JPH09236920A - Positive type photoresist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a chemical amplification type photoresist compsn. having high resolving power and forming a satisfactory resist pattern without causing problems such as the reduction of sensitivity with the lapse of time from exposure and post-exposure baking, the formation of a T-shaped top, the reduction of line width and the undercutting of the pattern. SOLUTION: This compsn. contains a resin whose solubility in an alkali developer is increased by the action of an acid, a compd. generating the acid when irradiated with active light or radiation and a solvent. The resin has at least one of acetal and silyl ether groups, the wt. average mol.wt. of the resin is 4,000-80,000 and the mol.wt. distribution is 1.6-4.0.

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 for manufacturing semiconductor integrated circuit devices, masks for manufacturing integrated circuits, printed wiring boards, liquid crystal panels, and the like.

[0002]

2. Description of the Related Art When a conventional resist comprising a novolak and a naphthoquinonediazide compound is used for lithographic pattern formation using far ultraviolet light or excimer laser light, novolak and naphthoquinonediazide have a strong absorption in the far ultraviolet region. Light hardly reaches the bottom of the resist, and only a low-sensitivity, tapered pattern can be obtained.

One of the means for solving such a problem is as follows.
It is a chemically amplified resist composition described in U.S. Pat. No. 4,491,628 and European Patent No. 249,139. A chemically amplified positive resist composition produces an acid in the exposed area by irradiation with radiation such as far-ultraviolet light, and the acid-catalyzed reaction causes solubility in the developing solution in the irradiated and non-irradiated areas of active radiation. Is a pattern forming material that changes the temperature and forms a pattern on the substrate.

[0004] 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-48-90303), 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-63-250542, Polym.Eng.Sce., Vol. 23, 101
2 (1983); ACS.Sym. 242, 11 (1984); Semicond
uctor World 1987, November, p. 91; Macromolecules, 2
Vol. 1, p. 1475 (1988); SPIE, vol. 920, p. 42 (1988);
Combination systems with esters or carbonate compounds of primary or secondary carbons (eg t-butyl, 2-cyclohexenyl). These systems also have high sensitivity and have a deep-UV compared to the naphthoquinonediazide / novolak resin system.
Since the absorption in the region is small, it can be an effective system for shortening the wavelength of the light source.

The above chemically amplified positive resist composition comprises 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. A three-component system, a two-component system composed of a resin having a group which becomes alkali-soluble by being decomposed by reaction with an acid, and a resin having a group which becomes alkali-soluble by being decomposed by a reaction with an acid; It can be broadly classified into a hybrid system comprising a low molecular weight dissolution inhibiting compound having an acid-decomposable group and a photoacid generator.

For example, WO94 / 01805 contains a compound having a C--O--C or C--O--Si bond which is decomposed by the action of an acid, a photoacid generator, an alkali-soluble resin and a specific amount of an amine or amide compound. The photosensitive composition is
Further, in JP-A-5-232706, a radiation-sensitive resin composition containing an alkali-soluble resin, a radiation-sensitive acid forming agent, and a dissolution control agent for the alkali-soluble resin having an acid-decomposable group, further containing a nitrogen-containing basic compound. However, in JP-A-6-242608, a low molecular weight compound having a tertiary alkyl ester group and having a molecular weight of 3000 or less, which has a solubility in an alkaline aqueous solution increased by the action of an acid, a polyhydroxystyrene resin, and a photoacid generator Positive-working photosensitive compositions containing agents are described. In addition, JP-A-4-19513
In No. 8, a resist material containing a p-tert-butoxy-α-methylstyrene polymer having a molecular weight distribution of 1 to 1.4 as a main component is disclosed in JP-A-4-350657 and JP-A-4-3657.
50658 is a resist material containing a resin having an acid-decomposable group having a molecular weight distribution of 1 to 1.4 as a main component, and JP-A-6-41222 discloses a resin having a molecular weight distribution of 1.01 to 1.50. Each of the resist materials containing the main component is disclosed.

[0008]

However, in the resist using such a composition, the sensitivity decreases with the passage of time between exposure and post-exposure bake (PEB), and there are problems such as T-top formation and line width narrowing. was there. Furthermore,
There is also a problem that biting occurs in the lower part of the obtained pattern (the line width near the substrate of the pattern becomes smaller), and improvement has been desired. As a result of diligent research on these points, the present inventors have at least one group selected from an acetal group and a silyl ether group as a group capable of being decomposed by an acid, and have a solubility in an alkali developing solution of an acid. The weight average molecular weight of the resin increases by the action of
.About.80,000 and the molecular weight distribution is 1.6 to 4.0.
The present invention has been achieved by using the chemically amplified positive resist composition containing a specific resin, which has high resolution and can solve the above problems.

The object of the present invention is to have a high resolution and to reduce sensitivity, T-top formation and line width narrowing due to the passage of time between exposure and post-exposure bake (PEB), and further digging into the lower part of the pattern. An object of the present invention is to provide an excellent chemically amplified positive photoresist composition that forms a good resist pattern without problems such as the above.

[0010]

The objects of the present invention are achieved by the following constitutions. (1) At least one selected from an acetal group and a silyl ether group as the group capable of decomposing with (a) an acid.
A resin having certain groups, the solubility of which in an alkali developing solution is increased by the action of an acid, and the weight average molecular weight of which is 4
000 to 80,000 and the molecular weight distribution (ratio Mw / Mn of weight average molecular weight to number average molecular weight) is 1.6 to
A positive photoresist composition comprising a resin of 4.0, (b) a compound that generates an acid upon irradiation with actinic rays or radiation, and (c) a solvent.

(2) (a) It has at least one group selected from an acetal group and a silyl ether group as a group capable of being decomposed by an acid, and its solubility in an alkali developing solution is increased by the action of an acid. A resin having a weight average molecular weight of 4000 to 80,000 and a molecular weight distribution (ratio of weight average molecular weight to number average molecular weight Mw / M
n) is 1.6 to 4.0, (a ') has at least one group selected from a tertiary alkyl ester group and a tertiary alkyl carbonate group, and has an alkaline aqueous solution. A positive photoresist composition containing a non-polymer type dissolution inhibiting compound whose solubility increases by the action of an acid, (b) a compound which generates an acid upon irradiation with actinic rays or radiation, and (c) a solvent. .

The present invention is a resin having at least one group selected from an acetal group and a silyl ether group as an acid-decomposable group, which is characterized by a specific molecular weight range and a specific molecular weight distribution range. A chemically amplified positive resist composition containing: The weight average molecular weight and the molecular weight distribution (Mw / Mn) in the present invention can be calculated by using gel permeation chromatography (GPC) with standard monodisperse polystyrene as a standard. The resin of the present invention only needs to have a molecular weight and a molecular weight distribution within a specific range and does not depend on its production method. Further, the present invention has a non-polymer type dissolution inhibitor having at least one kind of group selected from a tertiary alkyl ester group and a tertiary alkyl carbonate group, the solubility of which in an alkaline aqueous solution is increased by the action of an acid. It is preferable to contain a compound.

