JP3476374B2 - Positive photoresist composition for deep ultraviolet exposure - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photoresist composition used in an ultra-microlithography process such as production of an ultra-LSI or a high-capacity microchip and other photofabrication processes. More specifically, the present invention relates to a positive photoresist composition capable of forming a highly detailed pattern by using a deep ultraviolet region including excimer laser light.

[0002]

2. Description of the Related Art In recent years, the degree of integration of integrated circuits has increased, and it has become necessary to process ultrafine patterns having a line width of less than half a micron in the manufacture of semiconductor substrates such as VLSI. Has become. In order to meet the need, the wavelength used in the exposure apparatus used for photolithography has become shorter and shorter, and now it is considered to use excimer laser light (XeCl, KrF, ArF, etc.) having a short wavelength among far ultraviolet rays. Is getting up.
A chemically amplified resist is used as a pattern for lithography in this wavelength region.

Generally, chemically amplified resists can be roughly classified into three types, commonly called two-component type, 2.5-component type and three-component type. The two-component system combines a compound that generates an acid by photolysis (hereinafter referred to as a photoacid generator) and a binder resin. The binder resin is a resin having in its molecule a group (also referred to as an acid-decomposable group) that decomposes by the action of an acid to increase the solubility of the resin in an alkaline developer. The 2.5-component system further contains a low-molecular compound having an acid-decomposable group in such a 2-component system. The three-component system contains a photo-acid generator, an alkali-soluble resin and the above-mentioned low molecular weight compound.

The above chemically amplified resist is suitable as a photoresist for irradiation with ultraviolet rays or deep ultraviolet rays, but among them, it is necessary to meet the required characteristics in use. For example,
A hydroxystyrene-based polymer which has a small light absorption particularly when using a 248 nm light of a KrF excimer laser.
A resist composition using a polymer having an acetal group or a ketal group introduced as a protective group has been proposed. JP-A-2-141636, JP-A-2-19847, JP-A-4
For example, Japanese Patent Laid-Open No. 5-281745 and Japanese Patent Laid-Open No. 5-281745 are examples. In addition, similar compositions containing a t-butoxycarbonyloxy group or a p-tetrahydropyranyloxy group as an acid-decomposing group are disclosed in JP-A-2-209977 and JP-A-3-209977.
206458, Japanese Patent Laid-Open No. 19847/1990, and the like. These are 24 of the KrF excimer laser.
Although suitable when using 8 nm light, the sensitivity is low when using an ArF excimer laser as the light source, since the absorbance is still too large by nature. Further, there are other drawbacks associated therewith, such as deterioration of resolution, deterioration of focus tolerance, and deterioration of pattern profile, and there are still many points to be improved.

Therefore, as a photoresist composition for an ArF light source, a (meth) acrylic resin, which absorbs less than a partially hydroxylated styrene resin, is combined with a compound which generates an acid by light. Resist compositions have been proposed. For example, Japanese Patent Laid-Open No. 7-1
99467 and 7-252324. Above all, JP-A-6-289615 discloses a resin in which a tertiary carbon organic group is ester-bonded to oxygen of a carboxyl group of acrylic acid.

Further, Japanese Patent Application Laid-Open No. 7-234511 discloses an acid-decomposable resin containing acrylic acid ester or fumaric acid ester as a repeating unit. However, the pattern profile, the adhesion to the substrate and the like are insufficient and satisfactory performance is obtained. It is the actual situation that is not obtained.

Furthermore, a resin having an alicyclic hydrocarbon moiety introduced therein has been proposed for the purpose of imparting dry etching resistance, but the system becomes extremely hydrophobic as a harmful effect of introducing the alicyclic hydrocarbon moiety. In addition, it is difficult to develop with an aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH), which has been widely used as a resist developing solution in the related art, and the resist peels off from the substrate during development. In order to deal with such hydrophobicization of the resist, measures such as mixing an organic solvent such as isopropyl alcohol into the developing solution have been investigated, and although some results have been seen, the concern about swelling of the resist film and the process become complicated. It cannot be said that the problem has been solved. In the resist improvement approach, many measures have been taken to supplement various hydrophobic alicyclic hydrocarbon moieties by introducing hydrophilic groups.

[0008] Generally, a countermeasure has been taken to copolymerize a monomer having a carboxylic acid moiety such as acrylic acid or methacrylic acid with a monomer having an alicyclic hydrocarbon group. Along with this, the substrate adhesion tends to improve, but the dry etching resistance deteriorates,
Further, there are many problems such as a noticeable film deviation of the resist, and the above problems have not been solved yet. Further, in JP-A-7-234511, a monomer having a hydroxyl group or a cyano group in the molecule instead of a carboxylic acid group such as HEMA or acrylonitrile is copolymerized with a monomer having an alicyclic hydrocarbon group. The aim was to solve the developability, but it was completely insufficient.

On the other hand, in addition to the method of introducing an alicyclic hydrocarbon moiety into the side chain of the acrylate-based monomer, a method of imparting dry etching resistance utilizing an alicyclic hydrocarbon moiety as a polymer main chain has also been studied. There is. However, this system also has the above problem, and improvement by a similar approach is being investigated. For example, Journal of Photopoly
mer Science and Technology, Vol.10, 1997, p529-534
And Journal of Photopolymer Science and Technology,
In Vol.10, 1997, p521-528, introduction of a hydroxyl group is examined from the viewpoint of imparting substrate adhesion to the norbornene polymer main chain. However, satisfactory results have not been obtained for both developability and substrate adhesion. In SPIE, 3049, 92-105 (1988), a polymer obtained by ring-opening polymerization of a norbornene ring or a polymer having a norbornene ring in the main chain and having a carboxyl group and a t-butyl ester group is used. Compositions containing coalescence are disclosed. However, even with this technique, there is a drawback in that neither the substrate adhesion nor the standard developer suitability is practically sufficient.

Further, European Patent Publication No. 789278A2 discloses a polymer obtained by ring-opening polymerization of a norbornene ring, or a polymer having a norbornene ring in its main chain and containing a resin containing an acid-decomposable group and a carboxyl group. Compositions are disclosed. WO 97/33198 discloses a photoresist composition containing a resin obtained by polymerizing a monomer having a norbornene ring having an acid-decomposable group. In addition, in Japanese Patent Laid-Open No. 9-274318,
Further disclosed are photoresist compositions using a carboxylic acid.

Further, Japanese Patent Laid-Open No. 9-73173 and Japanese Patent Laid-Open No. 9-173173
-90637 and JP-A-10-161313 include an alkali-soluble group protected with a structure containing an alicyclic group and a structural unit capable of eliminating the alkali-soluble group with an acid to make it alkali-soluble. A resist material using an acid-sensitive compound is described.

The resin containing an acid-decomposable group as described above generally contains an aliphatic cyclic hydrocarbon group in the molecule at the same time. Therefore, it is also true that the resin has become hydrophobic due to these trends. On the other hand, onium salt compounds have been widely used as photoacid generators to be used for this purpose, and some results have been achieved. However, although the cause of the conventionally used onium salt compound is unknown, compatibility is poor during preparation of the resist and turbidity occurs, or insoluble matter precipitates over time, resulting in problems with stability over time. Left. Furthermore, there is room for improvement such as a decrease in sensitivity over time.

[0013]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve the problems of the above-mentioned microphotofabrication original performance improving technique using deep ultraviolet light, particularly ArF excimer laser light, It is an object of the present invention to provide a positive photoresist composition having good compatibility with a resin when dissolved in an organic solvent, excellent stability of the solution over time, and excellent sensitivity to a short wavelength light source.

[0014]

Means for Solving the Problems As a result of diligent studies of the constituent materials of a resist composition in a positive type chemically amplified system, the present inventors have found that a specific acid decomposable resin and a specific photoacid generator are used. The inventors have come to the present invention by knowing that the object of the present invention can be achieved. That is, the above object is achieved by the following configurations.

