JP2001066779A - Positive type photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce development defects and to make line edge roughness satisfactory by incorporating a specified compound which generates an acid, when it is irradiated with actinic rays or radiation, a resin having a group which is decomposed by the action of the acid to increase solubility in an alkali- developing solution and a basic nitrogen-containing compound. SOLUTION: A positive type photosensitive composition contains (a) at least one of compounds of the formula, etc., which generate an acid when irradiated with active light or radiation, (b) a resin having a group which is decomposed by the action of the acid to increase solubility in an alkali-developing solution and (c) a basic nitrogen-containing compound. In the formula, R1-R15 are each H, linear, branched or cyclic alkyl, linear, branched or cyclic alkoxy, hydroxy, halogen or the like and X is an anion of benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having one group selected from among the group comprising branched or cyclic >=8C alkyls and alkoxys.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a lithographic printing plate or an IC.
The present invention relates to a positive photosensitive composition used in a semiconductor manufacturing process such as the above, a circuit substrate such as a liquid crystal and a thermal head, and other photofabrication processes.

[0002]

2. Description of the Related Art Semiconductor manufacturing processes for lithographic printing plates and ICs,
Liquid crystal, the manufacture of circuit boards such as thermal heads, as well as other photosensitive compositions used in the photofabrication process, there are various compositions, generally a photoresist photosensitive composition is used, it is Broadly speaking, there are two types: positive and negative.

As one of the positive photoresist photosensitive compositions, there is a chemically amplified resist composition described in US Pat. No. 4,491,628 and European Patent No. 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.

[0004] Examples of such a combination include a combination of a compound that generates an acid by photolysis with an acetal or an O, N-acetal compound (Japanese Patent Application Laid-Open No. 48-89003), a combination of an orthoester or an amide acetal compound ( Combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-172014).
3429), a combination with an enol ether compound (JP-A-55-12995), a combination with an N-acyliminocarbonate compound (JP-A-55-126236),
Combination with a polymer having an orthoester group in the main chain (JP-A-56-17345), combination with a tertiary alkyl ester compound (JP-A-60-3625), combination with a silyl ester compound (JP-A-60-3625) Showa 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). Since these systems also have high sensitivity and low absorption in the far ultraviolet region, they can be effective systems for shortening the light source wavelength capable of ultrafine processing.

The above-mentioned positive chemically amplified resist comprises an alkali-soluble resin, a compound capable of generating an acid upon exposure to radiation (photoacid generator), and a compound having an acid-decomposable group and inhibiting dissolution of the alkali-soluble resin. It can be roughly classified into a two-component system comprising a component system, a resin having a group which is decomposed by the reaction with an acid and becomes alkali-soluble, and a photoacid generator. These two
In a three-component or three-component positive chemically amplified resist, the acid from the photoacid generator is interposed by exposure,
After the heat treatment, development is performed to obtain a resist pattern.

JP-A-63-149640 proposes to add an amine compound for stabilizing the sensitivity of a lithographic printing plate after exposure. However, when the amine compound is added, there is a problem that a part of the acid generated by the exposure is deactivated by the amine, and the sensitivity is lowered. Also, European Patent Publication EP-A-0975786.
Proposes to use a specific photoacid generator and add 4-dimethylaminopyridine as an amine to suppress the line width change. , The sensitivity was reduced. In addition, the resolution was not at a sufficient level.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a positive photosensitive composition having good development defects and good line edge roughness.

[0009]

The present invention has been achieved by the following constitutions. (1) (a) at least one of the compounds represented by the following general formulas (I) to (III) which generate an acid upon irradiation with actinic rays or radiation; (b) decomposed by the action of an acid; A resin having a group that increases the solubility of the resin composition, and (c) a basic nitrogen-containing compound.

[0010]

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(Where R¹~ R³⁷Is hydrogen atom, straight chain, minute
Branch, cyclic alkyl group, straight-chain, branched, cyclic alkoxy group,
A hydroxy group, a halogen atom, or -SR³⁸Table
You. R38 is a linear, branched, cyclic alkyl group or aryl
Represents a hydroxyl group. Where R¹~ R^FifteenAt least one of
One, R¹⁶~ R²⁷At least one of R²⁸~ R³⁷
At least one of which is hydroxy or alkoxy
Group. , X^-Is branched or cyclic having 8 or more carbon atoms
Groups selected from the group of alkyl and alkoxy groups
Having at least one linear or branched or cyclic carbon
Among groups of alkyl and alkoxy groups of prime numbers 4 to 7
Having at least two groups selected from
A chain, branched or cyclic alkyl group having 1 to 3 carbon atoms;
At least three groups selected from the group of alkoxy groups
Having benzenesulfonic acid, naphthalenesulfonic acid or
Represents an anthracenesulfonic acid anion. Or
Ester group, R³⁹—CO— group, R⁴⁰-CONH- group, R
⁴¹-NH- group, R⁴²—OCONH— group, R⁴³-NHCO
O-group, R⁴⁴—NHCONH— group, R ⁴⁵-NHCSN-
Group, R⁴⁶-SO_TwoFrom the group of NH- and nitro groups
Benzene sulfone having at least one selected group
Acid, naphthalenesulfonic acid or anthracenesulfonic acid
Represents an anion of an acid. R³⁹~ R⁴⁶Is linear, branched or
Represents a cyclic alkyl group or an aryl group. )

(2) In the compounds represented by the general formulas (1) to (3), at least one of R ^{1 to} R ^15
The above (1), wherein at least one of R ^{16 to} R ²⁷ and at least one of R ^{28 to} R ³⁷ are a hydroxy group, and both adjacent positions of the hydroxy group are not hydrogen atoms. Positive photosensitive composition.

(3) (d) A low molecular weight dissolution inhibiting compound having a molecular weight of 3000 or less, which has a group decomposable by an acid and whose solubility in an alkali developing solution is increased by the action of an acid,
The positive photosensitive composition according to the above (1) or (2), further comprising:

(4) (a) at least one of the compounds represented by the general formulas (I) to (III) which generate an acid upon irradiation with the above-mentioned actinic ray, (c) a basic nitrogen-containing compound, and (d)
A low molecular weight dissolution inhibiting compound having a molecular weight of 3000 or less, which has a group decomposable by an acid and whose solubility in an alkaline developer is increased by the action of an acid; and (e) insoluble in water and soluble in an alkaline developer A positive photosensitive composition comprising a resin.

(5) (b) A resin having a group which is decomposed by the action of an acid to increase the solubility in an alkaline developer is obtained by repeating at least one of the following general formulas (IV) and (V) The positive photosensitive composition according to any one of the above (1) to (4), which is a resin containing a structural unit.

[0016]

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(In the above formula, L represents a hydrogen atom, an optionally substituted linear, branched or cyclic alkyl group, or an optionally substituted aralkyl group. Z may be optionally substituted. , Represents a linear, branched or cyclic alkyl group or an optionally substituted aralkyl group. Z and L may combine to form a 5- or 6-membered ring.)

(6) (b) A resin having a group which is decomposed by the action of an acid and increases the solubility in an alkali developer is obtained by repeating at least one of the above-mentioned general formulas (IV) and (V) The positive photosensitive composition according to the above (5), which is a resin containing a structural unit, and wherein Z is a substituted alkyl group or a substituted aralkyl group.

The positive photosensitive composition of the present invention has good development defects by using the compounds represented by the above general formulas (I) to (III) as a compound which generates an acid upon irradiation with actinic rays. In addition, L. In the chemically amplified resist having good edge roughness, the problem that the sensitivity is lowered even if the added amount is increased to improve the line width is solved.
An excellent resist pattern was obtained.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, components such as a compound and a resin contained in the positive photosensitive composition of the present invention will be described in detail.

