TWI281597B - Chemically amplified positive resist composition - Google Patents

Abstract

This invention provides a chemically amplified positive resist composition containing the following four components: (A) a radiation sensitive acid generator. (B) A resin insoluble or hard-soluble to alkali aqueous solution but soluble to alkali aqueous solution upon reacting with an acid. (C) A basic compound. (D) A compound represented by the following formula (IV), wherein R9 and R10 independently represents an aryl group of which a part or all of the hydrogen atoms may be substituted by a hydroxyl group, an alkyl group, an alkoxy group or an alkoxycarbonyl group; R11-R16 independently represents a hydrogen atom or an alkyl group, or the following formula (V), wherein R17 represents an aryl group, of which a part or all of the hydrogen atoms may be substituted by a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or a N,N-dialkylamino group; R18 represents a hydrogen atom or an alkyl group, R19 and R20 independently represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, cyano group, or a benzoyl group. The compound has a mole absorption coefficient of from 100 to 50000 with respect the light of wavelength from 300 to 450 nm.

Description

1281597 ---------------------______---- V. Description of the invention (1) [Technical field to which the invention belongs], the present invention relates to the application of ultraviolet A photoresist composition having a high-energy radiation such as light (including g-rays, i-rays, excited lasers, etc.), electron beams, X-rays or radiant light to achieve photolithography, etc., particularly suitable for g The photoresist for exposure of rays and i-rays is %. [Previous Art] When manufacturing a semiconductor high integrated circuit or a liquid crystal display element, a photosensitive photoresist which is coated on a substrate is generally used, and a film of the resultant is exposed to ultraviolet light, electron beam, X-ray or radiation. High-energy radiant light such as light, (the sound is developed to form a predetermined resist pattern, that is, a so-called lithography is generally used. Therefore, in the manufacture of liquid crystal display elements, it is particularly desirable to have high sensitivity and High resolution. However, the conventional photoresist composition composed of a novolak resin and a naphthoquinone diazide sensitizer used in the manufacture of a liquid crystal display element is generally difficult to achieve both sensitivity and resolution improvement. For example, there is a disadvantage that the resolution is easily lowered when the sensitivity is improved. Moreover, in the exposure process of the lithographic photographing, due to the influence of the reflected light from the substrate, the planar uniformity of the size is often deteriorated. The object of the present invention is to provide a sense of dissimilarity and resolution and is less susceptible to reflected light from a substrate, which can be changed to a thief and a size. A chemically amplified positive photoresist composition having fewer photoresist patterns. ' That is, the present invention includes the following inventions:

The composition described in the item <7>, wherein the hydrogenated organic ammonium compound is a compound represented by the following formula (11I): R6 R5-N —R7

0H (III) (In the above formula, R 5 to R each independently represent a hydrocarbon group, or R and R 沄 a hydrocarbon group, and the R and R odors together with the nitrogen atom to which they are bonded form a cyclic heterocyclic group. Wherein at least one of the hydrogen atoms of R 5 to R may be hydroxy, nitro, cyano, alkylamino, hydrazine, Ν'-dialkylamino, alkoxy, cycloalkyloxy, aryloxy Base, alkylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, arylcarbonyloxy, alkoxy, cycloalkyloxycarbonyl, aryloxy The carbonyl group or the halogen atom is substituted. Further, the -CH2 group in the above hydrocarbon group may be substituted by the -c〇- group. The composition of the formula (III), wherein the organohydrogen phosphate compound is one or more selected from the group consisting of tetramethylammonium hydroxide and tetra-n-butyl hydroxide. VII, tetra-n-hexyl hydride, tetra-n-octyl hydride, phenyl trimethylammonium oxychloride, 3-(trifluoromethyl)phenyltriammonium hydroxide and a group of biliary assays The compound. The composition described in any one of <1> to <g>, wherein the '(D) component is a compound represented by the following formula (IV):

314227.ptd Page 11 1281597__ V. INSTRUCTIONS (5) (In the above formula, R and R 10 are each independently and represent an aryl group, and some or all of the hydrogen atoms on the aryl group may be partially or wholly made of a hydroxyl group, an alkyl group, or an alkoxy group. Substituted by alkoxycarbonyl group, R11 to R16 are each independently, and represent a hydrogen atom or an alkyl group. The composition according to any one of <1>, wherein the -(D) component is a compound represented by the following formula (V): r1 8 R17—(^C —R20 (V) ;19 (In the above formula, R 1 is an aryl group, and a part of a hydrogen atom or 1 ' 1 卩 on the aryl group may be a thiol group, an alkyl group, an alkoxy group, an alkoxy group or a Substituted by an N,N-dialkylamino group. R1 is a hydrogen atom or an alkyl group, and R1 and R 2 are independently derived from a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a cyano group or a benzoquinone. The composition described in the item <1>, wherein the component (D) is 1,7-bis-(3-methoxy-4-hydroxyphenyl)- The composition described in the item (1), wherein the component (D) is in the formula (V), wherein R is a compound of the formula (V), wherein R is a compound of the formula (V).沄3 _ 曱 oxy-4-hydroxyphenyl, R 1 昧 hydrogen atom, R 1 such as R 2 昧 ethoxy group of compounds. &lt; 1 4 &gt; as described in &lt; 1 1 &gt; a composition wherein, in the component (D), a compound of the formula (1), R1 is a 3-methoxy-4-hydroxyphenyl group, a R1 is a hydrogen atom, an R% is a cyano group, and a compound having an R 2 isopropyl isopropoxycarbonyl group. . [Description of the Invention] The present invention is described in detail as follows: The component (B) in the present invention is itself insoluble or poorly soluble in alkaline water.

