In the reaction mixture, add After Isobutyl ketone 1 1 5 5 g, it was washed three times with ion-exchanged water. 500 mM of methyl isobutyl ketone was added to the obtained resin solution, and concentrated under reduced pressure to obtain a concentrated solution of 3 43 5 g. To the obtained concentrated solution, 3,796 g of methyl isobutyl ketone and 4,990 g of η-heptane were added, and the mixture was stirred at 60 ° C for 1 hour. After standing, -49-(46) 200804983 i- separated the resin layer of the lower layer. The resin layer was diluted with propylene glycol monomethyl ether acetate (3,500 g, and concentrated to obtain 1 690 g of a linear phenolic resin solution. The weight average molecular weight of the obtained novolac resin was 7000. The obtained novolac resin was abbreviated as resin R3. Example 4 &lt;Synthesis of Resin R4&gt; In a four-necked flask equipped with a stirrer, a reflux cooling tube, and a thermometer, φ, 120 g of a resin R2, 320 g of methyl isobutyl ketone, and 0.007 g of p-toluenesulfonic acid were added. 15.3 g of cyclohexyl vinyl ether was added dropwise over a period of 5 minutes while stirring. After stirring at room temperature for 1 hour, 6.5 g of 1,4-cyclohexanedimethanol divinyl ether was dropped over 5 minutes. Stir at room temperature. After 2 hours, add 2g of triethylamine oxime, 152g of methyl isobutyl ketone, and then make 1 52 g of ion-exchanged water was subjected to liquid separation washing for 5 times. After the obtained resin solution was concentrated to 120 g, 370 g of propylene glycol monomethyl ether acetate was further added, and concentrated to a total amount of 150 g. The weight average molecular weight of the obtained resin was 46,900. The resin obtained is abbreviated as resin R4. Resin Synthesis Example 5 &lt;Synthesis of Resin A1&gt; Malaga-S2P (trade name) I50g of Jiushan Petrochemical Co., Ltd. of poly(P-hydroxystyrene) Dissolved in 600 g of methyl isobutyl ketone. The resulting solution was concentrated to give 50 g of a solution containing poly(P-hydroxystyrene). The resulting solution containing poly(p-hydroxystyrene) was added to a four-necked flask equipped with a stirrer, a reflux cooling tube and a thermometer, and methyl isobutyl ketone 3 3 0 g and yttrium toluene sulfonate 〇 2 g were added. Thereafter, 44.6 g of cyclohexylethyl-5 - 200804983 (47) enol was added dropwise at room temperature over a period of 5 minutes. After the resulting mixture was stirred at room temperature for 1 hour, 409 g of a resin R2 obtained by Resin Synthesis Example 2, 1670 g of methyl isobutyl ketone, and 42.9 g of 1,4-bis(vinyloxymethyl)cyclohexane were further added. Drop in 5 minutes. The resulting mixture was stirred at room temperature for 5 hours. After adding 6 g of triethylamine hydrazine to the obtained reaction mixture, it was washed 5 times with ion-exchanged water 1 〇 〇 〇 g. The resulting resin solution was concentrated to give a concentrated solution of 830 g. After adding 650 mg of propylene glycol monomethyl ether acetate to the concentrated solution, the concentrated resin solution 674 § 〇 was obtained to obtain a weight average molecular weight of 5 5 1 0 0. The obtained resin is abbreviated as Resin A1. Resin Synthesis Examples 6 to 8 &lt;Synthesis of Resins A2 to A4&gt;

