JPH11167199A - Positive photoresist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive photoresist composition having solved problems on troubles during the elapse of time after exposure until heat treatment and enhanced in sensitivity and resolution and capable of obtaining a superior resist pattern free of cracking of the resist pattern. SOLUTION: This composition comprises a resin having groups increasing solubility in an alkaline developing solution by decomposition due to action of an acid and a mixture of a photo-acid-generator (B-1) high in effect of lowering dissolution speed in an alkaline developing solution and a photo-acid- generator (B-2) small in effect of lowering the dissolution speed of an exposed part as compared with (B-1).

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 the process of manufacturing semiconductors such as lithographic printing plates and ICs, the manufacture of circuit boards such as liquid crystals and thermal heads, and other photofabrication processes. It is about.

[0002]

2. Description of the Related Art As one of positive photoresist compositions, there is a chemically amplified resist composition described in U.S. Pat. No. 4,491,628 and EP 249,139. The chemically amplified positive resist composition generates an acid in the exposed area by irradiation with radiation such as deep ultraviolet light, and the reaction using the acid as a catalyst dissolves the active radiation irradiated area and the non-irradiated area in the developing solution. This is a pattern forming material that changes the properties and forms a pattern on a substrate.

Examples of such a combination include a combination of a compound capable of generating an acid by photolysis with an acetal or an O, N-acetal compound (JP-A-48-90003), a combination of an orthoester or an amide acetal compound ( JP-A-5120714), a combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-1)
No. 33429), a combination with an enol ether compound (JP-A-55-12995), a combination with an N-acyliminocarbonate compound (JP-A-55-126236), a combination with a polymer having an orthoester group in the main chain. (JP-A-56-17345), a combination with a tertiary alkyl ester compound (JP-A-60-3625), and a combination with a silyl ester compound (JP-A-60-10247).
No.) and a combination with a silyl ether compound (Japanese Unexamined Patent Publication No.
0-37549, JP-A-60-112446) and the like. These have high photosensitivity because the quantum yield exceeds 1 in principle.

Similarly, systems which are stable under aging at room temperature, but are decomposed by heating in the presence of an acid and solubilized in alkali are disclosed in, for example, JP-A-59-45439, JP-A-60-3625, JP-A-62-2229242, JP-A-63-27829, JP-A-63-36240, JP-A-63-250642, Polym.Eng.Sce., Volume 23, 10
12 (1983); ACS.Sym. 242, 11 (1984); Semico
nductor World, 1987, November, p. 91; Macromolecule
s, Volume 21, p. 1475 (1988); SPIE, Volume 920, p. 42 (1988)
A compound that generates an acid upon exposure described in, for example,
Combination systems with esters or carbonate compounds of tertiary or secondary carbons (eg t-butyl, 2-cyclohexenyl). These systems also have high sensitivity and have a deep-U compared to the naphthoquinonediazide / novolak resin system.
Since the absorption in the V region is small, it can be an effective system for shortening the wavelength of the light source.

The above-mentioned positive chemically amplified resist comprises three components comprising an alkali-soluble resin, a compound capable of generating an acid upon exposure to radiation (photoacid generator), and a compound inhibiting dissolution of the alkali-soluble resin having an acid-decomposable group. It can be roughly classified into a two-component system comprising a resin having a group which is decomposed by the reaction with an acid and becomes alkali-soluble and a photoacid generator. In these two-component or three-component positive chemically amplified resists, a resist pattern is obtained by heat treatment and development with an acid from a photoacid generator being exposed by exposure. Here, as the photoacid generator used in the positive type chemically amplified resist as described above, N-imidosulfonate, N-oxime sulfonate, o-nitrobenzylsulfonate, trismethanesulfonate of pyrogallol, and the like are known. Japanese Patent Laid-Open Publication No.
No. 439, U.S. Pat. Nos. 4,173,476 and 4,1.
97, 174, Polym. Eng. Sci., 23 , 1012 (198
3)., J. Polym. Sci., Polym. Chem. Ed., 18 , 2677, 2
697 (1980) and 22, 1789 (1984), etc., sulfonium and iodonium PF ₆ ⁻ , AsF ₆ ⁻ , SbF
₆ ^- perfluoro Lewis acid salts such as have been used. However, when used for a resist material for semiconductors, there is a problem of contamination of phosphorus, arsenic, antimony and the like from a counter anion of the photoacid generator.

[0006] Therefore, these contamination-free sulfonium,
As an iodonium compound, JP-A-63-27829
JP-A-2-25850, JP-A-2-150848
JP-A-5-134414, JP-A-5-23270
A salt having a trifluoromethanesulfonic acid anion as a counter anion described in No. 5, etc. is used. However, in the case of this compound, since the diffusivity of trifluoromethanesulfonic acid generated by exposure in the resist film is large, the resist pattern is thinned over time until the heat treatment after the exposure, or the shape of the resist pattern surface is T-shaped. (T-to
There was a problem of exhibiting p). Further, as another counter anion of sulfonium and iodonium, use of a toluenesulfonic acid anion is disclosed in JP-A-2-25850 and JP-A-2-1850.
50848, JP-A-5-5993, JP-A-6-43
No. 653, JP-A-6-123972, etc., but the solubility in a commonly used resist solvent is not sufficient, and the amount of addition is limited, resulting in a problem in sensitivity. . From the viewpoint of improving the solvent solubility, sulfonium and iodonium salts of benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having one linear alkyl group or one alkoxy group are described in JP-A-6-199770. Have been. However, even in this case, the diffusivity of the generated acid in the resist film is not sufficiently reduced, and there has been a problem that the resist pattern becomes thinner with time until the heat treatment after exposure.

On the other hand, the combination of two kinds of photoacid generators can prevent the deterioration of the resist profile mainly with the lapse of time until the heat treatment after the exposure, as disclosed in Japanese Patent Application Laid-Open No. 5-1.
No. 81279, JP-A-5-323590 and JP-A-6-130666.

For example, in JP-A-5-181279, a compound (photoacid generator) which generates a strong acid (specifically, for example, sulfonic acid) upon exposure and a weak acid (specifically, for example, carboxylic acid) upon exposure It is described that it is possible to suppress the insolubilization of the resist surface over time until the heat treatment after exposure, that is, the formation of T-top, by combining a compound that generates the following.

JP-A-5-323590 discloses a compound (photoacid generator) that changes the solubility of a resist film after exposure to a developer, that is, contributes to image formation.
And compounds that do not contribute to image formation, increase the absolute amount of acid generated after exposure, relatively reduce the amount of acid consumed for impurities in the open air on the resist surface layer, It is described that it is possible to suppress the insolubilization of the resist surface over time until the heat treatment, that is, suppress the formation of T-top and obtain a resolving power. JP-A-6-1
Japanese Patent Publication No. 30666 also describes that a combination of a strong acid and a weak acid can also suppress a change in resist performance over time until a heat treatment after exposure. However, when any of the combinations was used, sufficient resolution was not obtained, and it was insufficient from the viewpoint of thinning of the resist pattern over time until the heat treatment after exposure, and satisfactory results were not obtained.

[0010]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art. More specifically, the problem of aging after exposure to heat treatment is solved, and sensitivity and resolution are improved. An object of the present invention is to provide a positive photoresist composition which is high and can obtain an excellent resist pattern without falling of the resist pattern.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies while paying attention to the above characteristics, and as a result, the object of the present invention is to use two types of the following specific photoacid generators in a positive-type chemical amplification system. Have been found to be achieved. That is, the present invention has the following configuration. (1) (A) a resin having a group which is decomposed by the action of an acid to increase the solubility in an alkali developer, and (B)
In a positive photoresist composition containing a compound that generates an acid upon irradiation with actinic rays or radiation (photoacid generator), the photoacid generator (B) has a large effect of slowing down the dissolution rate of an exposed portion. (B-1) A positive-type photo-curable composition comprising a mixture of (B-1) and a photoacid generator (B-2) having a small effect of lowering the dissolution rate of an exposed portion as compared with (B-1). Resist composition.

(2) The positive photoresist composition as described in (1) above, wherein the photoacid generator (B-1) satisfies the following conditions. A composition comprising the resin (A) and the photoacid generator (B-1) (the addition amount of the photoacid generator (B-1) in the composition is 0.001 per 10 g of the total solids).
Mol) is exposed to KrF excimer laser (exposure amount Eth × 10) and then dissolved in an alkaline developer (2.38 wt% aqueous solution of tetramethylammonium hydroxide). ₂ is in the range of 0.01 × S ₁ ≦ S ₂ ≦ 0.5 × S ₁ . Here, S ₁ is the dissolution rate in an alkali developing solution (2.38 wt% aqueous solution of tetramethylammonium hydroxide) of the resin alone in which all of the acid-decomposable groups contained in the resin (A) are deprotected. Represents

(3) The positive photoresist according to the above (1) or (2), wherein the photoacid generator (B-1) is a compound represented by the following general formula (I). Composition.

[0014]

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In the formula, R _{1 to} R ₃ may be the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group,
Alkoxy group, hydroxy group, halogen atom or -S-
R ₄ represents a group. R ₄ represents an alkyl group or an aryl group. X ^- is a group having at least one group selected from the group consisting of an alkyl group or an alkoxy group having 8 or more carbon atoms, or a group selected from the group consisting of an alkyl group or an alkoxy group having 4 to 7 carbon atoms. Or an anion of benzenesulfonic acid, naphthalenesulfonic acid, or anthracenesulfonic acid having at least two or having at least three groups selected from the group consisting of an alkyl group or an alkoxy group having 1 to 3 carbon atoms. l, m and n may be the same or different, and represent an integer of 1 to 3. When l, m and n are each 2 or 3, two of R _{2 to} R ₃ are bonded to each other to form 5 to 8 carbon atoms, hetero rings or aromatic rings. May be formed.