314227.ptd Page 12 1281597 V. INSTRUCTIONS (6) In the liquid, but chemically changed by the action of acid to become a resin soluble in an aqueous alkaline solution. The resin is usually a resin having a phenol skeleton or a base-soluble resin having a resin such as a (meth)acrylic acid skeleton, which is introduced into a protective group which can be cleaved by an action of an acid. Examples of the protecting group include a group in which a quaternary carbon atom such as a tert-butyl group, a tert-butoxycarbonyl group or a third butoxycarbonyl fluorenyl group is bonded to an oxygen atom; a tetrahydro-2 - port ratio σ nan Base, tetrahydro-2-pyranyl, 1-ethoxyethyl, 1-(2-methylpropoxy)ethyl, 1-(2-decyloxyethoxy)ethyl, 1 -(2-acetoxyethoxy)ethyl, 1-[2-(1-adamantyloxy)ethoxy]ethyl, [2-U-adamantanecarbonyloxy)ethoxy Alkyl group such as ethyl; ethyloxycyclohexyl, 4-mercaptotetrahydro-2-indanone-4-yl (derived from mevalonate), 2_ A residue (non-aromatic cyclic group) or the like of a non-aromatic cyclic compound such as mercapto-2-adamantyl or 2-ethyl-2-adamantyl. Among the above groups, the acetal type group is preferred from the viewpoints of low activation energy of the deprotection reaction and small influence of the temperature of the photoresist pattern on the post-exposure baking. Among the groups of the aldehyde type, from the viewpoint of easily obtaining a raw material, it is preferred to use an ethoxyethyl group, a 1-ethoxypropyl group and a 2-tetrahydropyranyl group. The component (B) is preferably a resin having a phenolic hydroxyl group and a phenolic hydroxyl group protected by an ethyl ethoxyethyl group, a 1-ethoxypropyl group or a 2-tetrazinium group. For example, a part of the hydroxyl group of the polyvinylphenol is a resin protected by 1-ethoxyethyl, 1-ethoxypropyl or 2-tetrahydropyranyl, or a part of the hydroxyl group of the phenolic acid varnish resin is ethoxylated. It is preferred that the base is protected by a ethyl group, an ethoxypropyl group or a 2-tetrahydropyrene.

314227.ptd Page 13 1281597 V. INSTRUCTION DESCRIPTION (7) The above protective group is formed by, for example, replacing a hydrogen atom of a phenolic hydroxyl group or a hydrogen atom of a carboxyl group. The protecting group can be introduced into a reactive resin having an acidic radical or a Wei group by a known protecting group introduction reaction. Further, the unsaturated compound having a protective group may be used as one of the monomers to form a component (B) by a copolymerization reaction. The chemically amplified positive photoresist composition of the present invention may contain other alkali-soluble resins as the binder component in addition to the component (B) without departing from the functional scope of the present invention. The soluble resin can be exemplified by a varnish resin or the like. The novolak resin is generally produced by condensing a phenolic compound and an acid in the presence of an acid catalyst. The phenolic compound used in the above-mentioned production of the novolak resin can be exemplified by I - such as argon, o-, m- or p--, 2, 3-, 2, 5-, 3, 4 or 3, 5 - Dioxane, 2,3,5-trimethylguanidine, 2_, 3- or 4-tert-butyl, 2-tris-butyl-4- or 5-nonylphenol, 2-, 4 - or 5-methyl resorcinol, 2-, 3- or 4-methoxyphenol, 2, 3-, 2, 5- or 3, 5-dimethoxyphenol, 2-methoxy Hydroquinone, 4-tert-butyl catechol, 2-, 3- or 4-ethylphenol, 2, 5 - or 3,5 - diethyl age, 2,3,5-triethyl Poly-ampl-triphenylmethane-based compound obtained by condensation of 2-, Cyan, 1,3, 1,5, or 1,7-dihydroxynaphthalene, xylenol, and hydroxybenzaldehyde. These phenolic compounds are used singly or in combination of two or more. The aldehyde used in the production of the phenolic lacquer resin may, for example, be an aliphatic acid such as furfural, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, acrolein or crotonaldehyde; cyclohexanal or cyclopentanal. , a cyclic aldehyde such as furan aldehyde or furyl acrolein

314227.ptd Page 14 1281597 V. Description of the invention (8); benzofural, o-, m- or p-methylphenylfurfural, p-ethylbenzoic acid, 2,4-, 2,5 Aromatic aldehydes such as -, 3,4 - or 3,5 - dimethylbenzophenone, o-, m- or p-hydroxybenzaldehyde; aromatic aldehydes such as phenylacetaldehyde or cinnamaldehyde Classes, etc. The aldehydes may be used singly or in combination of two or more. Among these aldehydes, tannic acid is preferred from the viewpoint of industrial availability. The acid catalyst used in the condensation reaction between the phenolic compound and the aldehyde may, for example, be an inorganic acid such as hydrochloric acid, sulfuric acid, perchloric acid or phosphoric acid; formic acid, acetic acid, oxalic acid, triacetic acid, p-toluene yellow An organic acid such as an acid; a divalent metal salt such as acetic acid, zinc sulfide or magnesium acetate. The acid catalysts may be used singly or in combination of two or more. The condensation reaction can be carried out according to a general method, for example, at 60 to 120 ° C for 2 to 30 hours. The novolak resin obtained by the condensation reaction can be obtained by, for example, fractional distillation to remove low molecular weight components or to narrow the molecular weight distribution range to become a high molecular weight component. Since the novolac resin is inexpensive, the production cost of the chemically amplified positive photoresist composition of the present invention can be reduced. With regard to the component (A) in the chemically amplified positive photoresist composition of the present invention, the substance itself or the photoresist composition containing the substance can be decomposed by the action of radiation such as light or electron rays to generate an acid. The acid generated by the component (A) acts on the component (B) to cleave the unstable group present in the acid of the component (B). The component (A) may, for example, be an onium salt compound, an S-three-pigmented organic halogen compound, a maple compound or a repeating acid compound. Among them, for strong absorption near 43 6 n m (g ray) and 3 6 5 n m (i ray), sensitivity, development, post-coating or post-exposure of the photoresist composition

