JP3852460B2 - Chemically amplified radiation sensitive resin composition - Google Patents

Description

  The present invention relates to a chemically amplified radiation sensitive resin composition, and more particularly, to a positive and negative chemically amplified radiation sensitive resin composition suitable for fine processing and for exposure with a KrF excimer laser.

In the field of microfabrication represented by the manufacture of integrated circuit elements, in order to obtain a higher degree of integration of integrated circuits, the processing size in lithography has been miniaturized. In recent years, the line width is 0.5 μm or less. Development of lithography technology capable of stably performing high-precision microfabrication has been strongly promoted, and a resist pattern having a line width of 0.5 μm or less is required to be formed with high accuracy even in the resist for that purpose. . In response to such a lithography technique, a lithography technique using radiation with a shorter wavelength has been studied.
Examples of the short wavelength radiation include ultraviolet rays typified by i-line (wavelength 365 nm), far ultraviolet rays typified by KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and synchrotron radiation. Charged particle beams such as X-rays and electron beams have been used, and various types of resists corresponding to these radiations have been proposed. In recent years, “chemically amplified resists” have attracted particular attention.
This chemically amplified resist generates an acid upon irradiation with radiation, and the catalytic action of this acid causes a chemical change (for example, polarity change, chemical bond cleavage, cross-linking reaction, etc.) in the resist film. A resist pattern is formed by utilizing the phenomenon that the solubility changes in the radiation irradiated portion.

Among such chemically amplified resists, those having relatively good resist performance include, for example, resins in which an alkali affinity group in an alkali-soluble resin is protected with a t-butyl group or a t-butoxycarbonyl group (for example, patent documents) 1), a resist using a resin having a similar alkali affinity group protected with a silyl group (for example, see Patent Document 2), a resin containing a (meth) acrylic acid component (for example, see Patent Document 3), and the like. Has been proposed.
However, these conventional chemically amplified resists can almost reproduce a resist pattern on a silicon substrate, but on a substrate having a high reflectivity represented by an aluminum substrate, the radiation reflected on the substrate at the time of radiation irradiation, It wraps around the area not irradiated with radiation (this phenomenon is called halation) and makes that part sensitive. This phenomenon is particularly noticeable in the stepped structure portion of the substrate. In the positive resist, a pattern called a notching is formed in the stepped portion, and in the negative resist, the pattern is thickened in the stepped portion. However, there is a problem that the resist pattern cannot be accurately reproduced, and as a result, resolution, pattern shape, focus tolerance, and the like are impaired.

JP-B-2-27660 Japanese Patent Publication No. 3-44290 Japanese Patent Laid-Open No. 4-39665

Here, with reference to the drawings, the halation phenomenon in the case of a positive resist will be described. In FIG. 1, reference numeral 1 is a resist composition coating, 2 is irradiated radiation, 3 is radiation reflected on a substrate, 4 is an inclined surface in a stepped structure portion of the substrate, and 5 is a substrate.
In this case, the radiation incident on the resist composition coating 1 is reflected by the inclined surface 4 of the substrate 5 and wraps around the right side of FIG. 1 to make the resist composition coating in that portion sensitive. As a result, the vicinity of the step portion is excessively sensitive, and a pattern narrowing 7 called notching is generated in the vicinity of the step portion of the resist pattern 6 as shown in FIG.

An object of the present invention is to provide a novel chemically amplified radiation-sensitive resin composition.
Another object of the present invention is to provide positive and negative chemically amplified radiation-sensitive resin compositions for exposure with a KrF excimer laser, which are excellent in sensitivity, resolution, developability, pattern shape and the like. .
Still another problem of the present invention is that not only a fine resist pattern can be accurately reproduced even on a substrate having a particularly high reflectivity, but also excellent in storage stability, even after a long time has elapsed after preparation of the composition, An object of the present invention is to provide a positive-type and negative-type chemically amplified radiation-sensitive resin composition for exposure with a KrF excimer laser capable of maintaining good sensitivity and pattern shape.

According to the present invention, the problem is
(A) Methylthiomethyl group, ethylthiomethyl group, t-butoxycarbonylmethyl group, 1-methylthioethyl group, 1-ethylthioethyl group, 1-cyclopropylethyl group, isopropyl group, sec-butyl group, t-butyl Group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group, methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, t-butoxycarbonyl group, t-pentyloxycarbonyl group, acetyl An alkali-insoluble or hardly-alkali-soluble resin protected with one or more acid-decomposable groups selected from the group consisting of a group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group and a cyclohexenyl group, A resin which becomes alkali-soluble when the decomposable group is decomposed, (b) A positive chemically amplified radiation-sensitive resin composition for exposure with a KrF excimer laser, comprising a radiation-sensitive acid generator that generates an acid upon irradiation with radiation and (c) anthracene-9-methanol ;
(A) an alkali-soluble resin, (b) a radiation-sensitive acid generator that generates an acid upon irradiation with radiation, (c) an anthracene-9-methanol and (d) an acid functional group in the presence of an acid 1 A compound having at least one kind of acid-decomposable substituent, wherein the acid-decomposable substituent is a methylthiomethyl group, an ethylthiomethyl group, a t-butoxycarbonylmethyl group, a 1-methylthioethyl group, a 1-ethylthioethyl group, 1-cyclopropylethyl group, isopropyl group, sec-butyl group, t-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group, methoxycarbonyl group, ethoxycarbonyl group, iso Propoxycarbonyl group, t-butoxycarbonyl group, t-pentyloxycarbonyl group, acetyl group, cyclopropyl group, cyclope A compound selected from the group consisting of a til group, a cyclohexyl group and a cyclohexenyl group, which has the property of controlling the alkali solubility of an alkali-soluble resin, decomposed in the presence of an acid, and has an alkali solubility of an alkali-soluble resin. A positive chemical amplification type for exposure with a KrF excimer laser, characterized by containing a compound having an action of reducing or eliminating the effect of controlling the pH, or an action of promoting alkali solubility of an alkali-soluble resin A radiation-sensitive resin composition; or (a) an alkali-soluble resin, (b) a radiation-sensitive acid generator that generates an acid upon irradiation with radiation, (c) anthracene-9-methanol and (e) in the presence of an acid. For exposure with a KrF excimer laser, characterized by containing a compound capable of crosslinking an alkali-soluble resin It is achieved by negative-type chemically amplified radiation sensitive resin composition.