[I] Basic nitrogen-containing compound (component (c)) Preferred basic nitrogen-containing compounds that can be used in the present invention are compounds that are more basic than phenol. Examples include the structures of formulas (A) to (E).

[0022]

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Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² are the same or different and are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, a hydroxyalkyl having 1 to 6 carbon atoms. Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R ²⁵¹ and R ²⁵² may be bonded to each other to form a ring.

[0024]

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Wherein R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶
Represents the same or different and represents an alkyl group having 1 to 6 carbon atoms)

More preferred compounds are nitrogen-containing cyclic compounds or two nitrogen atoms having different chemical environments in one molecule.
It is a basic nitrogen-containing compound having at least one compound. The nitrogen-containing cyclic compound more preferably has a polycyclic structure.
Preferred specific examples of the nitrogen-containing polycyclic compound include a compound represented by the following general formula (VI).

[0027]

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In the formula (VI), Y and W each independently represent a linear, branched or cyclic alkylene group which may contain a hetero atom and may be substituted. Here, examples of the hetero atom include a nitrogen atom, a sulfur atom, and an oxygen atom. The alkylene group preferably has 2 to 10 carbon atoms, and more preferably has 2 to 5 carbon atoms. Examples of the substituent of the alkylene group include an alkyl group having 1 to 6 carbon atoms, an aryl group, an alkenyl group, a halogen atom, and a halogen-substituted alkyl group. Further, specific examples of the compound represented by the general formula (VI) include the following compounds.

[0029]

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Of the above, 1,8-diazabicyclo [5.4.0] undec-7-ene and 1,5-diazabicyclo [4.3.0] non-5-ene are particularly preferred.

The basic nitrogen-containing compound having two or more nitrogen atoms having different chemical environments in one molecule is particularly preferably a compound containing both a substituted or unsubstituted amino group and a ring structure containing 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 indazole, 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 amino Morpholine, substituted or unsubstituted aminoalkylmorpholine and the like. Preferred substituents are an amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group It is.

Particularly preferred compounds are guanidine,
1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylamino Pyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethyl Pyridine, 4
-Aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N-
(2-aminoethyl) piperidine, 4-amino-2,
2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl -1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5
-Methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N-
(2-Aminoethyl) morpholine, trimethylimidazole, triphenylimidazole, methyldiphenylimidazole, and the like, but are not limited thereto.

The basic nitrogen-containing compounds used in the present invention can be used alone or in combination of two or more. The amount of the basic nitrogen-containing compound used is usually from 0.001 to 10 based on 100 parts by weight of the photosensitive composition (excluding the solvent).
Parts by weight, preferably 0.01 to 5 parts by weight. Within this range, the effects of the present invention can be effectively exhibited without lowering the sensitivity or deteriorating the developability of the exposed portion.

[II] Compounds represented by the general formulas (I) to (III) which generate an acid upon irradiation with actinic rays (component (a)) R ¹ to R ¹ in the above general formulas (I) to (III) The linear or branched alkyl group for R ⁴⁶ may have a substituent,
Methyl group, ethyl group, propyl group, n-butyl group, se
Those having 1 to 4 carbon atoms such as a c-butyl group and a t-butyl group are exemplified. The cyclic alkyl group may have a substituent, a cyclopropyl group, a cyclopentyl group,
Those having 3 to 8 carbon atoms such as a cyclohexyl group are exemplified. Examples of the alkoxy group represented by R ^{1 to} R ³⁷ 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. One. Examples of the halogen atom for R ^{1 to} R ³⁷ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the aryl group of R ^{38 to} R ⁴⁶ 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. Preferably, these substituents have 1 to 1 carbon atoms.
4 alkoxy groups, halogen atoms (fluorine atom, chlorine atom, iodine atom), aryl group having 6 to 10 carbon atoms, alkenyl group having 2 to 6 carbon atoms, cyano group, hydroxy group, carboxy group, alkoxycarbonyl Group, nitro group and the like.

The hydroxy group or the alkoxy group may be useful at any position in the general formulas (I), (II) and (III). The position is preferably away from other bonding positions (for example, the bonding position with the S cation of the sulfonium salt). In addition, in one structure, introduction of a large number of hydroxy groups or alkoxy groups increases the permeability to an alkaline solution, and thus one or two introductions are preferable. In addition, the introduction of a hydroxy group causes excessive permeability to an alkaline solution depending on its structure, but by introducing a substituent at a position adjacent thereto, the permeability to an alkaline solution can be controlled, which is preferable. .

The general formulas (I) to (II) used in the present invention
Sulfonium and iodonium compounds represented by I)
Its counter anion X^-As a branched or cyclic carbon number 8
Or more, preferably 10 or more alkyl groups or alcohols
It has at least one xy group, or is linear or branched
Or a cyclic alkyl group having 4 to 7 carbon atoms or alkoxy
Having at least two or more groups,
A branched or cyclic alkyl group having 1 to 3 carbon atoms or
Benzene sulfone having at least 3 alkoxy groups
Acid, naphthalenesulfonic acid or anthracenesulfonic acid
Having an anion of Or an ester group, R³⁸-CO
-Group, R³⁹-CONH- group, R⁴⁰-NH- group, R⁴¹-O
CONH- group, R⁴²-NHCOO- group, R⁴³-NHCO
NH- group, R ⁴⁴-NHCSN- group, R⁴⁵-SO_TwoNH-
At least a group selected from the group consisting of
Benzenesulfonic acid, naphthalenesulfonic acid with one
It also has an anthracene sulfonic acid anion.

As a result, the diffusivity of the acid (benzenesulfonic acid, naphthalenesulfonic acid or anthracenesulfonic acid having the above group) generated after exposure is reduced, and the solubility of the sulfonium and iodonium compounds in the solvent is improved. In particular, from the viewpoint of reducing the diffusivity, a linear alkyl group or an alkoxy group as the above group,
A branched or cyclic alkyl group or alkoxy group is more preferred. When the number of the above groups is one, the difference in diffusivity between a straight chain and a branched or cyclic one becomes more remarkable.

C 8 or more, preferably C 8 to C 2
Examples of the zero alkyl group include a branched or cyclic octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group,
Examples include a tridecyl group, a tetradecyl group, and an octadecyl group. 8 or more carbon atoms, preferably 8 to 20 carbon atoms
Examples of the alkoxy group include a branched or cyclic octyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, a dodecyloxy group, a tridecyloxy group,
Examples include a tetradecyloxy group and an octadecyloxy group. 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, an n-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. Hereinafter, specific examples of these compounds are shown, but the present invention is not limited thereto.

[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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The compounds represented by formulas (I), (II) and (III) can be used alone or in combination of two or more. The component (a), that is, the general formula (I), the general formula (II), and the general formula (II
The compound represented by I) is disclosed in U.S. Pat. No. 3,734,92.
8, Macromolecules, vol. 10, 1
307 (1977), Journal of Organic Chemistry, vol. 55,
4222 (1990), J. Radiat. Curing, vol. 5 (1), 2 (1978)
Can be synthesized by further exchanging the counter anion. The content of the component (a), that is, the compound represented by the general formula (I), the general formula (II) or the general formula (III) in the photosensitive composition is 0.1 to 0.1% of the solid content of the photosensitive composition. 1-20% by weight is suitable, preferably 0.5-10% by weight, more preferably 1-7% by weight.