(4) The positive photoresist composition as described in any of (1) to (3) above, wherein the photoacid generator (B-2) satisfies the following conditions. A composition comprising the resin (A) and the photoacid generator (B-2) (the addition amount of the photoacid generator (B-2) in the composition is 0.0
(0.1 mol) is exposed to KrF excimer laser (exposure amount Eth × 10) and then dissolved in an alkaline developer (2.38 wt% aqueous solution of tetramethylammonium hydroxide). S ₃
Is in the range of 0.5 × S ₁ <S ₃ . Here, S ₁ is the dissolution rate in an alkali developing solution (2.38 wt% aqueous solution of tetramethylammonium hydroxide) of the resin alone in which all of the acid-decomposable groups contained in the resin (A) are deprotected. Represents

(5) It has a group decomposable by an acid, and its solubility in an alkali developer is increased by the action of an acid.
The positive photoresist composition according to any one of the above (1) to (4), further comprising a low-molecular acid-decomposable dissolution inhibiting compound having a molecular weight of 3000 or less. (6) The positive photoresist composition as described in any of (1) to (6) above, which contains a resin that is insoluble in water and soluble in an aqueous alkaline solution. (7) A mixture of the photoacid generator (B-1) and the photoacid generator (B-2) according to the above (1), which generates an acid upon irradiation with actinic rays or radiation, a group decomposable by an acid. Characterized by containing a low molecular weight acid-decomposable dissolution inhibiting compound having a molecular weight of 3,000 or less, and a resin insoluble in water and soluble in an aqueous alkali solution, the solubility of which is increased by the action of an acid in an alkaline developer. Positive photoresist composition.

By using the positive photoresist composition of the present invention, in a chemically amplified resist, the problem with time from exposure to heat treatment can be brilliantly solved, and the photosensitivity and the resolution are high. An excellent resist pattern was obtained without falling down.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The photoacid generator (compound that generates an acid upon irradiation with actinic rays or radiation) used in the present invention is a photoacid generator (B-1) having a large effect of slowing down the dissolution rate of an exposed portion in an alkali developer, The effect of the photoacid generator (B-
The feature is that a photoacid generator (B-2) smaller than 1) is used in combination. [I-1] Photoacid Generator (B-1) The photoacid generator (B-1) has a large effect of reducing the dissolution rate of an exposed portion in an alkali developing solution, and specifically satisfies the following conditions. Is preferred.

The resin (A) and the photoacid generator (B-1)
(Film thickness 1.0 μm) of a composition consisting of the following (a photoacid generator (B-1) in the composition was added in an amount of 0.001 mol per 10 g of total solids) by KrF excimer laser exposure (Exposure amount Eth × 10) Alkaline developer (2.
The alkali dissolution rate S _{2 in a} 38% by weight aqueous solution of tetramethylammonium hydroxide) is in the range of 0.01 × S ₁ ≦ S ₂ ≦ 0.5 × S ₁ . Here, S ₁ is the dissolution rate in an alkali developing solution (2.38 wt% aqueous solution of tetramethylammonium hydroxide) of the resin alone in which all of the acid-decomposable groups contained in the resin (A) are deprotected. Represents The exposure amount Eth means the minimum exposure amount (Threshold sensitivity) required to resolve a large-area pattern (positive image).

Here, the dissolution rate in an alkaline developer can be measured using a DRM device manufactured by PERKIN ELMER.

Here, if 0.01 × S ₁ > S ₂ ,
The sensitivity and the resolving power are reduced, and the resist surface pattern exhibits a T-Top shape with the passage of time from the exposure to the heat treatment. on the other hand,
If S ₂ > 0.5 × S ₁ , the shape of the resist pattern becomes tapered, and the line width of the resist pattern becomes narrower with the passage of time from the exposure to the heat treatment.
S ₂ is preferably 0.05 × S ₁ ≦ S ₂ ≦ 0.5 × S ₁
And more preferably 0.07 × S ₁ ≦ S ₂ ≦
0.4 × S ₁ .

As the photoacid generator (B-1) satisfying the above conditions, specifically, a photoacid generator represented by the above general formula (I) is preferable. In the general formula (I), the alkyl group of R _{1 to} R ₄ may be a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl which may have a substituent. 1 carbon such as a group
To four. Examples of the cycloalkyl group include those having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group which may have a substituent. Examples of the alkoxy group include a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a t-butoxy group which may have a substituent. To four. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the aryl group include those having 6 to 14 carbon atoms which may have a substituent such as a phenyl group, a tolyl group, a methoxyphenyl group and a naphthyl group.

The further substituent is preferably an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom or an iodine atom), an aryl group having 6 to 10 carbon atoms, or a 2 to 6 carbon atoms. Alkenyl group, cyano group, hydroxy group, carboxy group, alkoxycarbonyl group, nitro group and the like. Sulfonium compound represented by the general formula (I) used in the present invention has a counter anion, X ^- as a linear, branched or cyclic carbon atoms 8
At least one or more, preferably at least one or more alkyl or alkoxy groups, or at least two or more linear, branched or cyclic C 4-7 alkyl or alkoxy groups. Or an anion of benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having at least three linear or branched alkyl or alkoxy groups having 1 to 3 carbon atoms. This reduces the diffusivity of the acid (benzenesulfonic acid, naphthalenesulfonic acid, or anthracenesulfonic acid having the above group) generated after exposure, and improves the solvent solubility of the sulfonium compound. In particular, from the viewpoint of reducing the diffusivity, a branched or cyclic alkyl group or alkoxy group is more preferable as the above group than a linear alkyl group or alkoxy group. The above group is 1
In this case, the difference in diffusibility between the linear and branched or cyclic forms becomes more remarkable.

C8 or more, preferably C8 to C2
Examples of the zero alkyl group include a linear, branched, or cyclic octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, and an octadecyl group. As the alkoxy group having 8 or more carbon atoms, preferably 8 to 20 carbon atoms, a linear, branched or cyclic octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group, tridecyl An oxy group, a tetradecyloxy group, an octadecyloxy group and the like can be mentioned. Examples of the alkyl group having 4 to 7 carbon atoms include a linear, branched, or cyclic butyl group, a pentyl group, a hexyl group, and a heptyl group. Examples of the alkoxy group having 4 to 7 carbon atoms include a linear, branched, or cyclic butoxy group, a pentyloxy group, a hexyloxy group, and a heptyloxy group. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, n
-A propoxy group and an isopropoxy group.

Further, X ^- in the aromatic sulfonic acid represented by, in addition to the above specific substituent, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), C6-10
It may contain as substituents aryl groups, cyano groups, sulfide groups, hydroxy groups, carboxy groups, nitro groups and the like. Further, when l, m, and n are each 2 or 3, two of two or three R _{1 to} R ₄ are bonded to each other to form a 5- to 5-carbon-containing heterocyclic or aromatic ring. A ring composed of eight elements may be formed.

The content of the photoacid generator (B-1) (preferably the compound represented by the general formula (I)) in the composition is 0.1 to 20% by weight based on the solid content of the whole composition. Is appropriate,
Preferably from 0.5 to 10% by weight, more preferably from 1 to 7%.
% By weight. Hereinafter, specific examples of the compound represented by Formula (I) are shown, but the invention is not limited thereto.

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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In the specific examples, n is a straight chain, s is a secondary, t is
Represents tertiary and i represents branching. The compound represented by the general formula (I) includes, for example, a corresponding Cl ⁻ salt (a compound in which X ⁻ is substituted with Cl ⁻ in the general formula (I)) and X ⁻ Y ⁺
(X ⁻ has the same meaning as in formula (I), and Y ⁺ is H ⁺ , Na ⁺ , K ⁺ , NH ₄ ⁺ , N (CH ₃ ))
₄ ^+, etc. show the cation of. ) Can be synthesized by salt exchange in an aqueous solution.

[I-2] Photoacid Generator (B-2) The photoacid generator (B-2) has an effect of lowering the dissolution rate of the exposed portion than the photoacid generator (B-1). It is preferably small and specifically satisfies the following conditions. A composition comprising the resin (A) and the photoacid generator (B-2) (the amount of the compound (B-2) in the composition is 0.1% in 10 g of the total solid content).
001 mol) (with a film thickness of 1.0 μm).
Alkali dissolution rate S in alkali developer (2.38 wt% aqueous solution of tetramethylammonium hydroxide) after excimer laser exposure (exposure amount Eth × 10)
₃ is in the range of 0.5 × S ₁ <S ₃ . Here, S ₁ is the dissolution rate in an alkali developing solution (2.38 wt% aqueous solution of tetramethylammonium hydroxide) of the resin alone in which all of the acid-decomposable groups contained in the resin (A) are deprotected. Represents Here, the dissolution rate in an alkali developer can be measured by the same method as described above. S ₃ is preferably in the range of 0.6 × S ₁ ≦ S ₃ , and more preferably 0.7 × S ₁ ≦ S ₃ . Specific examples of the compound (B-2) satisfying the above conditions include the following general formulas [II] to
The compound represented by [V] is preferable. General formula (II)

[0036]

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In the formula, C ₁ (carbon atom) and C ₂ (carbon atom) are linked by a single bond or a double bond, and R ₉ or R ₁₀ may be the same or different. (4)
(1) each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group (2) a monocyclic or polycyclic ring which may contain one or more hetero atoms (3) C ₁ and C form a fused aromatic ring containing _2, residues comprising (4) N-sulfonyloxy imide, R ₁₁
Represents an alkyl group, a halogenated alkyl group, a cyclic alkyl group, an alkenyl group, an aryl group which may have a substituent, an aralkyl group which may have a substituent, or a camphor group. General formulas (III) and (IV)

[0038]

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In the formula, R _{12 to} R ₁₆ may be the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group, a halogen atom, -SR _20.
Group (R ₂₀ represents an alkyl group or an aryl group), R ₁₇
To R ₁₉ may be the same or different, and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, —COOR
₂₁ groups (R ₂₁ represents an alkyl group or an alkenyl group), —O
COR ₂₂ group (R ₂₂ represents an alkyl group or an alkenyl group), provided that at least one of R _{17 to} R ₁₉ is an alkyl group, a cycloalkyl group, a —COOR ₂₁ group, a —OCOR ₂₂
When two of R _{17 to} R ₁₉ are a hydrogen atom, the remaining one is an alkyl group having 6 or more carbon atoms, a cycloalkyl group having 5 or more carbon atoms,
Or more alkenyl groups, R ₂₁ is an alkyl group having 5 or more carbon atoms, -COOR ₂₁ group which is an alkenyl group, and R ₂₂ is an alkyl group having 5 or more carbon atoms, -OCO which is an alkenyl group.
It represents an R ₂₂ group. General formula [V]

[0040]

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In the formula, R ₃₀ and R ₃₁ each independently represent a substituted or unsubstituted aryl group.