314227.ptd Page 15 1281597 V. Inventive Note (9) From the viewpoint of handling resistance, etc., the compound represented by the following formula (I) is preferably: R1

(In the above formula, R 1 to R each independently represent a hydrogen atom or a hydrocarbon group, and R 4 represents a hydrocarbon group. However, at least two of hydrogen atoms in the hydrocarbon group represented by R 1 to R may be a mercapto group, Nit', cyano, acrylamine, N,N '-dialkylamino, alkoxy, cycloalkyloxy, aryloxy, alkyl, carbyl, carbaryl, hydrazine Substituted by a carbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, an arylcarbonyloxy group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group or a halogen atom. Further, the above hydrocarbon At least one of the -CH 2 - groups in the group may be substituted by a -C0- group.) The hydrocarbon group represented by R1 in the above formula (I) is preferably a C6^ group. The groups represented by R and R are preferably a hydrogen atom, a Ch thiol group or the like. Further, the hydrocarbon group represented by R is preferably a Ch indenyl group, a Ch aryl group or the like. When R 1 to R 4 are a hydrocarbon group substituted by a halogen atom, the halogen atom may, for example, be an atom such as fluorine, chlorine or bromine. The compound represented by the formula (1) may, for example, be R昧2-indenylphenyl group, μ, R% hydrogen atom, R4^-n-propyl group, n-butyl group, n-octyl group or tolylylene group in the formula (1). 2,4,6-Trimethylphenyl, 2,4,6-triisopropylphenyl, 4-dodecylphenyl, 4-nonyloxyphenyl, 2-naphthyl, benzoinyl or the following (II) the group shown (however, R 1 to R are assigned to the above

314227.ptd Page 16 1281597 V. Inventions (ίο) h3c ch3

At least one hydrogen atom may be hydroxy, nitro, cyano, alkylamino, N,N-dialkylamino, alkoxy, cycloalkyloxy, aryloxy, alkylcarbonyl, cycloalkylcarbonyl Substituted by an arylcarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, an arylcarbonyloxy group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group or a halogen atom. ) compounds and the like. The compound of the formula (I) may be used in combination with the above-mentioned onium salt compound, the S-three-till-based base halogen compound, the maple compound, other other salt-sensitizing compounds, and the like. In this case, the content of the compound represented by the formula (I) is preferably 10% by weight or more based on the total amount of the radiation-sensitive linear acid generator, and more preferably 25% by weight or more. The sulfonate compound other than the compound represented by the formula (I), which is an iron salt compound, an S-triterpene organohalogen compound, or a maple compound, may be exemplified by the following compounds: diphenyliodonium trifluorosulfonate, 4-decyloxyphenylphenyliodonium hexafluoroantimonate, 4-methoxyphenylphenyliodonium trifluorodecane decanoate, bis(4-butylbutylphenyl)iodonium Fluoroborate, bis(4-butylenephenyl) hexahydrohexahydronate, bis(4-t-butylphenyl)-iron hexahydrate, change (4-butyl butyl) Phenyl) ruthenium iron trifluoromethane sulphate ^ triphenyl sulfonium hexafluorophosphate, trisyl hydrazine hexafluoroantimonate, triphenyl sulfonium trifluoro sulfonate, 4-pyridyl phenyl Phenylhydrazine perfluorobutane sulfonate,

S14227.ptd Page 17 1281597 V. INSTRUCTIONS (11) 4-Phenylphenyldiphenylphosphonium perfluorooctane sulfonate, 4-methoxyphenyldiphenylphosphonium hexafluoroantimonate, 4- Nonylphenyldiphenylphosphonium trifluoromethanesulfonate, p-tolyldiphenylphosphonium trifluoromethanesulfonate, 2,4,6-tridecylphenyldiphenylfluorene trifluoromethanesulfonate Acid salt, 4-tert-butylphenyldiphenylphosphonium trifluorosulfonate, 4-phenylthiophenyldiphenylphosphonium hexafluorophosphate, 4-phenylthiophenyldiphenylphosphonium Hexafluoroantimonate, 1-(2-naphthomethylmethyl)tetrahydrothiophene hexafluoroantimonate, di(2-naphthylmethyl)tetrahydrothiophene trifluoromethanesulfonate, 4-hydroxy-naphthyldimethylsulfonium hexafluoroantimonate, 4-hydroxy-1-naphthyldifluorenyltrifluorosulfonate, 2-mercapto-4,6-bis (three gas Base)-1,3,5-three tillage, 2, 4, 6-three (three gas methyl)-1,3,5-trianthene, 2-phenyl-4,6-double (three gas Base)-1,3,5-three D well, 2 -( 4 -phenylene)- 4,6-double (tri-gas sulfhydryl)-1,3,5-three tillage, 2-(4-A Oxyphenyl)-4,6-bis(trichloromethyl)-1,3, 5- Bismuth, 2-(4-methoxy-p-naphthyl)-4,6-bis(trimethyl)-1,3,5-trin, 2-(4-methoxy-naphthyl)-4, 6 - bis(trichloromethyl)-1,3,5-three tillage, 2 - (stupid 1 and [d ] [ 1,3 ] di-sigma-methane-5-yl)- 4,6-dual ( Trimethyl sulfhydryl)-1,3,5 tri-farming, 2-(4-methoxystyryl)-4,6-bis(triseodecyl)-1,3, 5-trin, 2 -( 3, 4, 5-trimethoxystyryl)-4,6-bis(trimethylsulfonyl)-1,3,5-trianthene, 2-(3,4-dimethoxyoxystyrene Base,-4,6-bis-J chloromethyl)-1,3,5-three-pronged, 2-(2,4-dimethoxystyryl)-4,6-bis (trimethyl fluorenyl) -1,3,5-trianthene, 2-(2-methoxystyryl)-4,6-bis(trimethylsulfonyl)-1,3, 5-trin, 2-(4-butyl Oxystyryl)-4,6-bis(trimethylmethyl)-1,3,5-triturated, 2-(4-pentyloxystyryl)-4,6,bis(trichloroguanidine) Base)-1,3,5-three tillage, 1-benzylidene-1-benzoinyl-pair