Chemically Amplified Radiation Sensitive Resin Composition The chemically amplified radiation sensitive resin composition of the present invention comprises a radiation sensitive acid generator (hereinafter referred to as “the acid”) that generates an acid upon irradiation with radiation (hereinafter referred to as “exposure”). contains an acid generator "as.), by a chemical reaction catalyzed by the acid generated by exposure state, and are not to form a pattern by changing the solubility in a developing solution between an exposed portion, the following resist composition (a) to (c) Ru Tona.

(I) (a) methylthiomethyl group, ethylthiomethyl group, t-butoxycarbonyl methyl group, 1-methylthioethyl group, 1-ethylthioethyl group, 1-Shikuropuropi Ruechiru group, an isopropyl group, sec- butyl group, t - butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group, main butoxycarbonyl group, an ethoxycarbonyl group, isopropoxycarbonyl group, t-butoxycarbonyl group, t-pentyloxycarbonyl An alkali-insoluble or hardly-alkali-soluble resin protected with an acid-decomposable group selected from the group consisting of a group, an acetyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cyclohexenyl group. Resin that becomes alkali-soluble when the degradable group is decomposed (hereinafter “ Decomposable group-containing resin "hereinafter.),
(B) an acid generator and (c) a positive chemically amplified radiation-sensitive resin composition containing anthracene-9-methanol (hereinafter referred to as “resist composition (I)”).

(B) (a) an alkali-soluble resin;
(B) an acid generator,
(C) anthracene-9-methanol and (d) consists presence at of compounds having one or more acid-decomposable substituent which may decompose to an acidic functional group of the acid, the acid-decomposable substituent methylthiomethyl group, ethylthiomethyl group, t-butoxycarbonyl methyl group, 1-methylthioethyl group, 1-ethyl Ruchioechiru group, 1-cyclopropylethyl group, an isopropyl group, sec- butyl group, t- butyl group, 1,1 dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group, a methoxycarbonyl group, ethoxycarbonyl two group, isopropoxycarbonyl group, t-butoxycarbonyl group, t-pen chill oxycarbonyl group, an acetyl group, a cycloalkyl a propyl group, a cyclopentyl group, selected from the group consisting of cyclohexyl and cyclohexenyl compound , Has the property of controlling the alkali solubility of the alkali-soluble resin, it is decomposed in the presence of an acid, or has the effect of reducing or eliminating the effect of controlling the alkali solubility of the alkali-soluble resin, or an alkali-soluble resin A compound that has the effect of promoting the solubility of alkali (hereinafter referred to as “solubility control agent”)
A positive chemically amplified radiation-sensitive resin composition (hereinafter referred to as “resist composition (b)”).

(C) (a) an alkali-soluble resin;
(B) an acid generator,
( C ) a compound that crosslinks an alkali-soluble resin in the presence of anthracene-9-methanol and ( e ) acid (hereinafter referred to as “crosslinking agent”).
A negative chemically amplified radiation-sensitive resin composition (hereinafter referred to as “resist composition (c)”).
Hereinafter, components other than the anthracene-9-methanol among the components constituting the resist compositions (a) to (c) will be described sequentially.

The acid-decomposable group-containing resin resist composition (a) used in the acid-decomposable group-containing resin resist composition contains, for example, an acidic functional group such as a phenolic hydroxyl group or a carboxyl group in an alkali-soluble resin described later in the presence of an acid. It is a resin that is protected by one or more acid-decomposable groups that can express alkali solubility by being decomposed, and is itself an alkali-insoluble or hardly alkali-soluble resin. The term “alkali-insoluble or alkali-insoluble” as used herein refers to a substitute for the resist film under the alkali development conditions employed when a resist pattern is formed from the resist film formed using the resist composition (a). When a film formed using only an acid-decomposable group-containing resin is developed, it means that 50% or more of the initial film thickness of the film remains after development.

The acid-decomposable group in the acid-decomposable group-containing resin, t- butyl group, t- butoxycarbonyl methyl group, such as t- butoxycarbonyl group is preferred.

The rate of introduction of acid-decomposable groups in the acid-decomposable group-containing resin (ratio of the number of acid-decomposable groups to the total number of acidic functional groups and acid-decomposable groups in the acid-decomposable group-containing resin) is preferably It is 15 to 100%, more preferably 15 to 80%, particularly preferably 15 to 60%.
The polystyrene-reduced weight molecular weight (hereinafter referred to as “Mw”) of the acid-decomposable group-containing resin measured by gel permeation chromatography is preferably 1,000 to 150,000, more preferably 3,000 to 100,000. 000.

The acid-decomposable group-containing resin can be produced, for example, by replacing the hydrogen atom of the acidic functional group in one or more alkali-soluble resins with one or more acid-decomposable groups. It can be produced by (co) polymerization of a monomer having an acid-decomposable group or (co) polycondensation of a polycondensation component having one or more acid-decomposable groups.
In the resist composition (A), the acid-decomposable group-containing resins can be used alone or in admixture of two or more.
In addition, the acid-decomposable group-containing resin used in the resist composition (a) has the property of controlling the alkali solubility of the alkali-soluble resin, and is decomposed in the presence of an acid to dissolve in an alkali-soluble resin. It has the effect of reducing or eliminating the property control effect or promoting the alkali solubility of the alkali-soluble resin, and falls within the category of a dissolution control agent in the resist composition (b).

Alkali-soluble resin Next, the alkali-soluble resin used in the resist composition (b) and the resist composition (c) is a functional group having an affinity with an alkali developer, for example, an acidic function such as a phenolic hydroxyl group or a carboxyl group. The resin is not particularly limited as long as the resin has at least one group and is soluble in an alkali developer.
Examples of such alkali-soluble resins include hydroxystyrene, hydroxy-α-methylstyrene, vinyl benzoic acid, carboxymethylstyrene, carboxymethoxystyrene, (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, A vinyl resin having a repeating unit in which a polymerizable double bond of at least one monomer having an acidic functional group such as citraconic acid, mesaconic acid or cinnamic acid is cleaved, or an acidic functional group represented by a novolac resin Examples thereof include condensation resins having a condensation system repeating unit containing.

When the alkali-soluble resin is the vinyl resin, the resin may be composed only of a repeating unit in which the polymerizable double bond of the monomer having an acidic functional group is cleaved. As long as it is soluble in the developer, it may further have one or more other repeating units.
Examples of such other repeating units include styrene, α-methylstyrene, vinyltoluene, maleic anhydride, (meth) acrylonitrile, crotonnitrile, maleinonitrile, fumaronitrile, mesaconnitrile, citracononitrile, itaconnitrile, (meta ) Polymerization of monomers with polymerizable double bonds such as acrylamide, crotonamide, maleamide, fumaramide, mesaconamide, citraconamide, itaconamide, vinylaniline, vinylpyridine, vinyl-ε-caprolactam, vinylpyrrolidone, vinylimidazole And a repeating unit in which an ionic double bond moiety is cleaved.