Photoacid Generator Represented by General Formula [II] In the general formula [II], R ₉ and R ₁₀ are (1)
In the case of the above, examples of the alkyl group include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group. Can be As the cycloalkyl group, a cyclopropyl group, a cyclopentyl group,
Those having 3 to 8 carbon atoms such as a cyclohexyl group and a cyclooctyl group are exemplified. Examples of the aryl group include those having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, a mesityl group, and a naphthyl group. R
_{If 9} and R ₁₀ strikes the case (2), it may be mentioned, for example, following such partial structures.

[0043]

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When R ₉ and R ₁₀ correspond to the case (3), for example, the following partial structures can be mentioned.

[0045]

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R₉ And R_TenCorresponds to case (4)
If so, at least two N-sulfonylos
The xyimide residue has the above partial structure (1) to (3)
R ₉ Or R_TenIs a single bond or as shown below
And those bonded by a suitable divalent organic group.
However, the following linking groups may be used alone or in combination of two or more.
used. [Divalent organic group]: -O-, -S-, -SO-, -SO
_Two -, -NH-, -CO-, -CO_Two -, -NHSO_Two 
-, -NHCO-, -NHCO_Two −,

[0047]

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(Wherein R ₁₅ and R ₁₆ each represent a hydrogen atom or a methyl group) In the general formula [II], the alkyl group of R ₁₁ is a linear or branched alkyl group having 1 to 20 carbon atoms. Groups. It is preferably a straight-chain or branched alkyl group having 1 to 16 carbon atoms, and more preferably one having 1 to 12 carbon atoms. An alkyl group having 21 or more carbon atoms is not preferred because sensitivity and resolution are reduced. Examples of the halogenated alkyl group include those in which one or two or more hydrogen atoms of the above alkyl group are halogenated. Examples of the halogen atom to be substituted include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Preferred are a fluorine atom, a chlorine atom and a bromine atom, and particularly preferred is a fluorine atom. However, a plurality of types of halogen atoms may be substituted per molecule. Examples of the cyclic alkyl group include a cycloalkyl group having 3 to 12 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group, and a polycyclic substituent such as a norbornyl group, an adamantyl group, and a tricyclodecanyl group. I can give it. Examples of the alkenyl group include a linear or branched alkenyl group having 1 to 20 carbon atoms. Preferably 1 to 1 carbon atoms
It is a straight-chain or branched alkenyl group having 6 carbon atoms, more preferably 1 to 12 carbon atoms. 21 carbon atoms
The use of more than two alkenyl groups is not preferred because the sensitivity and resolution are reduced.

The aryl group for R ₁₁ includes a phenyl group and a naphthyl group, and the aralkyl group includes a benzyl group. Examples of the substituent of the aryl group and the aralkyl group include a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a tert-butyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; a phenyl group; a toluyl group; Xylyl group,
Aryl group such as mesityl group, methoxy group, ethoxy group,
Lower alkoxy groups such as propoxy group, isopropoxy group, sec-butoxy group and tert-butoxy group, alkenyl groups such as vinyl group, allyl group, propenyl group and butenyl group, acyl groups such as formyl group and acetyl group, and hydroxy group And a carboxy group, a cyano group, a nitro group, a fluorine atom, a chlorine atom, a bromine atom and a halogen atom such as an iodine atom. Preferably, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a cyclohexyl group, a phenyl group,
Toluyl group, methoxy group, ethoxy group, propoxy group,
Lower alkoxy groups such as isopropoxy group, sec-butoxy group, tert-butoxy group, cyano group, nitro group,
It is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The substituents on the aryl group and the aralkyl group may be two or more types.

Specific examples of the compound represented by the general formula [II] are shown below, but it should not be construed that the invention is limited thereto.

[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057] Formula (III) or photoacid generator the general formula represented by (IV) in [III] or [IV], R ₁₂ ~
Examples of the alkyl group for R ₁₆ include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-butyl group. As the cycloalkyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group,
Those having 3 to 8 carbon atoms such as a cyclooctyl group are exemplified. Examples of the alkoxy group include an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The alkyl group of R ₂₀ groups -S-R _20, a methyl group, an ethyl group, a propyl group, an isopropyl group, n-
Examples thereof include an alkyl group having 1 to 4 carbon atoms such as a butyl group, a sec-butyl group and a tert-butyl group. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a mesityl group and a naphthyl group. Those having 6 to 14 carbon atoms can be mentioned.

R₁₇~ R₁₉As the alkyl group of
1 to 20 linear or branched alkyl groups
Can be. R₁₇~ R₁₉When two of them are hydrogen atoms (for example,
R ₁₇Is an alkyl group, and R₁₈, R₁₉Is a field of hydrogen atoms
), And the remaining one alkyl group has 6 or more carbon atoms.
Above, preferably a straight or branched chain having 6 to 20 carbon atoms.
Alkyl group, more preferably a straight chain having 6 to 16 carbon atoms
Or a branched alkyl group.
6 carbon atoms from the viewpoint of thinning of the resist pattern
Preferred is １６16 branched alkyl groups. No more than 5 carbon atoms
With sufficient solubility in normal resist solvents
When the number of carbon atoms is 21 or more, the sensitivity and the resolving power decrease. R
₁₇~ R₁₉When only one of them is a hydrogen atom or
Is not a hydrogen atom (for example, R₁₇Is a hydrogen atom,
R₁₈, R₁₉Is an alkyl group or R₁₇~ R₁₉Is everything
Alkyl group), R₁₇~ R₁₉Two or three of
Is an alkyl group represented by a straight chain having 1 to 16 carbon atoms.
Or a branched alkyl group, more preferably a carbon atom.
A linear or branched alkyl group of 1 to 14 is preferred
No. It is particularly advantageous in terms of sensitivity because it has 1 to 12 carbon atoms.
Linear or branched alkyl groups are preferred. 17 carbon atoms
If the number is more than one, the sensitivity and the resolving power decrease.

As the cycloalkyl group of R _{17 to} R ₁₉ ,
Those having 3 to 20 carbon atoms can be mentioned. However,
When two of R _{17 to} R ₁₉ are hydrogen atoms (for example, when R ₁₇ is a cycloalkyl group and R ₁₈ and R ₁₉ are hydrogen atoms), the remaining one represented cycloalkyl group has 5 or more carbon atoms, and is preferably Is a cycloalkyl group having 5 to 20 carbon atoms, more preferably a cycloalkyl group having 5 to 16 carbon atoms. If the number of carbon atoms is 4 or less, sufficient solubility in a normal resist solvent cannot be obtained, and if the number of carbon atoms is 21 or more, sensitivity and resolution deteriorate. When only one of R _{17 to} R ₁₉ is a hydrogen atom or when none of them is a hydrogen atom (for example, when R ₁₇ is a hydrogen atom and R ₁₈ and R ₁₉ are cycloalkyl groups, or when R _{17 to} R ₁₉ As a cycloalkyl group represented by two or three of R _{17 to} R ₁₉ , a cycloalkyl group having 3 to 16 carbon atoms is preferable, and a cycloalkyl group having 3 to 14 carbon atoms is more preferable. Is a cycloalkyl group. Particularly, a cycloalkyl group having 3 to 12 carbon atoms is preferable because it is advantageous in terms of sensitivity.
When the number of carbon atoms is 17 or more, the sensitivity and the resolution are reduced.

R₁₇~ R₁₉As the alkenyl group of
A straight-chain or branched alkenyl group of 2 to 20
be able to. R₁₇~ R₁₉When two of them are hydrogen atoms
(Eg R₁₇Is an alkenyl group;₁₈, R₁₉Is hydrogen
Atom), the remaining one alkenyl group includes carbon
A straight-chain or a straight-chain having 6 or more, preferably 6 to 20 carbon atoms
Is a branched alkenyl group, and more preferably has 6 to 6 carbon atoms.
It is 16 linear or branched alkenyl groups. Carbon number
Sufficient solubility in ordinary resist solvents for less than 5
Is not obtained, and sensitivity and resolution decrease when the number of carbon atoms is 21 or more.
I do. R₁₇~ R₁₉When only one of them is a hydrogen atom
Are not hydrogen atoms (for example, R₁₇Is a hydrogen atom
And R₁₈, R₁₉Is an alkenyl group or R₁₇~ R ₁₉
Is an alkenyl group), R₁₇~ R₁₉Two of
Alternatively, the alkenyl group represented by three has 2 to 2 carbon atoms.
Sixteen straight or branched alkenyl groups are preferred;
Preferably a linear or branched alkyl having 2 to 14 carbon atoms
It is a phenyl group. Particularly advantageous in terms of sensitivity, carbon number
2-12 straight or branched alkenyl groups are preferred
No. When the number of carbon atoms is 17 or more, the sensitivity and the resolution are reduced.

