JP2003207898A - Positive resist composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive resist composition which simultaneously satisfies high sensitivity, high resolution, a good pattern shape and good stability to PED (post-exposure delay) in vacuum. <P>SOLUTION: The positive resist composition is characterized in that it contains (A) a polymer which is insoluble or slightly soluble in an aqueous alkali solution and is made soluble in the aqueous alkali solution by the action of an acid, (B) a compound which generates a sulfonic acid upon irradiation with an actinic ray or a radiation, (C) a compound which generates a carboxylic acid upon irradiation with an actinic ray or a radiation and (D) a quaternary ammonium salt compound. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive resist composition suitable for use in an ultra-microlithography process such as the production of VLSI and high-capacity microchips and other photopublication processes. More specifically, the present invention relates to a positive photoresist capable of forming a highly precise pattern using electron beams, X-rays, EUV light, etc., and particularly fine processing of semiconductor devices using high-energy rays such as electron beams. The present invention relates to a positive resist composition that can be preferably used.

[0002]

2. Description of the Related Art Conventionally, in the manufacturing process of semiconductor devices such as IC and LSI, fine processing by lithography using a photoresist composition has been performed. In recent years, with the high integration of integrated circuits, formation of ultrafine patterns in the sub-micron region or the quarter-micron region has been required. Along with this, the exposure wavelength tends to be shorter, such as g-line to i-line and further to KrF excimer laser light. Furthermore, at present, in addition to excimer laser light, development of lithography using electron beams, X-rays, or EUV light is in progress.

In particular, electron beam lithography is positioned as a pattern forming technique for the next or next generation,
A positive resist having high sensitivity and high resolution is desired. In particular, high sensitivity is a very important issue for shortening the wafer processing time. However, in the case of positive resist for electron beam, when trying to achieve high sensitivity, stability after exposure in a vacuum causes stability. There is a problem that (hereinafter, abbreviated as PED in vacuum) is deteriorated, and development of a resist satisfying both of these is strongly desired. Further, there are similar problems in lithography using X-rays and EUV light, and it is necessary to solve these problems. Such electron beam, X-ray or E
As a resist suitable for a lithography process using UV light, a chemically amplified resist mainly utilizing an acid catalyst reaction is mainly used from the viewpoint of high sensitivity. For a positive resist, an alkaline aqueous solution is used as a main component. Is a polymer that is insoluble or sparingly soluble in, and has a property of being soluble in an alkaline aqueous solution by the action of an acid (hereinafter, may be abbreviated as an acid-decomposable resin), and a chemically amplified composition comprising an acid generator. It is being used effectively.

Regarding the positive resist for electron beam or X-ray, the resist technique for KrF excimer laser has been mainly diverted and studied so far. For example, Japanese Patent Laid-Open No. 2-
No. 19847 discloses a resist composition having a polymer in which the phenolic hydroxy groups of poly (p-hydroxystyrene) are wholly or partially protected with a tetrahydropyranyl group. Patent Document 1 (Japanese Patent Laid-Open No. 4-219757) similarly discloses 20 to 20% of the phenolic hydroxy group of poly (p-hydroxystyrene).
A resist composition containing a polymer, 70% of which is substituted with acetal groups, is disclosed.

Further, Patent Document 2 (Japanese Patent Laid-Open No. 5-32359)
No. 0) describes the use of two photoacid generators, and Patent Document 3 (JP-A-5-181279) discloses a photoacid generator that generates a strong acid and a photoacid that generates a weak acid. It is described that a generator is used in combination, and Patent Document 4 (JP-A-9-
No. 43837) discloses a photo-acid generator that generates acetic acid, and Patent Document 5 (JP-A-11-125907) discloses a compound that generates a carboxylic acid having a boiling point of 150 ° C. or higher and an acid other than the carboxylic acid. The use of a compound that generates Furthermore, Patent Document 6 (JP-A-4-51243) and Patent Document 7 (JP-A-6-252).
605) and Patent Document 8 (JP-A-7-28247) disclose the use of quaternary ammonium salt compounds.

However, even with the above-mentioned technique, at present, high sensitivity, high resolution, good pattern shape and PED characteristics in vacuum cannot be satisfied at the same time. Especially in vacuum
The characteristics are very important performances when performing exposure in a vacuum such as an electron beam or an X-ray. If the PED characteristics in a vacuum are poor, the initial drawing and the drawing are performed when the electron beam or the X-ray is drawn. The performance greatly changes at the end of, and as a result, the in-plane uniformity of the line width of the drawing pattern greatly varies, resulting in a significant decrease in yield. As described above, in the combination of the conventionally known techniques, it is difficult to combine sufficiently high sensitivity, high resolution, good pattern shape with electron beam or X-ray irradiation and good PED characteristics in vacuum. Therefore, it has been strongly desired to achieve both of them.

[0007]

[Patent Document 1] Japanese Unexamined Patent Publication No. 4-219757

[Patent Document 2] Japanese Patent Laid-Open No. 5-323590

[Patent Document 3] Japanese Unexamined Patent Publication No. 5-181279

[Patent Document 4] Japanese Patent Laid-Open No. 9-43837

[Patent Document 5] JP-A-11-125907

[Patent Document 6] Japanese Patent Laid-Open No. 4-51243

[Patent Document 7] JP-A-6-252605

[Patent Document 8] Japanese Patent Application Laid-Open No. 7-28247

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the problem of a technique for improving performance in microfabrication of semiconductor devices using high energy rays, especially electron beams, X-rays or EUV light. It is an object of the present invention to provide a positive resist composition which simultaneously satisfies sensitivity, high resolution, good pattern shape, and good PED characteristics in vacuum.

[0009]

As a result of intensive investigations by the present inventors, surprisingly, the object of the present invention is to include a polymer having an acid-decomposable group, a specific acid generator and a quaternary ammonium salt. The inventors have found that the above problems can be solved by a positive resist composition, and have completed the present invention. That is, the present invention is achieved by the following (1) to (4). (1) (A) a polymer that is insoluble or sparingly soluble in an alkaline aqueous solution and becomes soluble in the alkaline aqueous solution by the action of an acid,
(B) a compound that generates a sulfonic acid upon irradiation with actinic rays or radiation, (C) a compound that generates a carboxylic acid upon irradiation with actinic rays or radiation, and (D) a quaternary ammonium salt compound A positive resist composition.