14227.ptd Page 18 1281597 V. INSTRUCTIONS (12) Tosylate (commonly known as benzoin tosylate), 2-benzylidene-2-hydroxy-2-phenylethyl-p-oxime Benzene sulfonate (generally referred to as α-hydroxymethyl benzoin tosylate), 1,2,3-phenylbenzoic acid based three mesylate, 2,6-dinitrobenzene P-p-toluenesulfonate, 2-nitrobenzyl-p-toluenesulfonate, 4-nitrophenylindole p-toluenesulfonate, diphenyl di- maple, di-p-nonylbenzene Base two milled, bis(phenylsulfonyl)diazomethane, bis(4-phenylphenylsulfonyl)disazomethane, bis(p-tolylsulfonyl)diazo fluorene Alkane, bis(2,4-dimethylphenylsulfonyl)diazodecane, bis(cyclohexylsulfonyl)diazomethane, (benzylidene)(phenylindenyl)di Azomethane, Ν-(phenylsulfonyloxy) succinimide, Ν-(trifluoromethylsulfonyloxy) succinimide, Ν-(trifluoromethylsulfonyloxy) Indigo imine, Ν-(trifluoromethyl decyloxy)-5-n-baranyl-2,3-diweirylimine, Ν-(trifluoromethyl Oxy)naphthoquinone imine, Ν-(ία-樟-braylsulfonyloxy)benzonitrile, 4-methoxy-α-[[[4-methylphenyl)sulfonyl] Oxy]imino]benzonitrile or the like. The test compound (C) in the chemically amplified positive photoresist composition of the present invention may, for example, be a nitrogen-containing basic compound such as an organic ammonium hydroxide compound or an amine. Among them, an ammonium hydroxide compound represented by the following formula (I I I): R6 R5—N—R7 OH&quot; (III) R8 (in the above formula, R 5 to R 8 are each independently, showing a hydrocarbon group, or R and R tastes.

314227.ptd Page 19 1281597_ V. INSTRUCTIONS (13) Hydrocarbon groups, R and R together with the nitrogen atom to which they are bound form a heterocyclic bank. At this time, at least one of the hydrogen atoms of R5 to R may be hydroxy, nitro, cyano, alkylamino, hydrazine, Ν'-dialkylamino, alkoxy, cycloalkyloxy, aryloxy Base, alkylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, alkyl benzyloxy, cycloalkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyl, cycloalkyloxycarbonyl, aromatic Substituted by a oxycarbonyl group or a halogen atom. Further, the -CH 2 - group in the above hydrocarbon group may be substituted by a -C 0 - group). The (substituted) hydrocarbon group in R 5 to R 8 of the above formula (III) may, for example, be a decyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a third butyl group. Anthracene, n-pentyl, n-hexyl, cyclohexyl, n-octyl, 2-hydroxyethyl, phenyl, 3-(trifluoromethyl)phenyl, and the like. Preferred specific examples are tetramethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, tetra-n-octyl ammonium hydroxide, phenyltrimethylammonium hydroxide, 3-(trifluoromethyl)benzene hydroxide. Base triammonium hydroxide, trimethylammonium hydroxide, and the like. R and R are as follows: a combination of a nitrogen atom to form a cyclic heterocyclic group is exemplified by deuterium. A ring-forming group, an oxindole, a tetradentate ring group, a tetrahydrogen D-biting ring group, a π丫gyne ring group, and the like are specifically exemplified by the following compounds:

N4227.ptd Page 20 1281597

314227.ptd Page 21 1281597 V. Description of the invention (15) [In the above formula, R 2 and R 22 are each independently represented by a hydrogen atom, preferably c, a probe group, a C 5 — decyl group, or a C 6- group. 1 荇 base. At least one of the hydrogen atoms on the alkyl group, the cycloalkyl group or the aryl group may be substituted with an amine group or a C oximeoxy group. Further, the hydrogen atom on the above amine group may be substituted by C. R 23 , R 2 and R 25 are each independently and each represents a hydrogen atom, preferably a c 1 alkyl group, a C s group, or a (V oxo group. The alkyl group, a cycloalkyl group, At least one of the hydrogen atoms on the aryl group or the alkoxy group may be substituted by a hydroxyl group, an amine group or a c oxy group, and the hydrogen atom on the amine group may be substituted by a c η alkyl group. C1-tether, or Ch躁 alkyl is preferred. At least one of the hydrogen atoms on the alkyl or cycloalkane f may be substituted by a hydroxyl group, an amine group or a C1 probe group, and the hydrogen atom on the amine group may be substituted by a c-alkyl group. Preferably, A is a C2_Shenryo group, an M group, an imido group, a _s_ group or a _s_s- group and a siloxane group which may be a straight bond or a crypto bond.恭 夕 ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί ί The molar absorption I: the compound 'is preferably in the range of 4,000 to 50,000, more preferably in the range of 4 to 4 Å. The value ΐίίΓ and ί coefficient and the value of 1 mole of material can absorb light. Although the light of a certain wavelength passes through the material of π containing the length of the 乂mole), the light intensity is due to the absorption. The light intensity is determined by the ι genus, according to the plaque 1281597. 5. The invention (16) The law of Beer-Beer can be The correlation shown in the following formula is established: I = I 〇X 1 0 -bck The Mohr absorption coefficient is the value defined by k in the above formula (refer to "Chemical Dictionary 8", 1 8 5 pages, Japan Kyoritsu Publishing Co., Ltd. (R) is a compound represented by the following formula (IV) or (V). R11 〇R13 0 R16 R9—C=C—C—C—C—0==0—R10 (IV) l12 l14 L, r12 r14 r15 (In the above formula, R and R1G each represent an aryl group, respectively. A part or all of one of the hydrogen atoms on the aryl group may be substituted with an alkyl group, an alkoxy group or an alkoxy group. R 11 to R 1 may independently represent a hydrogen atom or an alkyl group.) R18 R17—C=^C— R20 (V) R19 (wherein R 1 is an aryl group, a part or all of a hydrogen atom on the aryl group may be partially or wholly represented by a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group or an N,Ν'-dioxane Substituted by a aryl group. R1 昧 hydrogen atom or alkyl group, R1 knows that R 2 ^ is independently, and represents a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a cyano group or a benzamidine group, respectively.) Among the compounds represented by the formula (V), the following compounds are more preferred. 1,7-bis-(3-indolyl-4-hydroxyphenyl)-1,6-heptadiene-3, 5-dione