[III] (a ') Other Photoacid Generating Compounds That Can Be Used in Combination In the photosensitive composition of the present invention, in addition to the above component (a) which generates an acid, it can be decomposed by irradiation with actinic rays or radiation. Other compounds that generate an acid (hereinafter, also referred to as “component (a ′)”) may be used in combination. The content of the component (a ′) which can be used in combination with the component (a) is preferably less than 70% by weight, more preferably 60% by weight of the total photoacid generator used.
And more preferably less than 50% by weight.

Examples of such photoacid generators that can be used in combination include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, and microresists. A known compound that generates an acid by light and a mixture thereof can be appropriately selected and used.

For example, SISchlesinger, Photogr.Sci.E
ng., 18,387 (1974), TSBal etal, Polymer, 21,423 (198
0) etc., U.S. Pat.No.4,069,055
No. 4,069,056, Re 27,992, Japanese Patent Application No. 3-140,140
Salt, DCNecker etal, Macrom
olecules, 17, 2468 (1984), CSwen et al, Teh, Proc. Con
f.Rad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Patent No.
Nos. 4,069,055 and 4,069,056, and phosphonium salts described in JVCrivello et al., Macromorecules, 10 (6), 1307 (19
77), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 10
No. 4,143, U.S. Pat.Nos. 339,049, 410,201, JP-A-2-150,848, Iodonium salts described in JP-A-2-296,514, etc., JVCrivello et al., Polymer J. 17, 73 (1985),
JVCrivello et al. J.Org.Chem., 43, 3055 (1978), WR
Watt etal, J. Polymer Sci., Polymer Chem. Ed., 22, 1789
(1984), JVCrivello etal, Polymer Bull., 14,279 (19
85), JVCrivello etal, Macromorecules, 14 (5), 1141
(1981), JVCrivello etal, J. PolymerSci., Polymer C
hem.Ed., 17,2877 (1979), European Patent Nos. 370,693, 3,90
No. 2,114, No. 233,567, No. 297,443, No. 297,442, U.S. Pat.Nos. 4,933,377, 161,811, No. 410,201, No. 3
No. 39,049, No. 4,760,013, No. 4,734,444, No. 2,833,82
No. 7, German Patent Nos. 2,904,626, 3,604,580, 3,60
No. 4,581, etc., sulfonium salt, JVCrivello eta
l, Macromorecules, 10 (6), 1307 (1977), JVCrivello e
tal, J. PolymerSci., Polymer Chem. Ed., 17,1047 (1979)
Selenonium salts, CSwen etal, Teh, Proc.C
onf.Rad.Curing ASIA, p478 Tokyo, Oct (1988) and the like, onium salts such as arsonium salts, U.S. Pat.
No. 5, JP-B-46-4605, JP-A-48-36281, JP-A-55-3
No. 2070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62-212401
No., JP-A-63-70243, organic halogen compounds described in JP-A-63-298339, etc., K. Meier et al., J. Rad.Curing, 13
(4), 26 (1986), TPGill et al., Inorg.Chem., 19, 3007 (1
980), D. Astruc, Acc. Chem. Res., 19 (12), 377 (1896), and organometallic / organic halides described in JP-A-2-14145, etc., S. Hayase et al., J. Polymer Sci. ., 25, 753 (1987), E.
Reichmanis etal, J.Pholymer Sci., Polymer Chem.Ed.,
23, 1 (1985), QQ Zhu et al., J. Photochem., 36, 85, 39, 317
(1987), B. Amit etal, Tetrahedron Lett., (24) 2205 (19
73), DHR Barton et al., J. Chem Soc., 3571 (1965), P.
M. Collins et al., J. Chem. Soc., Perkin I, 1695 (1975), M.
Rudinstein et al, Tetrahedron Lett., (17), 1445 (197
5), JWWalker etal J. Am. Chem. Soc., 110, 7170 (1988),
SCBusman et al., J. Imaging Technol., 11 (4), 191 (198
5), HM Houlihan et al, Macormolecules, 21, 2001 (198
8), PMCollins et al., J. Chem. Soc., Chem. Commun., 532
(1972), S. Hayase etal, Macromolecules, 18, 1799 (198
5), E. Reichmanis et al., J. Electrochem. Soc., Solid Sta.
te Sci.Technol., 130 (6), FMHoulihan etal, Macromo
lcules, 21, 2001 (1988), EP 0290,750, EP 046,
No. 083, No. 156,535, No. 271,851, No. 0,388,343, U.S. Pat.Nos. 3,901,710, 4,181,531, JP-A-60-19853
No. 8, a photoacid generator having an o-nitrobenzyl-type protecting group described in JP-A-53-133022, M. TUNOOKA etal, Polym
er Preprints Japan, 35 (8), G. Berner et al., J. Rad. Cur
ing, 13 (4), WJMijs et al, Coating Technol., 55 (69
7), 45 (1983), Akzo, H. Adachi et al, Polymer Preprints,
Japan, 37 (3), European Patent Nos. 0199,672, 84515, 19
No. 9,672, No. 044,115, No. 0101,122, U.S. Pat.
No. 564, 4,371,605, 4,431,774, JP-A-64-1814
No. 3, JP-A-2-245756, compounds capable of generating sulfonic acid by photodecomposition represented by iminosulfonate described in Japanese Patent Application No. 3-140109, etc., described in JP-A-61-166544 and the like. The disulfone compound of the above can be mentioned.

Further, a group that generates an acid by these lights,
Alternatively, a compound having a compound introduced into the main chain or side chain of a polymer, for example, MEWoodhouse et al., J. Am. Chem.
c., 104, 5586 (1982), SPPappas etal, J. Imaging Sc
i., 30 (5), 218 (1986), S. Kondo et al., Makromol. Chem., R
apid Commun., 9,625 (1988), Y.Yamada et al., Makromol.
Chem., 152, 153, 163 (1972), JVCrivello et al, J. Pol
ymerSci., Polymer Chem.Ed., 17, 3845 (1979), U.S. Pat.No. 3,849,137, German Patent No. 3914407, JP-A-63-26653
No., JP-A-55-164824, JP-A-62-69263, JP-A-63-69
No. 146038, JP-A-63-163452, JP-A-62-153853,
The compounds described in JP-A-63-146029 can be used.

Further, VNRPillai, Synthesis, (1), 1 (198
0), A. Abad etal, Tetrahedron Lett., (47) 4555 (197
1), DHR Barton et al., J. Chem. Soc., (C), 329 (1970),
Compounds that generate an acid by light described in U.S. Pat. No. 3,779,778 and European Patent 126,712 can also be used.

Among the above compounds which can be used together and which generate an acid by being decomposed by 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 (PAG)
An S-triazine derivative represented by 2).

[0054]

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

[0056]

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[0057]

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

[0059]

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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 include an aryl group, an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, a nitro group,
A carboxyl group, a hydroxy group and a halogen atom, and an alkyl group is an alkoxy group having 1 to 8 carbon atoms, a carboxyl group and an alkoxycarbonyl group.

Z^-Represents a counter anion, for example, B
F_Four ^-, AsF₆ ^-, PF₆ ^-, SbF₆ ^-, Si
F₆ ^2-, ClO_Four ^-, CF_ThreeSO_Three ^-Perfluoroa
Lucanesulfonic acid anion, pentafluorobenzenes
Sulfonic acid anion, naphthalene-1-sulfonic acid anion
Polynuclear aromatic sulfonate anions such as
Non-sulfonic acid anions, sulfonic acid group-containing dyes, etc.
But not limited to
No.

Further, two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded through a single bond or a substituent.