The —COOR ₂₁ group of R _{17 to} R ₁₉ and —OC
The alkyl group of R ₂₁ and R ₂₂ of the OR ₂₂ group has 1 carbon atom.
And up to 20 linear or branched alkyl groups. When two of R _{17 to} R ₁₉ are hydrogen atoms (for example, when R ₁₇ is a —COOR ₂₁ group and R ₁₈ and R ₁₉ are hydrogen atoms), the remaining one alkyl group of R ₂₁ or R ₂₂ is A straight-chain or branched alkyl group having 5 or more carbon atoms, preferably 6 to 20 carbon atoms, and more preferably a straight-chain or branched alkyl group having 6 to 16 carbon atoms. If the number of carbon atoms is 4 or less, sufficient solubility in a normal resist solvent cannot be obtained, and if the number of carbon atoms is 21 or more, sensitivity and resolution deteriorate. Is one but if none or when the hydrogen atom is not a hydrogen atom (e.g., R ₁₇ is a hydrogen atom of R ₁₇ to R _19, when R _18, R ₁₉ is -COOR ₂₁ group or R ₁₇
To R ₁₉ are all —COOR ₂₁ groups), and two or three R ₂₁ or R ₂₂ alkyl groups among R _{17 to} R ₁₉ are linear or branched alkyl groups having 1 to 16 carbon atoms. And more preferably a linear or branched alkyl group having 1 to 14 carbon atoms. Particularly, a linear or branched alkyl group having 1 to 12 carbon atoms is preferable because it is advantageous in terms of sensitivity. When the number of carbon atoms is 17 or more, the sensitivity and the resolution are reduced.

The —COOR ₂₁ group of R _{17 to} R ₁₉ and —OC
Examples of the alkenyl group of R ₂₁ and R _{22 in} the OR ₂₂ group include a linear or branched alkenyl group having 2 to 20 carbon atoms. When two of R _{17 to} R ₁₉ are hydrogen atoms (for example, when R ₁₇ is a —COOR ₂₁ group and R ₁₈ and R ₁₉ are hydrogen atoms), the remaining one alkenyl group of R ₂₁ and R ₂₂ is A straight-chain or branched alkenyl group having 5 or more carbon atoms, preferably 6 to 20 carbon atoms, and more preferably a straight-chain or branched alkenyl group having 6 to 16 carbon atoms. If the number of carbon atoms is 4 or less, sufficient solubility in a normal resist solvent cannot be obtained.
The resolution decreases. When one of R _{17 to} R ₁₉ is a hydrogen atom or when none of them is a hydrogen atom (for example, when R ₁₇ is a hydrogen atom and R ₁₈ and R ₁₉ are —COOR ₂₁ groups, or all of R _{17 to} R ₁₉ Is -COOR ₂₁ ), R _{17 to} R _17
As the alkenyl group for two or three of R ₂₁ and R ₂₂ among ₁₉ , a linear or branched alkenyl group having 2 to 16 carbon atoms is preferable, and a linear or branched alkenyl group having 2 to 14 carbon atoms is more preferable. Is preferred. Particularly, a linear or branched alkenyl group having 2 to 12 carbon atoms is preferable because it is advantageous in terms of sensitivity. When the number of carbon atoms is 17 or more, the sensitivity and the resolution are reduced.

Preferred substituents for R _{17 to} R ₁₉ are those having one substituent (the others being hydrogen atoms) having 6 to 16 carbon atoms.
-COO, wherein R ₂₁ is a linear or branched alkyl group or alkenyl group having 6 to 16 carbon atoms.
R ₂₁ is a straight or branched alkyl group having 1 to 12 carbon atoms when the number of substituents is 2 or 3, and R ₂₁ is a straight or branched alkyl group having 1 to 12 carbon atoms. A COOR ₂₁ group, wherein R ₂₂ is a —OCOR ₂₂ group, which is a linear or branched alkyl group having 1 to 12 carbon atoms.

Specific examples of the compound represented by the general formula [III] or [IV] are shown below, but the invention is not limited thereto.

[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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The photoacid generator represented by the general formula [V] In the general formula [V], R ₃₀ and R ₃₁ each independently represent a substituted or unsubstituted aryl group. Examples of the aryl group include those having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, a mesityl group, and a naphthyl group. Examples of the substituent include a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a tert-butyl group, a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a phenyl group, a toluyl group, a xylyl group,
Aryl group such as mesityl group, methoxy group, ethoxy group,
Lower alkoxy groups such as propoxy group, isopropoxy group, sec-butoxy group and tert-butoxy group, alkenyl groups such as vinyl group, allyl group, propenyl group and butenyl group, acyl groups such as formyl group and acetyl group, and hydroxy group And a carboxy group, a cyano group, a nitro group, a fluorine atom, a chlorine atom, a bromine atom and a halogen atom such as an iodine atom. Specific examples of the compound represented by the general formula [V] are shown below, but it should not be construed that the invention is limited thereto.

[0073]

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[0074]

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The content of the photoacid generator (B-2) (preferably the photoacid generator represented by the general formulas [II] to [V]) in the composition is 0.05 to 0.05% in the total solid content. 20% by weight is suitable, preferably 0.1 to 10% by weight, more preferably 0.2 to 7% by weight. Photoacid generator (B-1) [preferably a photoacid generator represented by the general formula [I]] or photoacid generator (B-2) [preferably represented by the general formulas [II] to [V] Are used alone or in combination of two or more.

In the present invention, the photoacid generator (B-
Use ratio (weight ratio) of 1) and the photoacid generator (B-2)
((B-1) / (B-2)) is preferably 1/99 to 99/1, more preferably 5/95 to 95/5,
Particularly preferably, it is 10/90 to 90/10. The content of all the photoacid generators in the composition of the present invention is preferably from 0.05 to 20% by weight, more preferably from 0.1 to 10% by weight, based on the total solids.

[II] Decomposed by the action of an acid,
Resin having a group that increases solubility in a developer Used in the chemically amplified resist in the present invention
Decomposed by acid to increase solubility in alkaline developer
As the resin having a group to be added, the main chain or side chain of the resin,
Alternatively, an acid-decomposable group is added to both the main chain and the side chain.
Resin. Of these, groups decomposable by acid are added to the side chain.
Is more preferable. Good as an acid-decomposable group
A preferred group is -COOA⁰, -OB⁰Group, and
Groups containing these include -R⁰-COOA⁰, Or-
A_r-OB⁰The group shown by these is mentioned. Where A⁰
Is -C (R⁰¹) (R⁰²) (R⁰³), -Si (R⁰¹)
(R⁰²) (R ⁰³) Or -C (R⁰⁴) (R⁰⁵) -O-
R⁰⁶Represents a group. B⁰Is -A⁰Or -CO-OA⁰Base
(R⁰, R⁰¹~ R⁰⁶, And Ar are the same as those described below.
Righteousness).

The acid-decomposable group is preferably a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, a tetrahydropyranyl ester group, an enol ether group, an enol ester group,
And a tertiary alkyl ester group and a tertiary alkyl carbonate group. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, an acetal group, and a tetrahydropyranyl ether group.

Next, the groups decomposable by these acids form side chains.
When the base resin is bonded with --OH in the side chain,
Or -COOH, preferably -R⁰-COOH or
-A _rIt is an alkali-soluble resin having an -OH group. An example
For example, the alkali-soluble resin described below can be mentioned.
You.

In addition, the dissolution rate S ₁ is determined by determining whether or not all of the acid-decomposable groups contained in the acid-decomposable group-containing resin have been deprotected, ie, the resin containing only alkali-soluble groups not protected by the acid-decomposable groups ( This represents the dissolution rate of the above base resin) alone in an alkali developing solution (2.38 wt% aqueous solution of tetramethylammonium hydroxide). The method for measuring the dissolution rate of a resin containing only an alkali-soluble group that is not protected by an acid-decomposable group can be performed by the same method as described above.

The alkali dissolution rate S ₁ of these alkali-soluble resins was measured at 2.38% by weight of tetramethylammonium hydroxide (TMAH) (23 ° C.).
Å / sec or more is preferred. Particularly preferably 330 °
/ Sec or more.

From the viewpoint of achieving a rectangular profile, an alkali-soluble resin having a high transmittance to far ultraviolet light or excimer laser light is preferable. Preferably, the transmittance at a wavelength of 248 nm with a thickness of 1 μm is 20 to 90%. From such a viewpoint, a particularly preferred alkali-soluble resin is o
-, M-, p-poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen- or alkyl-substituted poly (hydroxystyrene), part of poly (hydroxystyrene), O-alkylation Or an O-acylated product, a styrene-hydroxystyrene copolymer, an α-methylstyrene-hydroxystyrene copolymer and a hydrogenated novolak resin.

The resin having an acid-decomposable group used in the present invention is disclosed in EP 254853, JP-A No. 2-25
No. 850, No. 3-223860, No. 4-251259
As disclosed in US Pat. No. 6,086,098, 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 copolymerized with various monomers. Can be obtained.

Specific examples of the resin having a group decomposable by an acid used in the present invention are shown below, but the present invention is not limited thereto.

[0085]

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[0086]

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[0087]

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[0088]

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The content of the acid-decomposable group is determined by the number of acid-decomposable groups in the resin (B) and the number of alkali-soluble groups not protected by the acid-decomposable group (S). B /
It is represented by (B + S). The content is preferably 0.01 to
0.5, more preferably 0.05 to 0.40, and still more preferably 0.05 to 0.30. B / (B + S)>
A value of 0.5 is not preferred 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 standing waves may be remarkably left on the pattern side wall.