(1) Represented by the following general formula (I) which generates a sulfonic acid upon irradiation with actinic rays or radiation.
At least one of a compound and a partial structure containing an alicyclic hydrocarbon represented by the following general formulas (pI) to (pVI)
Positive-type photoresist composition for exposure to deep-ultraviolet light, containing an alkali-soluble group protected by a group, which is decomposed by the action of an acid to increase the solubility in alkali , or actinic rays or radiation. By irradiation of
Represented by the following general formula (II), which generates sulfonic acid
Compounds and represented by the following general formulas (pI) to (pVI)
At least one of the partial structures containing alicyclic hydrocarbons
Contains an alkali-soluble group protected by
Contains a resin that decomposes and increases solubility in alkalis
(However, 4-methylphenyldiphenylsulfonium
Trifluoromethanesulfonate and methacrylic acid 2-
Tree containing methyl-2-adamantyl as a monomer component
(Except when it contains fat and oil at the same time)
A positive photoresist composition for ultraviolet exposure.

[0016]

[Chemical 3]

In the formula (I) , R ₁ and R ₂ each have a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or a substituent. Optionally alkoxy group, optionally substituted alkoxycarbonyl group, optionally substituted acyl group, optionally substituted acyloxy group, nitro group, halogen atom, hydroxyl group Alternatively , it represents a carboxyl group. a: 1 to 5 and b: 1 to 5 . However, at least one of R ₁ and R ₂ has an alkyl group having 5 or more carbon atoms, which may have a substituent, a cycloalkyl group which may have a substituent, and a substituent. Represents an optionally substituted alkoxy group, an optionally substituted alkoxycarbonyl group, an optionally substituted acyl group, or an optionally substituted acyloxy group. In formula (II), R _{3 to} R ₅ each have a substituent.
Optionally substituted alkyl group, optionally substituted
Cycloalkyl group, optionally substituted alkoxy
Si group, alkoxycarbonyl which may have a substituent
Group, an optionally substituted acyl group, and a substituent
Optionally acyloxy group, nitro group, halogen atom,
Represents a hydroxyl group or a carboxyl group. 1: 1-5, m: 0-5, and n: 0-5. When 1 + m + n = 1, R ₃ has an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. Represents an optionally substituted alkoxycarbonyl group, an optionally substituted acyl group or an optionally substituted acyloxy group. In formula (I) or Formula (II), X: R- SO 3, R: which may have an aliphatic hydrocarbon group or a location <br/> substituent may have a substituent aromatic Represents a group hydrocarbon group.

[0018]

[Chemical 4]

In the formula, R ₁₁ is a methyl group, an ethyl group or n-
It represents a propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z represents an atomic group necessary for forming an alicyclic hydrocarbon group together with a carbon atom. R ₁₂ to R ₁₆ each independently of 1 to 4 carbon atoms, represents a linear or branched alkyl group or alicyclic hydrocarbon group, provided that at least one of R ₁₂ to R _14, or Either R ₁₅ or R ₁₆ represents an alicyclic hydrocarbon group. R ₁₇
To R ₂₁ are each independently a hydrogen atom, a C 1 to C 4,
It represents a linear or branched alkyl group or an alicyclic hydrocarbon group, provided that at least one of R _{17 to} R ₂₁ represents an alicyclic hydrocarbon group. Further, either R ₁₉ or R ₂₁ represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group. R ₂₂ , R ₂₃ and R ₂₅ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, and R ₂₄ represents the number of carbon atoms.
1-4 linear or branched alkyl groups or alicyclic groups
It represents a hydrocarbon group, provided that at least one of R _{22 to} R ₂₅ represents an alicyclic hydrocarbon group.

(2) The positive photo exposure for far-ultraviolet light exposure described in (1) above, wherein the resin contains a group represented by the following general formula (A), which is decomposed by the action of an acid. Resist composition. General formula (A) -C (= O) -O- _{R0 In} formula (A), _R0 is a tertiary alkyl group, a 1-alkoxyethyl group, an alkoxymethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, Trialkylsilyl group,
It represents a 3-oxocyclohexyl group or a lactone group.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds used in the present invention are described in detail below. [1] Photoacid generator represented by the general formula [I] or [II] In the general formula [I] or [II], the alkyl group represented by R _{1 to} R ₅ may have a substituent. Good, methyl, ethyl, propyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, t-amyl, decanyl, dodecanyl And a group having 1 to 25 carbon atoms such as a hexadecanyl group. The cycloalkyl group may have a substituent, a cyclopropyl group,
Examples thereof include those having 3 to 25 carbon atoms such as cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclododecanyl group and cyclohexadecanyl group. The alkoxy group may have a substituent, methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group or t-butoxy group, pentyloxy group, t -Amyloxy group, n-hexyloxy group, n-octyloxy group, n-
Examples thereof include those having 1 to 25 carbon atoms such as dodecaneoxy group.

The alkoxycarbonyl group may have a substituent, and may have a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group. Group or 2 to 25 carbon atoms such as t-butoxycarbonyl group, pentyloxycarbonyl group, t-amyloxycarbonyl group, n-hexyloxycarbonyl group, n-octyloxycarbonyl group, n-dodecaneoxycarbonyl group, etc. The following are listed. The acyl group may have a substituent and has 1 carbon atom such as formyl group, acetyl group, butyryl group, valeryl group, hexanoyl group, octanoyl group, t-butylcarbonyl group, t-amylcarbonyl group and the like. -25 are mentioned. The acyloxy group may have a substituent, and may have an acetoxy group, an ethylyloxy group, a butyryloxy group, a t-butyryloxy group, a t.
-Amylyloxy group, n-hexanecarbonyloxy group,
Examples thereof include those having 2 to 25 carbon atoms such as an n-octane carbonoxy group, an n-dodecane carbonoxy group, and an n-hexadecane carbonoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The substituent for these groups is preferably an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an acyl group, an acyloxy group, a cyano group, a hydroxyl group, Carboxy group,
Examples thereof include an alkoxycarbonyl group and a nitro group. As described above, at least one of R ₁ and R ₂ has an alkyl group which has 5 or more carbon atoms and may have a substituent, a cycloalkyl group which may have a substituent, It represents an alkoxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an acyl group which may have a substituent, and an acyloxy group which may have a substituent. . Examples of these substituents having 5 or more carbon atoms include those having 5 to 25 carbon atoms in the above specific examples. When l + m + n = 1,
R ₃ is an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkoxy which may have a substituent. A carbonyl group, an acyl group which may have a substituent, and an acyloxy group which may have a substituent. Further, R ₃ preferably has 2 or more carbon atoms, and more preferably has 4 or more carbon atoms.

Among the above, as the alkyl group which may have a substituent of R _{1 to} R ₅ , examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group and an n- group. Pentyl group, t-amyl group, n-hexyl group, n-octyl group, and decanyl group are preferable, and as the cycloalkyl group, a cyclohexyl group, cyclooctyl group, and cyclododecanyl group which may have a substituent are exemplified. Preferably, the alkoxy group may have a substituent,
Methoxy group, ethoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, pentyloxy group, t-amyloxy group, n-hexyloxy group,
An n-octyloxy group and an n-dodecaneoxy group are preferable, and the alkoxycarbonyl group may have a substituent, methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, sec- Butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, t-amyloxycarbonyl group, n-hexyloxycarbonyl group,
n-octyloxycarbonyl group and n-dodecaneoxycarbonyl group are preferable, and the acyl group may have a substituent, a formyl group, an acetyl group, a butyryl group,
A valeryl group, a hexanoyl group, an octanoyl group, a t-butylcarbonyl group, and a t-amylcarbonyl group are preferable, and the acyloxy group may have a substituent, an acetoxy group, an ethylyloxy group, a butyryloxy group, t
-Butyryloxy group, t-amylyloxy group, n-hexanecarbonyloxy group, and n-octanecarbonyloxy group are preferable.