Specific examples include the following compounds, but are 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 above-mentioned onium salts represented by the general formulas (PAG3) and (PAG4) are known, 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), HM Leicester, JA
me.Chem.Soc., 51,3587 (1929), JVCrivello etal, JP
olym. Chem. Ed., 18, 2677 (1980), U.S. Pat. Nos. 2,807,648 and 4,247,473, and JP-A-53-101,331.

(3) Disulfone derivatives represented by the following general formula (PAG5) or iminosulfonate derivatives represented by the following general formula (PAG6).

[0074]

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Where Ar^Three, Ar^FourAre each independently substituted
Or an unsubstituted aryl group. R ²⁰⁶Is replaced or
It represents an unsubstituted alkyl group or aryl group. 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.

[0076]

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[0077]

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[0078]

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[0079]

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[IV] (b) A resin having a group that decomposes under the action of an acid to increase the solubility in an alkaline developer (hereinafter, also simply referred to as “component (b)”) The chemically amplified resist of the present invention Examples of the resin having a group capable of decomposing with an acid used in (1) and increasing the solubility in an alkaline developer (also referred to as a group decomposable with an acid) include a main chain or a side chain of the resin, or a main chain and a side chain. Resin having acid-decomposable groups on both chains. Among them, a resin having a group which can be decomposed by an acid in a side chain is more preferable. A preferred group capable of being decomposed by an acid is -COOA
^0, a -O-B ⁰ group, the group further comprising them,
-R ⁰ -COOA ^0, or group represented by -Ar-O-B ^0. Here, A ⁰ is -C (R ⁰¹ ) (R ⁰² )
^{(R 03), - Si (} R 01) (R 02) (R 0 3) or -
And represents a C (R ⁰⁴ ) (R ⁰⁵ ) -OR ⁰⁶ group. B ⁰ is A ⁰
Or an -CO-O-A ⁰ group (R ^0, R ⁰¹ ~R ⁰⁶ and A
r is as defined below).

The acid-decomposable group is preferably a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, an enol ether group, an enol ester group, a tertiary alkyl ether group, or a tertiary alkyl ester. And tertiary alkyl carbonate groups. 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. Particularly preferred is an acetal group.

Next, when the groups decomposable by these acids are bonded as side chains, the base resin has —OH or —COOH, preferably —R ⁰ —COOH or —Ar—OH group on the side chain. It is an alkali-soluble resin. For example, an alkali-soluble resin described below can be used.

The alkali dissolution rate of these alkali-soluble resins was measured using a 0.261N tetramethylammonium hydroxide (TMAH) (at 23 ° C.).
A / sec or more is preferable. Particularly preferably 330A
Per second or more (where A is Angstroms). 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, a 1 μm film thickness of 24
The transmittance at 8 nm is 20 to 90%. From such a viewpoint, particularly preferred alkali-soluble resins are o-, m
-, P-poly (hydroxystyrene) and copolymers thereof, hydrogenated poly (hydroxystyrene), halogen or alkyl-substituted poly (hydroxystyrene), part of poly (hydroxystyrene), O-alkylated or O- An 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-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.

Pt-butoxystyrene / p-hydroxystyrene copolymer, p- (t-butoxycarbonyloxy) styrene / p-hydroxystyrene copolymer, p
-(T-butoxycarbonylmethyloxy) styrene /
p-hydroxystyrene copolymer, 4- (t-butoxycarbonylmethyloxy) -3-methylstyrene / 4
Hydroxy-3-methylstyrene copolymer, p- (t-
(Butoxycarbonylmethyloxy) styrene / p-hydroxystyrene (10% hydrogenated) copolymer, m-
(T-butoxycarbonylmethyloxy) styrene / m
-Hydroxystyrene copolymer, o- (t-butoxycarbonylmethyloxy) styrene / o-hydroxystyrene copolymer, p- (cumyloxycarbonylmethyloxy) styrene / p-hydroxystyrene copolymer, cumyl methacrylate / Methyl methacrylate copolymer,
4-t-butoxycarbonylstyrene / dimethyl maleate copolymer, benzyl methacrylate / tetrahydropyranyl methacrylate,

P- (t-butoxycarbonylmethyloxy) styrene / p-hydroxystyrene / styrene copolymer, pt-butoxystyrene / p-hydroxystyrene / fumaronitrile copolymer, t-butoxystyrene / hydroxyethyl methacrylate Copolymer, styrene / N- (4-hydroxyphenyl) maleimide / N-
(4-t-butoxycarbonyloxyphenyl) maleimide copolymer, p-hydroxystyrene / t-butyl methacrylate copolymer, styrene / p-hydroxystyrene / t-butyl methacrylate copolymer p-hydroxystyrene / t-butyl Acrylate copolymer, styrene / p-hydroxystyrene / t-butyl acrylate copolymer p- (t-butoxycarbonylmethyloxy) styrene / p-hydroxystyrene / N-methylmaleimide copolymer, t-butyl methacrylate / 1 -Adamantyl methyl methacrylate copolymer, p-hydroxystyrene / t-butyl acrylate / p-acetoxystyrene copolymer, p-hydroxystyrene / t-butyl acrylate / p- (t-butoxycarbonyloxy) styrene copolymer , P- hydroxystyrene / t-butyl acrylate / p-(t-butoxycarbonylmethyloxy)
Styrene copolymer,

[0088]

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In the present invention, as the resin having an acid-decomposable group (component (b)), a resin containing a repeating structural unit represented by the above-mentioned general formulas (IV) and (V) is preferable. Thereby, it has a high resolution and the performance change over time from exposure to heating is reduced.

The alkyl group in L and Z in the general formula (IV) includes methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, cyclopentyl, hexyl Group, cyclohexyl group, octyl group, dodecyl group, etc.
Straight-chain, branched or cyclic ones.

Preferred substituents of the alkyl group include an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acylamino group, a sulfonylamino group,
Examples include an alkylthio group, an arylthio group, and an aralkylthio group.Examples include a cyclohexylethyl group, an alkylcarbonyloxymethyl group, an alkylcarbonyloxyethyl group, an arylcarbonyloxyethyl group, an aralkylcarbonyloxyethyl group, an alkyloxymethyl group, and an aryloxy group. Methyl group, aralkyloxymethyl group, alkyloxyethyl group, aryloxyethyl group, aralkyloxyethyl group, alkylthiomethyl group, arylthiomethyl group, aralkylthiomethyl group,
Examples thereof include an alkylthioethyl group, an arylthioethyl group, and an aralkylthioethyl group. The alkyl in this case is not particularly limited, but may be any of a chain, a ring, and a branch, and examples thereof include a group such as a cyclohexylcarbonyloxyethyl group, a t-butylcyclohexylcarbonyloxyethyl group, and an n-butylcyclohexylcarbonyloxyethyl group. Can be mentioned. Also, the aryl is not limited, but includes, for example, a phenyloxyethyl group and the like, and may be further substituted, for example, a cyclohexylphenyloxyethyl group. The aralkyl is not particularly limited, but examples thereof include a benzylcarbonyloxyethyl group.

Examples of the aralkyl group in L and Z include those having 7 to 15 carbon atoms, such as a substituted or unsubstituted benzyl group and a substituted or unsubstituted phenethyl group. Preferred substituents of the aralkyl group include an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acylamino group, a sulfonylamino group, an alkylthio group, an arylthio group, an aralkylthio group, and the like. Examples include a benzyl group and a phenylthiophenethyl group. As described above, the introduction of a bulky group such as a phenyl group or a cyclohexyl group into the terminal of the substituted alkyl group or substituted aralkyl group can further improve edge roughness in combination with the acid generator of the present invention.