114227.ptd Page 23 1281597 V. INSTRUCTIONS (17) - (generally known as curcumin), 1,7-bis-(3-indolyl-4-ethyloxyphenyl)-1,6- Heptadiene-3, 5-dione, 1-(3-decyloxy-4-hydroxyphenyl)-7-(3-decyloxy-4-acetoxyphenyl)-1,6-g Di-sali-3,5-di-, 1,7-bis-(3-indolyl-4-hydroxyphenyl)-1,6-heptadiene-3, 5-dione, 1,7-bis- (3--Mercapto-4-ethenyloxyphenyl)-1,6-heptadiene-3, 5-dione, Bu (3-methyl-4-phenyl)-7-(3 -methyl_4-ethyloxyphenyl)-1,6-heptane-3,5-dione, 1,7-bis-(3-indolyl-4-hydroxyphenyl)-1 , 2, 6, 7-tetramethyl-1,6-heptadiene-3, 5-dione, 1,7-bis-(3-methoxy-4-ethenyloxyphenyl)-1 , 2, 6, 7-tetradecyl-1,6-heptadiene-3, 5-dione, Bu (3-,yl-4-hydroxyphenyl)-7-(3-methoxy-4 -Ethyloxyphenyl)-1,2,6,7-tetramethyl-1,6-heptadiene-3,5-dione, 1,7-bis-(3-decyloxy-4 -hydroxyphenyl)-4,4-dimercapto-1,6-heptadiene-3,5-dione, 1,7-bis-(3-decyloxy-4-ethenyloxyphenyl )-4,4-dimethyl-1,6-heptadiene-3, 5-di Ketone,: ί-(3-decyloxy-4-hydroxyphenyl 7-(3-methoxy-4-ethoxyphenyl)- 4,4-dimethyl-1,6-heptane Dilute-3,5-diindole α-cyanocinnamate, ethyl α-cyanocinnamate, isopropyl α-cyanocinnamate, n-cyano cinnamon n-butyl ester, 4- Ethyl hydroxy-α-cyanocinnamate, ethyl 4-trans-α-cyanocinnamate, isopropyl 4-amino-α-cyanocinnamate, 4-hydroxy-α-cyanocinnamic acid Butane vinegar, 4-ethoxy k U-cyanocinnamate 曱S, 4-ethoxy-α-cyanocinnamic acid vinegar, 4-ethoxy-α-cyanocinnamic acid isopropyl S , 4-ethoxy-α-cyanocinnamyl n-butyl ester, methyl 2, 4-dihydroxy-α-cyanocinnamate, ethyl 2, 4-dihydroxy-α-cyanocinnamate, 2, 4 -Dihydroxy-α-cyanocinnamic acid, isopropyl I, 2, 4-dihydroxy-α-cyanocinnamate, n-butyl, 3-methoxy-4-hydroxy

14227.ptd Page 24 1281597 V. INSTRUCTIONS (18) Methyl-α-cyanocinnamate, ethyl 3-methoxy-4-hydroxy-α-cyanocinnamate, 3-methoxy- Isopropyl 4-hydroxy-α-cyanocinnamate, n-butyl 3-methoxy-4-hydroxy-cyanocinnamate, 4-(anthracene, Ν'-diethylamino)-α-cyanide Methyl cinnamate, ethyl 4-(indole, Ν'-diethylamino)-α-cyanocinnamate, 4-(anthracene, Ν'-diethylamino)-α-cyano cinnamon Propyl acrylate, 4-(anthracene, Ν'-diethylamino)-α-cyanocinnamate n-butyl ester, 4-hydroxy-α-ethoxymethyl cinnamic acid 曱S, 4-hydroxyl group - Ethyl ethoxylated ethyl cinnamate, 4-hydroxy-α-ethoxycarbonyl cinnamic acid isopropyl ester, 4-hydroxy-α-ethoxycarbonyl cinnamic acid n-butyl ester, 2, 4-dihydroxyl - Ethoxycarbonyl cinnamate methyl ester, 2, 4-dihydroxy-ethoxycarbonyl cinnamic acid ethyl ester, 2, 4-dihydroxy-α-ethoxycarbonyl cinnamic acid isopropyl ester, 2, 4-di n-Butyl hydroxy-α-ethoxycarbonyl cinnamate, methyl 3-methoxy-4-hydroxy-α-decyloxycarbonyl cinnamate, 3-methoxy-4-trans-α-ethoxy Base Ethyl ester, 3-methoxy-4-hydroxy-α-ethoxycarbonyl cinnamic acid isopropyl ester, 3-methoxy-4-transalkyl-α-ethoxycarbonyl cinnamate n-butyl ester, 2- Benzyl-4_(Ν,Ν'-didecylamino)-(2-ethoxyisoyl cinnamic acid, SI, 2-hydroxy-4-(indole, Ν'-dimethylamino)-α -ethyl ethoxycarbonyl cinnamate, 2-hydroxy-4-(indole, Ν' _diethylamino)-α-ethoxycarbonyl cinnamic acid vinegar, 2-ethyl ethoxy-4~ (Ν,Ν'-diethylamino-ethoxy carbaryl cinnamate, 1,1-dicyano-2-(4-phenyl)ethylene, 1-cyano-:1 - Benzoyl-2-(3-decyloxy-4-phenyl)ethene, 1-cyano-1-methoxycarbonyl-2-(1-naphthyl)ethene, 1-cyano -1 -ethoxy methoxy-2 - (1 -caiyl) ethylene, 1-cyano-1-methoxycarboxy-2-(2-pyridyl-1 -naphthyl)ethylene, 1-cyano 1-Ethoxy-1-yl-2-(2-hydroxy-1-naphthyl)ethylene and the like.