The weight average molecular weight (Mw) of the resin having an acid-decomposable group is preferably in the range of 2,000 to 200,000. If the molecular weight is less than 2,000, the film loss is large due to the development of the unexposed portion. If the molecular weight exceeds 200,000, the dissolution rate of the alkali-soluble resin itself in alkali becomes slow and the sensitivity is lowered. More preferably, 5,
The range is from 000 to 100,000, and more preferably from 8,000 to 50,000. Further, the degree of dispersion (Mw / Mn) is preferably 1.0 to 4.0, more preferably 1.0 to 2.0, and particularly preferably 1.0 to 1.0.
6, the smaller the degree of dispersion, the better the heat resistance and image forming properties (pattern profile, defocus latitude, etc.). Here, the weight average molecular weight is defined as a polystyrene equivalent value of gel permeation chromatography.

In the present invention, two or more resins having a group decomposable with an acid may be used in combination. The amount of these resins used in the present invention is 40 to 99% by weight, preferably 60 to 95% by weight, based on the total weight of the photosensitive composition (excluding the solvent). Further, in order to adjust the alkali solubility, an alkali-soluble resin having no acid-decomposable group may be mixed.

It is preferable to mix an acid-decomposable low-molecular-weight dissolution inhibiting compound described later together with the photoacid generator and the resin having an acid-decomposable group. In this case, the content of the dissolution inhibiting compound is 3 based on the total weight of the composition (excluding the solvent).
-45% by weight, preferably 5-30% by weight, more preferably 10-20% by weight.

[III] Alkali-soluble resin used in the present invention In the present invention, it is preferable to use a resin that is insoluble in water and soluble in an aqueous alkali solution (hereinafter, also referred to as an alkali-soluble resin). As the alkali-soluble resin used in the present invention, for example, a novolak resin, a hydrogenated novolak resin,
Acetone-pyrogallol resin, o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene, hydrogenated polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o / p-
And m / p-hydroxystyrene copolymer, partially O-alkylated product relative to hydroxyl group of polyhydroxystyrene (for example, 5 to 30 mol% of O-methylated product, O- (1
-Methoxy) ethylated product, O- (1-ethoxy) ethylated product, O-2-tetrahydropyranylated product, O- (t-
Butoxycarbonyl) methylated product) or O-acylated product (for example, 5 to 30 mol% o-acetylated product,
O- (t-butoxy) carbonyl compound, etc.), styrene-
Maleic anhydride copolymer, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, carboxyl group-containing methacrylic resin and derivatives thereof, but are not limited thereto. . Particularly preferred alkali-soluble resins are novolak resins and o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrene, partial O-alkylation of polyhydroxystyrene, Or an O-acylated product, a styrene-hydroxystyrene copolymer, or an α-methylstyrene-hydroxystyrene copolymer. The novolak resin is obtained by subjecting a given monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

As the predetermined monomer, phenol, m
Cresols such as -cresol, p-cresol and o-cresol, xylenols such as 2,5-xylenol, 3,5-xylenol, 3,4-xylenol and 2,3-xylenol, m-ethylphenol, p- Alkylphenols such as ethylphenol, o-ethylphenol, pt-butylphenol, p-octylphenol, 2,3,5-trimethylphenol, p-methoxyphenol, m-methoxyphenol, 3,5-dimethoxyphenol, Alkoxyphenols such as -methoxy-4-methylphenol, m-ethoxyphenol, p-ethoxyphenol, m-propoxyphenol, p-propoxyphenol, m-butoxyphenol and p-butoxyphenol, 2-methyl-4-isopropyl Fenault Bis-alkylphenols etc., m
Hydroxychloro compounds such as -chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, and naphthol can be used alone or as a mixture of two or more, but are not limited thereto. It is not something to be done.

The aldehydes include, for example, formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-
Phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o -Methylbenzaldehyde, m-methylbenzaldehyde,
p-Methylbenzaldehyde, p-ethylbenzaldehyde, pn-butylbenzaldehyde, furfural, chloroacetaldehyde, and their acetal compounds, such as chloroacetaldehyde diethyl acetal, among which formaldehyde is used Is preferred. These aldehydes are used alone or in combination of two or more. As the acidic catalyst, hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid and the like can be used.

The weight-average molecular weight of the novolak resin thus obtained is preferably in the range of 1,000 to 30,000. If it is less than 1,000, the film loss of the unexposed portion after development is large, and if it exceeds 30,000, the developing speed is reduced. Particularly preferred are 2,000-20,
000. In addition, the weight average molecular weight of the polyhydroxystyrene other than the novolak resin, its derivative, and the copolymer is 2,000 or more, preferably 5,000.
~ 200,000, more preferably 10,000-1000
00. Further, from the viewpoint of improving the heat resistance of the resist film, 25,000 or more is preferable. here,
The weight average molecular weight is defined as a value in terms of polystyrene by gel permeation chromatography. In the present invention, these alkali-soluble resins may be used as a mixture of two or more kinds. The amount of alkali-soluble resin used is
4 based on the total weight of the photosensitive composition (excluding the solvent)
It is 0 to 97% by weight, preferably 60 to 90% by weight.

[IV] Low-molecular acid-decomposable dissolution inhibiting compound used in the present invention In the present invention, it is preferable to use a low-molecular acid-decomposable dissolution-inhibiting compound. The acid-decomposable dissolution inhibiting compound used in the present invention has at least two acid-decomposable groups in its structure, and at the position where the distance between the acid-decomposable groups is farthest away, the acid-decomposable group Is a compound having at least 8 bonding atoms excluding. In the present invention, the acid-decomposable dissolution-inhibiting compound preferably has at least two groups capable of being decomposed by an acid in its structure, and at the position where the distance between the acid-decomposable groups is farthest away, the acid-decomposable group A compound having at least 10, preferably at least 11, and more preferably at least 12 bonding atoms excluding the above, or a position where the distance between the acid-decomposable groups is the longest, having at least three acid-decomposable groups Is a compound having at least 9, preferably at least 10, and more preferably at least 11 bonding atoms excluding an acid-decomposable group. or,
The preferred upper limit of the number of the bonding atoms is 50, more preferably 30. In the present invention, when the acid-decomposable dissolution-inhibiting compound has three or more, preferably four or more acid-decomposable groups, and even when the compound has two acid-decomposable groups, the acid-decomposable groups are mutually present. If they are separated by a certain distance or more, the dissolution inhibiting property with respect to the alkali-soluble resin is significantly improved. Incidentally, the distance between the acid-decomposable groups in the present invention,
It is indicated by the number of via bond atoms excluding the acid-decomposable group. For example, in the case of the following compounds (1) and (2), the distance between the acid-decomposable groups is 4 bonding atoms, and in the compound (3), the bonding atom is 12 bonding atoms.

[0098]

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Further, the acid-decomposable dissolution-inhibiting compound of the present invention may have a plurality of acid-decomposable groups on one benzene ring, but preferably one compound on one benzene ring. It is a compound composed of a skeleton having an acid-decomposable group. Further, the molecular weight of the acid-decomposable dissolution-inhibiting compound of the present invention is 3,000 or less, preferably 500 to 3,000.
0, more preferably 1,000 to 2,500.

In a preferred embodiment of the present invention, an acid
A group which can be decomposed by, ie, -COO-A⁰, -OB⁰
As a group containing a group, -R⁰-COO-A⁰Or -A
r-OB⁰The group shown by these is mentioned. Where A
⁰Is -C (R⁰¹) (R⁰²) (R⁰³), -Si (R⁰¹)
(R⁰²) (R ⁰³) Or -C (R⁰⁴) (R⁰⁵) -O-
R⁰⁶Represents a group. B⁰Is A⁰Or -CO-OA⁰Base
Show. R⁰¹, R⁰², R⁰³, R⁰⁴And R⁰⁵Are the same
May be different from each other, and may include a hydrogen atom, an alkyl group,
Represents a chloroalkyl, alkenyl, or aryl group
Then R⁰⁶Represents an alkyl group or an aryl group. However
Then R⁰¹~ R⁰³At least two are groups other than hydrogen atoms
And R⁰¹~ R⁰³, And R⁰⁴~ R⁰⁶Two of
The groups may combine to form a ring. R⁰Has a substituent
Divalent or higher aliphatic or aromatic hydrocarbons
Represents a group, -Ar- has a monocyclic or polycyclic substituent
And a divalent or higher aromatic group which may be present.

Here, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group and a t-butyl group. Preferred are those having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group, and alkenyl groups having 2 to 2 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group. Preferably, the aryl group has 6 to 1 carbon atoms such as phenyl, xylyl, toluyl, cumenyl, naphthyl and anthracenyl.
Four are preferred. Further, as a substituent, a hydroxyl group,
Halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, the above alkyl group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, s
an alkoxy group such as an ec-butoxy group and a t-butoxy group,
Alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, aralkyl groups such as benzyl group, phenethyl group and cumyl group, aralkyloxy groups, acyl groups such as formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group, and valeryl group. Group, an acyloxy group such as a butyryloxy group, the above alkenyl group, a vinyloxy group.
Examples thereof include an alkenyloxy group such as a propenyloxy group, an allyloxy group, and a butenyloxy group, an aryloxy group such as the above-described aryl group and phenoxy group, and an aryloxycarbonyl group such as a benzoyloxy group.

The group decomposable by an acid 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 group. Alkyl ester groups, tertiary alkyl carbonate groups and the like. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group, and a tetrahydropyranyl ether group.