The alkali-soluble resin made of the vinyl resin can be produced, for example, by (co) polymerizing one or more monomers having an acidic functional group, optionally together with one or more other monomers. And (co) polymerization of one or more monomers with protected acidic functional groups, optionally with other monomers, and then the protected groups in the (co) polymer are converted to acidic functional groups. It can manufacture by converting into.
These (co) polymerizations are carried out by appropriately using a polymerization initiator such as a radical polymerization initiator, an anionic polymerization catalyst, a coordination anionic polymerization catalyst, a cationic polymerization catalyst or a polymerization catalyst depending on the type of monomer and reaction medium. It can be selected and carried out in an appropriate polymerization form such as bulk polymerization, solution polymerization, precipitation polymerization, emulsion polymerization, suspension polymerization, bulk-suspension polymerization.

Further, when the alkali-soluble resin is the condensation resin, the resin may be composed only of a condensation-type repeating unit containing an acidic functional group, as long as the produced resin is soluble in an alkali developer. Then, it can also have another repeating unit.
Such a condensation resin is, for example, an aqueous medium in the presence of an acidic catalyst, together with a polycondensation component capable of forming one or more phenols and one or more aldehydes, optionally with other condensation system repeating units. It can be produced by (co) polycondensation in or in a mixed medium of water and a hydrophilic solvent.
Examples of the phenols include o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2 , 3,5-trimethylphenol, 3,4,5-trimethylphenol and the like, and examples of the aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, glyoxal, Examples include glutaraldehyde, terephthalaldehyde, and isophthalaldehyde.

The content of the repeating unit having an acidic functional group in the alkali-soluble resin cannot be defined unconditionally depending on the types of other repeating units contained in some cases, but is usually 15 to 100 mol%, preferably 20 to 100 mol%. It is.
The Mw of the alkali-soluble resin varies depending on the desired properties of the resist composition (b) or the resist composition (c), but is preferably 1,000 to 150,000, more preferably 3,000 to 100,000. It is.
When the alkali-soluble resin has a repeating unit containing a carbon-carbon unsaturated bond, it can also be used as a hydrogenated product. The hydrogenation rate in this case is usually 70% or less, preferably 50% or less, more preferably 40% or less, of the carbon-carbon unsaturated bonds contained in the repeating unit. When the hydrogenation rate exceeds 70%, the solubility of the alkali-soluble resin in the alkali developer tends to be lowered.
In the resist composition (b) and the resist composition (c), alkali-soluble resins can be used alone or in admixture of two or more.

Acid generator resist composition (a), the acid generator used in the resist composition (ii) and the resist composition (iii), for example, onium salt compounds, halogen-containing compounds, sulfone compounds, sulfonate compounds, A quinonediazide compound etc. can be mentioned.
Specific examples of these acid generators include those shown below.

Onium Salt Compound Examples of the onium salt compound include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like.
Preferred onium salt compounds are diphenyliodonium trifluoromethanesulfonate, diphenyliodonium pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium naphthalenesulfonate, (hydroxyphenyl) benzylmethylsulfonium And toluene sulfonate.
Halogen-containing compounds Examples of halogen-containing compounds include haloalkyl group-containing hydrocarbon compounds, haloalkyl group-containing heterocyclic compounds, and the like.
Preferred halogen-containing compounds are (trichloromethyl) -s such as phenyl-bis (trichloromethyl) -s-triazine, methoxyphenyl-bis (trichloromethyl) -s-triazine, naphthyl-bis (trichloromethyl) -s-triazine. -Triazine derivatives, 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane and the like.

Sulfone Compound Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds thereof.
Preferred sulfone compounds are phenacylphenylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, bis (phenylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, 4-trisphenacylsulfone and the like.
Sulfonic acid ester compounds Examples of the sulfonic acid ester compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, imino sulfonates, and imide sulfonates.
Preferred sulfonic acid ester compounds include benzoin tosylate, pyrogallol tristriflate, nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, N- (trifluoromethylsulfonyloxy) maleimide, N- (trifluoromethylsulfonyl) Oxy) phthalimide, N- (trifluoromethylsulfonyloxy) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (Camphanylsulfonyloxy) naphthylimide and the like.

Quinonediazide compound Examples of the quinonediazide compound include 1,2-quinonediazidesulfonic acid ester compounds of polyhydroxy compounds, diazobenzoquinone compounds, diazonaphthoquinone compounds, and the like.
Examples of quinonediazide compounds include 1,2-benzoquinonediazide-4-sulfonyl group, 1,2-naphthoquinonediazide-4-sulfonyl group, 1,2-naphthoquinonediazide-5-sulfonyl group, 1,2-naphthoquinonediazide- Examples thereof include compounds having a 1,2-quinonediazidosulfonyl group such as a 6-sulfonyl group, and in particular, a 1,2-naphthoquinonediazide-4-sulfonyl group and / or a 1,2-naphthoquinonediazide-5-sulfonyl group. The compound which has is preferable.

Specific examples of such quinonediazide compounds include 1,2, quinonediazidesulfonic acid of (poly) hydroxyphenyl aryl ketone such as 2,3,4-trihydroxybenzophenone and 2,3,4,4′-tetrahydroxybenzophenone. Esters: 1,2 of bis [(poly) hydroxyphenyl] alkanes such as bis (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) methane and 2,2-bis (4-hydroxyphenyl) propane -Quinonediazide sulfonic acid esters; 4,4 ', 4 "-trihydroxytriphenylmethane, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane 1,2-quinonediazide sulfonic acid esters of (poly) hydroxytriphenylalkanes; 2,4,4-trimethyl-2 ′, 4 ′, 7-trihydroxy-2-phenylflavane, 2,4,4-trimethyl Examples include 1,2-quinonediazide sulfonic acid esters of (poly) hydroxyphenyl flavan such as -2 ', 4', 5 ', 6,7-pentahydroxy-2-phenylflavan.
Among these quinonediazide compounds, preferred compounds are 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane 1,2- -Naphthoquinonediazide-4-sulfonic acid ester and the like.
In the resist composition (a), the resist composition (b), and the resist composition (c), the acid generators can be used alone or in admixture of two or more.

Next, the dissolution control agent used in the resist composition (b) has the property of controlling the alkali solubility of the alkali-soluble resin described above, and is decomposed, for example, hydrolyzed in the presence of an acid. Thus, the compound has an action of reducing or eliminating the effect of controlling the alkali solubility of the alkali-soluble resin, or an action of promoting the alkali solubility of the alkali-soluble resin.