Here, the non-polymer type dissolution inhibiting compound has a structure in which an acid decomposable group is introduced into a compound having a constant molecular weight of 3000 or less and a single structure, and by the action of an acid, It is a compound that becomes alkali-soluble. Further, it is preferable that the non-polymer type dissolution inhibiting compound has a group that is decomposed by three or more acids in one molecule, and becomes alkali-soluble by the decomposition of this group. Further, in the present invention, an alkali-soluble resin containing no acid-decomposable group can be used in combination with the resin and the non-polymer type dissolution inhibiting compound.

The present invention has an acid-decomposable group,
A resin whose solubility in an alkali developing solution is increased by the action of an acid can be obtained by protecting the alkali-solubilizing group of an alkali-soluble mother resin with the above specific acid-decomposable group. The preferred protection rate is 10 with respect to the alkali solubilizing group.
It is preferable to protect mol% or more, more preferably 20 mol% or more, and particularly preferably 25 mol% or more with an acid-decomposable group.

Further, examples of preferable resin (a) which is a constituent feature of the present invention are shown below. The base resin, an alkali-soluble resin, contains at least 5 parts of p-hydroxystyrene.
A copolymer containing 0 mol% or more, a homopolymer thereof, or a partially hydrogenated resin is preferable. The resin obtained by protecting the resin (a) of the present invention with an acetal group or a silyl ether group has a molecular weight range of 4000 to 80,000, preferably 1
0000 to 80,000, more preferably 2000
It is 0 to 60,000. The range of molecular weight distribution of this resin is 1.6 to 4.0, preferably 1.6 to 3.0.
And more preferably 1.6 to 2.5. Also,
The non-polymer type dissolution inhibiting compound having a molecular weight of 3000 or less has a group that is decomposed by 3 or more acids in one molecule,
A compound that becomes alkali-soluble by the decomposition of this group is preferable.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds used in the present invention are described in detail below. In the component (a) of the present invention, a resin having a group capable of decomposing by an acid and having a solubility in an alkali developing solution increased by the action of an acid means a main chain or a side chain of a base resin, or a main chain. It is a resin having an acid-decomposable group in both the chain and the side chain. Of these, a resin having an acid-decomposable group in its side chain is more preferable.

The acetal group and the silyl ether group as the groups capable of being decomposed by an acid are --O--C (R ⁰⁴ ) (R ⁰⁵ ).
—O—R ⁰⁶ , or —O—Si (R ⁰⁷ ) (R ⁰⁸ ) (R ⁰⁹ )
Group. More preferably, the acid-decomposable group is -Ar-O
-C (R ⁰⁴ ) (R ⁰⁵ ) -O-R ⁰⁶ , or -Ar-OS
This is the case where the i (R ⁰⁷ ) (R ⁰⁸ ) (R ⁰⁹ ) group is bonded to the base resin.

R ⁰⁴ , R ⁰⁵ , R ⁰⁷ , R ⁰⁸ and R ⁰⁹ may be the same or different and each represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and R ⁰⁶ is An alkyl group or an aryl group is shown. However, at least two of R ^{07 to} R ⁰⁹ are groups other than a hydrogen atom, and two of R ^{04 to} R ⁰⁵ and R ^{07 to} R ⁰⁹ are different.
Two groups may combine to form a ring. However, a non-annular one is preferred. -Ar- represents a divalent or higher valent aromatic group which may have a monocyclic or polycyclic substituent. Here, as the alkyl group, those 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 are preferable. Those having 3 to 10 carbon atoms such as propyl group, cyclobutyl group, cyclohexyl group and adamantyl group are preferable, and alkenyl groups having 2 to 4 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group are preferable. Those having 6 to 14 carbon atoms, such as phenyl, xylyl, toluyl, cumenyl, naphthyl and anthracenyl, are preferred as the aryl group. As -Ar-, a phenylene group and a naphthylene group are preferable.

As the substituent, a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the above alkyl group, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group. Group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, and other alkoxy groups, methoxycarbonyl group, ethoxycarbonyl group, and other alkoxycarbonyl groups, benzyl group, phenethyl group, cumyl group, and other aralkyl groups, Acryl groups such as aralkyloxy groups, formyl groups, acetyl groups, butyryl groups, benzoyl groups, cyanayl groups, valeryl groups, acyloxy groups such as butyryloxy groups, the above alkenyl groups, vinyloxy groups, propenyloxy groups, allyloxy groups, butenyloxy groups. Alkenyloxy groups such as Serial aryl group, an aryloxy group such as phenoxy group, and an aryloxycarbonyl group such as benzoyloxy group.

Further, the acetal group is preferably

[0021]

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A group represented by, particularly preferably,

[0023]

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Examples include groups represented by: Further, preferably as a silyl ether group

[0025]

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Examples include groups represented by:

Next, as the base resin when these acid-decomposable groups are bonded as side chains, -OH or-is attached to the side chains.
COOH, in particular, -R ⁰ -COOH or -AR-O
An alkali-soluble resin having an H group is preferable, for example,
An alkali-soluble resin that does not contain an acid-decomposable group that can be used in the present invention (hereinafter simply referred to as an alkali-soluble resin), an alkali-soluble resin (preferably polyhydroxystyrene, novolac resin, or a derivative thereof), Alkali-soluble resin containing a p-hydroxystyrene unit (preferably poly (p-hydroxystyrene, p / m-hydroxystyrene, p / o-hydroxystyrene, p-hydroxystyrene-styrene copolymer), 4-hydroxy- 3-methylstyrene resin, 4-
Alkyl-substituted hydroxy resins such as hydroxy-3,5-dimethylstyrene resins, alkylated or acetylated OH moieties of the above resins are preferred.

Further, when a part of the phenol nuclei of the above resin (30 mol% or less of the total phenol nuclei) is hydrogenated, the transparency of the resin is improved, and it is preferable in terms of sensitivity, resolution and short formation of profile. . Examples of the alkali-soluble resin used in the present invention include novolac resin, hydrogenated novolak resin, acetone-pyrogallol resin, polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, and polyhydroxy. Part of styrene O-alkylated or O-acylated, styrene-
Examples thereof include, but are not limited to, a maleic anhydride copolymer, a carboxyl group-containing methacrylic resin and its derivative, a styrene-polyhydroxystyrene copolymer, and a hydrogenated polyhydroxystyrene.