In the resin synthesis example 5, the same applies to the resin synthesis example 5 except that the amount of 1,4 -bis(vinyloxymethyl)-cyclohexane used was changed to the amount described in the following Table 1. The method was carried out to obtain resins A2 to A4. The weight average molecular weight of the obtained resin was as shown in Table 1. [Table 1] Resin 1,4-bis(vinyloxymethyl) cyclohexane used (g) Resin obtained Weight average molecular weight resin Synthesis Example 6 A2 5 2.7 100531 Resin Synthesis Example 7 A3 5 3.3 120003 Resin Synthesis Example 8 A 4 7 1.0 143309 Examples 1 to 8 and Comparative Examples 1 to 4 - 51 - (48) 200804983 4- Next, Each of the resins was prepared by using the acid generator and the coolant shown below to prepare a resist composition to prepare an evaluation example. &lt;Acid generator&gt; S : (2-(4-methylphenyl)sulfonyloxyimine Base-2 H-thiophene-3 ·ylidene)-(2-methylphenyl)acetonitrile φ &lt;coolant&gt; Q : dicyclohexylmethylamine &lt;solvent&gt; propylene glycol monomethyl ether acetate 22 parts of the following components were mixed and dissolved, and the resulting solution was filtered through a filter made of a fluororesin having a pore size of 5 μm to prepare a photoresist liquid. And the amount of use is as shown in Table 2.) φ acid generator (type and amount of use are as described in Table 2). The coolant (type and amount of use are as described in Table 2). The photoresist is spin-coated on the dried film thickness of 2 〇μπι. After the photoresist is applied, it is pre-baked on a hot plate at 130 ° C for 5 minutes. The wafers of the photoresist film were formed in this manner, and the i-line stepping machine &quot;NSR 1 75 5 i7A" (NA=0.5) manufactured by Ricoh Co., Ltd. was used to expose the exposure amount in stages to form an exposure. Line and space pattern. After exposure, it is exposed to a hot plate at 130 ° C for 1 minute, then exposed to burn-52-200804983 (49), and then baked twice in 3.8 wt% tetramethylammonium hydroxide solution. After immersion development for 60 seconds, after development, it was baked at a temperature of 1201 on a hot plate for 1 minute. The black area pattern after development and after baking was observed by a scanning electron microscope, and the results are shown in the table. As shown in Fig. 3. In addition, the black area pattern referred to here uses a chrome layer (shading portion). Based on the glass swarf (transparent swarf) forming a linear reticle reel (Reticles) for exposure and development, the pattern of the photoresist layer remaining around the line and space pattern after exposure and development Applicability: Observe the state of the photoresist film after prebaking, which is X with coating marks; 〇 without coating marks. Analytical: The line and space pattern of 20 μιη unresolved is X; the resolution is 〇. Actual sensitivity: expressed by the exposure of the line and space pattern of 20μπι to 1:1. Crack resistance: The film after cracking in the pre-baked film is X; the film after pre-baking is not cracked, and the film after development is cracked: △: film after pre-baking and after development Those who have not cracked are sputum. Heat resistance: After the post-burning is repeated, the shape of the pattern changes greatly, so that the disappearance of the etching is X; the shape change of the pattern is extremely small, and it can be confirmed that the etcher is Δ; the shape of the pattern is almost unchanged. -53- 200804983 (50) [Table 2]

No. Resin / part of acid generator / part of coolant / part of Example 1 A 1 / 1 3 . 5 S / 0. 1 Q / 0. 0 1 9 Example 2 A 2 / 1 3 . 5 S / 0. 1 Q/0. 0 19 Embodiment 3 A3/1 3. 5 S/0. 1 Q/0. 0 19 Example 4 A4/1 3. 5 S/0. 1 Q/0. 0 24 Example 5 A4/1 3. 5 S/0. 0 7 Q/0. 0 17 Example 6 A4/1 3. 5 S/0. 13 Q/0. 0 31 Example 7 A2/6. 7 5 R1/3 3 75 R 2/3 . 3 7 5 ; S/0. 0 7 Q/0. 0 17 Example 8 A2/6. 7 5 R 1/3. 3 7 5 R 3/3 . 3 7 5 S /0. 0 7 Q/0. 0 17 Comparative Example 1 R 1 / 1 3 . 5 S/0. 1 Q/0. 0 2 4 Comparative Example 2 R 1 / 6 . 7 5 R 2 / 6 . 7 5 S/0. 1 Q/0. 0 2 4 Comparative Example 3 R 1 / 6 . 7 5 R3/6. 7 5 S/0. 1 Q/0. 024 Comparative Example 4 R4/1 3. 5 S/0 . 1 Q/0 · 0 2 4 -54- 200804983 ^ (51) [Table 3]