The dissolution control agent in the resist composition (b) comprises a compound having one or more acid-decomposable substituents that can be decomposed into acidic functional groups such as phenolic hydroxyl groups and carboxyl groups in the presence of an acid. A functional substituent is methylthiomethyl group, ethylthiomethyl group, t-butoxycarbonylmethyl group, 1-methylthioethyl group, 1-ethylthioethyl group, 1-cyclopropylethyl group, isopropyl group, sec-butyl group, t- Butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group, methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, t-butoxycarbonyl group, t-pentyloxycarbonyl group, Acetyl, cyclopropyl, cyclopentyl, cyclohexyl and cyclohexenyl Ru compound der selected from the group of.
The dissolution control agent may be a low molecular compound or a high molecular compound, but preferred dissolution control agents include polyhydric phenolic compounds such as bisphenol A, bisphenol F, and bisphenol S, or carboxylic acid compounds such as hydroxyphenylacetic acid, It is a compound into which an acid-decomposable substituent is introduced.
Specific examples of preferable low-molecular dissolution control agents are compounds represented by the following formulas (4) and (5).

As the polymer dissolution control agent, for example, the acid-decomposable group-containing resin can be used.
In the resist composition (b), the dissolution control agent can be used alone or in admixture of two or more for each of the low molecular compound and the high molecular compound (that is, the acid-decomposable group-containing resin). A low molecular compound and a high molecular compound can be used in combination.

Crosslinking agent Next, the crosslinking agent used in the resist composition (c) is a compound that crosslinks the alkali-soluble resin in the presence of an acid, for example, an acid generated by exposure.
Examples of such cross-linking agents include compounds having one or more substituents (hereinafter referred to as “crosslinkable substituents”) having cross-linking reactivity with the alkali-soluble resin described above.
Examples of the crosslinkable substituent include a group represented by the following formula.

(Here, m is 1 or 2, and X represents a single bond, —O—, —S—, —COO— or —NH— when m = 1, or when m = 2, A trivalent nitrogen atom, Y represents —O— or —S—, i represents an integer of 0 to 3, j represents an integer of 1 to 3, and i + j = 1 to 4.

(Wherein k is an integer of 1 or more, R ⁵ and R ⁶ may be the same as or different from each other, and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Z represents —O—, —COO; -Or -CO-, and R ⁷ represents an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an aralkyl group having 7 to 14 carbon atoms.)

(Here, R ⁸ , R ⁹ and R ¹⁰ may be the same as or different from each other, and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

(Wherein k is an integer of 1 or more, R ¹¹ and R ¹² may be the same or different from each other, each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹³ and R ¹⁴ are (It may be the same or different and represents an alkylol group having 1 to 5 carbon atoms.)

(Here, k is an integer of 1 or more, R ¹⁵ and R ¹⁶ may be the same or different from each other, and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹⁷ represents an oxygen atom or a sulfur atom. Or a divalent organic group forming a 3- to 8-membered ring having any hetero atom of a nitrogen atom.)

  Specific examples of such crosslinkable substituents include glycidyl ether group, glycidyl ester group, glycidyl amino group, methoxymethyl group, ethoxymethyl group, benzyloxymethyl group, dimethylaminomethyl group, diethylaminomethyl group, dimethylolamino. Examples thereof include a methyl group, a diethylolaminomethyl group, a bis (methoxymethyl) amino group, a morpholinomethyl group, an acetoxymethyl group, a benzoyloxymethyl group, a formyl group, an acetyl group, a vinyl group, and an isopropenyl group.

Examples of the compound having a crosslinkable substituent include a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol S epoxy compound, a novolac resin epoxy compound, a resole resin epoxy compound, and a poly (hydroxystyrene) epoxy compound. , Methylol group-containing melamine compound, methylol group-containing benzoguanamine compound, methylol group-containing urea compound, methylol group-containing glycoluril compound, methylol group-containing phenol compound, alkoxyalkyl group-containing melamine compound, alkoxyalkyl group-containing benzoguanamine compound, alkoxyalkyl group-containing Urea compounds, alkoxyalkyl group-containing glycoluril compounds, alkoxyalkyl group-containing phenolic compounds, carboxymethyl group-containing compounds Min compounds, carboxymethyl group-containing benzoguanamine compounds, carboxymethyl group-containing urea compound, carboxymethyl group-containing glycoluril compound include a carboxymethyl group-containing phenol compounds and the like.
Among these compounds having a crosslinkable substituent, a methylol group-containing phenol compound, a methoxymethyl group-containing melamine compound, a methoxymethyl group-containing urea compound, a methoxymethyl group-containing glycoluril compound, a methoxymethyl group-containing phenol compound, an acetoxymethyl group A contained phenol compound and the like are preferable.

  Among the compounds having a crosslinkable substituent, commercially available methoxymethyl group-containing melamine compounds include CYMEL300, CYMEL301, CYMEL303, CYMEL305 (trade name, manufactured by Mitsui Cyanamid), etc., which are commercially available methoxymethyl group-containing glycoluril compounds. Examples of the product include CYMEL1174 (trade name, manufactured by Mitsui Cyanamid), and commercially available products of methoxymethyl group-containing urea compounds include MX-290 (manufactured by Sanwa Chemical). The compound represented by 6), (7), (8) can be mentioned.

  Furthermore, as the cross-linking agent, a resin obtained by introducing the cross-linkable substituent into the acidic functional group in the alkali-soluble resin described above and imparting properties as a cross-linking agent can also be suitably used. In this case, the introduction rate of the crosslinkable functional group is usually 5 to 60 mol%, preferably 10 to 50 mol%, more preferably 15 to 40 mol%, based on all acidic functional groups in the alkali-soluble resin. Adjusted. If the introduction ratio of the crosslinkable functional group is less than 5 mol%, it is difficult to cause a sufficient crosslinking reaction, the residual film ratio is decreased, the resist pattern is likely to meander or swell, and if it exceeds 60 mol%. In addition, the alkali solubility of the alkali-soluble resin is lowered, and the developability tends to be lowered. In the resist composition (c), the crosslinking agents can be used alone or in admixture of two or more.

Various additives such as an acid diffusion controller, a surfactant, and a sensitizer are blended in the additive resist composition (a), resist composition (b), and resist composition (c) as necessary. be able to. The acid diffusion control agent is blended in the resin composition for the purpose of controlling the diffusion phenomenon in the resist film of the acid generated from the acid generator by exposure and suppressing undesirable chemical reactions in the unexposed areas. It is a component. By using such an acid diffusion control agent, it is possible to further improve the shape of the pattern to be formed, particularly wrinkle generation in the upper layer portion of the pattern, dimensional fidelity with respect to the mask dimension, and the like.