Particularly preferred alkali-soluble resins used in the present invention are novolac resins and alkali-soluble resins containing a p-hydroxystyrene unit (preferably poly (p-hydroxystyrene, p / m-hydroxystyrene, p / o- Hydroxystyrene, p-hydroxystyrene-styrene copolymer), 4-hydroxy-3-
Alkyl-substituted hydroxy resins such as methylstyrene resin, 4-hydroxy-3,5-dimethylstyrene resin,
An alkylated or acetylated product of the OH portion of the above resin, a partially hydrogenated polyhydroxystyrene resin, a polyhydroxystyrene resin, a partially hydrogenated novolak resin, and a partially hydrogenated polyhydroxystyrene resin.

In the present invention, polyhydroxystyrene is a p-hydroxystyrene monomer, m-hydroxystyrene monomer, o-hydroxystyrene monomer or a hydroxystyrene monomer in which the ortho position thereof is alkyl-substituted with 1 to 4 carbon atoms. A polymer obtained by polymerizing at least one kind of monomer selected from the above is shown.

The alkali dissolution rate of the alkali-soluble resin for the base resin was 1 as measured by 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C.).
It is preferably 70 Å / sec or more. Especially preferably 33
It is more than 0Å / sec (Å is Angstrom).
Further, an alkali-soluble resin having a high transmittance for far ultraviolet light or excimer laser light is preferable from the viewpoint of achieving a rectangular profile. Preferably 248 nm with a thickness of 1 μm
Transmittance is 20 to 80%.

From this point of view, the particularly preferable alkali-soluble resin for the base resin is polyhydroxystyrene,
Hydrogenated polyhydroxystyrenes, halogen- or alkyl-substituted polyhydroxystyrenes, partially o-acylated products of polyhydroxystyrenes, hydroxystyrene-styrene copolymers and hydrogenated novolak resins.

The resin having an acid-decomposable group of the present invention is described in European Patent 254853, JP-A-2-25850, and JP-A-3-25850.
No. 223860, No. 4-251259, etc., an alkali-soluble resin is reacted with a precursor of an acid-decomposable group, or an alkali-soluble resin monomer having an acid-decomposable group bonded to various monomers. It can be obtained by copolymerization.

The general formulas of the resin having an acid-decomposable group synthesized in this manner are illustrated in (a) to (f) below, but the present invention is not limited thereto.

[0035]

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Here, L: -OC (R ⁰⁴ ) (R ⁰⁵ ) -O- (R ⁰⁶ ), or -O.
—Si (R ⁰⁷ ) (R ⁰⁸ ) (R ⁰⁹ ) group. (However, R ⁰⁴ to R ⁰⁹ are defined as the same supra) R _1: R ₁ in the same molecule may be the same as or different from each other, a hydrogen atom or an alkyl group of C ₁ ~C _4, R _2, R ₄ : groups having the same name in the same molecule may be the same or different, each being a hydrogen atom or a C ₁ -C ₄ alkyl group; R ₃ : a hydrogen atom, a carboxyl group, a cyano group or a substituted aryl group; ₅ : hydrogen atom, cyano group or —COOR ₆ , R ₆ : C ₁ -C ₁₀ linear / branched or cyclic alkyl group, R ₇ : hydrogen atom or C ₁ -C ₄ alkyl group, Ar: monocyclic Or 1 which may have a polycyclic substituent
Valent aromatic group, k, l, k1, l1, m: each independently represents a natural number, n: 0 or 1.

More specifically, the following (i) to (vii) can be mentioned.

[0038]

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[0039]

[Chemical 6]

Two or more kinds of the resins as the component (a) in the present invention may be mixed and used. The amount of the resin (a) used is the total weight of the resist composition (excluding the solvent).
50 to 97% by weight, preferably 60 to 9% by weight, based on
0% by weight. When the use amount of the alkali-soluble resin is less than 50% by weight, dry etching resistance is deteriorated.

The non-polymer type dissolution inhibiting compound (a ') which is preferably used in the present invention is selected from a tertiary alkyl ester group and a tertiary alkyl carbonate group as the acid-decomposable group. It has at least one type of group, and these two types can be used in combination. In the compound, at least two acid-decomposable groups are present in the constitution, and at the position where the distance between the acid-decomposable groups is the longest, at least 10 bond atoms excluding the acid-decomposable group, preferably at least 11 or more preferably at least 12 compounds, or at least 3 acid-decomposable groups, and at least the bond atom excluding the acid-decomposable group at the position where the distance between the acid-decomposable groups is the longest. It is advantageous to use compounds which pass through 9, preferably at least 10 and more preferably at least 11.

The non-polymer type dissolution inhibiting compound suppresses the solubility of the alkali-soluble resin in alkali, and the acid generated upon exposure to light causes the acid-decomposable group to be deprotected. Has the effect of promoting JP-A-63-27829 and JP-A-3-198059 disclose a dissolution inhibiting compound having a skeleton compound of naphthalene, biphenyl and diphenylcycloalkane, but have a small dissolution inhibiting property for an alkali-soluble resin, and have a high profile and resolution. Is not enough.

In the present invention, a preferred non-polymer type dissolution inhibiting compound is a compound having a molecular weight of 3000 or less and having a molecular weight of 3000 or less in one molecule, and having a molecular weight of 3000 or less, 1/2 or more of the alkali-soluble groups are acid-decomposable. A compound protected by a group may be mentioned. The use of such a non-polymer type dissolution inhibiting compound leaving an alkali-soluble group is preferable in that the solvent solubility of the non-polymer type dissolution inhibiting compound is improved and the effect of the present invention is further enhanced.

In the present invention, the upper limit of the number of the bonding atoms is preferably 50, more preferably 30. In the present invention, when the non-polymer type dissolution inhibiting compound has three or more, preferably four or more acid-decomposable groups, and even if it 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.

The distance between the acid-decomposable groups in the present invention is represented by the number of via-bond atoms excluding the acid-decomposable groups. 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.

[0046]

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The non-polymeric dissolution-inhibiting compound of the present invention may have a plurality of acid-decomposable groups on one benzene ring, but preferably has one acid-decomposable group on one benzene ring.
It is a compound composed of a skeleton having two acid-decomposable groups. Further, the molecular weight of the non-polymeric dissolution inhibiting compound of the present invention is 3,000 or less, preferably 500 to 3,0.
00, more preferably 1,000 to 2,500.
When the molecular weight of the non-polymeric dissolution inhibiting compound of the present invention is in the above range, it is preferable in terms of high resolution.