No. Coating property aptitude actual sensitivity (msec) Crack resistance heat resistance Example 1 〇〇4 0 0 Δ Δ Example 2 〇〇3 7 0 〇Δ Example 3 〇〇3 8 0 〇〇Example 4 〇〇 4 9 0 〇〇 Example 5 〇〇 4 5 0 〇〇 Example 6 〇〇 4 9 0 〇〇 Example 7 〇〇 4 6 0 Δ Δ Example 8 〇〇 5 2 0 △ △ Comparative Example 1 X 〇 2 2 0 XX Comparative Example 2 X 〇 19 0 XX Comparative Example 3 〇〇 2 0 5 XX Comparative Example 4 Failure to resolve 20 // m lines and spaces

It is understood from Table 3 that the photoresist compositions of Examples 1 to 8 of the novel chemically-enhanced positive-type photoresist composition of the present invention do not have practical properties in terms of coatability, resolution, and actual sensitivity. The problem was compared with the photoresist compositions of Comparative Examples 1 to 4, and in addition to having excellent crack resistance, it exhibited extremely excellent properties in terms of heat resistance. The chemically-enhanced positive-type photoresist composition of the present invention has excellent crack resistance and excellent heat resistance, and is therefore highly suitable for forming bumps in the manufacture of semiconductor devices and forming circuit substrates. The circuit pattern or the thick film photoresist layer is formed to form a thick film such as a thick film photoresist pattern in the manufacture of a semiconductor device. -55-

Claims (1)

200804983 v (1) X. Patent Application No. 1 · A chemically-enhanced positive-type photoresist composition characterized by containing (A) a phenolic resin and a compound having at least two vinyl ether structures in the molecule, a resin obtained by reacting a part of a hydroxyl group in a molecule which may be substituted with a 1-alkoxyalkyl group or a 2-oxocycloalkyl group protected by poly(hydroxystyrene), and (B) an acid generator. 2. The chemically amplified positive-type photoresist composition according to claim 1, wherein the 1-alkoxyalkyl group which may be substituted is a 1-alkane which may be substituted by an alkoxy group or a decyloxy group. Oxyalkyl. 3. The chemically amplified positive-type photoresist composition according to claim 1, wherein the poly(hydroxystyrene)' is poly(p-hydroxystyrene). 4. The chemically amplified positive-type photoresist composition according to claim 1, wherein a part of the intramolecular hydroxyl group is protected by a substituted 1-alkoxyalkyl group or a 2-oxocycloalkyl group. Poly(hydroxystyrene) (wherein R1 is an alkyl group having 1 to 4 carbon atoms, and R2 is an alkyl group having 1 to 7 carbon atoms: further, R 1 and R 2 may be bonded to form a propyl group or a butyl group) (U ) -56 - 200804983 V (2) (lb) Poly(hydroxystyrene) formed by the structural unit shown. The chemically enhanced positive photoreactor of claim 4, wherein the structural unit represented by the formula (la) is the formula (Ic) (Ic) (wherein, and R2 have the same meaning as described above) The structural unit shown by the formula (Ib) is a structural unit represented by the formula (Id). The chemical type positive resist composition according to any one of claims 1 to 5, wherein the compound having at least two ethylene compounds in the molecule is 1,4-bis(vinyloxymethyl) Cyclohexane or 〖, 2 bis alkenyloxy) ethane. 7. The chemical nature of any of the first to fifth patent applications (Id) OH reinforced ether structure (B-reinforced -57-200804983 Ψ (3) type positive resist composition, wherein the compound having at least two vinyl ether structures in the molecule is 1,4-bis(vinyloxymethyl)cyclohexane The chemically amplified positive resist composition according to any one of claims 1 to 5, wherein the acid generator is of the formula (Ilia) (Ilia) Compound shown or formula (Illb) The compound shown. 