314227.ptd Page 25 1281597 V. INSTRUCTIONS (19) The above compounds may be used singly or in combination of two or more. Among them, 1,7-bis-(3-methoxy-4-hydroxyphenyl)-1,6-heptadiene-3,5-dione, 3-methoxy-4-hydroxy-α was used. Ethyl ethoxycarbonyl cinnamate and isopropyl 3-methoxy-4-hydroxy-α-cyanocinnamate are preferred. In the chemically amplified positive photoresist composition of the present invention, it is preferred to contain 0 to 1 part by weight of the component (A) for 100 parts by weight of the (?) component. Further, it is preferred that the component (B) in an amount of from 0.01 to 10 parts by weight based on 100 parts by weight of the component (B). Further, it is preferred that the component (B) of 100 parts by weight of the component (B) is contained in an amount of from 0.01 to 20%. The chemically amplified positive photoresist composition of the present invention may contain various additives such as a sensitizer, a depressant, another resin, an interface activator, a stabilizer, or a dye, if necessary, without affecting the function of the present invention. . The chemically amplified positive photoresist composition of the present invention is generally obtained by dissolving each component of (A) to (D) in a photoresist solvent to form a photoresist composition, which can be applied by a general spin coating method. The method is applied to a substrate such as a germanium wafer. The photoresist solvent to be used may be one which dissolves the above components, has an appropriate drying speed, and can give a uniform and smooth coating film when the solvent is evaporated. The photoresist solvent may, for example, be a glycol ether vinegar such as ethyl cellosolve acetate, methyl cellosolve acetate or propylene glycol monomethyl ether acetate; ethyl lactate or butyl acetate; An ester of amyl acetate or ethyl malonate; a ketone of acetone, hydrazine-isobutyl ketone, 2-heptanone or cyclohexanone; a cyclic ester of r-butyrolactone; Alcohols such as methoxy-butanol and the like. The above photoresist solvent

314227.ptd Page 26 1281597 V. INSTRUCTIONS (20) Can be used alone or in combination of two or more. The dried photoresist film coated on the substrate is usually subjected to exposure treatment by patterning, followed by heat treatment (PEB) for promoting the deprotection reaction, and then development using an alkali developer. The alkaline developer used is various aqueous alkaline solutions used in the field, and an aqueous solution of tetramethylammonium hydroxide or (2-ethyl)trimethylammonium hydroxide (commonly known as choline) is generally used. [Embodiment] The present invention will be more specifically described below by way of examples, but the present invention is not limited to the scope of the embodiments. Further, the % or the amount of the content or the amount shown in the examples is based on the weight unless otherwise specified. Further, the weight average molecular weight (M w ) and the polydispersity (M w / η η ) were determined by gel permeation chromatography using polystyrene as a standard. Synthesis Example 1: Synthesis of a compound of a part of polyhydroxystyrene by 1-ethoxyethylation in a four-necked flask of 5 Γ capacity, and placing 400 g of poly(p-hydroxystyrene) P-hydroxystyrene unit 3.33 mol) and 63. 0 mg (0.333 mmo 1 ) of p-indole carboxylic acid-hydrate, which was dissolved in 2400 g of alpha and isobutyl ketone in. 249 g (3.46 mol) of ethyl vinyl ether was added dropwise and the reaction was carried out at 27 ° C. • The reaction solution was washed with 193 g of ion-exchanged water. The above washing operation was repeated 5 times, and most of the hydrazine-isobutyl ketone was removed by distillation under reduced pressure. Then, 3,500 g of propylene glycol monomethyl ether acetate was added, followed by distillation under reduced pressure, and the azeotrope of propylene glycol monomethyl ether acetate was used to remove water and residual nails -

314227.ptd Page 27 1281597 V. INSTRUCTIONS (21) Isobutyl ketone, which is made into a solution of propylene glycol monomethyl ether acetate. The resulting liquid was a solution of a part of the hydroxyl group of poly(p-hydroxystyrene) as a 1-ethoxyethyl ether resin. The result of the analysis of the resin by 1H-NMR showed that 48% of the hydroxyl groups had been etherified by 1-ethoxylate. This resin is called B1 resin. Synthetic Example 2: The removal of the low molecular weight portion between the cresol novolac resin was carried out in a four-necked flask equipped with a reflux tube, a stirring device and a thermometer. 10. 2 g of oxalic acid dihydrate, ~) 7 g of 90% acetic acid and 20.3 g of methyl isobutyl ketone. The temperature was raised to 80 ° C, and 1 4 3 . 2 g of a 3 % formaldehyde aqueous solution was added dropwise over 1 hour. Then, the temperature was raised to the reflux temperature, and the temperature was kept under reflux for 12 hours. The obtained reaction liquid was diluted with methyl isobutyl ketone, washed with water, and dehydrated to obtain a methyl-isobutyl ketone solution containing 38.6 % of a phenolic acid varnish resin. 6 1 2g of the resin solution was placed in a 51 liter flask, diluted with 1119 g of hydrazine-isobutyl ketone, and 1 2 32 g of n-glycol was added; after stirring at 6 (Tt, it was allowed to stand and then separated, The lower layer of the powdered aldehyde clearing resin solution is obtained. · The novolac resin solution is diluted with propylene glycol methyl ether acetate, and then concentrated by concentration to obtain a solution of propylene glycol monomethyl ether acetate of the aldehyde varnish resin, &gt; The resin is called B2 resin. The above resin is subjected to gel permeation chromatography (GPC) analysis using polystyrene as a standard, and the area of unreacted monomer is deleted. The area I: is 1 0 0 0 The ratio of the following area to the total area is 3.28%. The average weight of the proton is 907θ〇