5 or 6 formed by combining L and Z with each other
Examples of the member ring include a tetrahydropyran ring and a tetrahydrofuran ring.

The ratio of the repeating structural unit represented by the general formula (IV) to the repeating structural unit represented by the general formula (V) in the resin is preferably from 1/99 to 60/40, more preferably from 1/99 to 60/40. It is 5/95 to 50/50, more preferably 10/90 to 40/60.

The resin containing the repeating structural units represented by the general formulas (IV) and (V) may include structural units derived from other monomers. Other monomers include hydrogenated hydroxystyrene; halogen, alkoxy or alkyl-substituted hydroxystyrene; styrene; halogen, alkoxy, acyloxy or alkyl-substituted styrene; maleic anhydride; acrylic acid derivative; methacrylic acid derivative; Examples include, but are not limited to:
The ratio between the structural units of the general formulas (IV) and (V) and the structural units of the other monomers is represented by a molar ratio of [(IV) +
(V)] / [other monomer components] = 100/0 to 50 /
50, preferably 100/0 to 60/40, and more preferably 100/0 to 70/30.

Specific examples of the resin containing a repeating structural unit represented by the above general formulas (IV) and (V) include:
The following are mentioned.

[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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In the above specific examples, Me is a methyl group, E
t represents an ethyl group, nBu represents an n-butyl group, iso-Bu represents an isobutyl group, and tBu represents a t-butyl group.

When an acetal group is used as the acid-decomposable group, a polyhydroxy compound is added in the synthesis stage to adjust the alkali dissolution rate and improve heat resistance to introduce a cross-linking site connecting the polymer main chain with a polyfunctional acetal group. May be. The amount of the polyhydroxy compound to be added is 0.01 to 5 mol%, more preferably 0.05 to 4 mol%, based on the amount of hydroxyl groups of the resin. Examples of the polyhydroxy compound include those having 2 to 6 phenolic hydroxyl groups or alcoholic hydroxyl groups, preferably 2 to 4 hydroxyl groups, and more preferably 2 to 4 hydroxyl groups.
Or three. Specific examples of the polyhydroxy compound are shown below, but the present invention is not limited thereto.

[0109]

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The weight average molecular weight (Mw) of the resin having an acid-decomposable group is preferably in the range of 2,000 to 300,000. If it is less than 2,000, the film thickness is greatly reduced due to the development of the unexposed portion. Here, the weight average molecular weight is defined as a polystyrene equivalent value of gel permeation chromatography.

The component (b) of the photosensitive composition of the present invention, that is, a resin having an acid-decomposable group, may be used as a mixture of two or more kinds. The amount of the component (b) used is 40 to 9 based on the total weight of the photosensitive composition (excluding the solvent).
It is 9% by weight, preferably 60 to 98% by weight.

[V] (d) Low-molecular acid-decomposable dissolution inhibiting compound The photosensitive composition of the present invention comprises (d) a low-molecular acid-decomposable dissolution-inhibiting compound (hereinafter, also simply referred to as “component (d)”). May be contained. The component (d) has a group that can be decomposed by an acid, and the solubility in an alkali developer increases by the action of an acid.
00, more preferably 300 to 1,500 low molecular weight compounds. When the content of the component (d) is combined with the acid-decomposable group-containing resin and the photoacid generator, the content is preferably 3 to 4 based on the total weight of the photosensitive composition (excluding the solvent).
It is 5% by weight, more preferably 5 to 30% by weight, still more preferably 10 to 20% by weight.

The preferred component (d), that is, the preferred acid-decomposable dissolution-inhibiting compound has at least two acid-decomposable groups in its structure, and the distance between the acid-decomposable groups is the longest. A compound that has at least 8 bonding atoms in position except for the acid-decomposable group. A more preferred acid-decomposable dissolution-inhibiting compound is (A) an acid-decomposable compound having at least two groups capable of being decomposed by an acid in its structure, and wherein the distance between the acid-decomposable groups is the farthest. At least 10 and preferably at least 11
, More preferably at least 12 compounds,
And (ii) at least three acid-decomposable groups, and the distance between the acid-decomposable groups is at least 9, and preferably at least 10, excluding the acid-decomposable groups at the farthest position. More preferably, it is a compound passing through at least 11. The upper limit of the number of the bonding atoms is preferably 50, and more preferably 30.

When the acid-decomposable dissolution-inhibiting compound has three or more, preferably four or more acid-decomposable groups, and also when it has two acid-decomposable groups, the acid-decomposable groups are mutually fixed at a certain level. If the distance is not less than the distance, the dissolution inhibiting property with respect to the alkali-soluble resin is significantly improved. The distance between the acid-decomposable groups 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 four bonding atoms each,
In compound (3), it has 12 bonding atoms.

[0115]

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The acid-decomposable dissolution-inhibiting compound may have a plurality of acid-decomposable groups on one benzene ring, but preferably one acid-decomposable group on one benzene ring. It is a compound composed of a skeleton having a group.

A group which can be decomposed by an acid, that is, —COO-A
⁰ and a group containing a —O—B ⁰ group include —R ⁰ —COO—
A ⁰ or a group represented by —Ar—O—B ⁰ is exemplified.
Here, A ⁰ represents -C (R ⁰¹ ) (R ⁰² ) (R ⁰³ ), -Si
^{(R 01) (R 02)} (R 0 3) or -C (R ⁰⁴⁾
It represents a (R ⁰⁵ ) -OR ⁰⁶ group. B ⁰ is A ⁰ or -CO-
It represents an ^OA group. R ⁰¹ , R ⁰² , R ⁰³ , R ⁰⁴ and R
⁰⁵ is the same or different and represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and R ⁰⁶ represents an alkyl group or an aryl group. However, at least two of R ^{01 to} R ⁰³ are groups other than hydrogen atoms, and even when two groups of R ^{01 to} R ⁰³ and R ^{04 to} R ⁰⁶ are bonded to form a ring. Good. R ⁰ represents a divalent or higher valent aliphatic or aromatic hydrocarbon group which may have a substituent, and -Ar- represents a divalent or higher valent which may have a monocyclic or polycyclic substituent. Shows an aromatic group.

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 are those 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,
Methoxycarbonyl group, alkoxycarbonyl group such as ethoxycarbonyl group, benzyl group, aralkyl group such as phenethyl group, cumyl group, aralkyloxy group, formyl group, acetyl group, butyryl group, benzoyl group, cyanyl group, acyl such as valeryl group Group, acyloxy group such as butyryloxy group, the above alkenyl group, 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-mentioned aryl group and phenoxy group, and an aryloxycarbonyl group such as a benzoyloxy group.

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

The component (d) is preferably selected from those described in JP-A No. 1-2
89946, JP-A-1-289947, JP-A-2-
2560, JP-A-3-128959, JP-A-3-1
58855, JP-A-3-179353, JP-A-3-179
191351, JP-A-3-200251, JP-A-3-3
JP-A-200252, JP-A-3-200253, JP-A-3-200254, JP-A-3-200255, JP-A-3-259149, JP-A-3-279958, JP-A-3-279959, JP-A-4-200 1650, JP-A-4-1651, JP-A-4-11260, JP-A-4
-12356, JP-A-4-12357, Japanese Patent Application No. 3-
No. 33229, Japanese Patent Application No. 3-230790, Japanese Patent Application No. 3-230
No. 320438, Japanese Patent Application No. 4-25157, Japanese Patent Application No. 4-
No. 52732, No. 4-103215, No. 4-
104542, Japanese Patent Application No. 4-107885, Japanese Patent Application No. 4
No. -107889, groups shown above some or all of the phenolic OH groups of the polyhydroxy compounds described herein, such as Nos. 4-152195, -R ⁰ -COO-
Protected compounds linked by A ⁰ or B ⁰ groups are 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 and 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, the following general formulas [I] to [VI]
II].