(2) The compound (C) which generates a carboxylic acid upon irradiation with actinic rays or radiation is represented by the following general formula (a):
The positive resist composition according to claim 1, which is a compound that generates a carboxylic acid represented by: Ra-COOH (a) (In the formula, Ra represents an alkyl group or an aryl group.) (3) (D) The quaternary ammonium salt compound is a compound represented by the following general formula (b), The positive resist composition as described in (1) or (2) above.

[0011]

[Chemical 2]

(Wherein R _{1 to} R ₄ each independently represents a hydrogen atom or an alkyl group, X is an OH group, a halogen atom, a Rb-COOH group or a RbSO ₃ H group (where Rb is a hydrogen atom, Represents an alkyl group or an aryl group), and two or more groups of R _{1 to} R ₄ may cooperate to form a ring.)

(4) The positive resist composition as described in any of (1) to (3) above, wherein the actinic ray or radiation is an electron beam or an X-ray.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. Component (A): Polymer that is insoluble or sparingly soluble in an alkaline aqueous solution and becomes soluble in an alkaline aqueous solution by the action of an acid. The component (A) used in the positive resist composition of the present invention is a resin main chain or side chain. A chain, or
A resin having acid-decomposable groups on both the main chain and side chains. Of these, a resin having a side chain having an acid-decomposable group is more preferable. Preferred groups as an acid-decomposable group are -COOA ⁰ and -O-B ⁰ groups, and as groups containing these groups, -R ⁰ -COOA ⁰ or -A _r -O-B ^{0 group.}
And a group represented by. Where A ⁰ is -C
(R ⁰¹ ) (R ⁰² ) (R ⁰³ ), -Si (R ⁰¹ ) (R ⁰² ).
(R ^{0 3} ) or —C (R ⁰⁴ ) (R ⁰⁵ ) —O—R ⁰⁶ group is shown. B ⁰ represents A ⁰ or a —CO—O—A ⁰ group (R ⁰ , R ^{01 to} R ⁰⁶ , and Ar have the same meanings as described below).

The acid-decomposable group is preferably a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, an enol ether group, an enol ester group, a tertiary alkyl ether group or a tertiary alkyl ester. Group, a tertiary alkyl carbonate group, and the like. More preferably, it is a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, an acetal group or a tetrahydropyranyl ether group.

Next, as the base resin when these acid-decomposable groups are bonded as side chains, --OH or --COOH, preferably --R ⁰ --COOH or --A _r --OH groups are attached to the side chains. It is an alkali-soluble resin that has. For example, the alkali-soluble resin described below can be mentioned.

The alkali dissolution rate of these alkali-soluble resins was 170 as measured by 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C.).
A / second or more is preferable. Especially preferably 330A
/ Sec or more (A is angstrom). From this point of view, particularly preferable alkali-soluble resin,
o-, m-, p-poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen- or alkyl-substituted poly (hydroxystyrene), part of poly (hydroxystyrene), O-alkyl Or an O-acylated product, a styrene-hydroxystyrene copolymer, an α-methylstyrene-hydroxystyrene copolymer and a hydrogenated novolac resin.

Component (A) used in the present invention is described in European Patent No. 254853, JP-A Nos. 2-25850 and 3-2.
As disclosed in Japanese Patent Nos. 23860, 4-251259, etc., an alkali-soluble resin is reacted with a precursor of an acid-decomposable group, or an acid-decomposable group-bonded alkali-soluble resin is bound. It can be obtained by copolymerizing a monomer with various monomers.

Specific examples of the component (A) used in the present invention are shown below, but the invention is not limited thereto.

[0020]

[Chemical 3]

[0021]

[Chemical 4]

[0022]

[Chemical 5]

[0023]

[Chemical 6]

[0024]

[Chemical 7]

[0025]

[Chemical 8]

[0026]

[Chemical 9]

The content of acid-decomposable groups is determined by the number of acid-decomposable groups in the resin (A) and the number of alkali-soluble groups not protected by acid-decomposable groups (S). A /
It is represented by (A + S). The content is preferably 0.01 to
0.7, more preferably 0.05 to 0.50, still more preferably 0.05 to 0.40. A / (A + S)>
A value of 0.7 is not preferable because it causes film shrinkage after PEB, poor adhesion to the substrate, and scum. On the other hand, A / (A + S) <
A value of 0.01 is not preferable because a standing wave may remain on the side wall of the pattern.

The weight average molecular weight (Mw) of the component (A) is
It is preferably in the range of 2,000 to 200,000. If it is less than 2,000, the film loss tends to be large due to the development of the unexposed area, and if it exceeds 200,000, the dissolution rate of the resin itself in alkali tends to be slow and the sensitivity tends to be lowered. More preferably from 5,000
The range is 100,000, and more preferably 8,000.
It is in the range of 0 to 50,000. In addition, the molecular weight distribution (M
w / Mn) is preferably 1.0 to 4.0, more preferably 1.0 to 2.0, and particularly preferably 1.0 to 1.6. Here, the weight average molecular weight is defined by the polystyrene conversion value of gel permeation chromatography. Moreover, you may use the polymer of a component (A) in combination of 2 or more types. The addition amount of the polymer of the component (A) is 80 with respect to the solid content of the positive resist composition.
〜98% by weight is suitable, preferably 85-96% by weight.

Component (B): a compound capable of generating a sulfonic acid upon irradiation with actinic rays or radiation. Examples of such a compound capable of generating a sulfonic acid upon irradiation with actinic rays or radiation include a photoinitiator for photocationic polymerization and a photoinitiator. A photopolymerization initiator for radical polymerization, a photobleaching agent for dyes, a photochromic agent, or a compound and a mixture thereof which generate a sulfonic acid by known light used for micro resists and the like are appropriately selected and used. be able to.

A compound in which a group capable of generating a sulfonic acid or a compound introduced into the main chain or side chain of a polymer upon irradiation with these actinic rays or radiations, for example,
JP-A-63-26653, JP-A-55-164824
No. 62-69263, 63-1460.
38, JP-A-63-163452, JP-A-62-1
The compounds described in JP-A No. 53853 and JP-A No. 63-146029 can be used. Further, compounds capable of generating an acid by light described in US Pat. No. 3,779,778 and European Patent 126,712 can also be used.

Further, known diazonium salts, phosphonium salts, iodonium salts, sulfonium salts, onium salts such as selenonium salts, which generate sulfonic acid, organic halogen compounds, o-nitrobenzyl sulfonate compounds, N
-Imino sulfonate compounds, N-imide sulfonate compounds, diazosulfone compounds, diazodisulfone compounds, disulfone compounds and the like can be mentioned.