I14227.ptd Page 28 1281597 V. INSTRUCTION OF THE INVENTION (22) In addition to the resins of the above-mentioned synthesis examples, the photoresist composition prepared by the following materials was used and evaluated. ' (A1 ) component · (5-indole phenyl sulfonyloxyimino-5H-cephen-2-propanidine)-(2-indolyl) acetonitrile (C1) component·· Tetramethylammonium (D1) component. 1,7-bis-(3-indolyl-4-hydroxyphenyl)-1,6-heptadiene-3,5-di-S (of wavelength of 436 nm) The Mohr absorption coefficient is 182 〇〇). (D2) Component: 3-decyloxy-4-hydroxy-indole: isopropyl cyanocinnamate (the molar absorption coefficient at the wavelength of 3 6 5 nm is 2 1 500). Further, Mohr absorption The coefficient is the DU 640 type instrument (product of Beckman Instruments), and the concentration of the (μ) component and the (D 2 ) component of the sterol solution is adjusted to 〇· 〇〇〇3 to 〇· 〇〇〇〇4 m 〇1 / 1 range, measured in a 1 cm long light path container. , fAj column 1 to 2 and a comparative example in which Β 1 resin and Β 2 resin are each taken in a mixture of 6.7 parts (for solid matter exchange), and 〇·1 part of (Α丨) component, 〇 · 5 parts of the (c丨) component of the test compound, and only in the examples 1 and 2, respectively, 25 parts (in the case of Example 1) of the (D1) component, and 〇·25 parts (D2) component (in the case of Example 2) [In any of Comparative Examples 1 and 2, any of the (D1) component and the (D2) component was not added]. The above-mentioned component glutinous rice was dissolved in 42 parts of the propylene glycol yeast early test. This solution was filtered with a fluorocarbon resin transition vessel of pore size 〇 · 5 # m to prepare a photoresist solution. On the tantalum wafer previously treated with hexamethylene dimethyl decane, the film thickness of the above photoresist solution after drying was as shown in Table 1 using a spin coater.

314227.ptd

1281597 V. Invention (23) Applying at the value of '. The prebaking after the application of the photoresist was carried out at 19 ° C for 60 seconds using a hot plate. On the wafer on which the photoresist film was formed as described above, Example 1 and Comparative Example 1 used a reduced projection exposure machine having a exposure wavelength of 436 nm (g-ray) ("NSR-1755 5g7A" manufactured by Nikon Corporation," = 0· • 5 4 ), Example 2 and Comparative Example 2 use a reduced projection exposure machine having an exposure wavelength of 3 5 5 nm (i-ray) (nkon NSR-2 0 0 5 i9Cn, NA = 0.5. 7以上的氢, The exposure is applied to the exposure of the line and the space pattern in a gradient manner. Then, the exposure plate is baked at 110 ° C for 60 seconds, and then 2.38% hydrogen. The tetramethylammonium hydroxide aqueous solution (Sumitomo Chemical Co., Ltd. product developer SOPD) was subjected to development treatment for 60 seconds. The developed pattern was observed using a scanning electron microscope, and the effect sensitivity and film thickness were investigated by the following methods. The dimensional change and the resolution caused by the change. The results are shown in Table 1. Effectiveness: First, with respect to Example 1 and Comparative Example 1 (g-ray), the film thickness was 1.54# m, Example 2 and comparison Example 2 (i-ray) was evaluated with a film thickness of 1 · 4 9 / zm. 1. The line and space pattern of 0/zm is expressed as the exposure amount of 1··1. The dimensional change caused by the change in film thickness: -) The exposure amount under the effect level is implemented according to the film thickness in Table 1, It is expressed by the size when changing the film thickness. The degree of drunkness: It is expressed by the minimum inch of the line and space pattern separated by the amount of exposure of the effect.

314227.ptd Page 30 1281597 V. INSTRUCTIONS (24) Table 1 Film Thickness (// m) Exposure (msec) Size (/zm) Resolution (β m) Example 1 1.54 135 1.00 0.41 1.61 135 0.93 Example 2 1.49 92 1.00 0.45 1.54 92 0.96 Comparative Example 1 1.54 165 1.00 0.53 1.61 165 0.86 Comparative Example 2 1.49 158 1.00 0.65 1.54 158 0.88 The chemically amplified positive photoresist composition according to the present invention can maintain high sensitivity and high resolution. The reflected light from the substrate is reduced to obtain a photoresist pattern having a small dimensional change. ^ -

314227.ptd Page 31 1281597 Schematic description of the diagram • No picture in this case liiii 14227.ptd Page 32

Claims (1)

