JP2003057827A - Positive resist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive resist composition excellent in sensitivity and resolution and satisfying even a rectangular pattern shape and good edge roughness. SOLUTION: The positive resist composition comprises a compound which generates an acid when irradiated with active light or radiation, 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 the acid and a compound which includes a specified sulfonimide structure.

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 an electron beam, an X-ray, an excimer laser or the like.

[0002]

2. Description of the Related Art Electron beam lithography is positioned as a next-generation or next-generation pattern forming technique, and a positive resist having high sensitivity, high resolution and a rectangular profile is strongly desired. In electron beam lithography, energy is supplied to a compound in a process in which an accelerated electron beam collides and scatters with atoms constituting a resist material to cause a reaction of the resist material to form an image. By using a highly accelerated electron beam, straightness is increased, the influence of electron scattering is reduced, and it is possible to form a rectangular pattern with high resolution and good edge roughness. Performance is increased and sensitivity is reduced. As described above, in electron beam lithography, there is a trade-off relationship between sensitivity, resolution, resist shape, and edge roughness, and there has been a problem how to achieve both of them.

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, JP 20
No. 00-181065 discloses a combination of a compound capable of generating an acid upon irradiation with an electron beam and an amine compound having a boiling point of 250 ° C. or lower. Further, EP 0919867 discloses a polymer having an acid decomposable group, an acid generator and an electron beam sensitizer. Combination of agents
Further, JP-A-7-508840 discloses the combined use of amide compounds. Furthermore, JP-A-3-
No. 200968 discloses maleimide compounds, JP-A-7-92.
No. 680 discloses the use of a sulfonamide compound, and JP-A No. 11-44950 discloses a sulfonimide compound containing a —SO ₂ —NH—SO ₂ — partial structure. However, none of them achieved high sensitivity, high resolution, rectangular resist shape, and good edge roughness at the same time. Here, the edge roughness means that, due to the characteristics of the resist, the edge of the resist line pattern and the substrate interface has a shape that irregularly fluctuates in a direction perpendicular to the line direction. When this pattern is observed from directly above, the edges look uneven. This unevenness is
Since it is transferred to the substrate by the etching process, if the unevenness is large, the electrical characteristics will be deteriorated and the yield will be reduced. Thus, in the conventionally known combination, it is difficult to have a sufficiently high sensitivity and high resolution under electron beam or X-ray irradiation, in addition to having a rectangular resist shape and good edge roughness, There has been a strong demand for compatibility of these. Further, in lithography using an excimer laser beam having a short wavelength such as KrF or ArF as an exposure light source, the target is to form an ultrafine pattern of 0.20 μm or less, but the sensitivity and resolution are the same as in electron beam lithography. There is a strong demand for a resist composition that does not satisfy all of the properties such as property, pattern shape, and edge roughness at the same time, and can satisfy these properties at the same time.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a technique for improving performance in fine processing of semiconductor devices using actinic rays or radiation, particularly electron beams, X-rays, KrF excimer laser light, and ArF excimer laser light. And a positive resist composition having excellent sensitivity and resolution, and a positive resist that simultaneously satisfies the characteristics of rectangular pattern shape and good edge roughness in addition to sensitivity and resolution. To provide a composition.

[0005]

As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by a resist composition containing a polymer having an acid-decomposable group and a specific sulfonimide type compound, The present invention has been reached. That is, the present invention is achieved by the following configurations. (1) (B) 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, and (C) a compound having a sulfonimide structure in the molecule represented by the following general formula (1). A positive resist composition comprising:

[0006]

[Chemical 2]

(In the formula, R ₁ , R ₂ and R ₃ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a heterocyclic group.)

(2) The positive resist composition as described in (1), which contains a compound (A) other than (C) which generates an acid upon irradiation with actinic rays or radiation. (3) The positive resist composition as described in (1) or (2), which further contains a nitrogen-containing basic compound. (4) The positive resist composition as described in any one of (1) to (3), wherein the actinic ray or radiation is an electron beam or an X-ray. (5) The actinic ray or radiation has a wavelength of 150 to 250 nm.
The excimer laser light of (1)-
The positive resist composition as described in any of (3).