The acid-decomposable dissolution-inhibiting compound is preferably a compound described in JP-A-1-289946 and JP-A-1-2899.
No. 47, JP-A-2-2560, JP-A-3-12895
9, JP-A-3-158855, JP-A-3-1793
No. 53, JP-A-3-191351, JP-A-3-200
No. 251, JP-A-3-200252, JP-A-3-20
0253, JP-A-3-200254, JP-A-3-2
0255, JP-A-3-259149, JP-A-3-259
279958, JP-A-3-279959, JP-A-4
JP-A-1650, JP-A-4-1651, JP-A-4-11
No. 260, JP-A-4-12356, JP-A-4-123
No. 57, Japanese Patent Application No. 3-33229, Japanese Patent Application No. 3-2307
No. 90, Japanese Patent Application No. 3-320438, Japanese Patent Application No. 4-251
No. 57, Japanese Patent Application No. 4-52732, Japanese Patent Application No. 4-1032
No. 15, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-107
No. 885, Japanese Patent Application No. 4-107889 and No. 4-1521
Compounds in which some or all of the phenolic OH groups of the polyhydroxy compound described in the specification such as No. 95 are bonded and protected by the above-mentioned groups, -R ⁰ -COO-A ⁰ or B ⁰ groups, included.

More preferably, JP-A-1-289946
JP-A-3-128959, JP-A-3-15885
5, JP-A-3-179353, JP-A-3-2002
No. 51, JP-A-3-200252, JP-A-3-200
255, JP-A-3-259149, JP-A-3-27
9958, JP-A-4-1650, JP-A-4-112
No. 60, JP-A-4-12356, JP-A-4-1235
7, Japanese Patent Application No. 4-25157, Japanese Patent Application No. 4-10321
No. 5, Japanese Patent Application No. 4-104542, Japanese Patent Application No. 4-1078
No. 85, Japanese Patent Application Nos. 4-107889 and 4-15219
No. 5 using the polyhydroxy compound described in the specification.

More specifically, general formulas [I] to [XV]
The compound represented by I] is mentioned.

[0106]

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[0107]

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[0108]

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[0109]

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R ¹⁰¹ , R ¹⁰² , R ¹⁰⁸ , R ¹³⁰ may be the same or different, and represent a hydrogen atom, —R ⁰ —COO—C
( ^R01 ) ( ^R02 ) ( ^R03 ) or -CO-OC ( ^R01 )
^{(R 0 2) (R 03} ), provided that the definition of R ^0, R ^01, R ⁰² and R ⁰³ are as defined above.

R ¹⁰⁰ : -CO-, -COO-, -NHC
ONH-, -NHCOO-, -O-, -S-, -SO
-, -SO _2- , -SO _3- , or

[0112]

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[0113] Here, G = 2 to 6, provided that at least one alkyl group of R ^0.99, R ¹⁵¹ when the ^{G = 2, R 150, R} 151: may be the same or different, a hydrogen atom, an alkyl Group, alkoxy group, -OH, -COOH,
-CN, halogen atom, -R ¹⁵² -COOR ^{15 3} or ^{-R 154 -OH, R 152, R} 154: an alkylene group, R ^153: a hydrogen atom, an alkyl group, an aryl group or an aralkyl group,, R ^99, R ¹⁰³ ~ R ¹⁰⁷ , R ¹⁰⁹ , R ^{111
~R 118, R 121 ~R 123,} R 128 ~R 129, R 131 ~
R ¹³⁴ , R ^{138 to} R ¹⁴¹ and R ¹⁴³ may be the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group; Halogen atom, nitro group, carboxyl group, cyano group, or -N ( ^R155 ) ( ^R156 ) ( ^R155 , ^R156 : H, alkyl group, or aryl group) ^R110 : single bond, alkylene group, or

[0114]

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R ¹⁵⁷ and R ¹⁵⁹ may be the same or different, and represent a single bond, an alkylene group, —O—, —S—, —CO
— Or a carboxyl group, R ¹⁵⁸ : a hydrogen atom, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, a nitro group, a hydroxyl group, a cyano group, or a carboxyl group, provided that the hydroxyl group is an acid-decomposable group (for example, t-butoxycarbonylmethyl group, tetrahydropyranyl group, 1-ethoxy-1-ethyl group,
(1-t-butoxy-1-ethyl group).

R ¹¹⁹ and R ¹²⁰ may be the same or different and each represents a methylene group, a lower alkyl-substituted methylene group, a halomethylene group, or a haloalkyl group, provided that the lower alkyl group means an alkyl group having 1 to 4 carbon atoms. R ^{124 to} R ¹²⁷ may be the same or different and may be a hydrogen atom or an alkyl group; R ^{135 to} R ¹³⁷ may be the same or different and a hydrogen atom;
An alkyl group, an alkoxy group, an acyl group, or an acyloxy group, R ¹⁴² : a hydrogen atom, —R ⁰ —COO—C (R ⁰¹ )
( ^R02 ) ( ^R03 ) or -CO-OC ( ^R01 ) ( ^R02 )
(R ⁰³ ), or

[0117]

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R ¹⁴⁴ and R ¹⁴⁵ may be the same or different and represent a hydrogen atom, a lower alkyl group, a lower haloalkyl group,
Or an aryl group, R ^{146 to} R ¹⁴⁹ : may be the same or different, and may be hydrogen, hydroxyl, halogen, nitro, cyano, carbonyl, alkyl, alkoxy, alkoxycarbonyl, aralkyl, aralkyloxy A group, an acyl group, an acyloxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group, or an aryloxycarbonyl group, provided that the four substituents having the same symbols do not have to be the same group. : —CO— or —SO ₂ —, Z, B: single bond or —O—, A: methylene group, lower alkyl-substituted methylene group, halomethylene group, or haloalkyl group; E: single bond or oxymethylene group , A to z, a1 to y1: when plural, the groups in () may be the same or different; a to q, s, t, v, g1 to i1, k1 m1, o1, q1, s1, u1: 0 or an integer of 1 to 5, r, u, w, x, y, z, a1~f1, p1, r1, t1, v1~x1: 0 or 1
An integer of 4, j1, n1, z1, a2, b2, c2, d2: an integer of 0 or 1 to 3, at least one of z1, a2, c2, d2 is 1 or more, y1: an integer of 3 to 8, (a + b), (e + f + g), (k + l + m), (q + r + s), (w + x + y), (c1 + d1), (g1 +
h1 + i1 + j1), (o1 + p1), (s1 + t1) ≧ 2, (j1 + n1) ≦ 3, (r + u), (w + z), (x + a1), (y + b1), (c1 + e1), (d1 + f1), (p1 + r1),
(t1 + v1), (x1 + w1) ≦ 4, provided that (w +
z), (x + a1) ≦ 5, (a + c), (b + d), (e + h), (f + i), (g + j), (k + n), (l + o), (m + p), (q
+ t), (s + v), (g1 + k1), (h1 + l1), (i1 + m1), (o1 + q1), (s1 + u1)
≦ 5.

[0119]

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[0120]

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[0121]

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[0122]

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Specific examples of the preferable compound skeleton are shown below.

[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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[0140]

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[0141]

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[0142]

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R in the compounds (1) to (63) represents a hydrogen atom,

[0144]

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Represents the following. However, at least two or three depending on the structure are groups other than hydrogen atoms, and each substituent R
Need not be the same group.

In the present invention, the amount of the dissolution-inhibiting compound added is 3 to 50% by weight based on the total weight of the photosensitive composition (excluding the solvent) when combined with the acid-generating compound and the alkali-soluble resin. Preferably it is in the range of 5 to 40% by weight, more preferably 10 to 35% by weight.

[V] Other Components Used in the Present Invention The photosensitive composition of the present invention may further contain, if necessary, a dye, a pigment, a plasticizer, a surfactant, a photosensitizer, and an organic basic compound. And phenolic O that promotes solubility in developing solutions
A compound having two or more H groups can be contained.

The compound having two or more phenolic OH groups that can be used in the present invention is preferably a phenol compound having a molecular weight of 1,000 or less. Further, it is necessary to have at least two phenolic hydroxyl groups in the molecule. If the number exceeds 10, the effect of improving the development latitude is lost. When the ratio of the phenolic hydroxyl group to the aromatic ring is less than 0.5, the film thickness dependency is large, and the development latitude tends to be narrow. If this ratio exceeds 1.4, the stability of the composition deteriorates, and it becomes difficult to obtain high resolution and good film thickness dependency, which is not preferable.

The preferable addition amount of the phenol compound is 2 to 50% by weight based on the resin, more preferably 5 to 50% by weight.
３０30% by weight. With an addition amount exceeding 50% by weight,
It is not preferable because a new defect that development residue is deteriorated and a pattern is deformed during development is generated.

Such a phenol compound having a molecular weight of 1,000 or less can be prepared by those skilled in the art by referring to the methods described in, for example, JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, and EP 219294. It can be easily synthesized at Specific examples of the phenol compound are shown below, but the compounds that can be used in the present invention are not limited to these.

Resorcin, phloroglucin, 2, 3, 4
-Trihydroxybenzophenone, 2,3,4,4'-
Tetrahydroxybenzophenone, 2,3,4,3 ',
4 ', 5'-hexahydroxybenzophenone, acetone-pyrogallol condensation resin, fluoroglucoside,
4,2 ', 4'-biphenyltetrol, 4,4'-thiobis (1,3-dihydroxy) benzene, 2,2',
4,4'-tetrahydroxydiphenyl ether, 2,
2 ', 4,4'-tetrahydroxydiphenylsulfoxide, 2,2', 4,4'-tetrahydroxydiphenylsulfone, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) Cyclohexane, 4,4- (α-methylbenzylidene) bisphenol, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene,
α, α ', α "-tris (4-hydroxyphenyl)-
1-ethyl-4-isopropylbenzene, 1,2,2-
Tris (hydroxyphenyl) propane, 1,1,2-
Tris (3,5-dimethyl-4-hydroxyphenyl)
Propane, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, 1,2-tetrakis (4-hydroxyphenyl) ethane, 1,1,3-tris (hydroxyphenyl) butane, para [α, α , Α ', α'-tetrakis (4-hydroxyphenyl)]-xylene.