In a preferred embodiment of the present invention, the acid-decomposable group in the tertiary alkyl ester group or the tertiary alkyl carbonate group used in the non-polymer type dissolution inhibiting compound is --COO--C (R ⁰¹ ) ( R ⁰² ) (R ⁰³ ),
In this case, the compound has a structure represented by the group —O—CO—O—C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ). More preferably the acid decomposable group ^{-R 0 -COO-C (R 01} )
(R ⁰² ) (R ⁰³ ), or —Ar—O—CO—O—C (R
⁰¹ ) (R ⁰² ) and (R ⁰³ ) are bonded to the compound.

R ⁰¹ , R ⁰² and R ^{03, which} may be the same or different, each represents an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group. Also, R ^{01 to} R ⁰³
Two groups in the above may combine to form a ring. However, a non-annular one is preferred. R ⁰ represents a divalent or higher aliphatic or aromatic hydrocarbon group which may have a substituent.

Here, the alkyl group is preferably one having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, and cycloalkyl group. Is preferably a group having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group, and the alkenyl group is 2 to 2 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group. Four aryl groups are preferable, and the aryl group has 6 to 1 carbon atoms such as phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group and anthracenyl group.
Four are preferred.

As the substituent, a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the above alkyl group, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group. Group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, and other alkoxy groups, methoxycarbonyl group, ethoxycarbonyl group, and other alkoxycarbonyl groups, benzyl group, phenethyl group, cumyl group, and other aralkyl groups, Acryl groups such as aralkyloxy groups, formyl groups, acetyl groups, butyryl groups, benzoyl groups, cyanayl groups, valeryl groups, acyloxy groups such as butyryloxy groups, the above alkenyl groups, vinyloxy groups, propenyloxy groups, allyloxy groups, butenyloxy groups. Alkenyloxy groups such as Serial aryl group, an aryloxy group such as phenoxy group, and an aryloxycarbonyl group such as benzoyloxy group.

Specific examples of the tertiary alkyl group of the tertiary alkyl ester group and the tertiary alkyl carbonate group include t-butyl group, t-pentyl group, t-hexyl group,
Particularly preferred is a t-butyl group.

Preferred non-polymer type dissolution inhibiting compounds of the component (a ') of the present invention are JP-A-1-289946, JP-A-1-289947, JP-A-2-2560, JP-A-3-128959 and JP-A-3-128959. Kaihei 3-158855, JP-A-3-179353, JP-A-3-191351,
JP-A-3-200251 and JP-A-3-200252
No. 3, JP-A-3-200253, JP-A-3-2000025
4, JP-A-3-200255, and JP-A-3-2591.
49, JP-A-3-279958, JP-A-3-279.
959, JP-A-4-1650, and JP-A-4-1651.
JP-A-4-11260, JP-A-4-12356
JP-A-4-12357, Japanese Patent Application No. 3-33229
No., Japanese Patent Application No. 3-230790, Japanese Patent Application No. 3-32043
8, Japanese Patent Application No. 4-25157, Japanese Patent Application No. 4-52732.
No., Japanese Patent Application No. 4-103215, Japanese Patent Application No. 4-104454
No. 2, Japanese Patent Application No. 4-107885, Japanese Patent Application No. 4-1078
No. 89, No. 4-152195, etc., the tertiary alkyl ester group having a part or all of the phenolic OH group of the polyhydroxy compound described above,
Included are compounds that are attached and protected by a primary alkyl carbonate group.

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.

Specific examples of such polyhydroxy compounds include compounds represented by the general formulas [I] to [XVI].

[0056]

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[0057]

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[0058]

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[0059]

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Here, R ¹⁰¹ , R ¹⁰² , R ¹⁰⁸ and R ¹³⁰ may be the same or different and each is a hydrogen atom, —R ⁰ —COO—C (R ⁰¹ ) (R
⁰²⁾ (R ⁰³⁾ or ^{-CO-O-C (R 01} ) (R 0 2) (R
⁰³ ) provided that the definitions of R ⁰ , R ⁰¹ , R ⁰² and R ⁰³ are the same as described above.

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

[0062]

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[0063] 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 To R ¹⁰⁷ , R ¹⁰⁹ , R ^{111 to} R ¹¹⁸ , R
^{121 to} R ¹²³ , R ^{128 to} R ¹²⁹ , R ^{131 to} R ¹³⁴ , R
^{138 to} R ¹⁴¹ and R ¹⁴³ may be the same or different and include 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, a 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

[0064]

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R ¹⁵⁷ and R ^159, which may be the same or different, are 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, which may be the same or different, are a methylene group, a lower alkyl-substituted methylene group, a halomethylene group, or a haloalkyl group, provided that the lower alkyl group in the present application means an alkyl group having 1 to 4 carbon atoms. , R ^{124 to} R ¹²⁷ : the same or different, hydrogen atom or alkyl group, R ^{135 to} R ¹³⁷ : the same or different, 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 )
(R ⁰² ) (R ⁰³ ) or -CO-O-C (R ⁰¹ ) (R ⁰² )
(R ⁰³ ), or

[0067]

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R ¹⁴⁴ and R ¹⁴⁵ may be the same or different and each is 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 represent a hydrogen atom, a hydroxyl group, a halogen atom, a nitro group, a cyano group, a carbonyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aralkyl group, and an aralkyloxy group. 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 symbol need not 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: at plural times, 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, z1, a
2, at least one of 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, except for the general formula [V], where (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.

[0069]

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[0070]

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[0071]

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[0072]

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Specific examples of preferable compound skeletons are shown below.

[0074]

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[0075]

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[0076]

[Chemical 21]

[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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R in the compounds (1) to (63) is a hydrogen atom or --CH ₂ --COO--C (CH ₃ ) ₂ C ₆ H ₅ , --C.
_{H 2 -COO-C (CH 3} ) 3 and -COO-C (C
It is a group selected from H ₃ ) ₃ . However, at least 2
Or three depending on the structure are groups other than hydrogen atoms, and the respective substituents R may not be the same group.

The amount of the non-polymeric dissolution inhibiting compound that can be used in the present invention is 3 to 50% by weight, preferably 5 to 35% by weight, based on the total weight of the resist composition (excluding the solvent). Is the range. If the addition amount of the non-polymer type dissolution inhibiting compound used in the present invention is less than 3% by weight, high resolution cannot be obtained, and if it is more than 50% by weight, storage stability is deteriorated and film shrinkage occurs, resulting in resist failure. Heat resistance deteriorates.

In the present invention, an alkali-soluble resin containing no acid-decomposable group is used, which improves the sensitivity. An alkali-soluble resin containing no acid-decomposable group (hereinafter simply referred to as an alkali-soluble resin) is an alkali-soluble resin (preferably polyhydroxystyrene, novolac resin, or a derivative thereof), p
-An alkali-soluble resin containing a hydroxystyrene unit (preferably poly (p-hydroxystyrene, p
/ M-hydroxystyrene, p / o-hydroxystyrene, p-hydroxystyrene-styrene copolymer), 4
Alkyl-substituted hydroxy resins such as -hydroxy-3-methylstyrene resin and 4-hydroxy-3,5-dimethylstyrene resin, and alkylated or acetylated OH moieties of the above resins are preferred.