[0123]

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[0124]

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[0125]

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Here, R¹⁰¹, R¹⁰², R¹⁰⁸,
R¹³⁰: Identical or different, a hydrogen atom, -R⁰-COO
-C (R⁰¹) (R⁰²) (R⁰³) Or -CO-OC
(R⁰¹) (R⁰²) (R ⁰³) Where R⁰, R⁰¹, R⁰²Passing
And R⁰³Is the same as defined above.

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

[0128]

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[0129] Here, G = 2 to 6, provided that at least one alkyl group among when G = 2 is ^{R 150, R 151, R 150} , R 151: the same or different, a hydrogen atom, an alkyl group, an alkoxy Group, —OH, —COOH, —CN, a halogen atom, —R ¹⁵² —COOR ¹⁵³ or —R ¹⁵⁴
—OH, R ¹⁵² , R ¹⁵⁴ : alkylene group, R ¹⁵³ : hydrogen atom, alkyl group, aryl group or aralkyl group, R ⁹⁹ , R ^{103 to} R ¹⁰⁷ , R ¹⁰⁹ , R ^{111 to} R ¹¹⁸ , R
^{128 to} R ¹²⁹ , R ^{131 to} R ¹³⁴ , R ¹³⁸ , R ¹³⁹ : the same or different, hydrogen atom, hydroxyl group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, aralkyl group, aralkyl An oxy group, a halogen atom, a nitro group, a carboxyl group, a cyano group, or -N ( ^R155 ) ( ^R156 ) ( ^R155 , ^R156 : H, an alkyl group, or an aryl group) ^R110 : a single bond, An alkylene group, or

[0130]

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R ¹⁵⁷ , R ¹⁵⁹ : the same or different, 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, a t-butoxycarbonylmethyl group, a tetrahydropyranyl group, a 1-ethoxy-1-ethyl group) ,
(1-t-butoxy-1-ethyl group).

R ¹¹⁹ and R ^{120 are the} same or different and are each a methylene group, a lower alkyl-substituted methylene group, a halomethylene group, or a haloalkyl group, provided that the lower alkyl group is an alkyl group having 1 to 4 carbon atoms; R ¹²⁴ to R ^127: the same or different, a hydrogen atom or an alkyl group, R ¹³⁵ to R ^137: the same or different, a hydrogen atom, an alkyl group, an alkoxy group, an acyl group or an acyloxy group,, R ¹⁴⁶ to R ^149: Same or different, hydrogen atom, hydroxyl group, halogen atom, nitro group, cyano group, carbonyl group, alkyl group, alkoxy group, alkoxycarbonyl group, aralkyl group, aralkyloxy group, acyl group, acyloxy group, alkenyl group, alkenyloxy Group, aryl group, aryloxy group, or aryloxycarbonyl group, provided that And each of the four substituents having the same symbol may not be the same group. Z, B: a single bond or —O—, A: a methylene group, a lower alkyl-substituted methylene group, a halomethylene group, or a haloalkyl group; a to v, c1 to r1: When plural, the groups in parentheses may be the same or different. a to q, s, t, v, g1 to i1, k1 to m1, o1, q1: 0 or 1-5
An integer of r, u, w, x, y, z, c1 to f1, p1, r1: 0 or an integer of 1 to 4, j1, n1, z1, a2, b2, c2, d2: 0 or 1 to 3 An integer of at least one of a2, c2, and d2 is 1 or more; (a + b), (e + f + g), (k + l + m), (q + r + s), (c1 + d1), (g1 + h1 + i1 + j
1), (o1 + p1) ≧ 2, (j1 + n1) ≦ 3, (r + u), (c1 + e1), (d1 + f1), (p1 + r1) ≦ 4, (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) ≦ 5.

[0133]

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[0134]

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[0135]

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Specific examples of preferred compound skeletons are shown below.

[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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[0143]

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[0144]

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[0145]

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[0146]

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[0147]

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[0148]

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[0149]

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R in the compounds (1) to (44) represents a hydrogen atom,

[0151]

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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
May 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 a photoacid generator and an alkali-soluble resin. , Preferably 5 to 40% by weight, more preferably 10 to 35% by weight.

[VI] (e) Resin Insoluble in Water and Soluble in Alkaline Developing Solution The composition of the present invention is used for controlling alkali solubility.
A resin that is insoluble in water and soluble in an alkali developer (hereinafter, also simply referred to as “component (e)”) can be contained. This resin has substantially no acid-decomposable groups. (E)
As the component, for example, novolak resin, 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, part of O- to hydroxyl group of polyhydroxystyrene
Alkyl compounds (for example, 5 to 30 mol% of O-methyl compound, O- (1-methoxy) ethyl compound, O- (1-ethoxy) ethyl compound, O-2-tetrahydropyranyl compound, O- (t- Butoxycarbonyl) methylated product) or O-acylated product (for example, 5 to 30 mol% of O-
Acetylated product, O- (t-butoxy) carbonylated product, etc.), styrene-maleic anhydride copolymer, styrene-
Examples thereof include, but are not limited to, hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, carboxyl group-containing methacrylic resin and its derivative, and polyvinyl alcohol derivative.

Particularly preferred alkali-soluble resins are novolak resins, o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrene, and a part of O-polystyrene. Alkylated or O-acylated products, styrene-hydroxystyrene copolymers, and α-methylstyrene-hydroxystyrene copolymers. 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.

The weight average molecular weight of the novolak resin is 1,
It is preferably in the range of 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 is the range of 2,000 to 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 to 20,000.
0, more preferably 8,000 to 100,000. Further, from the viewpoint of improving the heat resistance of the resist film, it is preferably 10,000 or more. 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 the alkali-soluble resin used is 40 to 97% by weight, preferably 60 to 90% by weight, based on the total weight of the photosensitive composition (excluding the solvent).

[VII] Other Components Used in the Present Invention The positive photosensitive composition of the present invention may further contain, if necessary, a dye, a pigment, a plasticizer, a surfactant, a photosensitizer, and a developing agent. A compound having two or more phenolic OH groups that promote solubility in a liquid 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 this phenol compound is 2 to 50% by weight, more preferably 5 to 30% by weight, based on the alkali-soluble resin. 50% by weight
If the addition amount exceeds the above range, the development residue becomes worse and a new defect that the pattern is deformed at the time of development occurs, which is not preferable.

Such a phenol compound having a molecular weight of 1,000 or less can be prepared by, for example, referring to the methods described in JP-A-4-122938, JP-A-2-28531, US Pat. No. 4,916,210, and EP 219294. ,
It can be easily synthesized by those skilled in the art. 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 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, the following spectral sensitizers are added to sensitize the photosensitive composition of the present invention to a longer wavelength region than the deep ultraviolet where the photoacid generator used has no absorption. Sensitivity can be given to i or g rays. 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,
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. 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 each of the above components and applied 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.

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-mentioned photosensitive composition is applied on a substrate (eg, silicon / silicon dioxide coating) to be used in the manufacture 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.

The developer for the photosensitive composition of the present invention includes:
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Inorganic alkalis such as sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, and 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.

[0168]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

(C) As the basic nitrogen-containing compound, the above-mentioned exemplified compounds (VI-1), (VI-2), (VI-3) and (VI)
-4) (Aldrich) was used.