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds used in the present invention are described in detail below. (1) The composition of the present invention, together with the component (C),
A component (A) other than the component (C) which can generate an acid upon irradiation with actinic rays or radiation can be preferably contained. As the component (A), any compound can be used as long as it is a compound that generates an acid upon irradiation with actinic rays or radiation.

Examples of compounds that generate an acid upon irradiation with actinic rays or radiation include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photobleaching agents for dyes, and photochromic agents. Alternatively, a known compound that generates an acid by light and a mixture thereof, which are used for a micro resist or the like, can be appropriately selected and used.

A compound in which an acid-generating group or a compound is introduced into the main chain or side chain of a polymer upon irradiation with these actinic rays or radiations, for example, JP-A-6-61
3-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038,
JP-A-63-163452, JP-A-62-15385
No. 3, compounds described in JP-A No. 63-146029 and the like can be used. Further, U.S. Pat. No. 3,779,7
Compounds capable of generating an acid by light, such as those described in No. 78 and EP 126,712, can also be used.

Further, known diazonium salts, phosphonium salts, iodonium salts, sulfonium salts, onium salts such as selenonium salts, organic halogen compounds, o-nitrobenzyl sulfonate compounds, N-imino sulfonate compounds, N-imido sulfonate compounds, diazo compounds. Examples thereof include sulfone compounds, diazodisulfone compounds and disulfone compounds.

Preferred are sulfonium or iodonium sulfonate compounds, N-hydroxyimide sulfonate compounds, and disulfonyldiazomethane compounds. Among these, particularly preferred are N-imide sulfonate compounds described in JP-A-10-7653, JP-A-11-2901 and the like, JP-A-4-21096.
No. 0, European Patent No. 417557 and other diazodisulfone compounds, sulfonium salts and iodonium salts represented by the following general formulas (I) to (III) can be mentioned, but the following general formula (I) to The sulfonium salt and iodonium salt represented by (III) are the most preferable.

[0014]

[Chemical 3]

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 a 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 preferably benzenesulfonic acid, naphthalenesulfonic acid, or 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, a group in which an organic group such as an alkyl group, an alkoxyl group, an acyl group, an acyloxyl group, a sulfonyl group, a sulfonyloxy group, a sulfonylamino group, an aryl group, an aralkyl group and an alkoxycarbonyl group is substituted with a fluorine atom is used. Can be mentioned. Further, the above benzenesulfonic acid, naphthalenesulfonic acid, or anthracenesulfonic acid,
It 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 an alkyl group 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 carbon atoms 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 one 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 these 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.

[0029]

[Chemical 4]

[0030]

[Chemical 5]

[0031]

[Chemical 6]

[0032]

[Chemical 7]

[0033]

[Chemical 8]

[0034]

[Chemical 9]

Further, an onium salt in which X ⁻ which is the 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. Further, X ⁻ is BF ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ^−.
It may be an onium salt which is an inorganic anion such as. In addition to the above examples, specific examples of the compounds represented by the general formulas (I) to (III) and other onium salts are shown below, but the invention is not limited thereto.

[Chemical 10]

[0036]

[Chemical 11]

[0037]

[Chemical 12]

[0038]

[Chemical 13]

[0039]

[Chemical 14]

[0040]

[Chemical 15]

[0041]

[Chemical 16]

The compounds of general formula (I) and general formula (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, condensation of phenyl sulfoxide and the corresponding aromatic compound using methanesulfonic acid / diphosphorus pentoxide or an acid catalyst such as aluminum chloride,
There is a method of salt exchange. 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 general formula (III) can be synthesized by reacting an aromatic compound with periodate.

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

[0044]

[Chemical 17]

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.

[0046]

[Chemical 18]

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.

[0049]

[Chemical 19]

[0050]

[Chemical 20]

[0051]

[Chemical 21]

[0052]

[Chemical formula 22]

The content of the component (A) used in the present invention is
Generally 0 to solid content of all positive resist composition
It is 20% by weight, preferably 0.5 to 10% by weight, more preferably 1 to 7% by weight.

(2) Component (B) used in the present invention,
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. The component (B) used in the positive resist composition of the present invention includes a resin main chain or side 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. A
r is an arylene group (preferably having 6 to 12 carbon atoms), and particularly preferably a phenylene group. R ⁰ is a single bond or an alkylene group (preferably having 1 to 6 carbon atoms), preferably a single bond or an alkylene group having 1 to 4 carbon atoms, and particularly preferably a single bond or 1 or 2 carbon atoms. Is an alkylene group.