As the alkyl group having 5 or more carbon atoms and optionally having a substituent, an n-pentyl group or a t-pentyl group may be used.
Amyl group, n-hexyl group, n-octyl group and decanyl group are preferred. A cycloalkyl group having 5 or more carbon atoms, which may have a substituent, is a cyclohexyl group,
A cyclooctyl group and a cyclododecanyl group are preferred. As the alkoxy group having 5 or more carbon atoms and optionally having a substituent, a pentyloxy group, a t-amyloxy group,
Hexyloxy group, n-octyloxy group and dodecaneoxy group are preferred. As the alkoxycarbonyl group having 5 or more carbon atoms and optionally having a substituent, a pentyloxycarbonyl group, a t-amyloxycarbonyl group,
Hexyloxycarbonyl group, n-octyloxycarbonyl group and dodecaneoxycarbonyl group are preferred. The acyl group having 5 or more carbon atoms and optionally having a substituent is preferably a pareryl group, a hexanoyl group, an octanoyl group or a t-amylcarbonyl group. As the acyloxy group having 5 or more carbon atoms and optionally having a substituent, a t-amylyloxy group, an n-hexanecarbonyloxy group, and an n-octanecarbonyloxy group are preferable. Substituents for these groups include methoxy group, ethoxy group, t-butoxy group, chlorine atom, bromine atom, cyano group,
A hydroxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group and a t-amyloxycarbonyl group are preferred.

In the sulfonium or iodonium compound represented by the general formula [I] or [II] used in the present invention, a sulfonic acid having a specific structure as described above is used as its counter anion, X ⁻ . Examples of the aliphatic hydrocarbon group which may have a substituent of R in the counter anion include a linear or branched alkyl group having 1 to 20 carbon atoms or a cyclic alkyl group. Further, R may be an aromatic group which may have a substituent. As the alkyl group for R, a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, which may have a substituent,
Examples thereof include those having 1 to 20 carbon atoms such as n-octyl group, 2-ethylhexyl group, decyl group and dodecyl group. The cyclic alkyl group may have a substituent,
Examples thereof include cyclopentyl group, cyclohexyl group, cyclooctyl group, cyclododecyl group, adamantyl group, norbornyl group, camphor group, tricyclodecanyl group, and menthyl group. Examples of the aromatic group include a phenyl group and a naphthyl group, which may have a substituent.

Among the above, the alkyl group which may have a substituent of R includes a methyl group, a trifluoromethyl group, an ethyl group, a pentafluoroethyl group, 2,2,2.
2-trifluoroethyl group, n-propyl group, n-butyl group, nonafluorobutyl group, n-pentyl group, n-hexyl group, n-octyl group, heptadecafluorooctyl group, 2-ethylhexyl group, decyl group , Dodecyl group,
Examples of the cyclic alkyl group include a cyclopentyl group, a cyclohexyl group and a camphor group. As the aromatic group, a phenyl group, naphthyl group, pentafluorophenyl group, p-toluyl group, p-, which may have a substituent,
Fluorophenyl group, p-chlorophenyl group, p-hydroxyphenyl group, p-methoxyphenyl group, dodecylphenyl group, mesityl group, triisopropylphenyl group,
4-hydroxy-1-naphthyl group, 6-hydroxy-2
-A naphthyl group may be mentioned.

Of the above substituents, more preferred R is
Specific examples of _{1 to} R ₅ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, t-amyl group, n-hexyl group,
n-octyl group, cyclohexyl group, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, t-butoxy group, pentyloxy group, t-amyloxy group, hexyloxy group, n-octyloxy group, methoxycarbonyl group , Ethoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, t-amyloxycarbonyl group, hexyloxycarbonyl group, n-octyloxycarbonyl group, formyl group, acetyl group, butyryl group, hexanoyl group, octanoyl group , T-butylcarbonyl group, t-amylcarbonyl group, acetoxy group, ethylyloxy group, butyryloxy group, t-butyryloxy group, t-amylyloxy group, n-hexanecarbonyloxy group, n-octanecarbonyloxy group, hydroxyl group, Chlorine atom, bromine atom, Is the Toro group. Specific examples of more preferable groups having 5 or more carbon atoms include n-pentyl group and t-
Amyl group, n-hexyl group, n-octyl group, decanyl group, cyclohexyl group, pentyloxy group, t-amyloxy group, hexyloxy group, n-octyloxy group, dodecaneoxy group, pentyloxycarbonyl group, t-amido Roxycarbonyl group, hexyloxycarbonyl group,
n-octyloxycarbonyl group, dodecaneoxycarbonyl group, pareryl group, hexanoyl group, octanoyl group, t-amylcarbonyl group, t-amylyloxy group,
and n-hexane carbonyloxy group and n-octene carbonyloxy group.

Specific examples of the more preferable sulfonic acid substituent R are methyl group, trifluoromethyl group, ethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, n-butyl group and nonafluoro group. Butyl group, n
-Hexyl group, n-octyl group, heptadecafluorooctyl group, 2-ethylhexyl group, camphor group, phenyl group, naphthyl group, pentafluorophenyl group, p-toluyl group, p-fluorophenyl group, p-chlorophenyl group, p-methoxyphenyl group, dodecylphenyl group, mesityl group, triisopropylphenyl group, 4-hydroxy-1-naphthyl group, and 6-hydroxy-2-naphthyl group.

The total number of carbon atoms in the generated acid is preferably 1 to 30. The number is more preferably 1-28, and even more preferably 1-25. If the total number of carbon atoms is less than one, pattern formation may be hindered due to the t-top shape, and if it exceeds 30 carbon atoms, development residues may occur, which is not preferable. Specific examples of the compound represented by the general formula [I] or [II] as the acid generator of the present invention include the following [I-1] to [I-18] and [II-1] to. [II-20] is shown, but the present invention is not limited thereto. These compounds are used alone or in combination of two or more.

[0031]

[Chemical 5]

[0032]

[Chemical 6]

[0033]

[Chemical 7]

[0034]

[Chemical 8]

[0035]

[Chemical 9]

The general formula [I] or a compound represented by [II], for example the corresponding Cl ^- salt (formula [I] or [II] with X ^- the Cl ^- compounds substituted with) and, X ^- Y ⁺
In expressed (X ^- is the general formula [I] or [II] in the case synonymous, Y ⁺ is ^{H +, Na +, K +} , NH 4 +, N (C
H ₃ ) ₄ ⁺ etc. are shown. ) And can be synthesized by salt exchange in an aqueous solution. In addition to the above chlorides, hydroxides or methanesulfonates can also undergo similar salt exchange. The amount of the photo-acid generator represented by the general formula [I] or [II] added to the composition is
In the total solid content of the positive photoresist composition, 0.01 to
It is preferably 5% by weight, more preferably 0.03 to 4% by weight, still more preferably 0.05 to 3% by weight. 0.0
If it is less than 1% by weight, the sensitivity is lowered, and if it exceeds 5% by weight, the optical absorption is excessively increased, and the problems of lowering the sensitivity, deterioration of profile and lowering of resolution are also caused.

[2] Resin which is decomposed by the action of an acid to increase its solubility in alkali (acid-decomposable resin) In the general formulas (pI) to (pVI), the alkyl group in R _{12 to} R ₂₅ is substituted or It represents a linear or branched alkyl group having 1 to 4 carbon atoms, which may be unsubstituted. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a t-butyl group. Further, as the further substituent of the alkyl group, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an acyl group, an acyloxy group, a cyano group, a hydroxyl group, Carboxy group, alkoxycarbonyl group,
A nitro group etc. can be mentioned.

The alicyclic hydrocarbon group for R _{12 to} R _{25 or} the alicyclic hydrocarbon group formed by Z and the carbon atom may be monocyclic or polycyclic. Specific examples thereof include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The carbon number is preferably 6 to 30, and particularly preferably 7 to 25. These alicyclic hydrocarbon groups may have a substituent. Below, the structural example of an alicyclic part is shown among alicyclic hydrocarbon groups.

[0039]

[Chemical 10]

[0040]

[Chemical 11]

[0041]

[Chemical 12]

In the present invention, the alicyclic moiety is preferably adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group. , A cycloheptyl group, a cyclooctyl group,
Examples thereof include a cyclodecanyl group and a cyclododecanyl group. More preferred are an adamantyl group, a decalin residue, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group.

Examples of the substituent of these alicyclic hydrocarbon groups include an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group and an alkoxycarbonyl group. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group, more preferably a substituent selected from the group consisting of a methyl group, an ethyl group, a propyl group and an isopropyl group. Represent Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group.