Preferred are sulfonium or iodonium sulfonate compounds, N-hydroxyimide sulfonate compounds, and disulfonyldiazomethane compounds. Of these, particularly preferred are N-imide sulfonate compounds described in JP-A-10-7653, JP-A-11-2901 and the like, JP-A-4-21.
No. 0960, European Patent No. 417557, and other diazodisulfone compounds described in the following general formula (I)
Examples of the sulfonium salt and iodonium salt represented by (III) include the following general formulas (I) to (II).
The sulfonium salt and iodonium salt represented by I) are the most preferable.

[0033]

[Chemical 10]

R in the general formulas (I) to (III)₁
~ R₃₇Are each independently a hydrogen atom, an alkyl group, an alcohol
Xy group, hydroxyl group, halogen atom, or -S
-R ₃₈Is a group that can be represented by. R₁~ R₃₇Represents
The alkyl group may be linear, branched or cyclic.
But it's okay. Examples of linear or branched alkyl groups include
For example, methyl group, ethyl group, propyl group, n-butyl group,
sec-butyl group, t-butyl group, etc., for example, having 1 carbon atom
~ 4 alkyl groups can be mentioned. Ring Archi
Group, for example, cyclopropyl group, cyclopentyl
Alkyl having 3 to 8 carbon atoms such as benzyl and cyclohexyl groups
A group can be mentioned.

The alkoxy group represented by R _{1 to} R ₃₇ may be linear, branched, or cyclic. Examples of the linear or branched alkoxy group include those having 1 to 8 carbon atoms such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, n-butoxy group,
Examples thereof include an isobutoxy group, a sec-butoxy group, a t-butoxy group and an octyloxy group. Examples of the cyclic alkoxy group include a cyclopentyloxy group and a cyclohexyloxy group.

The halogen atom represented by R _{1 to} R ₃₇ is
Examples thereof include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R ₃₈ in -S-R ₃₈ in which R ₁ to R ₃₇ represents the
It is an alkyl group or an aryl group. As the range of the alkyl group represented by R ₃₈ , for example, any of the alkyl groups already listed as the alkyl group represented by R _{1 to} R ₃₇ can be mentioned. The aryl group represented by R ₃₈ is a phenyl group,
Examples thereof include aryl groups having 6 to 14 carbon atoms such as a tolyl group, a methoxyphenyl group and a naphthyl group.

All of the alkyl groups represented by R _{1 to} R ₃₈ up to and including the aryl group may further have a substituent as part of the group. The substituent preferably has 1 to 4 carbon atoms.
A C6-10 aryl group, a C2-6 alkenyl group, a cyano group, a hydroxy group, a carboxy group, an alkoxycarbonyl group, a nitro group, a halogen atom (for example, , Fluorine atom, chlorine atom, iodine atom).

The groups represented by R _{1 to} R ₁₅ in the general formula (I) are
Two or more of them may combine to form a ring. The ring may be formed by directly bonding the ends of the groups represented by R _{1 to} R ₁₅ . They may be bound indirectly via one or more elements selected from carbon, oxygen, sulfur, and nitrogen to form a ring. The ring structure formed by combining two or more of R _{1 to} R ₁₅ is the same as the ring structure found in a furan ring, a dihydrofuran ring, a pyran ring, a trihydropyran ring, a thiophene ring, a pyrrole ring and the like. The structure of can be mentioned. R _{16 to} R in the general formula (II)
_{The same} can be said for ₂₇ . Two or more may be bonded directly or indirectly to form a ring. The same applies to R _{28 to} R ₃₇ in the general formula (III).

The general formulas (I) to (III) have X ⁻ . X ^{− in} general formulas (I) to (III) is an anion of an acid. The acid forming the anion is sulfonic acid,
Preferred are benzenesulfonic acid, naphthalenesulfonic acid, and anthracenesulfonic acid containing one or more fluorine atoms. The above benzenesulfonic acid, naphthalenesulfonic acid, or anthracenesulfonic acid may be directly substituted with a fluorine atom, or may be substituted with a substituent having a fluorine atom. As the substituent, an alkyl group, an alkoxyl group, an acyl group,
Acyloxyl group, sulfonyl group, sulfonyloxy group,
Examples thereof include groups in which an organic group such as a sulfonylamino group, an aryl group, an aralkyl group, and an alkoxycarbonyl group is substituted with a fluorine atom. Further, the above benzenesulfonic acid, naphthalenesulfonic acid, or anthracenesulfonic acid may be substituted with a halogen atom other than fluorine, a hydroxyl group, a nitro group, or the like.

The alkyl group bonded to benzenesulfonic acid forming an anion of X ⁻ has, for example, 1 to 1 carbon atoms.
2 is an alkyl group. The alkyl group may be linear, branched, or cyclic. At least one fluorine atom is substituted, preferably 25 or less. Specifically, trifluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, heptafluoropropyl group, heptafluoroisopropyl group, perfluorobutyl group, perfluorooctyl group, perfluorododecyl group, Examples thereof include a perfluorocyclohexyl group. Among them, all have 1 carbon atoms substituted with fluorine
-4 perfluoroalkyl groups are preferred.

The alkoxy group bonded to the above-mentioned benzenesulfonic acid or the like together with the alkyl group or alone is an alkoxy group having 1 to 12 carbon atoms. The alkoxy group may be linear, branched, or cyclic.
At least one fluorine atom is substituted, preferably 25 or less. Specific examples include a trifluoromethoxy group, a pentafluoroethoxy group, a heptafluoroisopropyloxy group, a perfluorobutoxy group, a perfluorooctyloxy group, a perfluorododecyloxy group and a perfluorocyclohexyloxy group.
Of these, perfluoroalkoxy groups having 1 to 4 carbon atoms, all of which are substituted with fluorine, are preferable.

The acyl group bonded to the above-mentioned benzenesulfonic acid or the like together with the alkyl group or alone is preferably one substituted with a fluorine atom having 2 to 12 carbon atoms and 1 to 23 carbon atoms. Specific examples include a trifluoroacetyl group, a fluoroacetyl group, a pentafluoropropionyl group and a pentafluorobenzoyl group.

The acyloxy group which is bonded to the above-mentioned benzenesulfonic acid or the like together with the alkyl group or alone is preferably one substituted with a fluorine atom having 2 to 12 carbon atoms and 1 to 23 carbon atoms. Specific examples include a trifluoroacetoxy group, a fluoroacetoxy group, a pentafluoropropionyloxy group and a pentafluorobenzoyloxy group. The sulfonyl group bonded to the above-mentioned benzenesulfonic acid or the like together with the alkyl group or alone is preferably one substituted with a fluorine atom having 1 to 12 and 1 to 25 carbon atoms. Specific examples include a trifluoromethanesulfonyl group, a pentafluoroethanesulfonyl group, a perfluorobutanesulfonyl group, a perfluorooctanesulfonyl group, a pentafluorobenzenesulfonyl group, and a 4-trifluoromethylbenzenesulfonyl group.