Further, when a part of the phenol nuclei of the above resin (30 mol% or less of the total phenol nuclei) is hydrogenated, the transparency of the resin is improved, and it is preferable in terms of sensitivity, resolution and short profile formation. . Examples of the alkali-soluble resin used in the present invention include novolac resin, hydrogenated novolak resin, acetone-pyrogallol resin, polyhydroxystyrene, halogen- or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, and polyhydroxy. Part of styrene O-alkylated or O-acylated, styrene-
Examples thereof include, but are not limited to, a maleic anhydride copolymer, a carboxyl group-containing methacrylic resin and its derivative, a styrene-polyhydroxystyrene copolymer, and a hydrogenated polyhydroxystyrene.

Particularly preferred alkali-soluble resins used in the present invention are novolac resins and alkali-soluble resins containing a p-hydroxystyrene unit (preferably poly (p-hydroxystyrene, p / m-hydroxystyrene, p / o- Hydroxystyrene, p-hydroxystyrene-styrene copolymer), 4-hydroxy-3-
Alkyl-substituted hydroxy resins such as methylstyrene resin, 4-hydroxy-3,5-dimethylstyrene resin,
An alkylated or acetylated product of the OH portion of the above resin, a partially hydrogenated polyhydroxystyrene resin, a polyhydroxystyrene resin, a partially hydrogenated novolak resin, and a partially hydrogenated polyhydroxystyrene resin.

In the present invention, the polyhydroxystyrene is a p-hydroxystyrene monomer, an m-hydroxystyrene monomer, an o-hydroxystyrene monomer or a hydroxystyrene monomer in which the ortho position thereof is alkyl-substituted with 1 to 4 carbon atoms. A polymer obtained by polymerizing at least one kind of monomer selected from the above is shown.

The novolak resin can be obtained by addition-condensing aldehydes in the presence of an acidic catalyst with a predetermined monomer as a main component.

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.

Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, 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 its acetal form, such as chloroacetaldehyde diethyl acetal, can be used, and among these, formaldehyde is preferably used.

These aldehydes may be 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 content of the alkali-soluble resin containing no acid-decomposable group is 50% by weight or less, preferably 30% by weight, based on the total of the resin and the acid-decomposable group-containing resin.
Hereafter, it is more preferably 20% by weight or less.

The photoacid generator used in the present invention is a compound which generates an acid upon irradiation with actinic rays or radiation.
Examples of the compound used in the present invention that decomposes upon irradiation with actinic rays or radiation to generate an acid include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photobleaching agents for dyes, and photochromic Well-known light (UV rays of 400 to 200 nm, deep UV rays, particularly preferably g line, h line, i line, KrF excimer laser beam), ArF excimer laser beam, electron beam used for agents or micro resists. A compound which generates an acid by X-ray, molecular beam or ion beam and a mixture thereof can be appropriately selected and used.

Other compounds which generate an acid upon irradiation with actinic rays or radiation used in the present invention include, for example, SI Schlesinger, Photogr. Sci. Eng., 18, 3
87 (1974), TSBal et al, Polymer, 21,423 (1980) and the like, diazonium salts, U.S. Pat.Nos. 4,069,055 and 4,06.
Ammonium salts described in 9,056, Re 27,992, Japanese Patent Application No. 3-140,140, etc., DC Necker et al., Macromolecules, 1
7,2468 (1984), CSWenetal, Teh, Proc.Conf.Rad.Curing
ASIA, p478 Tokyo, Oct (1988), U.S. Pat.No. 4,069,055
No. 4,069,056, etc.
vello etal, Macromorecules, 10 (6), 1307 (1977), Chem.
& Eng.News, Nov. 28, p31 (1988), EP 104,143,
U.S. Pat.Nos. 339,049, 410,201, JP-A-2-150,84
No. 8, iodonium salts described in JP-A-2-296,514 etc.,
JVCrivello et al, Polymer J. 17, 73 (1985), JVCrive
llo etal. J. Org. Chem., 43, 3055 (1978), WRWatt eta
l, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984),
JVCrivello etal, Polymer Bull., 14,279 (1985), JV
Crivello et al, Macromorecules, 14 (5), 1141 (1981), J.
V. Crivello etal, J. PolymerSci., Polymer Chem. Ed., 17,
2877 (1979), European Patent Nos. 370,693 and 3,902,114
233,567, 297,443, 297,442, U.S. Pat.
No. 33,377, No. 161,811, No. 410,201, No. 339,049,
No. 4,760,013, No. 4,734,444, No. 2,833,827, Dokoku Patent No. 2,904,626, No. 3,604,580, No. 3,604,581, etc.
ecules, 10 (6), 1307 (1977), JVCrivello etal, J. Polym
erSci., Polymer Chem. Ed., 17, 1047 (1979), etc., selenonium salts, CSWen et al., Teh, Proc. Conf. Rad.
g Onium salts such as arsonium salts described in ASIA, p478 Tokyo, Oct (1988) and the like, U.S. Pat.No. 3,905,815, JP-B-46
No. 4605, JP-A-48-36281, JP-A-55-32070, JP-A
No. 60-239736, JP-A-61-169835, JP-A-61-169837
JP-A-62-58241, JP-A-62-212401, JP-A-63-
No. 70243, organic halogen compounds described in JP-A-63-298339, K. Meier et al, J. Rad. Curing, 13 (4), 26 (1986),
TPGill et al, Inorg. Chem., 19,3007 (1980), D.Astru
c, Acc.Chem.Res., 19 (12), 377 (1896), Organometallic / organic halides described in JP-A-2-61445, S. Hayase et.
al, J. Polymer Sci., 25, 753 (1987), E. Reichmanis et al.
J.Pholymer Sci., Polymer Chem.Ed., 23, 1 (1985), QQZh
u etal, J. Photochem., 36, 85, 39, 317 (1987), B. Amit eta
l, Tetrahedron Lett., (24) 2205 (1973), DHR Barton eta
l, J. Chem Soc., 3571 (1965), PM Collins et al., J. Chem.
SoC., Perkin I, 1695 (1975), M. Rudinstein et al, Tetrahe
dron Lett., (17), 1445 (1975), JWWalker etal J. Am. Che
m.Soc., 110, 7170 (1988), SCBusman et al., J. Imaging Te
chnol., 11 (4), 191 (1985), HMHoulihan et al, Macormole
cules, 21, 2001 (1988), PM Collins et al., J. Chem. Soc.,
Chem.Commun., 532 (1972), S. Hayase et al, Macromolecule
s, 18,1799 (1985), E. Reichmanis et al, J. Electrochem. So
c., Solid State Sci. Technol., 130 (6), FMHoulihan et.
al, Macromolcules, 21, 2001 (1988), EP 0290,750
Nos. 046,083, 156,535, 271,851, 0,38
No. 8,343, U.S. Pat.
etal, Polymer Preprints Japan, 35 (8), G. Berner etal,
J.Rad.Curing, 13 (4), WJMijs etal, Coating Techno
l., 55 (697), 45 (1983), Akzo, H. Adachi et al, Polymer Pr
eprints, Japan, 37 (3), European Patent Nos. 0199,672 and 84515
No. 199,672, No. 044,115, No. 0101,122, U.S. Pat.Nos. 618,564, 4,371,605, 4,431,774, JP-A-64-18143, JP-A-2-245756, Japanese Patent Application No. 3- Compounds which generate sulfonic acid upon photolysis, such as the iminosulfonates described in 140109 and the like, and disulfone compounds described in JP-A-61-166544 and the like can be mentioned.