1281597 Amendment No. 91934911 6. Patent Application Range 1. A chemically amplified positive photoresist composition characterized by the following four components (A) to (D): (A) Radiation-sensitive linear acid generator, its composition As shown in the following formula (I), R1 vrR4 (1) 〇 (In the above formula, R 1 to R 3 are each independently, and represent a hydrogen atom or a C 眞 C ^ hydrogen hydride group (that is, a C to C i butyl group), and R 4 represents a C to C ^ carbon hydride group, However, R 1 to R indicate that at least one of the hydrogen atoms in the C 戽 C 丨 hydrocarbon group may be hydroxy, nitro, cyano, alkylamino, N, Ν'-dialkylamino, alkoxy , cycloalkyloxy, aryloxy, alkylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyl, cycloalkane Substituted by a oxycarbonyl group, an aryloxycarbonyl group or a halogen atom, further, at least one of -CH2- in the above C to C i hydrocarbon group may be substituted by a -C0- group), (B) itself is insoluble Or it is difficult to dissolve in an alkaline aqueous solution, but it can become a resin soluble in an alkaline aqueous solution by the action of an acid, (C) an organic compound which is an organic compound, (D) for a wavelength of 300 to A compound having a molar absorption coefficient in the range of 100 to 50,000 in the range of 45 Onm, the composition of which is represented by the following formula (IV), 314227 Revised. ptc Page 33 1281597 _ Case No. 91934911_March Year March 珥曰 Amendment VI, Patent Application Range R9 oneΪ u CIR”11 RIC one 3 - 4 R1—.—^1 Γ15 R10 6 R1丨C 6 c, the burning, the single base from C by R1 can produce straight C β (1 part R shows the whole, or the sub-taken part from a base 1 Μ ^ sub-base and the original oxygen R nitrogen基 氧 C 、 至 基 基 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 其 : : : : : : :利(I sub-specializes the original nitrogen application, such as neutral and phenoxymethyl, I 3 4 I 6 , base 4 2 benzene, base W 9Iη 醯 2 (I stupid I I 4 Lower, or base, $, 甲, 乙, 基,基基基一一一一正6 2 , 4 , 基基基基, 笨正基基 (However, R 1 to R indicate that at least one of the hydrogen atoms in the above group may be a trans group, a deradyl group, a cyano group, an acryl group, an N,N-dialkylamino group, an alkoxy group, a cycloalkyl group. Oxy, aryloxy, alkyl fluorenyl, cycloalkylcarbonyl, arylcarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyl, cycloalkyloxy Carbonyl group, aryl group 314227 Revised. ptc Page 34 1281597 n _ Case No. 911349 Π _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ 3. The chemically amplified positive photoresist composition according to claim 1, wherein the component (B) has a S-component and a divalent group, and is 1-ethoxyethyl or 1-ethoxy. A resin which is protected by a propyl group or a 2-tetrazolium π-pyranyl group. 4. A chemically amplified positive photoresist composition according to item 3 of the patent application, wherein the component (B) is a part of a hydroxyl group which is ethoxylated ethyl, : 1-ethoxypropyl or 2-tetrahydropyridyl A phenol-protected polyvinyl phenol. 5. A chemically amplified positive photoresist composition according to claim 3, wherein the component (B) is a 1-ethoxyethyl group. A novolak resin protected by 1-ethoxypropyl or 2-tetrahydropyranyl. 6. The chemically amplified positive photoresist composition according to any one of claims 1 to 5, wherein the organoammonium hydroxide compound is a compound represented by the following formula (III): R6 R5-N-R7 OH ' (III) R8 (In the above formula, R 5 to R 8 are each independently, showing a C to C 丨 hydrocarbon group, or R and R odor C to C ^ a hydrogenation group, and the R and R odors are respectively bound to the nitrogen The atoms together form a cyclic heterocyclic group, wherein at least one of the hydrogen atoms of R 5 to R « t may be hydroxy, nitro, cyano, alkylamino, N, Ν'-dialkylamino, alkane Oxyl, cycloalkyloxy, aryloxy, 314227 Revised Edition.ptc Page 35 1281597 _ Case No. 91934941 March 9 Amendment _ VI. Application for patent range Hyunjiji, ring-based base, aryl-based Weiji, courtyard-based base oxygen, naphthenic Substituted by a carbonyloxy group, an arylcarbonyloxy group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group or a halogen atom, and further, the -CH 2 - group in the above Ci-hydrogen group can be Replaced by -C 0 - group). 7. The chemically amplified positive photoresist composition according to claim 6, wherein the organoammonium hydroxide compound represented by the formula (III) is one or more selected from the group consisting of tetramethylammonium hydroxide and tetra-n-butylammonium hydroxide. a compound in the group consisting of tetra-n-hexyl oxyhydroxide, tetra-n-octyl hydride, phenyltrimethyl hydroxide, 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, and choline By. 8. The chemically amplified positive photoresist composition according to any one of claims 1 to 5, wherein the component (D) is a compound represented by the following formula (V): R18 R17—0=01 R20 (V) R19 (in the above formula, R 1 is an aryl group, and part or all of the hydrogen atom on the aryl group may be partially or wholly represented by a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group or a fluorene, Ν'-dialkyl group. Substituted with an amine group, R 1 昧 hydrogen atom or alkyl group, R 1 and R 2G are each independently, and represent a hydrogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, a cyano group or a benzyl group. 9. The chemically amplified positive photoresist composition according to any one of claims 1 to 5, wherein the component (D) is 1,7-bis-(3-methoxy-4-hydroxyphenyl)- 1,6-glycosyl-3,5-dione. 314227 Revised Edition. ptc Page 36 1281597 Λ _ Case No. 91934911 and March 9th Amendment _ VI. Patent Application Range 10. The chemically amplified positive photoresist composition of claim 8 of the patent scope, (D) The compound of the formula (V) wherein R 1 沄 3 - methoxy-4-hydroxyphenyl, R 1 昧 hydrogen atom, R 1 and R 2 taste ethoxycarbonyl group. 1 1. A chemically amplified positive photoresist composition according to claim 8 wherein (D) is a compound of formula (V) wherein R1沄3-methoxy-4-hydroxyphenyl, R1昧 hydrogen atom, R A compound of cyano, R 2 -isopropoxycarbonyl. 314227 Revised Edition.ptc第37页