9. A patented type of positive resistive composition, wherein The chemical enhancement of any of items 1 to 5, the acid generator is a compound of the formula (Illb) (Illb). The chemically amplified positive-type photoresist composition according to any one of claims 1 to 5, wherein the ruthenium contains a 1-alkoxyalkyl group having a part of a hydroxyl group in the molecule which may be substituted or Poly(hydroxystyrene) protected by 2-oxocycloalkyl, novolac resin, poly(hydroxystyrene) and p-acid are -58- 200804983 (4) Unstable base, which itself is insoluble in aqueous alkali solution Or at least one resin selected from the group consisting of a resin in which the aqueous alkali solution is soluble, by the action of an acid. The chemically amplified positive-type photoresist composition according to any one of claims 1 to 5, wherein the ruthenium contains a part of a hydroxyl group in the molecule which may be substituted with a 1-alkoxyalkyl group or 2 a poly(hydroxystyrene) protected by an oxocycloalkyl group and a novolac resin. The chemically amplified positive-type photoresist composition according to any one of claims 1 to 5, wherein the ruthenium contains a 1-alkoxyalkyl group having a part of a hydroxyl group in the molecule which may be substituted. Or a poly(hydroxystyrene) protected by a 2-oxocycloalkyl group, a novolac resin, and a group which is unstable to an acid, which itself is insoluble or poorly soluble in an aqueous alkali solution, and the aqueous alkali solution is affected by the action of an acid. It is a soluble resin. The chemically-enhanced positive-type photoresist composition according to any one of claims 1 to 5, wherein the content of the acid generator is based on the total solid content of the photoresist composition Φ It is 0.1 to 10% by weight. A resin characterized by a novolac resin and a compound having at least two vinyl ether structures in a molecule, and a 1-alkoxyalkyl group or a 2-oxygen group which may be substituted with a part of a hydroxyl group in the molecule. A resin obtained by reacting a poly(hydroxystyrene) protected by a cycloalkyl group. A resin according to claim 14 wherein the alkoxyalkyl group which may be substituted is a 1-alkoxyalkyl group which may be substituted by an alkoxy group or a decyloxy group. A resin according to claim 14 wherein poly(hydroxystyrene) is poly(P-hydroxystyrene). -59-200804983 (5) 1 7. The resin of claim 14, wherein a part of the hydroxyl group in the molecule may be protected by a substituted 1-alkoxyalkyl group or a 2-oxocycloalkyl group. Poly(hydroxystyrene) is, formula (la) (wherein, R1 is an alkyl group having 1 to 4 carbon atoms, and R2 is an alkyl group having 1 to 7 carbon atoms: further, R1 and R2 may be bonded to form a propyl group or a butyl group). (lb) The poly(hydroxystyrene) formed by the structural unit shown is 18. The resin of the Clause 17 of the patent application, wherein the structural unit shown by the formula (la) is the formula (〗 〖c) (wherein, R1 and R2 have the same meanings as described above) the structural unit shown, and the structural unit represented by the formula (lb) is a formula (Id - 60 - 200804983 (6) (Id) The structural unit shown. 19. In any one of claims 14 to 18, the compound having at least two vinyl ether structures in the molecule is ethylene oxymethyl)cyclohexane or 1,2-bis(ethyleneoxy)B. Alkyl 2 0. In any one of claims 14 to 18, the compound having at least two vinyl ether structures in the molecule is ethyleneoxymethyl)cyclohexane. Resin, its 1,4-double (ruthenium resin, its 1,4-double (-61 - 200804983 七无··明说单单符符表 is the generation of map elements on behalf of the map refers to the table: the case map If you have a chemical formula, please reveal the chemical formula that best shows the characteristics of the invention: no -4-