Further, a group generating an acid by these light,
Alternatively, a compound in which a compound is introduced into the main chain or side chain of a polymer, for example, ME Woodhouse et al., J. Am. Chem.
Soc., 104, 5586 (1982), SPPappas etal, J. Imaging Sc
i., 30 (5), 218 (1986), S. Kondoetal, Makromol.Chem., Rap
id Commun., 9,625 (1988), Y.Yamadaetal, Makromol.Che
m., 152, 153, 163 (1972), JVCrivello etal, J. PolymerS
ci., Polymer Chem. Ed., 17, 3845 (1979), U.S. Pat.
49,137, United States Patent No. 3914407, JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038.
JP-A-63-163452, JP-A-62-153853, JP-A-63-163452
Compounds described in JP-A-146029 can be used.

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

Among the compounds which decompose to generate an acid upon irradiation with actinic rays or radiation, those which are particularly effectively used are described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
The oxazole derivative represented by 1) or the general formula (PA)
An S-triazine derivative represented by G2).

[0108]

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In the formula, R ²⁰¹ is a substituted or unsubstituted aryl group or alkenyl group, R ²⁰² is a substituted or unsubstituted aryl group, alkenyl group, alkyl group or —C (Y) ₃
Show Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited thereto.

[0110]

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[0111]

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[0112]

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(2) An iodonium salt represented by the following general formula (PAG3) or a sulfonium salt represented by the following general formula (PAG4).

[0114]

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Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Preferred substituents include an alkyl group, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a carboxyl group, an alkoxycarbonyl group, a hydroxy group, a mercapto group, and a halogen atom.

R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferably, an aryl group having 6 to 14 carbon atoms, 1 to 8 carbon atoms
And substituted derivatives thereof. Preferred substituents are those having 1 to 8 carbon atoms for the aryl group.
And an alkyl group having 1 to 8 carbon atoms, a nitro group, a carboxyl group, a hydroxy group and a halogen atom. The alkyl group is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group or an alkoxycarbonyl group. is there.

Z ⁻ represents a counter anion, for example, BF ₄ ⁻ ,
_{^{AsF 6 -, PF 6 -,}} SbF 6 -, SiF 6 2-, ClO 4 -,
CF ₃ SO ₃ ^-, etc. perfluoroalkane sulfonate anion, pentafluorobenzenesulfonic acid anion, condensed polynuclear aromatic sulfonic acid anion such as naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, a sulfonic acid group-containing dyes Examples include, but are not limited to:

Two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded to each other via a single bond or a substituent.

Specific examples include the compounds shown below, but the invention is not limited thereto.

[0120]

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[0121]

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[0122]

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[0123]

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[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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The onium salts represented by the general formulas (PAG3) and (PAG4) are known, and for example, JWKnapczyk.
etal, J. Am. Chem. Soc., 91, 145 (1969), ALMaycok eta
l, J.Org.Chem., 35,2532, (1970), E.Goethas et al, Bul
l.Soc.Chem.Belg., 73,546, (1964), HMLeicester, JA
me.Chem.Soc., 51,3587 (1929), JVCrivello etal, J.Po
Chem. Ed., 18,2677 (1980), U.S. Pat. Nos. 2,807,648 and 4,247,473, and JP-A-53-101,331.

(3) A disulfone derivative represented by the following general formula (PAG5) or an iminosulfonate derivative represented by the general formula (PAG6).

[0133]

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In the formula, Ar^Three, Ar^FourAre each independently substituted
Or an unsubstituted aryl group. R ²⁰⁶Is replaced or
An unsubstituted alkyl group and an aryl group are shown. A is a substitution
Or unsubstituted alkylene, alkenylene, arylene
Shows a substituent group. Specific examples include the compounds shown below.
However, the present invention is not limited to these.

[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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In the present invention, the compound capable of generating an acid upon irradiation with actinic rays or radiation is preferably an onium salt, disulfone, 4-position DNQ sulfonate ester or triazine compound.

The amount of the compound which decomposes upon irradiation with actinic rays or radiation to generate an acid is usually 0.0 based on the total weight of the photosensitive composition (excluding the coating solvent).
It is used in the range of 0.01 to 40% by weight, preferably 0.0
It is used in an amount of 1 to 20% by weight, more preferably 0.1 to 5% by weight. If the amount of the compound that decomposes upon irradiation with actinic rays or radiation to generate an acid is less than 0.001% by weight, the sensitivity is low, and if the amount is more than 40% by weight, the light absorption of the resist is high. This is not preferable because the profile is deteriorated and the process (especially baking) margin is narrowed.

Organic basic compounds can be used in the compositions of the present invention. This is preferable because the storage stability is improved and the line width change due to PED is reduced. 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).

[0143]

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More preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, and particularly preferably a ring structure containing a substituted or unsubstituted amino group and a nitrogen atom. And 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 may be 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 above effects 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 area tends to deteriorate.

The chemically amplified positive resist composition of the present invention may further contain, if necessary, a surfactant, a dye, a pigment, a plasticizer, a photosensitizer and a phenolic OH group for promoting solubility in a developing solution. A compound having two or more can be contained.

Suitable surfactants are specifically polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether,
Polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether; polyoxyethylene alkyl allyl ethers such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitan monolaurate ,
Sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate and other sorbitan fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxy Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as ethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; EFTOP EF301, EF303;
EF352 (manufactured by Shin-Akita Chemical Co., Ltd.), MegaFac F1
71, F173 (manufactured by Dainippon Ink Co., Ltd.), Flora
FC430, FC431 (Sumitomo 3M Limited)
Made), Asahi Guard AG710, Surflon S-38
2, SC101, SC102, SC103, SC10
Fluorinated surfactants such as 4, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.), and organosiloxane polymer KP3
No. 41 (manufactured by Shin-Etsu Chemical Co., Ltd.) or acrylic acid-based or methacrylic acid-based (co) polymerized polyflow No. 41 75, N
o. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like.