As the acid diffusion controller, for example, a nitrogen compound that can maintain basicity after exposure or after heating can be preferably used.
Specific examples of such nitrogen compounds include ammonia, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, aniline, N-methylaniline, N, N -Dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, 1-naphthylamine, 2-naphthylamine, diphenylamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, pyrrolidone, piperidine, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, thiabendazole, pyridine, 2-methylpyridine, 4-ethylpyridine, 2-phenylpyridine Gin, 4-phenylpyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, 2-benzylpyridine, nicotinamide, dibenzoylthiamine, ribofuramine tetrabutyrate, 4,4′-diaminodiphenylmethane 4,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- ( 4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) Yl) -1-methylethyl] benzene, and the like.
Among these acid diffusion control agents, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, benzimidazole, 4-phenylpyridine, 4,4′-diaminodiphenyl ether, nicotinamide and the like preferable.
The acid diffusion controller can be used alone or in admixture of two or more.
The compounding amount of the acid diffusion controller varies depending on the type, combination with the acid generator, etc., but is usually 10 parts by weight or less, preferably 5 parts by weight, per 100 parts by weight of the total resin components in the resin composition. It is as follows. When the compounding amount of the acid diffusion controller exceeds 10 parts by weight, the sensitivity and the developability of the exposed part tend to decrease.

The surfactant exhibits an effect of improving the coating property and striation of each resist composition, developability as a resist, and the like.
Examples of such surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate. In addition to the rate, the following trade names are KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), F-top EF301, EF303, EF352 (manufactured by Tochem Products), Megafax F171, F172, F173 (manufactured by Dainippon Ink and Chemicals), Florard FC430, FC431 (manufactured by Sumitomo 3M), Asahi Examples include Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass).
These surfactants can be used alone or in admixture of two or more.
The compounding amount of the surfactant is usually 2 parts by weight or less per 100 parts by weight of the total resin components of each resist composition.

The sensitizer absorbs radiation energy and transmits the energy to the acid generator, thereby increasing the amount of acid generated. The resist is formed from each resist composition. It has the effect of improving the apparent sensitivity.
Preferred sensitizers include ketones, benzenes, acetophenones, benzophenones, naphthalenes, biacetyl, eosin, rose bengal, pyrenes, phenothiazines and the like.
These sensitizers can be used alone or in admixture of two or more. The compounding amount of the sensitizer is usually 50 parts by weight or less, preferably 30 parts by weight or less, per 100 parts by weight of the total resin components of each resist composition.
In addition, by blending dyes or pigments, the latent image in the exposed area can be visualized, and the influence of halation during exposure can be further alleviated. By blending an adhesion assistant, adhesion to the substrate can be improved. be able to.
Furthermore, other additives include antihalation agents such as azo compounds and amine compounds, shape improvers, storage stabilizers, antifoaming agents, and the like.

Compounding Composition of Chemically Amplified Radiation Sensitive Resin Composition The compounding composition of each component in the resist composition (a), resist composition (b) and resist composition (c) is exemplified below. That is,
In the resist composition (a), the acid generator is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 15 parts by weight, particularly preferably 0, per 100 parts by weight of the acid-decomposable group-containing resin. 2 to 10 parts by weight, and anthracene-9-methanol is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and particularly preferably 0.2 to 5 parts by weight. .
In the resist composition (a), if the amount of the acid generator is less than 0.05 parts by weight, it may be difficult to effectively cause a chemical change due to the catalytic action of the acid generated by exposure. If it exceeds the parts by weight, there may be uneven coating when the resist composition (a) is applied, or scum or the like may occur during development. Further, when the blending amount of anthracene-9-methanol is less than 0.05 parts by weight, the radiation reflected from the substrate surface cannot be sufficiently absorbed, and the antihalation effect which is the main function and effect of the present invention is sufficiently expressed. On the other hand, if the amount exceeds 20 parts by weight, the radiation absorption capacity of the resist composition (b) becomes too large, and the amount of radiation reaching the vicinity of the substrate is reduced. There is a tendency to decrease. The resist composition (a) can be blended with the low-molecular dissolution control agent in an amount of preferably 50 parts by weight or less per 100 parts by weight of the acid-decomposable group-containing resin.

In the resist composition (b), the acid generator is preferably from 0.05 to 20 parts by weight, more preferably from 0.1 to 15 parts by weight, particularly preferably from 0.5 to 100 parts by weight per 100 parts by weight of the alkali-soluble resin. 10 parts by weight, and the dissolution control agent is preferably 5 to 150 parts by weight, more preferably 5 to 100 parts by weight, particularly preferably 5 to 50 parts by weight, and more preferably anthracene-9-methanol. 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and particularly preferably 0.2 to 5 parts by weight.
In the resist composition (b), if the blending amount of the acid generator is less than 0.05 parts by weight, it may be difficult to effectively cause a chemical change due to the catalytic action of the acid generated by exposure. If it exceeds the parts by weight, there may be uneven coating when the resist composition (b) is applied, or scum or the like may occur during development. On the other hand, when the blending amount of the dissolution control agent is less than 5 parts by weight, the required effect based on the dissolution control agent may not be sufficiently exhibited. On the other hand, when the blending amount exceeds 150 parts by weight, the film-forming property and film of the resist composition (b) There exists a tendency for intensity | strength etc. to fall. Furthermore, when the blending amount of anthracene-9-methanol is less than 0.05 parts by weight, the radiation reflected from the substrate surface cannot be sufficiently absorbed, and the antihalation effect which is the main function and effect of the present invention is sufficiently exhibited. On the other hand, if the amount exceeds 20 parts by weight, the radiation absorption capacity of the resist composition (b) becomes too large, and the amount of radiation reaching the vicinity of the substrate is reduced. There is a tendency to decrease.