R ^{01 to} R ⁰³ are each independently an alkyl group (preferably having 1 to 8 carbon atoms), a cycloalkyl group (preferably having 4 to 10 carbon atoms), an aryl group (preferably having 6 to 15 carbon atoms). And these groups may cooperate with each other to form a ring or a bridged ring. R ^{01 to} R ⁰³ are preferably each independently an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and particularly preferably, each independently. In addition,
4 are an alkyl group, a cyclohexyl group, and a phenyl group. R ⁰⁴ and R ⁰⁵ are each independently a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 8), preferably a hydrogen atom,
It is an alkyl group having 1 to 6 carbon atoms, particularly preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁰⁶ is
An alkyl group (preferably having a carbon number of 1 to 15) which may contain an ether group or a thioether group, a cycloalkyl group (preferably having a carbon number of 4 to 10), an aryl group (preferably having a carbon number of 6 to 15), or these It is a group combining the groups of. R ⁰⁶ is preferably an alkyl group having 1 to 12 carbon atoms, which may contain an ether group or a thioether group, a cycloalkyl group having 5 to 8 carbon atoms, and 6 to 6 carbon atoms.
A 12-aryl group, or a group obtained by combining these groups, and particularly preferably an alkyl group having 1 to 8 carbon atoms which may include an ether group or a thioether group, a cyclohexyl group, a phenyl group, a naphthyl group, or these. It is a group combining the groups of. Furthermore, R ⁰⁶ is R ⁰⁴ or R ⁰⁵
It is also preferable to form a ring in cooperation with.

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 matrix resin in the case where the group capable of decomposing by an acid is bonded as a side chain, -OH or -COOH in the side chain, preferably -R ⁰ -COOH or -A _r -OH group 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 (B) used in the present invention is described in European Patent 254853, JP-A-2-25850 and JP-A-3-2.
As disclosed in No. 23860, No. 4-251259, etc., an alkali-soluble resin is reacted with a precursor of an acid-decomposable group, or an alkali-soluble resin monomer having an acid-decomposable group bonded thereto is used. It can be obtained by copolymerization with various monomers.

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

[0061]

[Chemical formula 23]

[0062]

[Chemical formula 24]

[0063]

[Chemical 25]

[0064]

[Chemical formula 26]

[0065]

[Chemical 27]

[0066]

[Chemical 28]

[0067]

[Chemical 29]

The content of acid-decomposable groups is determined by the number of acid-decomposable groups in the resin (B) and the number of alkali-soluble groups not protected by acid-decomposable groups (S). B /
It is represented by (B + 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. B / (B + 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, B / (B + 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 (B) is
It is preferably in the range of 2,000 to 200,000. If it is less than 2,000, the film loss is large due to the development of the unexposed area, and if it exceeds 200,000, the dissolution rate of the alkali-soluble resin itself in alkali becomes slow and the sensitivity is lowered. More preferably, 5,000 to 100,0
Range of 00, more preferably 8,000 to 50,
The range is 000. In addition, molecular weight distribution (Mw / Mn)
Is preferably 1.0 to 4.0, more preferably 1.0.
˜2.0, 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 (B) in combination of 2 or more types. The amount of the component (B) polymer added is
80 to 98% by weight is suitable, and preferably 85 to 96% by weight, based on the solid content of the positive resist composition.

(3) The component (C) used in the resist composition of the present invention will be described for the compound represented by the general formula (1) and having a sulfonimide structure in the molecule. In the general formula (1), R ₁ , R ₂ and R ₃ are each independently
Alkyl group (preferably having 1 to 12 carbon atoms), cycloalkyl group (preferably having 4 to 18 carbon atoms), aryl group (preferably having 6 to 20 carbon atoms), aralkyl group (preferably having 7 to 20 carbon atoms) or hetero. Represents a cyclic group (in particular, an aromatic group containing a hetero atom is preferable, a heterocyclic group containing 4 to 10 carbon atoms is preferable, and an aromatic group containing a hetero atom having 4 to 10 carbon atoms is particularly preferable). Any of these groups may have a substituent. As these substituents, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, iodine atom), an alkyl group having 1 to 4 carbon atoms substituted with a halogen atom. Group, aryl group having 6 to 10 carbon atoms, alkenyl group having 2 to 6 carbon atoms, cyano group, hydroxy group, carboxy group, 2 carbon atoms
Examples include an alkoxycarbonyl group having 5 to 5 carbon atoms, an alkylcarbonyloxy group having 2 to 5 carbon atoms, and a nitro group.