In the above resins, the general formulas (pI) to (pV)
Examples of the alkali-soluble group protected by the structure represented by I) include various groups known in the technical field. Specific examples thereof include a carboxylic acid group, a sulfonic acid group, a phenol group and a thiol group, and a carboxylic acid group and a sulfonic acid group are preferable. The alkali-soluble group protected by the structures represented by the general formulas (pI) to (pVI) in the resin is preferably the following general formula (pVI).
Examples thereof include groups represented by I) to (pXI).

[0045]

[Chemical 13]

Here, R _{11 to} R ₂₅ and Z are the same as defined above. In the above resin, the repeating unit having an alkali-soluble group protected by the structures represented by the general formulas (pI) to (pVI) is preferably a repeating unit represented by the following general formula (pA).

[0047]

[Chemical 14]

Here, R represents a hydrogen atom, a halogen atom or a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of R may be the same or different. A is a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a urea group, alone or in combination of two or more. Represents a combination of groups. R _a represents any one group of formulas (pI) ~ (pVI). Hereinafter, specific examples of the monomer corresponding to the repeating unit represented by the general formula (pA) will be shown.

[0049]

[Chemical 15]

[0050]

[Chemical 16]

[0051]

[Chemical 17]

[0052]

[Chemical 18]

[0053]

[Chemical 19]

[0054]

[Chemical 20]

In the above resin, the above general formula (pI) to
In addition to the repeating unit having an alkali-soluble group protected by the structure represented by (pVI), other repeating units may be included. Such other repeating unit is preferably a repeating unit represented by the following general formula (AI).

[0056]

[Chemical 21]

R has the same meaning as above. B is a halogen atom, a cyano group, a group that decomposes by the action of an acid, -C (=
O) represents -Y-A-R _c9 or -COOR _c11 . Y: an oxygen atom, a sulfur _{atom, -NH -, - NHSO 2 -} ,
Divalent bonding group selected from _{-NHSO 2 NH-, R c9: -COOH} , -COOR c10 (. R c10 those having the same meaning as R _c11, and representing the following lactone structure), - C
N, a hydroxyl group, an alkoxy group which may have a substituent,
_{-CO-NH-R c11, -CO} -NH-SO 2 -R c11
Alternatively, it represents the following lactone structure.

R _c11 : an alkyl group which may have a substituent, a cyclic hydrocarbon group which may have a substituent, A: a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, It represents a single group or a combination of two or more groups selected from the group consisting of a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a urea group.

[0059]

[Chemical formula 22]

R ₂₉ represents a linear or branched alkyl group having 1 to 4 carbon atoms which may have a substituent. n
Represents an integer of 1 to 4. The group capable of decomposing by the action of the acid, preferably a group represented by _{-C (= O) -X 1 -R} 0. Here, R ₀ is a t-butyl group,
tertiary alkyl group such as t-amyl group, isobornyl group, 1
1-alkoxyethyl group such as ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyloxyethyl group, 1-methoxymethyl group, 1
Examples thereof include an alkoxymethyl group such as an -ethoxymethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a trialkylsilyl group, a 3-oxocyclohexyl group and the like. X ₁ is an oxygen atom, a sulfur atom, —NH—,
It represents —HNSO ₂ — or —NHSO ₂ HN—, but is preferably an oxygen atom.

The above alkyl group has 1 to 10 carbon atoms.
A straight-chain or branched alkyl group, more preferably a straight-chain or branched alkyl group having 1 to 6 carbon atoms, still more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, n. A butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group.

The above-mentioned cyclic hydrocarbon group is, for example, a cyclic alkyl group or a bridged hydrocarbon, and is a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a boronyl group, an isoboranyl group, a tricyclodecanyl group, a dicyclohexyl group. Cyclopentenyl group, nobornane epoxy group,
Menthyl group, isomenthyl group, neomenthyl group, tetracyclododecanyl group and the like can be mentioned.

As the above alkoxy group, a methoxy group,
C1-C1 such as ethoxy, propoxy, butoxy
Four can be mentioned.

Examples of the further substituent in the above alkyl group, cyclic alkyl group and alkoxy group include hydroxyl group, halogen atom, carboxyl group, alkoxy group, acyl group, cyano group and acyloxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group, and examples of the acyl group include formyl group, acetyl group and the like, acyloxy group Examples thereof include acetoxy group and the like.

Examples of the alkylene group and the substituted alkylene group represented by A in the above formulas (AI) and (pA) include the groups shown below. -[C (R _a ) (R _b )] _r -In the formula, R _a and R _{b are a} hydrogen atom, an alkyl group, a substituted alkyl group,
Represents a halogen atom, a hydroxyl group, an alkoxy group, which may be the same or different, and the alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group, more preferably methyl. Represents a substituent selected from the group consisting of a group, an ethyl group, a propyl group and an isopropyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. The alkoxy group has 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group.
I can name one thing. r represents an integer of 1 to 10. In the above, the halogen atom is a chlorine atom,
Examples thereof include bromine atom, fluorine atom and iodine atom. The B is preferably an acid-decomposable group or a mevalonic lactone group.

The acid-decomposable resin in the present invention has a structure represented by the above general formulas (pI) to (pVI) in a copolymerization component such as the repeating unit represented by the above general formula (AI). It is preferable to contain an acid-decomposable group other than the protected alkali-soluble group. As such an acid-decomposable group that can be used in combination, a group represented by the above-mentioned —C (═O) —O—R ₀ is preferable.

In addition to the above, the acid-decomposable resin is used for the purpose of adjusting dry etching resistance, standard developing solution suitability, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc. which are general requirements for resists. And can be used as a copolymer with various monomer repeating units.

Examples of such repeating units include, but are not limited to, repeating units corresponding to the following monomers. Thereby, the performance required for the resin, particularly (1) solubility in a coating solvent, (2) film-forming property (glass transition point), (3)
Alkali developability, (4) Membrane slippage (hydrophobicity, selection of alkali-soluble groups), (5) Adhesion of unexposed area to substrate,
(6) It is possible to finely adjust the dry etching resistance.
Examples of such copolymerizable monomers include addition polymerizable unsaturated bonds selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like. Examples thereof include compounds having one.

Specifically, for example, acrylates such as alkyl (wherein the alkyl group has 1 to 1 carbon atoms).
0) is preferred) Acrylate (eg, methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, acrylic acid-
t-octyl, chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, Tetrahydrofurfuryl acrylate etc.);

Methacrylic acid esters, such as alkyl (alkyl groups preferably having 1 to 10 carbon atoms) methacrylate (eg, methyl methacrylate,
Ethylmethacrylate, propylmethacrylate, isopropylmethacrylate, amylmethacrylate, hexylmethacrylate, cyclohexylmethacrylate,
Benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate,
5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.);

Acrylamides such as acrylamide, N-alkyl acrylamides (wherein the alkyl group has 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, t-butyl group, heptyl group, octyl group) Group, cyclohexyl group, hydroxyethyl group, etc.), N, N-dialkylacrylamide (alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, Cyclohexyl group etc.), N-
Hydroxyethyl-N-methylacrylamide, N-2
-Acetamidoethyl-N-acetylacrylamide and the like;

Methacrylamides, such as methacrylamide, N-alkylmethacrylamides (alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl, cyclohexyl). Groups, etc.), N, N-dialkylmethacrylamides (such as ethyl groups, propyl groups, and butyl groups as alkyl groups), N-hydroxyethyl-N-methylmethacrylamides, etc .;

Allyl compounds, such as allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate), allyloxy. Ethanol, etc .;

Vinyl ethers such as alkyl vinyl ethers (eg hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl). Butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.);

Vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barrate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, Vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate, etc .;

Dialkyl itaconates (eg dimethyl itaconate, diethyl itaconate, dibutyl itaconate etc.); Dialkyl esters of fumaric acid (eg dibutyl fumarate etc.) or monoalkyl esters;
Acrylic acid, methacrylic acid, crotonic acid, itaconic acid,
Examples thereof include maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, and maleironitrile. In addition, addition polymerizable unsaturated compounds copolymerizable with the above various repeating units may be used.

In the acid-decomposable resin, the molar ratio of each repeating unit is such that the dry etching resistance of the resist, suitability for a standard developing solution, substrate adhesion, resist profile, and resolution and heat resistance which are general requirements for resists. ,
It is appropriately set to adjust the sensitivity and the like.