In the resist composition (c), the acid generator is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 15 parts by weight, particularly preferably 0.5 to 100 parts by weight per 100 parts by weight of the alkali-soluble resin. 10 parts by weight, the cross-linking agent is preferably 3 to 85 parts by weight, more preferably 5 to 75 parts by weight, particularly preferably 10 to 65 parts by weight, and further anthracene-9-methanol is preferably 0.00. It is 05-20 weight part, More preferably, it is 0.1-10 weight part, Most preferably, it is 0.2-5 weight part.
In the resist composition (c), if the blending amount of the acid generator is less than 0.05 parts by weight, it may be difficult to effectively cause a chemical change due to the catalytic action of the acid generated by exposure. If it exceeds the parts by weight, uneven coating may occur when the resist composition (c) is applied, or scum may occur during development. Further, if the blending amount of the crosslinking agent is less than 3 parts by weight, the crosslinking reaction generally tends to be insufficient, and there is a risk that the remaining film ratio will decrease, the resist pattern meanders or swells, and on the other hand, if it exceeds 85 parts by weight. , Scum increases and developability tends to decrease. Furthermore, when the blending amount of anthracene-9-methanol is less than 0.05 parts by weight, the radiation reflected from the substrate surface cannot be sufficiently absorbed, and the antihalation effect which is the main function and effect of the present invention is sufficiently exhibited. On the other hand, if the amount exceeds 20 parts by weight, the radiation absorption capacity of the resist composition (c) becomes too large, and the amount of radiation reaching the vicinity of the substrate is reduced. There is a tendency to decrease.

Here, the preferable compounding composition of the main components in the resist composition (A), the resist composition (B), and the resist composition (C) will be illustrated more specifically below.
A preferred resist composition (A) comprises 100 parts by weight of an acid-decomposable group-containing resin, 0.05 to 20 parts by weight of an acid generator, and 0.05 to 20 parts by weight of anthracene-9-methanol , and a more preferred resist composition. The product (a) comprises 100 parts by weight of an acid-decomposable group-containing resin, 0.1 to 15 parts by weight of an acid generator, and 0.1 to 10 parts by weight of anthracene-9-methanol. ) Comprises 100 parts by weight of an acid-decomposable group-containing resin, 0.5 to 10 parts by weight of an acid generator, and 0.2 to 5 parts by weight of anthracene-9-methanol .

A preferred resist composition (b) comprises 100 parts by weight of an alkali-soluble resin, 0.05 to 20 parts by weight of an acid generator, 5 to 150 parts by weight of a dissolution controller, and 0.05 to 20 parts by weight of anthracene-9-methanol. Become
Further preferable resist composition (b) is 100 parts by weight of an alkali-soluble resin, 0.1 to 15 parts by weight of an acid generator, 5 to 100 parts by weight of a dissolution control agent, and 0.1 to 10 parts by weight of anthracene-9-methanol. Consists of
Particularly preferred resist composition (b) is 100 parts by weight of an alkali-soluble resin, 0.5 to 10 parts by weight of an acid generator, 5 to 50 parts by weight of a dissolution control agent, and 0.2 to 5 parts by weight of anthracene-9-methanol. Consists of.

A preferred resist composition (c) comprises 100 parts by weight of an alkali-soluble resin, 0.05 to 20 parts by weight of an acid generator, 3 to 85 parts by weight of a crosslinking agent, and 0.05 to 20 parts by weight of anthracene-9-methanol. ,
A more preferred resist composition (c) comprises 100 parts by weight of an alkali-soluble resin, 0.1 to 15 parts by weight of an acid generator, 5 to 75 parts by weight of a crosslinking agent, and 0.1 to 10 parts by weight of anthracene-9-methanol. Become
A particularly preferred resist composition (c) comprises 100 parts by weight of an alkali-soluble resin, 0.5 to 10 parts by weight of an acid generator, 10 to 65 parts by weight of a crosslinking agent, and 0.2 to 5 parts by weight of anthracene-9-methanol. Become.

Preparation of Solution The chemically amplified radiation-sensitive resin composition of the present invention is dissolved in a solvent so that the solid content concentration is, for example, 5 to 50% by weight, preferably 15 to 40% by weight. A resist solution is prepared by filtering through a filter having a pore size of about 0.2 μm.
Examples of the solvent used for preparing the resist solution include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate;
Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether;
Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate;

Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate, n-butyl lactate and isobutyl lactate;
Methyl formate, ethyl formate, n-propyl formate, isopropyl formate, n-butyl formate, isobutyl formate, n-amyl formate, isoamyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, acetic acid Isobutyl, n-amyl acetate, isoamyl acetate, n-hexyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, butyric acid aliphatic carboxylic acid esters such as n-propyl, isopropyl butyrate, n-butyl butyrate, isobutyl butyrate;
Ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxy Methyl propionate, ethyl 3-ethoxypropionate, methyl 3-methoxy-2-methylpropionate (methyl β-methoxybutyrate), 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3 -Other esters such as methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate;

Aromatic hydrocarbons such as toluene and xylene;
Ketones such as methyl ethyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone;
Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone;
Examples include lactones such as γ-butyrolactone.
These solvents are used alone or in admixture of two or more.

  The amount of the solvent used in the resist solution in the present invention is usually 20 with respect to 100 parts by weight of the total solid content of the acid-decomposable group-containing resin, alkali-soluble resin, acid generator, dissolution controller, crosslinking agent, additive and the like. To 3,000 parts by weight, preferably 50 to 3,000 parts by weight, and more preferably 100 to 2,000 parts by weight.

Formation of resist pattern When forming a resist pattern from the chemically amplified radiation-sensitive resin composition of the present invention, the resist solution prepared as described above is appropriately applied by spin coating, cast coating, roll coating, etc. For example, a resist film is formed by coating on a substrate such as a silicon wafer or a wafer coated with aluminum and performing a heat treatment (hereinafter referred to as “pre-bake”) as necessary. The resist film is exposed to form a predetermined pattern. The radiation used for exposure is a KrF excimer laser. Further, the exposure conditions such as the exposure amount are appropriately selected according to the composition of the chemically amplified radiation-sensitive resin composition, the type of each additive, and the like.
Further, when forming a resist pattern using the chemically amplified radiation-sensitive resin composition of the present invention, a protective film is formed on the resist film to prevent the influence of basic impurities contained in the environmental atmosphere. It can also be provided.
In the present invention, in order to improve the apparent sensitivity of the resist film, it is preferable to perform a heat treatment after exposure (hereinafter referred to as “post-exposure baking”). The heating conditions for post-exposure baking vary depending on the composition of the chemically amplified radiation-sensitive resin composition, the type of each additive, etc., but are usually 30 to 200 ° C., preferably 50 to 150 ° C.

Then, a predetermined resist pattern is formed by developing with an alkaline developer.
Examples of the alkali developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, Dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, 1,5-diazabicyclo- [ An alkaline aqueous solution in which an alkaline compound such as 4,3,0] -5-nonene is dissolved in a concentration of usually 1 to 10% by weight, preferably 2 to 5% by weight is used.
In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, or a surfactant can be added to the developer composed of the alkaline aqueous solution.
In addition, when using the developing solution which consists of alkaline aqueous solution in this way, generally it wash | cleans with water after image development.
The chemical amplification type radiation sensitive resin composition of the present invention and the method of forming a resist pattern using the composition have been described in detail above. However, the present invention is based on the technical idea and within the technical scope. In the above, various modifications and variations other than those described above can be adopted.