These surfactants may be added alone or in some combinations. A preferable addition amount is 100 parts of the composition (excluding the solvent).
0.0005 to 0.01 parts by weight with respect to parts by weight. Suitable dyes include oily dyes and basic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink # 312, Oil Green B
G, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (all manufactured by Orient Chemical Industries, Ltd.), Crystal Violet (CI42555), Methyl Violet (CI42535), Rhodamine B (CI45)
170B), malachite green (CI42000),
Examples thereof include methylene blue (CI52015).

Further, the following chemical sensitizing positive resist of the present invention is added by adding a spectral sensitizer as described below to sensitize the photo-acid generator to be used in the longer wavelength region than far ultraviolet which does not have absorption. Can be made sensitive to the i or g line. Examples of suitable spectral sensitizers include benzophenone, p, p'-tetramethyldiaminobenzophenone, p, p'-tetraethylethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, and pyrene. , Perylene,
Phenothiazine, benzyl, acridine orange, benzoflavin, cetoflavin-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.

Examples of the compound having two or more phenolic OH groups which promote the solubility in a developing solution include polyhydroxy compounds, and the polyhydroxy compounds are preferably phenols, resorcin, phloroglucin, phlorogluside, 2, 3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene,
Tris (4-hydroxyphenyl) methane, Tris (4
-Hydroxyphenyl) ethane, 1,1'-bis (4-
(Hydroxyphenyl) cyclohexane.

The chemical amplification type positive resist composition of the present invention is prepared by dissolving each of the above-mentioned components in a solvent and coating it on a support. Solvents that can be used include ethylene dichloride, cyclohexanone and cyclohexanone. Pentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, Ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate,
Propyl pyruvate, N, N-dimethylformamide,
Dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents may be used alone or as a mixture.

The above chemically amplified positive resist composition is coated on a substrate (eg, silicon / silicon dioxide coating) used for the production of precision integrated circuit devices by an appropriate coating method such as a spinner or a coater, and then the predetermined composition is prepared. A good resist pattern can be obtained by exposing through the mask of No. 1, baking, and developing.

The developer for the chemically amplified positive resist composition of the present invention includes, for example, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium phosphate, sodium metasilicate, and aqueous ammonia. , Primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine,
Alcohol amines such as triethanolamine, amides such as formamide and acetamide, tetramethylammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, tetraethylammonium hydroxide, tributylmethylammonium hydroxide, tetraethanolammonium hydroxide , Methyltriethanol ammonium hydroxide,
Quaternary ammonium salts such as benzylmethyldiethanolammonium hydroxide, benzyldimethylethanolammonium hydroxide, benzyltriethanolammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide, alkalis such as cyclic amines such as pyrrole and piperidine Aqueous solutions, etc.

[0154]

(Synthesis of alkali-soluble resin of the present invention)

[Synthesis Example I-1] 27.5 g (0.17 mol) of p-acetoxystyrene and 3.15 g (0.030 mol) of styrene were dissolved in 120 ml of butyl acetate, and azo was prepared at 80 ° C under a nitrogen stream and stirring. Bisisobutyronitrile (AIB
N) 0.033 g was added three times every two hours, and finally, stirring was continued for another two hours to carry out a polymerization reaction.
The reaction solution was poured into 600 ml of hexane to precipitate a white resin. After drying the obtained resin, methanol 150m
It was dissolved in 1. To this, 7.7 g of sodium hydroxide (0.
Aqueous solution (19 mol) / water (50 ml) was added, and the mixture was heated under reflux for 3 hours to hydrolyze. After that, water 20
By adding 0 ml to dilute and neutralizing with hydrochloric acid,
A white resin precipitated.

The precipitated resin was separated by filtration, washed with water and dried to obtain 21 g of resin. By NMR measurement, it was confirmed that the composition of this resin was p-hydroxystyrene / styrene = about 85/15, and that the weight average molecular weight was 27,000 by GPC measurement. Its molecular weight distribution was 1.9. (Resin X) 11.8 g of the obtained resin and 2.5 g of t-butyl vinyl ether were dissolved in 70 ml of dehydrated tetrahydrofuran,
0.05 g of p-toluenesulfonic acid monohydrate was added at room temperature. This solution was replaced with nitrogen, sealed and stirred at room temperature for 20 hours. Then, the reaction solution was neutralized with triethylamine, and ion-exchanged water 1 liter / triethylamine 0.
It was put into 7 g of the solution while stirring. The precipitated resin was separated by filtration, washed with water, and dried at 70 ° C. under reduced pressure. 12.5 g of a white resin was obtained, and it was confirmed by NMR that 20% of the OH groups of the raw material resin were t-butoxy-1-ethylated (t-butyl acetalized). According to GPC measurement, the weight average molecular weight was 29000 and the molecular weight distribution was 2.0. (Resin A used in Examples)

Synthesis Example I-2 11.8 g of the resin (X) obtained in Synthesis Example 1 and 3.8 g of trimethylsilyl chloride were dissolved in 70 ml of dehydrated tetrahydrofuran, and 3.7 g of triethylamine was added dropwise at room temperature. This solution was purged with nitrogen, sealed and stirred at room temperature for 10 hours. After that, the reaction liquid was deionized water 1 liter / triethylamine 0.7.
It was put into the solution of g with stirring. The precipitated resin was separated by filtration, washed with water, and dried under reduced pressure at 40 ° C. 13.6 g of a white resin was obtained, and it was confirmed by NMR that 30% of the OH groups of the raw material resin had been silyl etherified. According to GPC measurement, the weight average molecular weight was 28,000 and the molecular weight distribution was 2.0. (Resin B used in Examples)

Synthesis Example I-3 48.1 g of poly (p-hydroxystyrene) (weight average molecular weight 11,000, molecular weight distribution 1.10) and 0.47 g of 1,4-dihydroxycyclohexane were dissolved in 250 ml of dehydrated tetrahydrofuran. It was kept at room temperature. 13. Add t-butyl vinyl ether to this solution.
0 g and p-toluenesulfonic acid monohydrate 0.19 g
Was added, and the atmosphere was replaced with nitrogen, and the vessel was sealed and stirred at room temperature for 20 hours. Thereafter, the reaction solution was neutralized with triethylamine, and poured into a solution of 3 liters of ion-exchanged water / 3 g of triethylamine with stirring. The precipitated resin was separated by filtration, washed with water, and dried at 70 ° C. under reduced pressure. 56g of white resin
And 27% of the OH groups of the starting resin were found to be t-
It was confirmed that it was butoxy-1-ethylated (t-butylacetalized). According to GPC measurement, the weight average molecular weight was 22,000 and the molecular weight distribution was 1.8. (Resin C used in Examples)