In the acid-decomposable resin, general formulas (pI) to (pV)
The content of the repeating unit having an alkali-soluble group protected by the partial structure represented by I) is 30 to 70 mol% in all the monomer repeating units, preferably 35 to 65 mol%, and more preferably It is 40 to 60 mol%. Also,
In the acid-decomposable resin, the content of the repeating unit containing an acid-decomposable group other than the alkali-soluble group protected by the partial structure represented by any one of the general formulas (pI) to (pVI) is the same as all monomer repeating units. 70 mol% or less, preferably 5 to 65
Mol%, more preferably 10 to 60 mol%. The content of the carboxyl group that imparts adhesion is 2.0 in the resin.
It is less than or equal to meq / g, preferably 1.8 meq /
g or less, more preferably 1.5 meq / g or less.

The content of the repeating unit based on the monomer of the additional copolymerization component in the resin can also be appropriately set according to the desired performance of the resist, but in general, it is an essential repeating unit. 99 to the total number of moles
The amount is preferably mol% or less, more preferably 90 mol% or less, still more preferably 80 mol% or less.

The acid-decomposable resin has a weight average molecular weight (Mw: polystyrene standard) of preferably 1,0.
00 to 1,000,000, more preferably 1,500
~ 500,000, more preferably 2,000-20
50,000, more preferably 2,500 to 100,
The range is 000, and the larger the value, the higher the heat resistance and the like, but the lower the developability and the like. The acid-decomposable resin used in the present invention can be synthesized according to a conventional method (for example, radical polymerization).

In the positive photoresist composition of the present invention, the addition amount of the acid-decomposable resin in the entire composition is preferably 40 to 99.99% by weight, and more preferably 50 to 99. It is 97% by weight.

Next, in the positive photoresist composition of the present invention, a compound (photoacid generator) which generates an acid upon irradiation with actinic rays or radiation represented by the above general formula [I] or [II] is added. The photoacid generator that can be used in combination will be described.

The photo-acid generator needs to satisfy two properties. That is, (1) transparency to exposure light (provided that there is no light bleaching property), and (2) sufficient photodegradability for ensuring resist sensitivity. However, although the molecular design guideline satisfying such contradictory requirements is not clear at present, the following examples can be given. That is, JP-A-7-25846,
Aliphatic alkylsulfonium salts having a 2-oxocyclohexyl group described in JP-A-7-28237, JP-A-7-92675, and JP-A-8-27102, and N-hydroxysuccinimide sulfonate. Kind of things can be mentioned. Furthermore, J. Phot
Opolym. Sci. Technol., Vol 7, No3, p 423 (1994) and the like, a sulfonium salt represented by the following general formula (VI) and a disulfone compound represented by the following general formula (VII). Examples thereof include compounds represented by the following general formula (VIII).

[0084]

[Chemical formula 23]

Here, R _{12 to} R ₁₅ each represent an alkyl group or a cyclic alkyl group. These may be the same as or different from each other. Further, N-hydroxymaleinimide sulfonates represented by the following general formula (IX) are also suitable.

[0086]

[Chemical formula 24]

R ₁₆ and R _{17, which} may be the same or different, each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a cycloalkyl group. R ₁₆ and R ₁₇ may be bonded via an alkylene group to form a ring. R ₁₈ represents an alkyl group, a perfluoroalkyl group, a cycloalkyl group or a camphor substituent. Such N-hydroxymaleinimide sulfonates are particularly preferable in terms of photosensitivity.

As the alkyl group having 1 to 6 carbon atoms for R ₁₆ and R ₁₇ in the above general formula (IX), a methyl group,
Ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group,
Mention may be made of n-hexyl groups. Of these, a methyl group, an ethyl group and a propyl group are preferable, and a methyl group and an ethyl group are more preferable. Examples of the cycloalkyl group having 6 or less carbon atoms include cyclopropyl group, cyclopentyl group and cyclohexyl group. Preferred are cyclopentyl group and cyclohexyl group. R ₁₆ ,
Examples of the case where R _17's form a ring with each other by an alkylene chain include the case of forming a cyclohexyl group, a norbornyl group, and a tricyclodecanyl group.

The alkyl group represented by R _{18 is} a linear group having 1 to 20 carbon atoms such as methyl group, ethyl group and propyl group.
Individual alkyl groups, isopropyl groups, isobutyl groups, t
Examples thereof include branched alkyl groups having 1 to 20 carbon atoms such as an ert-butyl group and a neopentyl group. It is preferably a linear or branched alkyl group having 1 to 16 carbon atoms, and more preferably 4 to 15 carbon atoms.
Is a straight-chain or branched alkyl group. As a perfluoroalkyl group, a linear carbon number of 1 to 20 including a trifluoromethyl group and a pentafluoroethyl group
And a branched perfluoroalkyl group having 1 to 20 carbon atoms, such as a perfluoroalkyl group, a heptafluoroisopropyl group, and a nonafluorotert-butyl group. Preferred is a linear or branched perfluoroalkyl group having 1 to 16 carbon atoms. As the cyclic alkyl group, a cyclopentyl group, a monocyclic cyclic alkyl group such as a cyclohexyl group, a decalyl group,
Examples thereof include plural cyclic alkyl groups such as a norbornyl group and a tricyclodecanyl group.

The amount of such a photoacid generator that can be used in combination in the composition is preferably 0.01 to 5% by weight, more preferably 0.1% by weight based on the total solid content of the positive photoresist composition. It is from 03 to 3% by weight, more preferably from 0.05 to 2% by weight.

In the positive photoresist composition of the present invention, in addition to the above-mentioned photo-acid generator, the following photo-acid generator may be used in combination.