The positive-type and negative-type chemically amplified radiation-sensitive resin composition of the present invention has a particularly high anti-halation effect and accurately reproduces a fine resist pattern even on a substrate having a high reflectance such as an aluminum substrate. It has excellent storage stability, can maintain good sensitivity and pattern shape even after a long time after preparation of the composition, and has excellent sensitivity, resolution, developability, and pattern shape. Yes. Moreover, the positive and negative chemically amplified radiation sensitive resin compositions of the present invention can effectively respond to a KrF excimer laser.
Therefore, the positive-type and negative-type chemically amplified radiation-sensitive resin compositions of the present invention can be used very suitably as a chemically amplified resist for manufacturing semiconductor devices, which is expected to be further refined in the future. .

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, these examples are merely for illustrating preferred embodiments of the present invention, and the present invention is not limited to these examples.
Here, the measurement of Mw and the evaluation of the resist were carried out according to the following procedure.
Mw
Using Tosoh Co., Ltd. GPC columns (G2000H _XL : 2, G3000H _XL : 1, G4000H _XL : 1), with flow rate of 1.0 ml / min, elution solvent tetrahydrofuran, and column temperature of 40 ° C. The measurement was performed by gel permeation chromatography using monodisperse polystyrene as a standard.
The exposure amount for forming a line-and-space pattern (1L / 1S) with a sensitivity of 0.4 μm in a one-to-one line width was taken as the optimum exposure amount, and the sensitivity (unit mJ / cm ² ) was evaluated based on this optimum exposure amount. .
The minimum dimension (unit: μm) of the resist pattern that is resolved when the exposure is performed with the optimum resolution exposure amount is defined as the resolution.
Developability is considered “good” when development residue, scum, etc. are not observed after developable alkali development, and developability is “bad” when at least one of these requirements is not met .

As shown in FIG. 1, when an aluminum substrate having a step structure is used and the obtained resist pattern is observed from above using a scanning electron microscope, pattern thinning (notching) or thickening is recognized. In the case where it was not, the anti-halation effect was regarded as “good”, and when the pattern was thinned (notched) or thickened, the anti-halation effect was regarded as “bad”.
The lower side dimension La and the upper side dimension Lb of a 1 L / 1S square cross section formed on a patterned silicon wafer with a line width of 0.4 μm are measured using a scanning electron microscope,
0.85 ≦ La / Lb ≦ 1.0
If the pattern sidewall is small, and the pattern near the substrate is not chipped, the pattern top overhang and the pattern head are not thin, the pattern shape is considered to be “good”. When at least one of the above is not satisfied, the pattern shape is determined to be “defective”.

Production of acid-decomposable group-containing resin Synthesis Example 1
After dissolving 67 g (0.5 mol) of p-isopropenylphenol and 64 g (0.5 mol) of t-butyl acrylate in 131 g of propylene glycol monomethyl ether, 8 g of azobisisobutyronitrile was added, and then nitrogen was added. Under the atmosphere, the reaction temperature was kept at 60 ° C., and the polymerization was carried out for 10 hours. After the polymerization, the reaction solution was dropped into 5 liters of hexane to solidify the resin, and the recovered resin was separated and then washed 5 times with 1 liter of hexane each time. Thereafter, the copolymer was redissolved in acetone, and then dropped into a large amount of water and solidified to obtain a white resin (yield 56%).
This resin had Mw = 12,400, and as a result of analysis by ¹³ C-NMR, the copolymerization ratio (molar ratio) of p-isopropenylphenol and t-butyl acrylate was 50:50. This resin is referred to as a resin (A).

Synthesis example 2
To a solution obtained by dissolving 12 g of poly (p-vinylphenol) and 5 g of triethylamine in 50 g of dioxane, 11 g of di-t-butyl carbonate was added with stirring, and the mixture was further stirred at room temperature for 6 hours, and oxalic acid was added. Thus, triethylamine was neutralized. Next, the reaction solution was dropped into a large amount of water to solidify the resin, and the recovered resin was washed several times with pure water to obtain a white resin (yield 85%).
The obtained resin had Mw = 9,200, and as a result of analysis by ¹³ C-NMR, 85% of the hydrogen atoms of the phenolic hydroxyl group in poly (p-vinylphenol) were substituted with t-butoxycarbonyl groups. It had a structure. This resin is referred to as resin (B).

Synthesis example 3
After dissolving 78 g (0.5 mol) of tetrahydropyranyl acrylate and 42 g (0.5 mol) of methyl methacrylate in 80 g of propylene glycol monomethyl ether and adding 3 g of azobisisobutyronitrile, the reaction temperature was changed. Polymerization was performed for 10 hours in a nitrogen atmosphere while maintaining at 80 ° C. After the polymerization, the reaction solution was dropped into a large amount of water to solidify the resin, and the recovered resin was dried overnight in a vacuum drier maintained at 50 ° C. to give tetrahydropyranyl acrylate / white powdery powder / 96 g of methyl methacrylate copolymer resin was obtained.
The obtained resin had Mw of 25,400, and as a result of ¹³ C-NMR measurement, the copolymerization ratio (molar ratio) of tetrahydropyranyl acrylate and methyl methacrylate was 50:50. This resin is referred to as “resin (C)”.

Synthesis example 4
120 g of a vinylphenol mixture having a composition of 20% by weight of p-vinylphenol, 65% by weight of p-ethylphenol and 15% by weight of other components (10% by weight of water, 4% by weight of p-cresol, 1% by weight of phenol) and acrylic 17 g of acid t-butyl and 50 g of propylene glycol monomethyl ether were mixed to obtain a uniform solution. Next, bubbling was performed with nitrogen gas for 30 minutes, and 1.9 g of 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) (2 mol% based on the total monomers) was added as a radical initiator. After that, while continuing bubbling, the reaction temperature was kept at 40 ° C. and polymerization was performed for 7 hours. After the polymerization, the reaction solution was dropped into a large amount of hexane to solidify the resin. After the recovered resin is dissolved in acetone, the operation of coagulation in hexane is repeated to completely remove unreacted monomers, and the resin is dried at 50 ° C. under reduced pressure to obtain a white resin (yield 55%). Got.
This resin had Mw = 31,000, and as a result of analysis by ¹³ C-NMR, the copolymerization ratio (molar ratio) of p-vinyl and t-butyl acrylate was 60:40. This resin is referred to as a resin (D).