Preferred organic basic compounds that can be used in the present invention are compounds that are more basic than phenol. Among them, a nitrogen-containing basic compound is preferable. Preferred chemical environments include the structures of the following formulas (A) to (E).

[0153]

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Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, and particularly preferred is a ring structure containing a substituted or unsubstituted amino group and a nitrogen atom. 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 indazol,
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 Or, unsubstituted aminomorpholine, substituted or unsubstituted aminoalkylmorpholine and the like can be mentioned. Preferred substituents are an amino group,
An aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group, a hydroxyl group, and a cyano group. As particularly preferred compounds, guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 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,
Examples include, but are not limited to, N-aminomorpholine and N- (2-aminoethyl) morpholine.

These nitrogen-containing basic compounds are used alone or in combination of two or more. The amount of the nitrogen-containing basic compound to be used is generally 0.001-10 parts by weight, preferably 0.01-5 parts by weight, per 100 parts by weight of the photosensitive resin composition (excluding the solvent). If the amount is less than 0.001 part by weight, the effects of the present invention cannot be obtained. On the other hand, if it exceeds 10 parts by weight, the sensitivity tends to decrease and the developability of the unexposed part tends to deteriorate.

Preferred dyes include oil dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green BG, Oil Blue BOS, Oil Blue # 60
3. Oil black BY, oil black BS, oil black T-505 (all manufactured by Orient Chemical Co., Ltd.), crystal violet (CI42555), methyl violet (CI42535), rhodamine B
(CI45170B), malachite green (CI42
000), methylene blue (CI52015) and the like.

Further, a spectral sensitizer as described below is added to sensitize the photosensitive composition of the present invention to a longer wavelength region than far ultraviolet where the photoacid generator used has no absorption. Sensitivity can be given to the i or g line. Suitable spectral sensitizers include, specifically, benzophenone,
p, p'-tetramethyldiaminobenzophenone, p,
p'-tetraethylethylaminobenzophenone, 2-
Chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin, setoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4-nitroaniline,
N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,
9-benzanthrone, dibenzalacetone, 1,2-
Naphthoquinone, 3,3′-carbonyl-bis (5,7-
Dimethoxycarbonylcoumarin) and coronene, but are not limited thereto. Further, these spectral sensitizers can also be used as a light absorbing agent for far ultraviolet light of a light source. In this case, the light absorbing agent exerts the effect of improving the standing wave by reducing the reflected light from the substrate and reducing the influence of multiple reflection in the resist film.

The photosensitive composition of the present invention is dissolved in a solvent capable of dissolving the above-mentioned components, and coated on a support. Examples of the solvent used herein include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, and 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, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

[0159] A surfactant may be added to the above solvents. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol 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 Surfactants such as polyoxyethylene sorbitan fatty acid esters such as acrylates and the like, 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,
Fluorinated surfactants such as SC103, SC104, SC105 and SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and acrylic or methacrylic (co) polymerized polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like. The amount 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 solids in the composition of the present invention. These surfactants may be added alone or in some combination.

The above photosensitive composition is applied on a substrate (eg, silicon / silicon dioxide coating) which is used for the production of precision integrated circuit devices by a suitable application method such as a spinner or a coater, and then passed through a predetermined mask. By exposing, baking and developing, a good resist pattern can be obtained.

Examples of the developer for the photosensitive composition of the present invention include:
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 triethylamine and methyldiethylamine Use alkaline aqueous solutions such as triamines, alcoholamines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and pichelidine. be able to. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution.

[0162]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the contents of the present invention are not limited thereto. [Synthesis Example 1] 4,4'-bis (diphenylsulfonio)
20.9 g of 45% aqueous solution of diphenyl sulfide Cl salt
(0.015 mol) was dissolved in 200 ml of ion-exchanged water. To this solution, a solution of 10.5 g (0.030 mol) of a sodium salt of hard (branched) dodecylbenzenesulfonic acid having the following structure in 400 ml of ion-exchanged water was added at room temperature with stirring. The precipitated viscous solid was separated by decanting, and washed with 1 L of ion-exchanged water. The obtained viscous solid was dissolved in 100 ml of acetone and poured into 500 ml of ion-exchanged water with stirring to cause recrystallization. The precipitate was dried at 50 ° C. under vacuum to obtain 15.9 g of a glassy solid. By NMR measurement, it was confirmed that this solid was the compound (I-4) of the present invention.

[0163]

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[Synthesis Example 2] Instead of 10.5 g (0.030 mol) of sodium dodecylbenzenesulfonate of Synthesis Example 1, 9.3 g (0.030 mol) of sodium salt of branched octyloxybenzenesulfonic acid was used. And others are Synthesis Example 1.
In the same manner as in 13.6 g of a glassy solid was obtained. By NMR measurement, it was confirmed that this solid was the compound (I-8) of the present invention.

Synthesis Example 3 In place of 10.5 g (0.030 mol) of sodium dodecylbenzenesulfonate of Synthesis Example 1, 25.7 g (0.030 mol) of a 40% aqueous solution of sodium dibutylnaphthalenesulfonic acid was used. The other conditions were the same as in Synthesis Example 1 to obtain 15.2 g of a glassy solid. NM
By R measurement, this solid was converted to the compound (I-15) of the present invention.
Was confirmed. Hereinafter, in the same manner as described above, the compound represented by the general formula (I) of the present invention was synthesized.

Synthesis Example (4) Synthesis of Compound [III-1] 45% aqueous solution of triphenylsulfonium Cl salt
Dilute 2 g with 300 mL of distilled water and then commercially available sodium dodecylbenzenesulfonate (soft type)
An aqueous solution in which 4 g was dissolved in 300 mL of distilled water was dropped over 1 hour. Since a viscous white precipitate was obtained, this was washed with distilled water, dissolved in methanol, and then crystallized in distilled water. The obtained solid was dried at 50 ° C. under reduced pressure to obtain 30 g of the target product [III-1] as a white solid.

Synthesis Example (5) Synthesis of Compound [III-9] To a reaction vessel equipped with a stirrer, a cooler, a thermometer, and a dropping device, 15.1 g of commercially available triisopropylbenzenesulfonyl chloride and 250 mL of isopropyl alcohol were added. And uniform. To this homogeneous solution, an aqueous solution in which 4 g of sodium hydroxide was dissolved in 250 mL of distilled water was dropped over 30 minutes. This was heated and stirred at 100 ° C. for 5 hours. The solvent was distilled off from the obtained solution under reduced pressure, and 300 m
L was added. 33.2 g of a 45% aqueous solution of triphenylsulfonium Cl salt was added to the obtained aqueous solution of hydrolysis of triisopropylbenzenesulfonyl chloride in distilled water 30.
The aqueous solution diluted with 0 mL was added dropwise over 30 minutes. Since a viscous white precipitate was obtained, this was washed with distilled water, dissolved in methanol, and then crystallized in distilled water. The obtained solid was dried at 50 ° C. under reduced pressure to obtain 32 g of the target product [III-9] as a white solid.

Synthesis Example (6) Synthesis of Compound [III-26] 45% aqueous solution of triphenylsulfonium Cl salt
2 g was diluted with 300 mL of distilled water, and then an aqueous solution in which 18.9 g of commercially available sodium 4-carboxybenzenesulfonate undecaester was dissolved in 300 mL of distilled water was added dropwise over 1 hour. Since a viscous white precipitate was obtained, this was washed with distilled water, dissolved in methanol, and then crystallized in distilled water. The obtained solid was dried under reduced pressure at 50 ° C. to obtain the target product [III-26] 3 as a white solid.
3 g were obtained.

Synthesis Example (7) Synthesis of Compound [IV-2] Compound [IV-2] was prepared in the same manner as in Synthesis Example (4) except that diphenyliodonium salt was used in place of triphenylsulfonium Cl salt. Was synthesized.

Synthesis Example (8) Synthesis of Compound [II-1] 4 equipped with a reflux condenser, a thermometer, a dropping device, and a stirrer
5 g of N-hydroxyphthalimide and p
5.8 g of toluenesulfonyl chloride, acetone 1
Then, 100 mL of the mixture was stirred, and triethylamine 3.2 was added thereto.
6 g was added dropwise over 30 minutes, and the mixture was stirred at room temperature for 1 hour. The obtained reaction mixture was crystallized in distilled water, and the precipitated powder was collected by filtration. 9.6 g of the target compound [II-1]
I got

Synthesis Example (9) Synthesis of Compound [II-15] 4 equipped with a reflux condenser, a thermometer, a dropping device, and a stirrer
28. N-hydroxyamine (hydrochloride) in a one-necked flask
4 g, 100 mL of distilled water, and sodium hydroxide 1
An aqueous solution in which 5.8 g was dissolved in 50 mL of distilled water was added dropwise over 20 minutes. After completion of the dropwise addition, 50 g of methyl-substituted maleic anhydride was added, and the mixture was stirred at room temperature for 3 hours, and further heated and stirred under reflux conditions for 3 hours. After completion of the reaction, an aqueous solution of hydrochloric acid was added, and the mixture was further saturated with sodium chloride and extracted with ethyl acetate. The obtained ethyl acetate solution was concentrated to obtain crude crystals of an N-hydroxyimide of methyl-substituted maleic anhydride. This was recrystallized from toluene to obtain 32 g of N-hydroxyimide crystals of methyl-substituted maleic anhydride. Next, 5 g of the N-hydroxyimide derivative of the methyl-substituted maleic anhydride obtained above, 7.3 g of p-methoxybenzenesulfonyl chloride, and 100 mL of acetone were charged into the same apparatus and stirred, and 3.76 g of triethylamine was added thereto for 30 minutes. And the mixture was stirred at room temperature for 1 hour. The obtained reaction mixture was crystallized in distilled water, and the precipitated powder was collected by filtration.
10.2 g of the target compound [II-15] was obtained.