The amount of the photoacid generator usable in combination as described below in the composition is 2% by weight or less, more preferably 1% by weight, based on the total solid content of the positive photoresist composition.
The following is good. For example SISchlesinger, Photogr.Sci.E
ng., 18,387 (1974), TSBal etal, Polymer, 21,423 (198
0) the diazonium salts described in U.S. Pat. No. 4,069,055
No. 4,069,056, Re 27,992, JP-A-3-140,14
Ammonium salts described in No. 0, DC Necker et al, Macr
omolecules, 17,2468 (1984), CSWen et al, Teh, Proc.Co
nf.Rad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.Nos. 4,069,055, 4,069,056 and other phosphonium salts, JVCrivello et al., Macromorecules, 10 (6), 1307.
(1977), Chem. & Eng. News, Nov. 28, p31 (1988), European Patents 104,143, 339,049, 410,201, JP-A-2-150,848, JP-A-2-296,514, etc. The iodonium salts listed, JV Crivello et al, Polymer J. 17, 73 (198
5), JVCrivello et al. J. Org. Chem., 43, 3055 (1978).
, WRWatt et al, J. Polymer Sci., Polymer Chem. Ed., 2
2,1789 (1984), JVCrivello et al, Polymer Bull., 14,
279 (1985), JVCrivello et al, Macromorecules, 14 (5),
1141 (1981), JVCrivello et al, J.PolymerSci., Polym
Chem. Ed., 17, 2877 (1979), European Patent No. 370,693,
161,811, 410,201, 339,049, 233,56
7, 297,443, 297,442, U.S. Pat.No. 4,933,
377, 3,902,114, 4,760,013, 4,734,44
No. 4, No. 2,833,827, Dokoku Patent No. 2,904,626, No. 3,
604,580, 3,604,581, etc., sulfonium salts, JVCrivello et al, Macromorecules, 10 (6), 1307 (19)
77), JVCrivello et al, J. PolymerSci., Polymer Che
m.Ed., 17, 1047 (1979) etc., selenonium salt, C.
S.Wen etal, Teh, Proc.Conf.Rad.Curing ASIA, p478 Toky
o, Oct (1988) and other onium salts such as arsonium salts, U.S. Pat.No. 3,905,815, JP-B-46-4605, JP-A-48-36281, JP-A-55-32070, JP-A-60. -239736
JP-A-61-169835, JP-A-61-169837, JP-A-61-169837
62-58241, JP-A-62-212401, JP-A-63-70243,
Organic halogen compounds described in JP-A-63-298339, K.
Meier et al, J. Rad. Curing, 13 (4), 26 (1986), TPGill
et al, Inorg. Chem., 19,3007 (1980), D.Astruc, Acc.Chem.
Res., 19 (12), 377 (1896), organic metal / organic halides described in JP-A No. 2-161445, S. Hayase et al, J. Polym.
er Sci., 25, 753 (1987), E. Reichmanis et al., J. Pholymer
Sci., Polymer Chem. Ed., 23,1 (1985), QQZhu et al., J.
Photochem., 36,85,39,317 (1987), B. Amit et al, Tetrahe
dron Lett., (24) 2205 (1973), DHR Barton et al, J. Chem
Soc., 3571 (1965), PMCollins et al, J. Chem. SoC., Per
kin I, 1695 (1975), M. Rudinstein et al, Tetrahedron Le
tt., (17), 1445 (1975), JWWalker et al J.Am.Chem.So
c., 110,7170 (1988), SCBusman et al, J. Imaging Techn
ol., 11 (4), 191 (1985), HMHoulihan etal, Macormolecu
les, 21,2001 (1988), PMCollins et al, J. Chem. Soc., Che
m.Commun., 532 (1972), S. Hayase et al, Macromolecules, 1
8, 1799 (1985), E. Reichmanisetal, J. Electrochem. Soc.,
Solid State Sci.Technol., 130 (6), FMHoulihan eta
l, Macromolcules, 21, 2001 (1988), European Patent 0290,750
No., No. 046,083, No. 156,535, No. 271,851, No. 0,
388,343, U.S. Pat.Nos. 3,901,710, 4,181,531
JP-A-60-198538, JP-A-53-133022 and the like, a photo-acid generator having an o-nitrobenzyl type protecting group, M.
TUNOOKA et al, Polymer Preprints Japan, 35 (8), G. Bern
er etal, J.Rad.Curing, 13 (4), WJMijs etal, Coating
Technol., 55 (697), 45 (1983), Akzo, H.Adachi et al, Pol
ymer Preprints, Japan, 37 (3), European Patent 0199,672,
No. 84515, No. 044,115, No. 618,564, No. 0101,122
U.S. Pat.Nos. 4,371,605 and 4,431,774.
64-18143, JP-A-2-245756, JP-A-3-140109 and the like compounds such as iminosulfonates which photolyze to generate sulfonic acid, JP-A-61-166544 and the like. Mention may be made of the mentioned disulfone compounds.

Further, a group generating an acid by these light,
Alternatively, a compound in which a compound is introduced into the main chain or side chain of a polymer, for example, ME Woodhouse et al., J. Am. Chem. So.
c., 104,5586 (1982), SPPappas et al, J. Imaging Sc
i., 30 (5), 218 (1986), S.Kondoetal, Makromol.Chem., Ra
pid Commun., 9,625 (1988), Y.Yamada et al, Makromol.C
hem., 152,153,163 (1972), JVCrivello et al, J.Polym
erSci., Polymer Chem. Ed., 17,3845 (1979), U.S. Pat.No. 3,849,137, United States Patent No. 3914407, JP-A-63-266.
53, JP 55-164824, JP 62-69263, JP
63-146038, JP-A-63-163452, JP-A-62-153853
The compounds described in JP-A-63-146029 and the like can be used.

Furthermore, VNR Villai, Synthesis, (1), 1 (198
0), A. Abad et al, Tetrahedron Lett., (47) 4555 (1971),
DHR Barton et al., J. Chem. Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, European Patent 126,712 and the like which generate an acid by light can also be used.

Among the compounds which can be used in combination and generate an acid upon irradiation with actinic rays or radiation, those which are particularly effectively used are shown below.

[0096]

[Chemical 25]

A positive photoresist composition is suitable for the purpose of improving the alkali solubility of the system and for controlling the glass transition temperature of the system to prevent the film from becoming brittle and the heat resistance from deteriorating. You may add a suitable alkali-soluble low molecular weight compound. As the alkali-soluble low molecular compounds, dialkyl sulfonamide compounds and dialkyl sulfonyl Louis bromide (-SO ₂ -NH-CO-) compounds, dialkyl Soo imide (-SO ₂ -NH
Examples thereof include compounds having an acidic group in the molecule such as —SO ₂ —) compounds. The content of the alkali-soluble low molecular weight compound is 4 with respect to the binder resin.
It is preferably 0% by weight or less, more preferably 30% by weight or less, and further preferably 25% by weight or less.

The positive-working photosensitive composition of the present invention may further contain an acid-decomposable dissolution inhibiting compound, a dye, a plasticizer, a surfactant, a photosensitizer, an organic basic compound, and a developing solution, if necessary. A compound or the like that promotes solubility can be contained.

The photosensitive composition of the present invention is dissolved in a solvent that dissolves each of the above components and coated on 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-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in a mixture.

Among the above solvents, the preferred solvent is 2-
Heptanone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate , N-methylpyrrolidone, and tetrahydrofuran.

A surfactant 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 alkyl allyl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, Sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as rate, F-top EF301, E 303, EF352 (manufactured by Shin Akita Kasei Co., Ltd.), Megafac F171, F173 (manufactured by Dainippon Ink Co., Ltd.), Flora - de FC430, FC43
1 (manufactured by Sumitomo 3M Limited), Asahi Guard AG71
0, Surflon S-382, SC101, SC102,
Fluorine-based surfactants such as SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), acrylic acid-based or methacrylic acid-based (co) polymerization polyflow No. 75, No. 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.

Such a positive photoresist composition of the present invention is coated on a substrate to form a thin film. The thickness of this coating film is preferably 0.4 to 1.5 μm. Spinning the photosensitive composition onto a substrate (eg, silicon / silicon dioxide coating) as used in the manufacture of precision integrated circuit devices,
A good resist pattern can be obtained by applying an appropriate coating method such as a coater, exposing through a predetermined mask, baking and developing. Here, the exposure light is far ultraviolet rays having a wavelength of preferably 250 nm or less, more preferably 220 nm or less. Specifically, a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F ₂ excimer laser (157 nm), an X-ray, an electron beam and the like can be mentioned, and an ArF excimer laser (193 nm) is particularly preferable.

The developing solution for the photosensitive composition of the present invention includes:
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Inorganic alkalis such as sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, and tertiary amines such as triethylamine and methyldiethylamine. Use alkaline aqueous solutions such as triamines, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and pyrelidine. be able to. Furthermore, alcohols and surfactants may be added in appropriate amounts to the alkaline aqueous solution before use.

[0104]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to the following examples. Synthesis Example 1 (Synthesis of Photoacid Generator [I-3]) 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 added dropwise over 2 hours while cooling in an ice bath. The reaction solution was stirred as it was for 2 hours and then stirred at room temperature overnight to complete the reaction. After completion of the reaction, 50 ml of distilled water was added dropwise to the reaction solution while cooling with an ice bath, extraction was performed, the organic layer was washed with water, aqueous sodium hydrogen carbonate and water, the obtained organic layer was concentrated, and di (t-amylphenyl) ) 40 g of iodonium sulfate was obtained. The target product [I-3] was obtained by performing a salt exchange reaction between the obtained sulfate and potassium heptadecafluorooctane sulfonate.

Synthesis Example 2 (Synthesis of Photoacid Generator [I-6]) 90 g of n-octylphenyl ether, 39.5 g of potassium iodate, 81 g of acetic anhydride, 180 of dichloromethane
Mix 6 mL of concentrated sulfuric acid while cooling with an ice bath.
Was added dropwise over 2 hours. The reaction solution was stirred as it was for 2 hours and then stirred at room temperature overnight to complete the reaction. After completion of the reaction, 50 mL of distilled water was added dropwise to the reaction solution while cooling with an ice bath, extraction was performed, the organic layer was washed with water, aqueous sodium hydrogen carbonate and water, and the obtained organic layer was concentrated to give di (n-octyloxy). 45 g of phenyl) iodonium sulfate was obtained. The target sulfate [I-6] was obtained by performing a salt exchange reaction between the obtained sulfate and potassium heptadecafluorooctane sulfonate.