R ₁ , R ₂ and R ₃ are preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent and a cycloalkyl having 4 to 15 carbon atoms which may have a substituent. A group, an aryl group having 6 to 18 carbon atoms which may have a substituent, an aralkyl group having 7 to 15 carbon atoms which may have a substituent, and a hetero atom which may have a substituent. It is an aromatic group having 4 to 6 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms which may have a substituent, and an aromatic group having 5 to 12 carbon atoms which may have a substituent. A cycloalkyl group (cyclohexyl group, cyclooctyl group, etc.), an aryl group having 6 to 15 carbon atoms which may have a substituent, an aralkyl group having 7 to 15 carbon atoms which may have a substituent,
4 to 4 carbon atoms containing a hetero atom which may have a substituent
It is an aromatic group of 6 and particularly preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent (methyl group, ethyl group, n-propyl group, n-butyl group, t-butyl group). Etc.), an aryl group having 6 to 14 carbon atoms which may have a substituent (phenyl group, naphthyl group, anthryl group), an aralkyl group having 7 to 12 carbon atoms which may have a substituent (benzyl Group, a phenethyl group, etc.) and a hetero atom-containing aromatic group having 5 to 6 carbon atoms (2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-thiophenyl group, etc.).

Further, as R ₁ , an alkyl group having 1 to 6 carbon atoms which may have a substituent (methyl group, ethyl group, n-propyl group, t-butyl group, n-hexyl group, etc.) A cycloalkyl group having 6 to 12 carbon atoms which may have a substituent (cyclohexyl group, cyclooctyl group, etc.), an aryl group having 6 to 10 carbon atoms which may have a substituent (phenyl group, Naphthyl group, p-toluyl group, etc.), aromatic group having 4 to 6 carbon atoms containing a hetero atom (nitrogen atom, sulfur atom, etc.) which may have a substituent (2
-Pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-
Thiophenyl group), and R ₂ and R ₃ each independently represent an alkyl group having 1 to 12 carbon atoms which may have a substituent (methyl group, ethyl group, n-butyl group, n-).
Octyl group, n-dodecyl group, trifluoromethyl group,
Nonafluorobutyl group, perfluorooctyl group, etc.),
An optionally substituted aryl group having 6 to 10 carbon atoms (phenyl group, naphthyl group, fluorine-substituted phenyl group, trifluoromethyl group-substituted phenyl group, alkoxyphenyl group, etc.), having a substituent It is preferably an aralkyl group having 7 to 15 carbon atoms (benzyl group, phenethyl group, etc.). Specific examples of the compound containing a sulfonimide structure in the molecule of the component (C) are shown below, but of course the invention is not limited thereto.

[0073]

[Chemical 30]

[0074]

[Chemical 31]

The content of the component (C) is usually 0.01 to 20% by weight, preferably 0.02 to 15% by weight, particularly preferably 0.03, based on the solid content of the resist composition.
10 to 10% by weight. As the compound as the component (C), one type may be used, or two or more types may be mixed and used.
The compound of the component (C) may be used alone, or may be used in combination with the compound of the component (A) which is another acid generator. The usage ratio (weight ratio) of both is (C) / (A) = 100/0
Used in 5 to 95/95, preferably 100/0 to 10/9
0, particularly preferably 100/0 to 20/80.

(4) Other components used in the positive resist composition of the present invention In the positive resist composition of the present invention, if necessary, a radical generator, a nitrogen-containing basic compound, a dye, and an interface are further added. Activators and the like can be included.

(4) -1 Nitrogen-containing basic compound 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.