(A) Synthesis of acid-generating compound Synthesis of compound (I-6) A solution of methanesulfonic acid / diphosphorus pentoxide (10/1) in 12.4 g of diphenylsulfoxide and 7.5 g of 2,6-dimethylphenol was used. 30 ml were added. After the exotherm subsided, the mixture was heated at 50 ° C. for 2 hours, and then the reaction solution was poured on ice. This aqueous solution was washed with toluene and filtered, and then a solution prepared by dissolving 200 g of ammonium iodide in 400 ml of water was added. The precipitated powder was collected by filtration and washed with water to obtain diphenyl (4-hydroxy-3,5-dimethylphenyl) sulfonium iodide.

50 g of diphenyl (4-hydroxy-3,5-dimethylphenyl) sulfonium iodide was dissolved in 500 ml of methanol, and 29 g of silver oxide was added thereto.
Was added and stirred for 4 hours. After filtering the reaction solution,
36 g of 4,6-triisopropylbenzenesulfonic acid were added. The powder obtained by concentrating this solution was sufficiently washed with water and recrystallized from methanol / acetone / water (3/2/2) to obtain 40 g of a compound (I-6). Using the same method, other compounds were also synthesized.

[Synthesis Example I-1] <Synthesis of Alkali-Soluble Resin (R-1)> 32.4 g (0.2 mol) of p-acetoxystyrene was added to butyl acetate 12
0 ml, and added with azobisisobutyronitrile (AIBN) 0.033 g three times every 2.5 hours at 80 ° C. under a nitrogen stream and stirring, and finally, stirring was continued for another 5 hours. A polymerization reaction was performed. The reaction solution was poured into 1200 ml of hexane to precipitate a white resin. After drying the obtained resin, it was dissolved in 150 ml of methanol. To this, 7.7 g (0.19 mol) of sodium hydroxide
An aqueous solution of 50 ml of water / water was added, and the mixture was heated under reflux for 3 hours to be hydrolyzed. Thereafter, 200 ml of water was added for dilution, and neutralized with hydrochloric acid to precipitate a white resin. This resin was separated by filtration, washed with water and dried. Further, it was dissolved in 200 ml of tetrahydrofuran, and dropped and reprecipitated in 5 L of ultrapure water with vigorous stirring. This reprecipitation operation was repeated three times. The obtained resin is placed in a vacuum dryer at 120 ° C., 1
After drying for 2 hours, an alkali-soluble poly (p-hydroxystyrene) resin (R-1) was obtained. The weight average molecular weight (polystyrene equivalent value measured by the GPC method) of the obtained resin was 15,000.

[Synthesis Example I-2] <Synthesis of alkali-soluble resin (R-2)> Poly (p-hydroxystyrene) (VP800, manufactured by Nippon Soda Co., Ltd.)
0) was defined as an alkali-soluble resin (R-2). The weight average molecular weight was 9,800.

[Synthesis Example II-1] <Synthesis of 2-thienylcarbonyloxyethyl vinyl ether (X-1)> 100 g of thiophen-2-carboxylic acid (thenoyl acid) was added to 500 ml of DMAc (N, N-
Dimethylacetamide), 31 g of sodium hydroxide was added, and the mixture was stirred at room temperature for 10 minutes. Thereto was added 2-chloroethyl vinyl ether (112 g), and the mixture was stirred at 120 ° C for 2 hours (salt was precipitated). Water and ethyl acetate were added to the reaction solution, a liquid separation operation was performed, and water washing was performed three times. The obtained organic phase was dried, concentrated, and then subjected to distillation under reduced pressure to obtain the target product (X-1). The target compound was identified by NMR.

[Synthesis Example II-2] <Synthesis of 4-t-butylcyclohexylcarbonyloxyethyl vinyl ether (X-2)> Synthesis Example II except that 4-t-butylcyclohexanecarboxylic acid was used as a raw material.
The same procedure as in -1 was carried out to obtain the desired product (X-2).

[Synthesis Example II-3] <Synthesis of Vinyloxyethylpyrrolidone (X-3)> The desired product (X-3) was prepared in the same manner as in Synthesis Example II-1, except that 2-pyrrolidone was used as a raw material. ) Got.

[Synthesis Example II-4] <Synthesis of cyclohexylethyl vinyl ether (X-4)> Synthesis Example II-1 except that cyclohexylmagnesium bromide or cyclohexyllithium was used as a raw material.
By the same operation as in, the desired product (X-4) was obtained.

[Synthesis Example II-5] <Cyclohexylthioethyl vinyl ether (X-5)
Synthesis of Compound (X-5) in the same manner as in Synthesis Example II-1 except that cyclohexanethiol was used as a raw material.
I got

Ethyl vinyl ether was designated as (X-6) and isobutyl vinyl ether was designated as (X-7).

The vinyl ether (X-1) synthesized above
To (X-7) are shown below.

[0181]

Embedded image

[Synthesis Example III-1] <Synthesis of Alkali-Soluble Resin (B-1)> Synthesis Example I-1
20 g of the alkali-soluble resin (R-1) obtained in (1) above was mixed with propylene glycol monomethyl ether acetate (PG
MEA) and dehydrated by distillation under reduced pressure.
11 g of vinyl ether (X-1) synthesized in II-1 and p
-Toluenesulfonic acid (40 mg) was added, and the mixture was stirred at room temperature for 2 hours. 42 mg of triethylamine was added to the reaction solution, and then ultrapure water and ethyl acetate were added to carry out liquid separation, followed by washing three times with water. Ethyl acetate and water were distilled off by distilling the obtained organic phase under reduced pressure to obtain the alkali-soluble resin (B-1) having a substituent according to the present invention.

[Synthesis Examples III-2 to III-7] <Synthesis of alkali-soluble resins (B-2) to (B-7)>
The alkali-soluble resins (B-2) to (B-7) were synthesized in the same manner as in Synthesis Example III-1, except that the resin and vinyl ether were changed as described in Table A below.

[Synthesis Example III-8] <Synthesis of alkali-soluble resin (B-8)> Synthesis Example I-1
20 g of the alkali-soluble resin (R-1) obtained in (1) above was mixed with propylene glycol monomethyl ether acetate (PG
MEA) and dehydrated by distillation under reduced pressure. Then, 11 g of vinyl ether (X-1) and p-toluenesulfonic acid 4
0 mg was added and the mixture was stirred at room temperature for 2 hours. 2.0 g of pyridine and 2.1 g of acetic anhydride were added to the reaction solution, and the mixture was stirred for 1 hour. Thereafter, ultrapure water and ethyl acetate were added to carry out a liquid separation operation, followed by washing three times with water. Ethyl acetate and water were removed by distilling the obtained organic phase under reduced pressure, and the alkali-soluble resin (B-8) having a substituent according to the present invention was removed.
I got

[Synthesis Examples III-9 to III-14] <Synthesis of Alkali-Soluble Resins (B-9) to (B-14)> The resins and vinyl ethers were changed as shown in Table A below. In the same manner as in Example III-8, the resin (B-
9) to (B-14) were synthesized.

[Synthesis Examples III-15 to III-21] <Synthesis of Alkali-Soluble Resins (B-15) to (B-21)> As the raw materials of Synthesis Examples III-1 to III-7, alkali-soluble resins (R Synthesis Example II except that the alkali-soluble resin (R-2) obtained in Synthesis Example I-2 was used instead of -1).
In the same manner as in I-1 to III-7, each resin (B-1
5) to (B-21) were synthesized.

[Synthesis Examples III-22 to III-28] <Synthesis of Alkali-Soluble Resins (B-22) to (B-28)> As a raw material of Synthesis Examples III-8 to III-14, an alkali-soluble resin (R Synthesis Example 1 except that the alkali-soluble resin (R-2) obtained in Synthesis Example I-2 was used instead of -1).
In the same manner as in III-8 to III-14, each resin (B-
22) to (B-28) were synthesized.