The sulfonyloxy group bonded to the benzenesulfonic acid or the like together with the alkyl group or alone is preferably one substituted with a fluorine atom having 1 to 12 and 1 to 25 carbon atoms. Specific examples include a trifluoromethanesulfonyloxy group, a perfluorobutanesulfonyloxy group and a 4-trifluoromethylbenzenesulfonyloxy group. The sulfonylamino group bonded to the benzenesulfonic acid or the like together with an alkyl group or alone has a carbon number of 1 to
Preferred is 12 which is substituted with 1 to 25 fluorine atoms. Specifically, a trifluoromethanesulfonylamino group, a perfluorobutanesulfonylamino group,
Examples thereof include perfluorooctanesulfonylamino group and pentafluorobenzenesulfonylamino group.

The aryl group which is bonded to the benzenesulfonic acid or the like together with the alkyl group or alone is preferably an aryl group substituted with a fluorine atom having 6 to 14 and 1 to 9 carbon atoms. Specific examples thereof include a pentafluorophenyl group, a 4-trifluoromethylphenyl group, a heptafluoronaphthyl group, a nonafluoroanthranyl group, a 4-fluorophenyl group, and a 2,4-difluorophenyl group. The aralkyl group that is bonded to the benzenesulfonic acid or the like together with the alkyl group or alone is preferably an aralkyl group substituted with a fluorine atom having 7 to 10 or 1 to 15 carbon atoms. Specific examples thereof include a pentafluorophenylmethyl group, a pentafluorophenylethyl group, a perfluorobenzyl group, a perfluorophenethyl group and the like. The alkoxycarbonyl group bonded to the benzenesulfonic acid or the like together with the alkyl group or alone has 2 to 13 carbon atoms, 1 to 1 carbon atom,
Those substituted with 25 fluorine atoms are preferred.
Specific examples include a trifluoromethoxycarbonyl group, a pentafluoroethoxycarbonyl group, a pentafluorophenoxycarbonyl group, a perfluorobutoxycarbonyl group and a perfluorooctyloxycarbonyl group.

Of such anions, the most preferred X ^- is a fluorine-substituted benzenesulfonate anion,
Of these, pentafluorobenzene sulfonate anion is particularly preferable. Further, benzenesulfonic acid having a fluorine-containing substituent, naphthalene sulfonic acid, or anthracene sulfonic acid, a linear, branched or cyclic alkoxy group, an acyl group, an acyloxy group, a sulfonyl group,
It may be substituted with a sulfonyloxy group, a sulfonylamino group, an aryl group, an aralkyl group, an alkoxycarbonyl group (these carbon number ranges are the same as those described above), a halogen (excluding fluorine), a hydroxyl group, a nitro group and the like.

Specific examples of the compounds represented by the general formulas (I) to (III) are shown below, but the invention is not limited thereto.

[0048]

[Chemical 11]

[0049]

[Chemical 12]

[0050]

[Chemical 13]

[0051]

[Chemical 14]

[0052]

[Chemical 15]

[0053]

[Chemical 16]

Further, an onium salt in which X ⁻ which is an anion of the acid in the general formulas (I) to (III) is benzenesulfonic acid which is unsubstituted or has a substituent other than a fluorine atom may be used. Examples of this substituent include an alkyl group, an alkoxyl group, an acyl group, an acyloxy group, an aryl group, a hydroxyl group, a nitro group, a halogen atom (C
1, Br, etc.) and the like. Further, an onium salt in which X ^- is an anion of an alkanesulfonic acid having 1 to 20 carbon atoms may be used, and in this case, an onium salt having an anion of a fluorine-substituted alkanesulfonic acid is more preferable. In addition to the above examples, the formula (I)
Specific examples of the compound represented by (III) and other onium salts are shown below, but the invention is not limited thereto.

[0055]

[Chemical 17]

[0056]

[Chemical 18]

[0057]

[Chemical 19]

[0058]

[Chemical 20]

[0059]

[Chemical 21]

[0060]

[Chemical formula 22]

[0061]

[Chemical formula 23]

The compounds of the above general formulas (I) and (II) can be synthesized by the following method. For example, an aryl Grignard reagent such as aryl magnesium bromide is reacted with phenyl sulfoxide, and the resulting triarylsulfonium halide is salt-exchanged with the corresponding sulfonic acid. There is another way. For example, there is a method in which phenyl sulfoxide and the corresponding aromatic compound are condensed and salt-exchanged using an acid catalyst such as methanesulfonic acid / diphosphorus pentoxide or aluminum chloride. Further, it can be synthesized by a method in which a diaryl iodonium salt and a diaryl sulfide are condensed and salt-exchanged using a catalyst such as copper acetate. In any of the above methods, phenyl sulfoxide may have a substituent substituted on the benzene ring, or may not have such a substituent. The compound of the general formula (III) can be synthesized by reacting an aromatic compound with periodate.

When the compound as the component (B) is a disulfone compound, an N-imidosulfonate compound, or a diazodisulfone compound, the compounds represented by the following general formula (PAG
Compounds represented by 5), (PAG6) and (PAG7) are preferable.

[0064]

[Chemical formula 24]

In the formula, Ar³, Ar^FourReplace each independently
Or an unsubstituted aryl group. R ²⁰⁶Is replaced or
An unsubstituted alkyl group and an aryl group are shown. If A is replaced
Or unsubstituted alkylene group, alkenylene group, aryle
Group.

[0066]

[Chemical 25]

In the formula, R represents a linear, branched or cyclic alkyl group or an aryl group which may be substituted.

The following general formulas (PAG5) and (PA
Specific examples of the compound represented by G6) or (PAG7) are shown below, but the invention is not limited thereto.

[0069]

[Chemical formula 26]

[0070]

[Chemical 27]

[0071]

[Chemical 28]

[0072]

[Chemical 29]

The content of the component (B) used in the present invention is generally preferably 1 to 30% by weight, more preferably 2 to 20% by weight, based on the solid content of the entire positive resist composition. Particularly preferred is 3 to 15% by weight.