[0078]

[Chemical 32]

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² may be the same or different and each represents 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 ratio of the acid generator and the nitrogen-containing basic compound used in the composition is (acid generator) / (nitrogen-containing basic compound)
(Mole ratio) = 2.5 to 300 is preferable. If the molar ratio is less than 2.5, the sensitivity may be low and the resolution may be lowered. If the molar ratio is more than 300, the resist pattern may become thicker with the lapse of time after the post-exposure heat treatment, and the resolution may be lowered. . The (acid generator) / (nitrogen-containing basic compound) (molar ratio) is preferably 5.0 to 20.
0, and more preferably 7.0 to 150.

(4) -2 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.

(4) -3 Solvents The composition of the present invention is applied to a support by dissolving it in a solvent that dissolves the above components. 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.

(4) -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 (manufactured by Dainippon Ink Co., Ltd.), Fluoro FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Asahi Guard AG710, Surflon S-.
382, SC101, SC102, SC103, SC1
04, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) and other fluorochemical surfactants, Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), organosiloxane polymer KP3
41 (manufactured by Shin-Etsu Chemical Co., Ltd.) or acrylic acid-based or methacrylic acid-based (co) polymer Polyflow No. 75, N
o. 95 (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd.) and the like. The content of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solid content in the composition of the present invention. These surfactants may be added alone or in some combinations.

In the step of forming a pattern on a resist film in the production of precision integrated circuit devices, etc., a positive electrode of the present invention is formed on a substrate (eg, silicon / silicon dioxide covering, glass substrate, transparent substrate such as ITO substrate). A good resist pattern can be formed by applying a mold resist composition and then irradiating with actinic rays or radiation, followed by heating, developing, rinsing and drying. The actinic ray or radiation is preferably an electron beam, X-ray, light having a wavelength of 150 to 250 nm (KrF excimer laser (248 nm), Ar).
F excimer laser (193 nm), F2 excimer laser (157 nm), etc.
An electron beam and a KrF excimer laser are particularly preferable.

In the present invention, if necessary, a commercially available inorganic or organic antireflection film can be used. Further, an antireflection film may be coated on the upper 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.

Further, 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.

The developer for the positive resist composition of the present invention includes sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, inorganic alkalis such as 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 alkali such as quaternary ammonium salt, cyclic amines such as pyrrole and piperidine, and the like 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.

[0093]

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

Synthesis Example 1: Synthesis of Resin Example (B-21) 32.4 g (0.2 mol) of p-acetoxystyrene and 7.01 g (0.07 mol) of t-butyl methacrylate were dissolved in 120 ml of butyl acetate. Under a nitrogen stream and stirring,
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 Resin Example (B-3) Poly (p-hydroxystyrene) (VP-8 manufactured by Nippon Soda Co., Ltd.)
000) 10 g was dissolved in pyridine 50 ml, and thereto was added dropwise di-t-butyl dicarbonate 3.63 g with stirring at room temperature. After stirring at room temperature for 3 hours, the solution was added dropwise to a solution of 1 L of ion-exchanged water / 20 g of concentrated hydrochloric acid. The deposited powder was filtered, washed with water, and dried to obtain Resin Example (B-3).

Synthesis Example 3: Synthesis of Resin Example (B-32) 83.1 g (0.5 mol) of p-cyclohexylphenol was dissolved in 300 ml of toluene, then 150 g of 2-chloroethyl vinyl ether, 25 sodium hydroxide.
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. THF (80) was added with 20 g of poly (p-hydroxystyrene) (VP-8000 manufactured by Nippon Soda Co., Ltd.) and 6.5 g of 4-cyclohexylphenoxyethyl vinyl ether.
It is dissolved in ml and p-toluenesulfonic acid 0.01
g was added and reacted at room temperature for 18 hours. The reaction solution was added dropwise to 5 L of distilled water with vigorous stirring, and the precipitated powder was filtered and dried to obtain Resin Example (B-32).

Other resins were synthesized by the same method. The weight average molecular weight of the resin used in the following examples and the molar ratio of repeating units are as follows. Resin Weight average molecular weight Molar ratio of repeating units ^* (B-2) 7500 30/70 (B-3) 8500 25/75 (B-4) 8500 25/75 (B-5) 13500 40/60 (B-13 ) 8000 65/35 (B-21) 12000 65/35 (B-22) 15000 20/80
(B-24) 14000 30/70 (B-26) 11500 15/60/25 (B-28) 15000 78/22 (B-30) 8000 80/20 (B-31) 15000 65/10/25 ( B-32) 12000 82/18 (B-33) 12000 15/75/10 * From the left of each repeating unit of the parentheses in the resin structure illustrated above.