Synthetic Example 3 (Synthesis of Photoacid Generator [I-9]) The salt exchange of the di (t-amylphenyl) iodonium sulfate obtained in Synthetic Example (1) with sodium pentafluorobenzene sulfonate is carried out. Is the target compound [I-9]
Was synthesized.

Synthesis Example 4 (Synthesis of Photoacid Generator [I-5]) To 40 g of iodobenzene, 91 g of peracetic acid was slowly added dropwise, and the reaction solution was stirred at 30 ° C. for 2 hours. When a white powder was projected, it was cooled with ice and the precipitate was collected by filtration to collect 38 g of iodosobenzene diacetate. Thus obtained, 50 g of iodosobenzene diacetate, 30 g of octylphenyl ether, 70 g of acetic anhydride and 725 mL of glacial acetic acid were mixed, and concentrated sulfuric acid 8 while cooling in an ice bath.
g was added dropwise over 1 hour. After 1 hour, an aqueous solution in which 31 g of NaBr was dissolved in 150 mL was added dropwise, and 42 g of an iodonium bromide salt, which is a white powder deposited, was recovered. The obtained iodonium bromide salt and trifluoromethanesulfonate are subjected to salt exchange to obtain the desired product [I-5].
Got

Synthesis Example 5 (Synthesis of Photoacid Generator [II-3]) 50 g of diphenyl sulfoxide was added to 800 m of mesitylene.
It was dissolved in L, 200 g of aluminum chloride was added thereto, and this was stirred at 80 ° C. for 24 hours. After the reaction was completed, the reaction solution was slowly poured into 2 L of ice. 400 mL of concentrated hydrochloric acid was added here, and it heated at 70 degreeC for 10 minutes. The reaction solution was cooled to room temperature, washed with ethyl acetate, and filtered. A solution prepared by dissolving 200 g of ammonium iodide in 400 mL of distilled water was added to the filtrate. The precipitated powder is collected by filtration, washed with water, washed with ethyl acetate and dried to give sulfonium iodide 72
g was obtained. 50 g of the obtained sulfonium iodide was dissolved in 300 mL of methanol, 31 g of silver oxide was added thereto, and the mixture was stirred for 4 hours. After the reaction solution was filtered, it was salt-exchanged with heptadecafluorooctane sulfonic acid potassium salt to recover 40 g of the desired product [II-3].

Synthesis Example 6 (Synthesis of Photoacid Generator [II-2]) Using octylbenzene instead of mesitylene of Synthesis Example (5), the corresponding sulfonium iodide was synthesized and then synthesized. [II-2] was synthesized in the same manner as in Synthesis Example (5) by salt exchange with potassium trifluoromethanesulfonate in the same manner as in Example (5).

Synthetic Example 7 (Photoacid generator [II-8]) After synthesizing the corresponding sulfonium iodide by using octyloxybenzene instead of mesitylene of Synthetic Example (5), a synthetic example ( The target compound [II-8] was obtained by salt exchange with nonafluorobutane sulfonic acid potassium salt in the same manner as in 5).

Synthesis Example 8 (Synthesis of Photoacid Generator [II-14]) 50 g of diphenyl sulfoxide and 45 g of 2,6-xylenol were mixed with methanesulfonic acid / phosphorus pentoxide (10 /
1) 100 mL of the solution was added. After the fever subsides, 5
Heated at 0 ° C. for 4 hours. After the reaction was completed, the reaction solution was poured into ice. After this aqueous solution was washed with toluene and filtered, an aqueous solution prepared by dissolving 200 g of ammonium iodide in 400 mL of distilled water was added, and the precipitated powder was collected by filtration. The filter cake obtained was washed with water and dried to obtain sulfonium iodide. 50 g of the obtained sulfonium iodide was added to 300 m of methanol.
It was dissolved in L, 31 g of silver oxide was added thereto, and the mixture was stirred for 4 hours. The reaction solution was filtered and then salt-exchanged with heptadecafluorooctane sulfonic acid potassium salt to recover 43 g of the desired product, [II-14].

Synthesis Example 9 (Synthesis of Resin A) Resin A was synthesized by the synthesis method described in Example 7 of JP-A-9-73173, page (27). That is, 2-methyladamantyl methacrylate methacrylate and 3-oxocyclohexyl methacrylate methacrylate were charged into a polymerization vessel at a ratio of 4: 6 to prepare a 2 mol / L toluene solution. A polymerization initiator, AIBN, was added to this toluene solution in an amount of 5 mol%, and polymerization was carried out at 80 ° C. for about 8 hours. After completion of the polymerization, methanol was used as a precipitant for purification. 2-methyladamantylmethacrylate represented by the following formula /
A 3-oxocyclohexyl methacrylate copolymer was obtained. The resulting copolymer has a composition ratio (m: n) of 4
It had a weight average molecular weight (Mw) of 15,000 at 9:51 and a dispersity (Mw / Mn) of 2.4. Resin A

[0113]

[Chemical formula 26]

Synthesis Example 10 (Synthesis of Resin B) Resin B was synthesized by the synthesis method described in JP-A 9-90637, page 18, page 13. That is, a methacrylic acid (±) -mevalonic lactone ester / 2-methyl-2-adamantyl methacrylate copolymer was synthesized. 4.96 g in a well-dried 100 ml eggplant-shaped flask containing a Teflon ^™ coated star rubber.
(25 mmol) methacrylic acid (±) -mevalonic lactone ester, 5.87 g (25 mmol) 2-methyl-2-adamantyl methacrylate, 16.7 ml dioxane and 1.23 g (9 mmol) azo. Bisisobutyronitrile (AIBN) was added, and the mixture was stirred at 80 ° C. for 8 hours under a nitrogen atmosphere. The reaction solution was diluted with tetrahydrofuran (THF) and then added dropwise to 1 liter of methanol containing a small amount of hydroquinone. The precipitate formed is filtered off with a glass filter, and it is 1 at 0.1 mmHg and 45 ° C.
It was dried for 6 hours. The obtained white powder was dissolved again in THF, and the same precipitation-drying operation as described above was repeated twice to obtain the desired white copolymer powder. Yield =
7.44 g (68.7%). The copolymerization ratio of the obtained copolymer was lactone: adamantyl = 46.5: 53.5, the weight average molecular weight was 14000 (converted to standard polystyrene), and the dispersity was 2.0.

Synthetic Examples 11 to 14 (Synthesis of Resins C to F) By the same method as in Synthetic Example 9 or 10, resins containing the following monomers in the following molar ratios were synthesized. Resin C: Copolymer of the monomer example 5 and mevalonic lactone methacrylate (molar ratio 50/50) (weight average molecular weight: 13500) Resin D: of the monomer example 11 and 3-oxocyclohexyl methacrylate and acrylic acid Copolymer (molar ratio 50/40/10) (weight average molecular weight: 13000) Resin E: Copolymer of the monomer example 15 and mevalonic lactone methacrylate (molar ratio 50/50) (weight average molecular weight: 14000) ) Resin F: copolymer of the above-mentioned monomer example 33 and mevalonic lactone methacrylate (molar ratio 50/50) (weight average molecular weight: 14500)

[Example] As shown in Table 1, 10 g of each resin synthesized in the above synthesis example and 0.3 g of each photo-acid generator were added to a solid content of 1 g.
0.1% after being dissolved in 2-heptanone (mixing 2-hydroxypropionic acid as needed) at a ratio of 4% by weight.
A positive photoresist composition solution was prepared by filtration with a μm microfilter. [Comparative Examples 1 and 2] Instead of the photoacid generator of the above Examples,
A positive photoresist composition solution was prepared in the same manner as in the above example except that triphenylsulfonium hexafluoroantimonate (B1) or triphenylsulfonium trifluoromethanesulfonate (B2) was used.

(Evaluation Test) The obtained positive photoresist composition solution was applied onto a silicon wafer using a spin coater and dried at 130 ° C. for 60 seconds, about 0.5 μm.
Of the positive type photoresist film was prepared and exposed to the ArF excimer laser (193 nm). A heat treatment after exposure was performed at 130 ° C. for 60 seconds, development was performed with a 2.38% tetramethylammonium hydroxide aqueous solution, and rinsing was performed with distilled water to obtain a resist pattern profile.