Component (C): a compound capable of generating a carboxylic acid upon irradiation with actinic rays or radiation. Such a carboxylic acid-generating compound is not particularly limited, but is represented by the general formula (a): Ra-COOH. Compounds that generate a carboxylic acid of the structure shown are preferred. Specific examples include a carboxylic acid salt compound represented by the general formula (a) of sulfonium or iodonium and a carboxylic acid ester compound represented by the general formula (a) of N-hydroxyimide. Among these, compounds represented by the following general formulas (c), (d) and (e) are preferable.

[0075]

[Chemical 30]

In the general formulas (c) to (e), R _{1 to} R
₃₇ is each independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, or -SR
_A group that can be represented by ₃₈ .

Ra represents an alkyl group or an aryl group. The alkyl group as Ra may be linear or branched, and may have a substituent, and preferably has 1 carbon atom.
To 30 linear or branched alkyl groups. The aryl group as Ra may have a substituent and is preferably an aryl group having 6 to 20 carbon atoms.

The substituent which the alkyl group of Ra may have is, for example, an aryl group (phenyl group, naphthyl group, etc.), a cycloalkyl group (cyclohexyl group, cycloheptyl group, etc.), a hydroxy group, an alkoxy group. (Methoxy group, ethoxy group, butoxy group, octyloxy group, etc.), halogen atom (iodine atom, bromine atom, chlorine atom, fluorine atom), alkyl group substituted with halogen atom, alkylcarbonyl group (methylcarbonyl group, ethyl) Carbonyl group, butylcarbonyl group, etc.), alkylcarbonyloxy group (methylcarbonyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, etc.),
Alkyloxycarbonyl group (methoxycarbonyl group,
Ethoxycarbonyl group, butoxycarbonyl group, etc.), cyano group, nitro group, N-alkylaminocarbonyl group,
Examples thereof include N, N-dialkylaminocarbonyl group and alkylcarbonylamino group. Examples of the substituent that the aryl group of Ra may have include, for example, an alkyl group (a methyl group, an ethyl group, an isopropyl group, a butyl group, a t-butyl group, an octyl group, etc.) and a substituent of the above alkyl group. The same as those given as examples can be mentioned.

Ra is more preferably a linear or branched alkyl group having 1 to 24 carbon atoms which may have a substituent, a phenyl group which may have a substituent, or a substituent. A naphthyl group which may be substituted, particularly preferably an alkyl group having 1 to 18 carbon atoms which may have a substituent,
It is a phenyl group which may have a substituent.

Particularly, for the alkyl group as Ra, an alkyl group having 1 to 4 carbon atoms or a perfluoroalkyl group having 1 to 8 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms or a carbon atom is more preferable. A perfluoroalkyl group of the formulas 1 to 6, particularly preferably a methyl group, an ethyl group,
A trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a nonafluorobutyl group.

[0081] R ₁ to R ₃₇ is, R ₁ to R ₃₇ in the above (B) the general formula described in component (I) ~ the general formula (III)
And the same applies to the explanation of each substituent. Specific examples of the compounds represented by the general formulas (c) to (e) are shown below, but the compounds are not limited thereto.

[0082]

[Chemical 31]

[0083]

[Chemical 32]

[0084]

[Chemical 33]

[0085]

[Chemical 34]

[0086]

[Chemical 35]

[0087]

[Chemical 36]

The content of the component (C) used in the present invention is 0.01 based on the solid content of the entire positive resist composition.
-10 weight% is preferable, 0.02-7 weight% is more preferable, 0.03-5 weight% is especially preferable.

Component (D): quaternary ammonium salt compound The quaternary ammonium salt compound of the component (D) is not particularly limited, but is particularly a compound represented by the following general formula (b). It is preferable.

[0090]

[Chemical 37]

(In the formula, R _{1 to} R ₄ each independently represent a hydrogen atom or an alkyl group (preferably having a carbon number of 1 to 22). The alkyl group as R _{1 to} R ₄ has a substituent. Optionally, as the substituent, a hydroxy group, a carbon number of 1 to
4 alkoxy group, phenyl group and the like. Two or more of R _{1 to} R ₄ may together form a ring. R _{1 to} R ₄ are preferably each independently a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and particularly preferably, each independently an alkyl group having 1 to 12 carbon atoms (methyl group, ethyl group, Propyl group, isopropyl group,
Butyl group, t-butyl group, hexyl group, octyl group, decyl group, dodecyl group, etc.).

X is an OH group, a halogen atom (fluorine atom,
Chlorine atom, bromine atom, iodine atom, etc.), Rb—COOH group or RbSO ₃ H group. Here, Rb represents a hydrogen atom, an alkyl group, or an aryl group. The alkyl group as Rb preferably has 1 to 11 carbon atoms,
It may have a substituent. The aryl group preferably has 6 to 12 carbon atoms and may have a substituent. Here, as the substituent of the alkyl group, a phenyl group,
Examples thereof include a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom and the like), amino group and the like. As the substituent of the aryl group, an alkyl group having 1 to 4 carbon atoms, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.),
Examples thereof include an amino group, a nitro group and a cyano group.

X is preferably an OH group, a chlorine atom,
Bromine atom, alkylcarboxylic acid group having 1 to 8 carbon atoms (CH
₃ -COOH group, C ₂ H ₅ -COOH group, C ₄ H ₉ -COO
H group, C ₈ H ₁₇ —COOH group and the like), and particularly preferably OH group, chlorine atom, bromine atom, and alkylcarboxylic acid group having 1 to 4 carbon atoms. Specific examples of the compound as the component (D) are shown below, but the present invention is not limited thereto.

[0094]

[Chemical 38]

As the compound of the component (D) used in the present invention, one type may be used, or two or more types may be used in combination. The content of the component (D) used in the present invention is preferably 0.01 to 5% by weight, more preferably 0.01 to 3% by weight, and is 0 based on the solid content of the entire positive resist composition. .02
~ 1 wt% is particularly preferred. Component (B) and (C)
The total amount of the component acid generator and the proportion of the component (D) quaternary ammonium salt compound used in the composition are (total amount of the acid generator).
/ (D component) (molar ratio) = 1.0 to 500 is preferable. If the molar ratio is less than 1.0, the sensitivity may be low, and if it exceeds 500, the resolution and the line edge roughness may be deteriorated. (Total amount of acid generator)
/ (D component) (molar ratio) is preferably 3.0 to 30.
0, and more preferably 5.0 to 200.

Component (E): Other components used in the composition of the present invention In the positive resist composition of the present invention, a dye and a component other than the quaternary ammonium salt of the component (D) may be added, if necessary. A nitrogen-containing basic compound, a solvent, a surfactant, a radical generator, etc. can be contained.