[0188]

[Table 1]

Examples 1 to 39 and Comparative Examples 1 to 3 [Preparation and Evaluation of Photosensitive Composition] Each material shown in the following Table B was dissolved in 8 g of PGMEA (propylene glycol monoethyl ether acetate), and 0.2 μm Then, a resist solution was prepared by filtration through a filter. This resist solution was applied on a silicon wafer using a spin coater, and dried on a vacuum suction type hot plate at 130 ° C. for 60 seconds to obtain a 0.8 μm-thick resist film.

[0190]

[Table 2]

[0191]

[Table 3]

In Table B above, the non-polymeric dissolution inhibiting compound is a compound (41) which is a specific example of the skeleton, and has a structure represented by the following (g-1). The photoacid generators and organic basic compounds used in Examples and Comparative Examples are shown below.

[0193]

Embedded image

The resist film was exposed using a 248 nm KrF excimer laser stepper (NA = 0.45). After the exposure, heating was performed for 60 seconds on a hot plate at 100 ° C., and immediately immersed in an aqueous solution of 0.26 N tetramethylammonium hydroxide (TMAH) for 60 seconds,
Rinse with water for 30 seconds and dry. The pattern on the silicon wafer thus obtained was observed with a scanning electron microscope, and the performance of the resist was evaluated. Table-
C.

[Sensitivity] Indicates the minimum exposure for reproducing a 0.30 μm line and space mask pattern. [Resolution] Represents a limit resolution at an exposure amount for reproducing a 0.30 μm line and space mask pattern.

[Remaining standing wave] The side wall of the resist pattern obtained by the 0.30 μm line and space mask pattern was observed with a scanning electron microscope.
Grading was performed. ：: When there is no standing wave and the pattern side wall is clean. ：: When the standing wave is slightly observed or when the pattern side wall has irregularities. X: When the standing wave can be clearly confirmed. XX: Standing. If the waves are very strong

[Development Defects] Each resist film was applied to a thickness of 0.5 μm on a 6-inch Bare Si substrate, and dried at 130 ° C. for 60 seconds on a vacuum suction hot plate. next,
0.35 μm contact hole pattern (Hole D
ukon ratio = 1: 3) through a test mask
After exposure with a stepper NSR-1505EX, post-exposure heating was performed at 130 ° C. for 90 seconds. Continue with 2.3
After paddle development with 8% TMAH (tetramethylammonium hydroxide aqueous solution) for 60 seconds, the resultant was washed with pure water for 30 seconds and spin-dried. The number of development defects (development defects by KLA) of the thus obtained sample was measured by a KLA-2112 machine manufactured by KLA Tencor Co., Ltd., and the obtained primary data value was defined as the number of development defects. After checking by SEM, the following three-stage evaluation was performed. ：: Not recognized at all or confirmed at the level of 1 or 2 △: Approximately 10 or less confirmed ×: Number of more than 10 confirmed

[0198]

[Table 4]

As is clear from the results shown in Table C, the positive photoresist compositions of the respective examples obtained satisfactory results, while the photoresist compositions of the respective comparative examples showed the following results.
The edge roughness was very poor and the development defect was poor.

[0200]

The positive photoresist composition of the present invention has good development defects and very good LER (line edge roughness).

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shinichi Kanna 4,000 Kawajiri, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Inside Fujisha Shin Film Co., Ltd. Incorporated F term (reference) 2H025 AA03 AA04 AB15 AB16 AC08 AD03 BE07 BE10 CB14 CB17 CB45 CB52 CB55 CC01 FA17 2H096 AA25 AA26 BA09 BA11 EA05 GA08

Claims (6)

[Claims] (1) by irradiation with actinic rays or radiation
Formulas represented by the following general formulas (I) to (III) that generate an acid
At least one of the compounds, (b) is decomposed by the action of an acid,
Trees with groups that increase solubility in alkaline developers
Fat, and (c) a basic nitrogen-containing compound.
Bodi type photosensitive composition characterized by the above-mentioned. Embedded image(Where R¹~ R³⁷Is a hydrogen atom, linear, branched, or cyclic
Kill group, linear, branched, cyclic alkoxy group, hydroxy
Group, halogen atom, or -SR³⁸Represents a group. R ³⁸Is
Represents a linear, branched, or cyclic alkyl group or an aryl group.
Where R¹~ R^FifteenAt least one of R¹⁶~ R²⁷
At least one of R²⁸~ R³⁷Less of
One is a hydroxy group or an alkoxy group. X^-
Is a branched or cyclic alkyl group having 8 or more carbon atoms;
At least one group selected from the group of alkoxy groups
Having, linear, branched or cyclic C 4-7 alkyl
Groups selected from the group consisting of
Having at least two, or linear, branched or cyclic
Of the group of alkyl and alkoxy groups having 1 to 3 carbon atoms
Benzene sulf having at least three groups selected from
Fonic acid, naphthalenesulfonic acid or anthracene
Represents the anion of phonic acid. Or an ester group, R³⁹−
CO-group, R⁴⁰-CONH- group, R⁴¹-NH- group, R⁴²
—OCONH— group, R⁴³-NHCOO- group, R⁴⁴-NH
CONH- group, R ⁴⁵-NHCSN- group, R⁴⁶-SO_TwoN
Reduce the number of groups selected from the group of H-groups and nitro groups
Benzenesulfonic acid and naphthalene sulfo
Acid or an anthracenesulfonic acid anion.
R³⁹~ R⁴⁶Is a linear, branched or cyclic alkyl group or
Represents an aryl group. ) 2. A compound represented by the general formula (1) to (3), at least one of R ¹ to R ^{1 5,} R ¹⁶ -
At least one of hydroxy groups of the at least one and R ²⁸ to R ³⁷ of R ^27, and positive photosensitive according to claim 1, wherein both the adjacent position to the hydroxy group and wherein the non-hydrogen atoms Composition. (D) having a group which can be decomposed by an acid, wherein the solubility in an alkaline developer is increased by the action of an acid;
3. The positive photosensitive composition according to claim 1, further comprising a low molecular weight dissolution inhibiting compound having a molecular weight of 3000 or less. (A) at least one of the compounds represented by the general formulas (I) to (III) which generate an acid upon irradiation with actinic light according to claim 1, (c) a basic nitrogen-containing compound,
(D) having a group decomposable by an acid and having an increase in solubility in an alkaline developer due to the action of an acid having a molecular weight of 3000
A positive photosensitive composition comprising the following low molecular weight dissolution inhibiting compound and (e) a resin insoluble in water and soluble in an alkali developing solution. 5. A resin having a group which decomposes under the action of an acid to increase solubility in an alkaline developer, wherein at least one resin selected from the following formulas (IV) and (V):
The positive photosensitive composition according to any one of claims 1 to 4, which is a resin containing two repeating structural units. Embedded image (In the above formula, L represents a hydrogen atom, an optionally substituted straight-chain, branched or cyclic alkyl group, or an optionally substituted aralkyl group. Z represents an optionally substituted straight-chain, And a branched or cyclic alkyl group or an aralkyl group which may be substituted. Z and L may combine to form a 5- or 6-membered ring.) 6. The resin (b) having a group which decomposes under the action of an acid and increases the solubility in an alkali developer, is selected from the general formulas (IV) and (V) according to claim 5. A resin containing one repeating structural unit,
6. The positive photosensitive composition according to claim 5, wherein Z is a substituted alkyl group or a substituted aralkyl group.