[Synthesis Example I-4] Poly (p-hydroxystyrene) (weight average molecular weight 11,000, molecular weight distribution 1.
10) 48.1 g of dehydrated tetrahydrofuran 250 ml
It was dissolved in and kept at room temperature. To this solution, 14.0 g of t-butyl vinyl ether and 0.19 g of p-toluenesulfonic acid monohydrate were added, and the mixture was purged with nitrogen, sealed, and stirred at room temperature for 20 hours. Thereafter, the reaction solution was neutralized with triethylamine, and poured into a solution of 3 liters of ion-exchanged water / 3 g of triethylamine with stirring. The precipitated resin was separated by filtration, washed with water, and dried at 70 ° C. under reduced pressure. 56 g of a white resin was obtained, and it was confirmed by NMR that 26% of the OH groups of the raw material resin were t-butoxy-1-ethylated (t-butyl acetalized). According to GPC measurement, the weight average molecular weight was 12,000 and the molecular weight distribution was 1.2. (Resin D used in Comparative Example)

[Synthesis Examples I-5 to I-8] In Synthesis Example I-1, resins having different molecular weights and molecular weight distributions are synthesized by changing only the amount of AIBN used, and a predetermined amount of t-butyl vinyl ether is reacted. To obtain resins E to H.
The synthesis results are shown in Table 1.

[Synthesis Examples I-9 to I-11] Synthesis Example I-3
In, the weight average molecular weight and the molecular weight distribution of the poly (p-hydroxystyrene) used were changed, and resins I to K protected with t-butyl vinyl ether were synthesized. The synthesis results are shown in Table 1.

[0161]

[Table 1]

[Synthesis Example II-1] α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene 8.48 g (0.020 mol) of N, N
-To a solution of 120 ml of dimethylacetamide, 4.2 g (0.03 mol) of potassium carbonate and 12.3 g (0.063 g) of t-butyl bromoacetate were added, and the mixture was stirred at 120 ° C for 7 hours.
Stirred for hours. Then, the reaction solution was poured into 1.5 liters 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)) to obtain 13 g of the target product. It was It was confirmed by NMR that this was the non-polymer type dissolution inhibiting compound [II-1] used in Examples and Comparative Examples. [Synthesis Example II-2] 1,3,3,5-tetrakis (4-hydroxyphenyl) instead of α, α ′, α ″ -tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene A non-polymeric dissolution inhibiting compound [II-2] was synthesized in the same manner as in Synthesis Example [II-1] except that 6.6 g of pentane was used, and each compound used in Examples is also shown below.

[0163]

Embedded image

[0164]

Embedded image

[Examples 1 to 11, Comparative Examples 1 to 6] [Preparation and Evaluation of Photosensitive Composition] Each material shown in Table 2 was PG
It was dissolved in 8 g of MEA (propylene glycol monoethyl ether acetate) and filtered through a 0.2 μm filter to prepare a resist solution. This resist solution was applied on a silicon wafer using a spin coater and dried on a vacuum adsorption type hot plate at 120 ° C. for 60 seconds to obtain a resist film having a film thickness of 0.8 μm.

This resist film was exposed using a 248 nm KrF excimer laser stepper (NA = 0.45). After the exposure, the film was heated on a hot plate at 100 ° C. for 60 seconds, immediately immersed in a 0.26 N aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsed with water for 30 seconds, and dried. The pattern on the silicon wafer thus obtained was observed with a scanning electron microscope to evaluate the performance of the resist. Table 3 shows the results.

The resolving power represents a limiting resolving power in an exposure amount for reproducing a mask pattern of 0.40 μm. The sensitivity decrease rate due to PED (exposure-time between exposure and bake) is the sensitivity when PED is 90 minutes (exposure amount for reproducing 0.40 μL / S mask pattern) without PED (5 minutes or less). The value divided by the sensitivity (exposure amount for reproducing a 0.40 μL / S mask pattern) in the case of was shown.

In the T-top formation by PED, the profile when PED is 90 minutes and the profile when PED is not present (5 minutes or less) are compared. What was judged to be ○, T
-The one with top formation is indicated by x.

The change in line width due to PED is the same as that without PED (5
Min.)) (0.40 μL / S mask pattern exposure dose) and PED at the same exposure amount of 90 minutes, the 0.40 μL / S mask pattern bottom dimension is 0.40 ± 0 Those that were within 0.04 μL / S were represented by ◯, and those that were outside the range were represented by x. The bite under the pattern is 0.40 μmL / S. By observing the bite between the bottom edge of the mask pattern and the silicon wafer interface (the line width near the substrate of the pattern becomes small), the bite that does not bite is ○, slightly bite The ones in which the presence of swelling is shown are indicated by Δ, and the ones with remarkable bite are indicated by x.

[0170]

[Table 2]

[0171]

[Table 3]

From the results shown in Table 3, the resist of the present invention has a high resolution, a decrease in sensitivity due to aging between exposure and post-exposure bake, T-top formation, a change in line width, and biting under the pattern. It can be seen that it has a good resist pattern without

[0173]

Industrial Applicability The present invention is free from problems such as sensitivity deterioration with time between exposures (PEB) after exposure, problems such as T-top formation and line width narrowing, and defects such as biting under the pattern. A chemically amplified positive photoresist composition capable of forming a resist can be provided.

Claims (2)

[Claims] 1. A resin having (a) at least one group selected from an acetal group and a silyl ether group as a group capable of being decomposed by an acid, the solubility of which in an alkali developing solution is increased by the action of an acid. And its weight average molecular weight is 4,000 to 80,000, and its molecular weight distribution (ratio Mw / Mn of weight average molecular weight to number average molecular weight) is 1.
A positive photoresist composition comprising a resin of 6 to 4.0, (b) a compound that generates an acid upon irradiation with actinic rays or radiation, and (c) a solvent. 2. A resin having (a) at least one group selected from an acetal group and a silyl ether group as a group capable of being decomposed by an acid, and having a solubility in an alkali developing solution increased by the action of an acid. And its weight average molecular weight is 4,000 to 80,000, and its molecular weight distribution (ratio Mw / Mn of weight average molecular weight to number average molecular weight) is 1.
A resin having 6 to 4.0, (a ') at least one group selected from a tertiary alkyl ester group and a tertiary alkyl carbonate group, and having a solubility in an alkaline aqueous solution of an acid. A positive photoresist composition comprising: a non-polymeric dissolution inhibiting compound increased by 1.), (b) a compound that generates an acid upon irradiation with actinic rays or radiation, and (c) a solvent.