(E) -1 Dyes Suitable dyes include oil dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 1
03, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-5.
05 (all manufactured by Orient Chemical Industry Co., Ltd.), crystal violet (CI42555), methyl violet (CI42535), rhodamine B (CI45170).
B), malachite green (CI42000), methylene blue (CI52015) and the like.

(E) -2 Nitrogen-containing basic compound other than quaternary ammonium salt of component (D) The nitrogen-containing basic compound used in the present invention is preferably a nitrogen-containing basic compound having a stronger basicity than phenol. As a preferable chemical environment, the structures of the following formulas (A) to (E) can be mentioned.

[0099]

[Chemical Formula 39]

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² may be the same or different and each is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, or 1 carbon atom. ~ 6 hydroxyalkyl group or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R is
²⁵¹ and R ²⁵² may combine with each other to form a ring. R
²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ^{256, which} may be the same or different, each represents an alkyl group having 1 to 6 carbon atoms. More preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, and particularly preferably both a substituted or unsubstituted amino group and a ring structure containing a nitrogen atom. It is a compound containing or a compound having an alkylamino group.

Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, imidazole, Substituted or unsubstituted pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted Alternatively, unsubstituted aminomorpholine, substituted or unsubstituted aminoalkylmorpholine and the like can be mentioned. Preferred substituents are amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group. Is.

Particularly preferred compounds are guanidine,
1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2-phenylimidazole, 4,5-diphenylimidazole, 2 , 4,5-Triphenylimidazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2
-(Aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4 -Aminoethylpyridine,

3-aminopyrrolidine, piperazine, N-
(2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-
Iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole,
5-amino-3-methyl-1-p-tolylpyrazole,
Pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6
-Dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine and the like, but not limited thereto. These nitrogen-containing basic compounds may be used alone or in combination of two or more.

The total amount of the acid generators (B) and (C) and the proportion of the nitrogen-containing basic compound used in the composition are:
(Acid generator) / (nitrogen-containing basic compound) (molar ratio) =
It is preferably 2.5 to 300. The molar ratio is 2.
If it is less than 5, the sensitivity may be low and the resolution may be lowered, and if it is more than 300, the resist pattern may be thickened with the lapse of time after the exposure and the heating treatment, and the resolution may be lowered. The (acid generator) / (nitrogen-containing basic compound) (molar ratio) is preferably 5.0 to 200, more preferably 7.0 to 150.

(E) -3 Solvents The composition of the present invention is dissolved in a solvent that dissolves each of the above components and applied onto a support. As the solvent used here,
Ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethyl sulfoxide, N-methyl Pyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

(E) -4 Surfactants Surfactants may be added to the above solvent. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, etc. Sorbitans such as polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate Fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopal Te - door,

Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate, Ftop EF301, EF3
03, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Megafac F171, F173 (Dainippon Ink and Chemicals, Inc.)
Manufactured by Sumitomo 3M Limited, Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, S
C104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.)
Fluorine-based surfactants such as Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), organosiloxane polymer K
P341 (manufactured by Shin-Etsu Chemical Co., Ltd.) or acrylic acid-based or methacrylic acid-based (co) polymer Polyflow No. 7
5, No. 95 (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.) and the like. The content of these surfactants is usually 2 per 100 parts by weight of the solid content in the composition of the present invention.
It is not more than 1 part by weight, preferably not more than 1 part by weight. These surfactants may be added alone or in some combinations.

In the production of precision integrated circuit devices, etc., a pattern forming process on a resist film is performed by using a substrate (eg, silicon / silicon dioxide coated substrate, glass substrate, ITO substrate,
Quartz / chromium oxide coated substrate, etc.) is coated with the positive resist composition of the present invention, followed by irradiation with actinic rays or radiation, and heating, development, rinsing, and drying to form a good resist pattern. be able to. Here, as the actinic ray or radiation, electron beam, X-ray, EUV light, excimer laser light having a wavelength of 150 to 250 nm and the like can be used, but electron beam, X-ray and EUV light are preferable.

In the present invention, a commercially available inorganic or organic antireflection film can be used if necessary. Further, an antireflection film may be applied to the lower layer of the resist for use.

The antireflection film used as the lower layer of the resist may be an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, or amorphous silicon, or an organic film type composed of a light absorber and a polymer material. Can be used. The former is a vacuum deposition device, C for film formation.
Equipment such as VD equipment and sputtering equipment is required.
Examples of the organic antireflection film include Japanese Patent Publication No. 7-69611.
Comprising a condensate of a diphenylamine derivative and a formaldehyde-modified melamine resin, an alkali-soluble resin, and a light absorber, and a reaction product of a maleic anhydride copolymer and a diamine-type light absorber described in US Pat. No. 5,294,680. Containing a resin binder described in JP-A-118631 and a methylol melamine-based thermal crosslinking agent, JP-A-6-1
No. 18656, an acrylic resin type antireflection film having a carboxylic acid group, an epoxy group and a light absorbing group in the same molecule, consisting of a methylol melamine and a benzophenone type light absorbing agent described in JP-A-8-87115, and JP-A-8-17950.
The polyvinyl alcohol resin described in No. 9 to which a low molecular weight light absorber is added may be used.

As the organic antireflection film, DUV30 series manufactured by Brewer Science Co. or DUV-4
0 series, Shipley AR-2, AR-3, AR
It is also possible to use a commercially available organic antireflection film such as -5.

As the developing solution for the positive resist composition of the present invention, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine Primary amines such as diethylamine, di-
Secondary amines such as n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and primary amines such as choline. An aqueous solution of alkalis such as quaternary ammonium salts, cyclic amines such as pyrrole and piperidine (usually 0.1 to 10% by weight) can be used. Furthermore, alcohols such as isopropyl alcohol and surfactants such as nonionic surfactants may be added to the aqueous solution of the above alkalis in appropriate amounts. Of these developers, quaternary ammonium salts are preferable, and tetramethylammonium hydroxide and choline are more preferable.

[0113]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the contents of the present invention are not limited thereto.