[Stability of Composition Solution with Time]: The prepared positive photoresist composition solution (coating solution) was allowed to stand at 4 ° C. for 1 week, and then the number of particles was counted by a particle counter manufactured by Rion. [Sensitivity]: It was defined as the minimum exposure amount (mJ / cm ² ) for reproducing a 0.35 μm mask pattern. The evaluation results are shown in Table 1.

[0119]

[Table 1]

As is clear from the results shown in Table 1, the positive photoresist compositions for deep-UV exposure using the resin and the photo-acid generator according to the present invention gave satisfactory results, respectively. The positive photoresist composition of No. 1 was unsatisfactory in the stability over time and the sensitivity of the composition solution.

[0121]

INDUSTRIAL APPLICABILITY As described above, the positive photoresist composition of the present invention is particularly suitable for light in the wavelength region of 170 nm to 220 nm, has high sensitivity and high resolution, and has a composition. It is possible to improve the temporal stability of the product solution, and it has extremely high practicality.

Continuation of the front page (56) Reference JP-A-10-254136 (JP, A) JP-A-10-97060 (JP, A) JP-A-8-29987 (JP, A) JP-A-7-333834 (JP , A) JP 6-199770 (JP, A) JP 4-219757 (JP, A) JP 9-73173 (JP, A) JP 9-90637 (JP, A) JP 10-161313 (JP, A) JP 10-274852 (JP, A) JP 2000-47387 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F ^7/ 00- 7/42

Claims (3)

(57) [Claims] 1. A compound represented by the following general formula (I) which generates sulfonic acid upon irradiation with actinic rays or radiation,
And an alkali-soluble group protected by at least one of the alicyclic hydrocarbon-containing partial structures represented by the following general formulas (pI) to (pVI), which is decomposed by the action of an acid and has a solubility in an alkali. Increasing resin (However, the following general
The monomer represented by the formula (Q) is used as a structural unit of a repeating unit.
A positive photoresist composition for deep-UV exposure. [Chemical 1] In formula (I), R ₁ and R ₂ are each a hydrogen atom, an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or a substituent. Alkoxy group, alkoxycarbonyl group which may have a substituent, acyl group which may have a substituent, acyloxy group which may have a substituent, nitro group, halogen atom, hydroxyl group or carboxyl group Represents a: 1 to 5, b: 1 to 5, However, at least one of R ₁ and R ₂ has an alkyl group having 5 or more carbon atoms, which may have a substituent, a cycloalkyl group which may have a substituent, and a substituent. Represents an optionally substituted alkoxy group, an optionally substituted alkoxycarbonyl group, an optionally substituted acyl group or an optionally substituted acyloxy group. _{X: R-SO 3, R} : represents an optionally have may have a substituent aliphatic hydrocarbon group or a substituted aromatic hydrocarbon group. [Chemical 2] In the formula, R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z together with a carbon atom forms an alicyclic hydrocarbon group. Represents the atomic groups required to do so. R ₁₂ to R ₁₆ each independently of 1 to 4 carbon atoms, represents a linear or branched alkyl group or alicyclic hydrocarbon group, provided _that at least one of R 12 _{to R 14,} or Either R ₁₅ or R ₁₆ represents an alicyclic hydrocarbon group. R _{17 to} R ₂₁ are each independently a hydrogen atom or a carbon number of 1 to
It represents four linear or branched alkyl groups or alicyclic hydrocarbon groups, provided that at least one of R _{17 to} R ₂₁ represents an alicyclic hydrocarbon group. In addition, R ₁₉ , R ₂₁
Represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group. R ₂₂ , R ₂₃ and R ₂₅ are each independently a hydrogen atom,
Represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, and R ₂₄ represents 1 to 4 carbon atoms;
It represents a linear or branched alkyl group or an alicyclic hydrocarbon group, provided that at least one of R _{22 to} R ₂₅ represents an alicyclic hydrocarbon group. [Chemical 3] In formula (Q), R101 represents a hydrogen atom or a methyl group,
R102 to R104 may be the same or different and each is a hydrogen atom.
Or represents an alkyl group. R105 and R106 are
May be the same or different, hydrogen atom, alkyl group or halo
A gen atom is represented, and X1 is a halogen atom. A is
Single bond, alkylene group, substituted alkylene group, ether
Group, ester group, thioether group, carbonyl group, amine
Group, sulfonamide group, urethane group and urea group.
One group selected from the group consisting of or two or more of them
Represents a group combining the above. m1 is 1, 2 or 3, n1
Represents 0, 1 or 2, and the sum of m1 and n1 represents 3. 2. A compound represented by the following general formula (II), which generates sulfonic acid upon irradiation with actinic rays or radiation, and an alicyclic hydrocarbon represented by the following general formulas (pI) to (pVI). A resin containing an alkali-soluble group protected by at least one of the partial structures containing, and being decomposed by the action of an acid to increase the solubility in alkali (provided that
The monomer represented by the general formula (Q) has a repeating unit structure unit
( Except when contained as a position) (however, 4-
Methylphenyldiphenylsulfonium trifluoromethanesulfonate and a resin containing 2-methyl-2-adamantyl methacrylate as a monomer component at the same time are not included), which is a positive photoresist composition for deep UV exposure. [Chemical 4] In formula (II), R _{3 to} R ₅ are each an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, and an alkoxy group which may have a substituent. An alkoxycarbonyl group which may have a substituent, an acyl group which may have a substituent, an acyloxy group which may have a substituent, a nitro group, a halogen atom,
Represents a hydroxyl group or a carboxyl group. 1: 1-5, m: 0-5, and n: 0-5. When l + m + n = 1, R ₃ has an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. It represents an optionally substituted alkoxycarbonyl group, an optionally substituted acyl group or an optionally substituted acyloxy group. _{X: R-SO 3, R} : represents an optionally have may have a substituent aliphatic hydrocarbon group or a substituted aromatic hydrocarbon group. [Chemical 5] In the formula, R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z together with a carbon atom forms an alicyclic hydrocarbon group. Represents the atomic groups required to do so. R ₁₂ to R ₁₆ each independently of 1 to 4 carbon atoms, represents a linear or branched alkyl group or alicyclic hydrocarbon group, provided _that at least one of R 12 _{to R 14,} or Either R ₁₅ or R ₁₆ represents an alicyclic hydrocarbon group. R _{17 to} R ₂₁ are each independently a hydrogen atom or a carbon number of 1 to
It represents four linear or branched alkyl groups or alicyclic hydrocarbon groups, provided that at least one of R _{17 to} R ₂₁ represents an alicyclic hydrocarbon group. In addition, R ₁₉ , R ₂₁
Represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group. R ₂₂ , R ₂₃ and R ₂₅ are each independently a hydrogen atom,
Represents a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group, and R ₂₄ represents 1 to 4 carbon atoms;
It represents a linear or branched alkyl group or an alicyclic hydrocarbon group, provided that at least one of R _{22 to} R ₂₅ represents an alicyclic hydrocarbon group. [Chemical 6] In formula (Q), R101 represents a hydrogen atom or a methyl group,
R102 to R104 may be the same or different and each is a hydrogen atom.
Or represents an alkyl group. R105 and R106 are
May be the same or different, hydrogen atom, alkyl group or halo
A gen atom is represented, and X1 is a halogen atom. A is
Single bond, alkylene group, substituted alkylene group, ether
Group, ester group, thioether group, carbonyl group, amine
Group, sulfonamide group, urethane group and urea group.
One group selected from the group consisting of or two or more of them
Represents a group combining the above. m1 is 1, 2 or 3, n1
Represents 0, 1 or 2, and the sum of m1 and n1 represents 3. 3. The positive photo exposure for deep UV exposure according to claim 1, wherein the resin contains a group represented by the following general formula (A), which is decomposed by the action of an acid. Resist composition. General formula (A) -C (= O) -O-R _{0 In} formula (A), R ₀ is a tertiary alkyl group, a 1-alkoxyethyl group, an alkoxymethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, Trialkylsilyl group,
It represents a 3-oxocyclohexyl group or a lactone group.