Example 1 (1) Coating of Resist (Component A): Acid Generator I-1 0.05 g (Component B): Resin B-21 0.94 g propylene glycol monomethyl ether acetate 8.5 g 0.1 g of N-phenylbis (trifluoromethanesulfonimide (CC-3) manufactured by Tokyo Kasei Co., Ltd. was added as a C component, and 1,5-diazabicyclo [4.3.0] -5 was further added. -Nonene (hereinafter abbreviated as D-1) 0.005 g, and Megafac F176 as a surfactant (manufactured by Dainippon Ink and Chemicals, hereinafter abbreviated as W-1)
0.001 g was added and dissolved, and the resulting solution was added to 0.1
A resist solution was obtained by microfiltration with a membrane filter having a diameter of μm. This resist solution was applied onto a 6-inch silicon wafer by Tokyo Electron Spin Coater Mar.
It was applied using k8 and baked at 110 ° C. for 90 seconds to obtain a uniform film having a thickness of 0.30 μm.

(2) Preparation of resist pattern and its evaluation An electron beam drawing device (HL75 manufactured by Hitachi) was formed on this resist film.
Electron beam irradiation was performed using 0 and an acceleration voltage of 50 KeV). After irradiation, it was baked at 110 ° C. for 90 seconds, and 2.38 wt% tetramethylammonium hydroxide (TM)
AH) After dipping for 60 seconds using an aqueous solution, then for 30 seconds,
Rinse with water and dry. The obtained pattern was evaluated by the following method. (2-1) Sensitivity The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope. 0.20 μm line (line: space =
The minimum irradiation energy for resolving 1: 1) was defined as the sensitivity. (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 0.14 μm line pattern at the irradiation dose showing the above sensitivity was observed using a scanning electron microscope,
Three-stage evaluation of rectangular, slightly tapered, and tapered was performed. (2-4) Edge roughness SEM measures the distance from the reference line where the edge should be in the range of 5 μm in the longitudinal direction of the line roughness pattern.
(S-8840 manufactured by Hitachi, Ltd.) was used to measure 30 points, the standard deviation was calculated, and 3σ was calculated. The smaller the value, the better the property. As a result of Example 1, the sensitivity was 8.0 μC / cm ² , the resolution was 0.10 μm, the pattern shape was rectangular, and the edge roughness was 9.5 nm, which was good.

Example 2 N- (2-pyridyl) -bis (trifluoromethane) sulfonimide (C manufactured by Tokyo Kasei Co., Ltd.) was used in place of the compound CC-3 as the component C used in Example 1.
Except for using C-4), resist coating and electron beam exposure evaluation were conducted in the same manner as in Example 1. Table 2 shows the evaluation results
It was shown to.

[Examples 3 to 10] Using the compounds shown in Table 1, resist coating and electron beam exposure evaluation were performed in the same manner as in Example 1. The evaluation results are shown in Table 2.

Comparative Example 1 Resist coating and electron beam exposure evaluation were performed in the same manner as in Example 1 except that the component C was not used. The evaluation results are shown in Table 2.

[Comparative Examples 2 and 3] p-toluenesulfonamide (hereinafter abbreviated as C-A) and succinimide (hereinafter abbreviated as C-B) were used instead of the C component in the examples. The resist coating and the electron beam exposure evaluation were performed in the same manner as in Example 1 except that the above was used. The evaluation results are shown in Table 2.

The other compounds used in the examples are shown below. Nitrogen-containing basic compound (D-2): 2-phenylbenzimidazole Nitrogen-containing basic compound (D-3): Dicyclohexylmethylamine surfactant (W-2): Polysiloxane polymer KP3
41 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0105]

[Table 1]

[0106]

[Table 2]

As is clear from the results shown in Table 2, the positive resist composition of the present invention in which the component C having a specific sulfonimide structure is combined is a comparative example containing no component C when exposed to radiation. It can be seen that, as compared with Comparative Examples containing other amide compounds and imide compounds having different skeleton structures from the C component, the sensitivity and the resolution are high, and the pattern shape and edge roughness are excellent.