1. Synthesis example Synthesis example 1: Synthesis of polymer (B-21) of component (B), which is insoluble or sparingly soluble in an alkaline aqueous solution and is soluble in the alkaline aqueous solution by the action of an acid, p-acetoxystyrene 32 0.4 g (0.2 mol) and 7.01 g (0.07 mol) of t-butyl methacrylate were dissolved in 120 ml of butyl acetate, and a nitrogen stream and stirring were performed.
Azobisisobutyronitrile (AIBN) at 80 ℃
Polymerization reaction was carried out by adding 0.033 g three times at intervals of 2.5 hours, and finally by continuing stirring for further 5 hours.
The reaction solution was poured into 1200 ml of hexane to deposit a white resin. After drying the obtained resin, methanol 200
Dissolved in ml. 7.7g of sodium hydroxide
An aqueous solution of (0.19 mol) / water (50 ml) was added, and the mixture was heated under reflux for 1 hour for hydrolysis. Then, 200 ml of water was added to dilute the mixture, and the mixture was neutralized with hydrochloric acid to precipitate a white resin. The resin was filtered off, washed with water and dried.
Further, it was dissolved in 200 ml of tetrahydrofuran, added dropwise to 5 L of ultrapure water with vigorous stirring, and reprecipitated. This reprecipitation operation was repeated 3 times. The obtained resin was dried in a vacuum dryer at 120 ° C. for 12 hours to obtain a poly (p-hydroxystyrene / t-butyl methacrylate) copolymer.

Synthesis Example 2: Synthesis of Polymer (B-3) Poly (p-hydroxystyrene) (VP-manufactured by Nippon Soda Co., Ltd.)
8000) 10 g was dissolved in pyridine 50 ml, and thereto was added dropwise di-t-butyl dicarbonate 3.63 g under stirring at room temperature. After stirring at room temperature for 3 hours, deionized water 1L /
It was added dropwise to a solution of concentrated hydrochloric acid 20 g. The deposited powder is filtered,
A polymer (B-3) was obtained by washing with water and drying.

Synthesis Example 3: Synthesis of polymer (B-32) 83.1 g (0.5 mol) of p-cyclohexylphenol was dissolved in 300 ml of toluene, and then 150 g of 2-chloroethyl vinyl ether and 2 parts of sodium hydroxide.
5 g, tetrabutylammonium bromide 5 g, and triethylamine 60 g were added, and the mixture was reacted at 120 ° C. for 5 hours. The reaction solution was washed with water, excess chloroethyl vinyl ether and toluene were distilled off, and the resulting oil was purified by distillation under reduced pressure to give 4-cyclohexylphenoxyethyl vinyl ether. Poly (p-hydroxystyrene)
(Nippon Soda Co., Ltd. VP-8000) 20 g, 4-cyclohexylphenoxyethyl vinyl ether 6.5 g TH
It was dissolved in 80 ml of F, 0.01 g of p-toluenesulfonic acid was added, and the mixture was reacted at room temperature for 18 hours. The reaction liquid was added dropwise to 5 L of distilled water with vigorous stirring, and the powder that precipitated was filtered and dried to obtain a polymer (B-32).

Other polymers were synthesized by the same method. The weight average molecular weight, the molecular weight dispersity (Mw / Mn), and the molar ratio of repeating units of the polymers used in the following examples are as follows. Polymer Weight average molecular weight Molecular weight dispersity Molar ratio of repeating units B-3 8000 1.25 25/75 B-5 12000 1.40 40/60 B-21 15000 1.20 65/35 B-30 8000 1.25 80 / 20 B-31 15000 1.20 65/10/25 B-32 12000 1.40 80/20 * In order from the left of each repeating unit of the parentheses in the resin structure illustrated above.

Synthesis Example 4: Compound (4-1) Triphenylsulfonium Acetate (c) which Generates Carboxylic Acid by Irradiation with Actinic Rays or Radiation of Component (C)
-1) Dissolve 50 g of synthetic diphenyl sulfoxide in 800 ml of benzene, add 200 g of aluminum chloride thereto, and add 2
Refluxed for 4 hours. The reaction solution was slowly poured into 2 L of ice, 400 ml of concentrated hydrochloric acid was added, and the mixture was heated at 70 ° C. for 10 minutes. This aqueous solution was washed with 500 ml of ethyl acetate and filtered, and then 200 g of ammonium iodide was added to 400 ml of water.
What was melt | dissolved in was added. The precipitated powder was collected by filtration, washed with water, washed with ethyl acetate and dried to obtain 70 g of triphenylsulfonium iodide. 30.5 g of triphenyl iodide was dissolved in 1000 ml of methanol, 19.1 g of silver oxide was added to this solution, and the mixture was stirred at room temperature for 4 hours. The solution was filtered and to this was added an excess of a solution of commercial tetraammonium acetate. The reaction solution was concentrated, dissolved in 500 ml of dichloromethane, and the solution was washed with a 5% aqueous solution of tetramethylammonium hydroxide and water. The organic layer is dried over anhydrous sodium sulfate and then concentrated to give triphenylsulfonium acetate (c-1).
was gotten.

(4-2) Synthesis of di (4-t-amylphenyl) iodonium acetate (e-1) 60 g of t-amylbenzene, potassium iodate 39.5
g, 81 g of acetic anhydride, and 170 ml of dichloromethane were mixed, and 66.8 g of concentrated sulfuric acid was slowly added dropwise thereto under ice cooling. After stirring under ice cooling for 2 hours, the mixture was stirred at room temperature for 10 hours. Water (500 ml) was added to the reaction mixture under ice cooling, the mixture was extracted with dichloromethane, the organic layer was washed with sodium hydrogen carbonate and water, and then concentrated to obtain di (4-t-amylphenyl) iodonium sulfate. The sulphate was added to a solution of excess commercial tetraammonium acetate. Water 500 was added to this solution, this was extracted with dichloroethane, and the organic layer was washed with a 5% tetramethylammonium hydroxide aqueous solution and water. The organic layer was dried over anhydrous sodium sulfate and then concentrated to obtain di (4-t-amylphenyl) iodonium acetate (e-1). Other compounds were also synthesized using the same method as above.

[Example 1] (1) Preparation and coating of positive resist (A) component: acid-decomposable polymer B-21 0.94 g (B) component: sulfonic acid generator I-1 0.05 g ( C) component: carboxylic acid generator c-1 0.003 g (D) component: quaternary ammonium salt D-4 0.002 g is dissolved in propylene glycol monomethyl ether acetate 8.5 g, and Megafac F176 is further used as a surfactant. (Manufactured by Dainippon Ink and Chemicals, Inc., hereinafter W
(Abbreviated as -1) 0.001 g was added and dissolved, and the resulting solution was microfiltered with a membrane filter having a diameter of 0.1 μm to obtain a resist solution. This resist solution was applied onto a 6-inch silicon wafer using a spin coater Mark8 manufactured by Tokyo Electron, and baked at 110 ° C. for 90 seconds to obtain a uniform film having a thickness of 0.30 μm.