Synthesis Example (10) Synthesis of Compound [II-16] The target compound was obtained in the same manner as in Synthesis Example (9) except that 2-mesitylenesulfonyl chloride was used instead of p-methoxybenzenesulfonyl chloride. [II-
16] was synthesized.

[Synthesis Example 1 of Dissolution Inhibitor Compound] 1-
42.4 g (0.10 mol) of [α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene was added to N, N -Dissolved in 300 ml of dimethylacetamide, added with 49.5 g (0.35 mol) of potassium carbonate and 84.8 g (0.33 mol) of cumyl bromoacetate, and then stirred at 120 ° C for 7 hours. The reaction mixture was poured into 2 liters of ion-exchanged water, neutralized with acetic acid, and extracted with ethyl acetate.The ethyl acetate extract was concentrated and subjected to column chromatography (carrier: silica gel, developing solvent: ethyl acetate / The compound was purified by n-hexane = 3/7 (volume ratio).
70 g of (CH ₃ ) O—C ₂ H ₅ group were obtained.

[Synthesis Example 2 of Dissolution Inhibitor Compound] α,
α, α ', α', α ", α" -hexakis (4-hydroxyphenyl) -1,3,5-triethylbenzene 14.3 g
(0.020 mol) of N, N-dimethylacetamide 1
In a 20 ml solution, 21.2 g (0.15 mol) of potassium carbonate and 27.1 g (0.14 mol) of t-butyl bromoacetate were added.
Mol) was added and the mixture was stirred at 120 ° C for 7 hours. Thereafter, the reaction mixture was poured into 1.5 l of water and extracted with ethyl acetate. After drying over magnesium sulfate, the extract was concentrated and purified by column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-hexane = 2/8 (volume ratio)), and as a result, a pale yellow powder was obtained. 24 g were obtained. N
According to MR, this is a compound example (62: R is all TBE)
Group). Hereinafter, other dissolution inhibiting compounds were synthesized in the same manner as described above.

[Preparation and Evaluation of Photosensitive Composition (Resist)] A photosensitive composition (formulation is shown in Table 1 below) using the compound of the present invention, an additive and triphenylimidazole (TPI) shown in the above Synthesis Examples. Described) were prepared.

[0176]

[Table 1]

The abbreviations used in Table 1 represent the following contents. <Polymer> In parentheses, the molar ratio is PHS / EES p-hydroxystyrene / p- (1-ethoxyethoxy) styrene copolymer (70/30) (weight average molecular weight 21,000) PHS / BES p-hydroxystyrene / p- (1-t-butoxyethoxy) styrene copolymer (70/30) (weight average molecular weight 22,000) PHS / TBOMS p-hydroxystyrene / t-butoxycarbonylmethyloxystyrene copolymer (80/20) (weight average) PHS / THPS p-hydroxystyrene / p- (2-tetrahydropyranyloxy) styrene copolymer (70/30) (weight average molecular weight 22,000) PHS / St p-hydroxystyrene / styrene copolymer (85 / 15) (weight average molecular weight 35,000)

<Acid-decomposable group in dissolution inhibitor>

[0179]

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Each of the solids shown in Table 1 was dissolved in 9.5 g of propylene glycol monomethyl ether acetate, and filtered through a 0.2 μm filter to prepare a resist. The resist solution was applied on a silicon wafer using a spin coater, and dried on a vacuum suction type hot plate at 110 ° C. for 90 seconds to obtain a resist film having a thickness of 0.83 μm. 248 nm Kr
Exposure was performed using an F excimer laser stepper (NA = 0.42). Immediately after the exposure, each was heated for 60 seconds on a vacuum adsorption hot plate at 100 ° C., and immediately immersed in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds.
Rinse with water for 2 seconds and dry. The profile of the pattern on the silicon wafer obtained in this way, the sensitivity,
The resolving power was evaluated and compared as follows. The results are shown in Table 2 below.

[Profile] The profile including the standing wave and the pattern collapse is obtained by observing the pattern on the silicon wafer obtained by the above method with a scanning electron microscope (SEM).
In particular, SEM photographs were visually evaluated for standing waves and pattern collapse. When the standing wave was judged to be within the allowable range, it was evaluated as ○, and when it was not acceptable, it was evaluated as ×. On the other hand, when the pattern collapse was observed, it was evaluated as x, and when it was not observed, it was evaluated as o. [Sensitivity] Sensitivity was defined as an exposure amount for reproducing a 0.35 μm mask pattern. [Resolving power] The resolving power was defined as the critical resolving power at the exposure dose for reproducing a 0.35 μm mask pattern. [Line width change by heating immediately after exposure and 2 hours after heating] In the same manner as described above, 2 hours after exposure, the film was heated as described above, and immediately developed with the above developer to obtain 0.35%.
The line width of the μm mask pattern was measured, and the rate of change from the 0.35 μm mask pattern line width when heat treatment was performed immediately after exposure was calculated. When the change rate is less than 10%, 10
% Or more was evaluated as x.

[0182]

[Table 2]

From the results shown in Table 2, the resist of the present invention has high sensitivity and resolving power, the line width narrows over time from exposure to heat treatment, and the residual level of standing waves is within an acceptable range. It can be seen that the photosensitive composition does not collapse the pattern and gives a good profile.

[0184]

EFFECTS OF THE INVENTION The chemically amplified positive photoresist composition of the present invention has excellent sensitivity and resolving power, and does not exhibit a narrow line width or a T-top shape over time from exposure to heat treatment. Further, it is possible to provide a photosensitive composition in which standing waves are suppressed from remaining, and the pattern does not collapse.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kenichiro Sato 4,000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Inside Fujisha Shin Film Co., Ltd.

Claims (7)

[Claims] 1. A resin having a group which decomposes under the action of an acid to increase the solubility in an alkaline developer, and (B) a compound which generates an acid upon irradiation with actinic rays or radiation (photoacid (B) is a photo-acid generator (B-1) having a large effect of slowing down the dissolution rate of the exposed portion;
A positive photoresist composition comprising a mixture of a photoacid generator (B-2) having a small effect of lowering the dissolution rate of an exposed portion as compared to 1). 2. The positive photoresist composition according to claim 1, wherein the photoacid generator (B-1) satisfies the following conditions. A composition comprising the resin (A) and the photoacid generator (B-1) (the photoacid generator (B
An alkali developing solution (2) obtained by exposing a coating film (film thickness: 1.0 μm) of which the addition amount of (-1) is 0.001 mol in 10 g of the total solid content) to KrF excimer laser (exposure amount: Eth × 10). (38% by weight aqueous solution of tetramethylammonium hydroxide), the alkali dissolution rate S ₂ is in the range of 0.01 × S ₁ ≦ S ₂ ≦ 0.5 × S ₁ . Here, S ₁ is the dissolution rate in an alkali developing solution (2.38 wt% aqueous solution of tetramethylammonium hydroxide) of the resin alone in which all of the acid-decomposable groups contained in the resin (A) are deprotected. Represents 3. The positive photoresist composition according to claim 1, wherein the photoacid generator (B-1) is a compound represented by the following general formula (I). Embedded image In the formula, R _{1 to} R ₃ may be the same or different and represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a hydroxy group, a halogen atom, or a —S—R ₄ group. R ₄ represents an alkyl group or an aryl group. X ^- is,
It has at least one group selected from the group of alkyl groups or alkoxy groups having 8 or more carbon atoms, or has 4 to 4 carbon atoms.
It has at least two groups selected from the group consisting of seven alkyl groups or alkoxy groups, or has 1 to 3 carbon atoms.
Benzenesulfonic acid, naphthalenesulfonic acid, or anthracenesulfonic acid anion having at least three groups selected from the group consisting of a plurality of alkyl groups or alkoxy groups. l, m and n may be the same or different;
Shows an integer of 1 to 3. When l, m and n are each 2 or 3, two of R _{2 to} R ₃ are bonded to each other to form 5 to 8 carbon atoms, hetero rings or aromatic rings. May be formed. 4. The positive photoresist composition according to claim 1, wherein the photoacid generator (B-2) satisfies the following condition. A composition comprising the resin (A) and the photoacid generator (B-2) (the photoacid generator (B
An alkali developing solution (2) obtained by exposing a coating film (film thickness: 1.0 μm) of KrF excimer laser exposure (exposure amount: Eth × 10) to a coating film (film thickness: 1.0 μm) of which the amount of addition of (-2) is 0.001 mol in 10 g of the total solid content) (3.38% by weight aqueous solution of tetramethylammonium hydroxide), the alkali dissolution rate S ₃ is in the range of 0.5 × S ₁ <S ₃ . Here, S ₁ is the dissolution rate in an alkali developing solution (2.38 wt% aqueous solution of tetramethylammonium hydroxide) of the resin alone in which all of the acid-decomposable groups contained in the resin (A) are deprotected. Represents 5. A low-molecular-weight acid-decomposable dissolution-inhibiting compound having a molecular weight of 3,000 or less, which has a group decomposable by an acid and whose solubility in an alkali developer is increased by the action of an acid. The positive photoresist composition according to claim 1. 6. The positive photoresist composition according to claim 1, further comprising a resin that is insoluble in water and soluble in an aqueous alkaline solution. 7. A mixture of the photoacid generator (B-1) and the photoacid generator (B-2) according to claim 1, which generates an acid upon irradiation with actinic rays or radiation, which can be decomposed by an acid. A low molecular weight acid-decomposable dissolution inhibiting compound having a molecular weight of 3,000 or less, and a resin which is insoluble in water and soluble in an aqueous alkali solution, having a group, whose solubility in an alkali developer is increased by the action of an acid. Characteristic positive photoresist composition.