Production of alkali-soluble resin Synthesis Example 5
88 g of pt-butoxystyrene was dissolved in 80 g of propylene glycol monomethyl ether, and 2 g of azobisisobutyronitrile was added, followed by polymerization for 10 hours in a nitrogen atmosphere while maintaining the reaction temperature at 80 ° C. After the polymerization, an aqueous sulfuric acid solution was added, and a hydrolysis reaction was performed at 80 ° C. for 8 hours. Next, ethyl acetate was added to the reaction solution, and after washing with water, the solvent was replaced with acetone. The obtained resin solution is dropped into a large amount of water to solidify the resin, and the recovered resin is dried overnight in a vacuum drier kept at 50 ° C. to obtain a white fine powdered poly (p-hydroxystyrene) ) 48 g was obtained.
The obtained resin had Mw of 10,000. This resin is referred to as “resin (E)”.

Synthesis of dissolution control agent Synthesis Example 6
After dissolving 15 g of bisphenol A in tetrahydrofuran, 2 times the amount of di-t-butyl dicarbonate and 0.3 times the amount of triethylamine are added to the total number of moles of phenolic hydroxyl groups in bisphenol A, and 6% under reflux. Reacted for hours. Subsequently, the reaction solution was dropped into water, and the resulting precipitate was recovered and dried overnight in a vacuum dryer maintained at 50 ° C., to obtain the dissolution control agent (a) of the formula (4).

Examples 1-5 and 8-11, Comparative Examples 1-4
After mixing each component shown in Table 1 (parts are based on weight), foreign matters were removed by microfiltration with a filter having a pore size of 0.2 μm to prepare a resist solution.
This resist solution was spin-coated on a silicon wafer and pre-baked under the conditions shown in Table 2 to form a resist film having a thickness of 1 μm. The resist film was exposed with a KrF excimer laser (wavelength 248 nm) through a pattern mask, and then post-exposure baking was performed under the conditions shown in Table 2. Subsequently, using 2.38 wt% tetramethylammonium hydroxide aqueous solution, alkali development was performed at 23 ° C. for 60 seconds, followed by washing with water to form a resist pattern, and the resist was evaluated.
The evaluation results are shown in Table 3.

Here, components other than the resins (A) to (E) , anthracene-9-methanol and the dissolution control agent (a) are as follows.

Acid generator (α): N- (trifluoromethylsulfonyloxy) -bicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximide (β): N- (campanylsulfonyloxy) naphthylimide (γ): triphenylsulfonium triflate (δ): 2- (4-methoxy-1) -Naphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine (ε): bis (cyclohexylsulfonyl) diazomethane

Cross-linking agent (c): hexa (methoxymethyl) melamine (d): tetra (methoxymethyl) urea

Acid diffusion controller (A): Tripropylamine (I): Tri-n-butylamine

solvent
BA: n-butyl acetate
EEP: ethyl 3-ethoxypropionate
EL: Ethyl lactate
MMP: methyl 3-methoxypropionate
PGMEA: Propylene glycol monomethyl ether acetate

It is a longitudinal cross-sectional view explaining the halation phenomenon of a positive resist. It is a top view which illustrates the thinning of a resist pattern.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Coating of resist composition 2 Radiation irradiated 3 Radiation reflected on substrate 4 Inclined surface 5 Substrate 6 Resist pattern 7 Thinning of pattern

Claims (4)

  (A) Methylthiomethyl group, ethylthiomethyl group, t-butoxycarbonylmethyl group, 1-methylthioethyl group, 1-ethylthioethyl group, 1-cyclopropylethyl group, isopropyl group, sec-butyl group, t-butyl Group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group, methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, t-butoxycarbonyl group, t-pentyloxycarbonyl group, acetyl An alkali-insoluble or hardly-alkali-soluble resin protected with one or more acid-decomposable groups selected from the group consisting of a group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group and a cyclohexenyl group, A resin which becomes alkali-soluble when the decomposable group is decomposed, (b) A positive chemically amplified radiation-sensitive resin composition for exposure with a KrF excimer laser, comprising a radiation-sensitive acid generator that generates an acid upon irradiation with radiation and (c) anthracene-9-methanol .   (A) a phenolic hydroxyl group or a carboxyl group in an alkali-soluble resin comprising a vinyl resin having a repeating unit in which at least one polymerizable double bond of the group (a) hydroxystyrene and (meth) acrylic acid is cleaved; Methylthiomethyl group, ethylthiomethyl group, t-butoxycarbonylmethyl group, 1-methylthioethyl group, 1-ethylthioethyl group, 1-cyclopropylethyl group, isopropyl group, sec-butyl group, t-butyl group, 1 , 1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group, methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, t-butoxycarbonyl group, t-pentyloxycarbonyl group, acetyl group, cyclo Propyl group, cyclopentyl group, cyclohexyl And a positive type for exposure by a KrF excimer laser according to claim 1, which is protected with one or more acid-decomposable groups selected from the group of cyclohexenyl groups and is itself an alkali-insoluble or hardly-alkali-soluble resin. Chemically amplified radiation sensitive resin composition.   (A) an alkali-soluble resin, (b) a radiation-sensitive acid generator that generates an acid upon irradiation with radiation, (c) an anthracene-9-methanol and (d) an acid functional group in the presence of an acid 1 A compound having at least one kind of acid-decomposable substituent, wherein the acid-decomposable substituent is a methylthiomethyl group, an ethylthiomethyl group, a t-butoxycarbonylmethyl group, a 1-methylthioethyl group, a 1-ethylthioethyl group, 1-cyclopropylethyl group, isopropyl group, sec-butyl group, t-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group, methoxycarbonyl group, ethoxycarbonyl group, iso Propoxycarbonyl group, t-butoxycarbonyl group, t-pentyloxycarbonyl group, acetyl group, cyclopropyl group, cyclope A compound selected from the group consisting of a til group, a cyclohexyl group and a cyclohexenyl group, which has the property of controlling the alkali solubility of an alkali-soluble resin, decomposed in the presence of an acid, and has an alkali solubility of an alkali-soluble resin. A positive chemical amplification type for exposure with a KrF excimer laser, characterized by containing a compound having an action of reducing or eliminating the effect of controlling the pH, or an action of promoting alkali solubility of an alkali-soluble resin Radiation sensitive resin composition.   (A) an alkali-soluble resin, (b) a radiation-sensitive acid generator that generates an acid upon irradiation with radiation, (c) a compound that crosslinks the alkali-soluble resin in the presence of anthracene-9-methanol and (e) an acid. A negative-type chemically amplified radiation-sensitive resin composition for exposure with a KrF excimer laser.

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