(2) Preparation of positive type resist pattern and its evaluation This resist film was irradiated with an electron beam by using an electron beam drawing apparatus (HL750 manufactured by Hitachi, Ltd., accelerating voltage 50 KeV). After irradiation, bake at 110 ° C. for 90 seconds to 2.3.
After dipping for 60 seconds using an 8 wt% tetramethylammonium hydroxide (TMAH) aqueous solution, 30
Rinse with water for seconds and dry. The obtained pattern was evaluated by the following method. (2-1) Sensitivity The cross-sectional shape of the obtained pattern was taken by scanning electron microscope (Co., Ltd.)
It observed using Hitachi S-4300). 0.1
The sensitivity was defined as the minimum irradiation energy when resolving a 5 μm line (line: space = 1: 1). (2-2) Resolving power The limiting resolving power (the line and the space are separated and resolved) at the irradiation dose showing the above sensitivity was defined as the resolving power. (2-3) Pattern shape The cross-sectional shape of the 0.15 μm line pattern at the irradiation dose showing the above sensitivity was observed using a scanning electron microscope (S-4300 manufactured by Hitachi, Ltd.), and a rectangular shape, slightly tapered shape, Three-step evaluation of taper was performed. (2-4) PED characteristic in vacuum A wafer is set in a vacuum chamber, electron beam irradiation is performed at an irradiation amount showing the above sensitivity, and immediately after irradiation or after 3 hours, 110 ° C., 90 seconds baking (heat treatment) as described above. After that, development processing was performed to obtain a line pattern. Then, it was baked immediately after electron beam irradiation and developed to obtain 0.15 μm.
A line pattern and a 0.15 μm line pattern obtained by baking after 3 hours of electron beam irradiation and development processing were performed using a scanning electron microscope (S-922 manufactured by Hitachi, Ltd.).
The line width was measured at 0), and the difference between the two was taken as the PED characteristic in vacuum. The result of Example 1 shows that the sensitivity is 5.5 μC / cm ² ,
Resolution is 0.10 μm, pattern shape is rectangular, in vacuum P
The ED was 1.5 nm, which was very good.

[Examples 2 to 15 and Comparative Examples 1 to 3] Using the compounds shown in Table 1, resist formation, coating, and electron beam irradiation were performed to form a pattern in the same manner as in Example 1, An evaluation was made.

In Comparative Example 1, without using the component (C),
As the component (D), (D-2) (tetraethylammonium hydroxide salt disclosed in JP-A-4-51243) was used.

In Comparative Example 2, without using the component (D),
As the component (C), (c-1) (triphenylsulfonium acetate disclosed in JP-A-9-43837) was used.

In Comparative Example 3, the component (D) was not used,
As component (C), (c-9) (JP-A-11-12590).
The diphenyliodonium-octanoate disclosed in Japanese Patent No. 7) was used. The evaluation results are shown in Table 2.

[0126]

[Table 1]

[0127]

[Table 2]

In Table 1, other abbreviations mean the following. (C-9): diphenyliodonium-octanoate nitrogen-containing basic compound (E-1): tri-n-hexylamine nitrogen-containing basic compound (E-2): benzimidazole surfactant (W-2) : Polysiloxane polymer KP3
41 (manufactured by Shin-Etsu Chemical Co., Ltd.)

As is clear from the results in Table 2, the compound of the present invention containing both the component (C) which generates a carboxylic acid upon irradiation with actinic rays or radiation and the component (D) quaternary ammonium salt compound. The composition is a composition containing only the component (C) or only the component (D) upon irradiation with radiation, or a composition of a comparative example containing the component (C) and a non-quaternary ammonium salt type nitrogen-containing basic compound. It can be seen that, compared with the object, it has high sensitivity and high resolution, and the pattern shape and PED in vacuum are also excellent.

[Examples 16 to 25 and Comparative Examples 4 to 6] Using the compounds shown in Table 3, resist formation, coating and electron beam irradiation were carried out in the same manner as in Example 1 to form patterns. An evaluation was made.

In Comparative Example 4, without using the component (C),
(D-4) was used as the component (D).

In Comparative Example 5, without using the component (D),
(C-10) was used as the component (C).

In Comparative Example 6, the component (D) was not used,
(C-10) was used as the component (C), and E-1 was used as the nitrogen-containing compound. The evaluation results are shown in Table 4.

[0134]

[Table 3]

[0135]

[Table 4]

[0136]

According to the present invention, there is provided a positive resist composition which simultaneously satisfies high sensitivity, high resolution, good pattern shape, and good PED characteristics in vacuum with respect to pattern formation by irradiation with actinic rays or radiation. Can be provided.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08F 222/40 C08F 222/40 G03F 7/004 501 G03F 7/004 501 H01L 21/027 H01L 21/30 502R (72) Inventor Koji Shirakawa 4000 Kawajiri, Yoshida-cho, Hara-gun, Shizuoka Prefecture F-term of Fuji Shashin Film Co., Ltd. (reference) 2H025 AA01 AA02 AA03 AB16 AC05 AC06 AD03 BE00 BG00 FA03 FA12 FA17 4J100 AA20R AB02P AB02R AB07P AB07Q AL08R AL34Q AM10R AM45R AM49Q AM49R BA02P BA02Q BA03Q BA03R BA04P BA11Q BA11R BA15P BA15Q BC04P BC04Q BC09Q BC43P BC43Q BC43R BC53P BC53Q

Claims (4)

[Claims] 1. A polymer which is insoluble or sparingly soluble in an alkaline aqueous solution and becomes soluble in the alkaline aqueous solution by the action of an acid, (B) a compound which generates a sulfonic acid upon irradiation with actinic rays or radiation, and (C) an activity. A positive resist composition comprising a compound that generates a carboxylic acid upon irradiation with light or radiation, and (D) a quaternary ammonium salt compound. 2. The compound (C) which generates a carboxylic acid upon irradiation with actinic rays or radiation is a compound which generates a carboxylic acid represented by the following general formula (a): The positive resist composition as described in 1. Ra-COOH (a) (In the formula, Ra represents an alkyl group or an aryl group.) 3. A quaternary ammonium salt compound (D) is a compound represented by the following general formula (b):
The positive resist composition according to claim 1. [Chemical 1] (In the formula, R _{1 to} R ₄ each independently represent a hydrogen atom or an alkyl group, and X represents an OH group, a halogen atom, or Rb—CO.
An OH group or an RbSO ₃ H group (wherein Rb represents a hydrogen atom, an alkyl group or an aryl group);
Two or more groups of _{1 to} R ₄ may together form a ring. ) 4. The positive resist composition as claimed in claim 1, wherein the actinic ray or radiation is an electron beam or an X-ray.