Example 11 (1) Coating of resist (component A): PAG3-1 0.05 g (component B): Resin B-22 0.94 g was dissolved in propylene glycol monomethyl ether acetate 8.5 g. , C component as compound CC-6
0.07 g was added, and Compound D-1 was added to 0.005
g and compound W-1 (0.001 g) were 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 and baked in the same manner as in Example 1 to obtain a uniform film having a thickness of 0.30 μm.

(2) Preparation of resist pattern and its evaluation On this resist film, KrF excimer stepper (FPA3000EX-5 manufactured by Canon Inc., wavelength 248 nm) was used.
Was used for pattern exposure. The treatment after exposure and the evaluation of the pattern were performed in the same manner as in Example 1.

The result of Example 11 shows that the sensitivity is 28 mJ / c.
m ² , the resolution was 0.13 μm, the pattern shape was rectangular, and the edge roughness was 7.0 nm, which was good.

[Examples 12 to 18] Using the compounds shown in Table 3, resist coating and Kr were carried out in the same manner as in Example 11.
The exposure was evaluated by an F excimer stepper. The evaluation results are shown in Table 4.

[Comparative Example 4] Resist coating and exposure evaluation with a KrF excimer excimer stepper were performed in the same manner as in Example 11 except that the component C was not used. The evaluation results are shown in Table 4.

[0113]

[Table 3]

[0114]

[Table 4]

Example 19 (1) Coating of Resist (Component B): 0.93 g of Resin B-4 (Component C): 0.08 g of Compound CC-6 was dissolved in 8.5 g of propylene glycol monomethyl ether. , 0.003 g of compound D-1, and W
0.001 g of -1 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 used in Example 1.
In the same manner as above, coating and baking were performed to obtain a uniform film having a thickness of 0.30 μm. Further, exposure and evaluation were performed in the same manner as in Example 11.

The result of Example 19 shows that the sensitivity is 35 mJ / c.
m ² , the resolution was 0.14 μm, the pattern shape was rectangular, and the edge roughness was 9.0 nm, which was good.

[Examples 20 to 24] Using the compounds shown in Table 5, resist coating and Kr were carried out in the same manner as in Example 11.
The exposure was evaluated by an F excimer stepper. The evaluation results are shown in Table 6.

[Comparative Example 5] The compound of the component (A) shown in Table 5 was used instead of the compound of the component (C) used in Example 19, and resist coating was carried out in the same manner as in Example 11. K
The exposure was evaluated by an rF excimer stepper. The evaluation results are shown in Table 6.

[0119]

[Table 5]

[0120]

[Table 6]

As described above, it is understood that the composition of the present invention has good performance not only when exposed to electron beams but also when exposed to KrF excimer laser light.

[0122]

INDUSTRIAL APPLICABILITY According to the present invention, the pattern formation by irradiation with actinic rays or radiation is excellent in sensitivity and resolution,
Further, it is possible to provide a positive resist composition excellent in pattern shape and edge roughness.

Continued front page    (72) Inventor Jun Momota             Fuji-Sha, 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture             Shin Film Co., Ltd. (72) Inventor Koichi Kawamura             Fuji-Sha, 4000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture             Shin Film Co., Ltd. F-term (reference) 2H025 AA01 AA02 AA03 AB16 AC05                       AC06 AC08 AD03 BE00 BE10                       BG00 CC20

Claims (5)

[Claims] 1. A polymer (B) which is insoluble or sparingly soluble in an alkaline aqueous solution and becomes soluble in an alkaline aqueous solution by the action of an acid, and (C) which contains a sulfonimide structure in the molecule represented by the following general formula (1). A positive resist composition containing a compound. [Chemical 1] (In the formula, R ₁ , R ₂ and R ₃ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or a heterocyclic group.) 2. The positive resist composition according to claim 1, which further comprises (A) a compound that generates an acid upon irradiation with actinic rays or radiation, other than the component (C). 3. The positive resist composition as claimed in claim 1, further comprising a nitrogen-containing basic compound. 4. The positive resist composition as claimed in claim 1, wherein the actinic ray or radiation is an electron beam or an X-ray. 5. The actinic ray or radiation has a wavelength of 150 to 25.
The positive resist composition according to claim 1, wherein the positive resist composition is 0 nm excimer laser light.