JPH1097075A - Positive photoresist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photoresist compsn. having superior sensitivity and resolving power and less liable to a change in resist performance such as the formation of a T-top, the lowering of DOF or the deterioration of resolving power by incorporating a specified resin and/or a resin contg. specified repeating units. SOLUTION: This photoresist compsn. contains a resin represented by formula I and/or a resin contg. repeating structural units represented by formulae II, III, etc., and having a structure crosslinked by a combining group represented by formula IV in each of the units represented by the formula III, a compd. generating an acid when irradiated with active light or radiation and a compd. represented by formula V, etc. In the formulae I-IV, Rx is H or methyl, each of Rd, Re, Rg and Rh is H, 1-8C straight chain alkyl, etc., Rf is 1-6C straight chain alkylene, etc., l+m=100 and 0.05<=m/(l+m)<=0.90. In the formula V, A is H or hydroxyl, each of R1 -R7 is H, etc., each of (k) to (n) is 0 or an integer of 1-3 and (p) is an integer of 1-3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a chemically amplified positive photoresist composition used in the manufacture of semiconductor integrated circuit devices, masks for manufacturing integrated circuits, printed wiring boards, liquid crystal panels, and the like. The present invention relates to a chemically amplified positive photoresist composition in which the variation in resist performance with time is small.

[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. 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 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-mentioned positive chemically amplified resist comprises three components consisting of an alkali-soluble resin, a compound capable of generating an acid upon exposure to radiation (photoacid generator), and a compound inhibiting dissolution of the alkali-soluble resin having an acid-decomposable group. It can be roughly classified into a two-component system comprising a resin having a group which is decomposed by the reaction with an acid and becomes alkali-soluble and a photoacid generator.

In such a chemically amplified positive resist, the resist performance changes with the passage of time between exposure and post-exposure bake (PEB) (the effect of PED is large).
There was a problem. In particular, T-top formation, line width change,
A serious problem is a decrease in defocus latitude (DOF), a decrease in resolution, and a decrease in sensitivity.

Japanese Patent Application Laid-Open No. 4-217251 discloses a technique for adding a compound having a specific structure and having a phenolic OH group to a chemically amplified resist composition. However, even with this technique, the resolution is insufficient, and the resist performance such as T-top formation has changed due to the aging between exposure and post-exposure bake (PEB).

[0009]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a resist having excellent sensitivity and resolution, such as T-top formation, DOF reduction, resolution reduction and sensitivity reduction, with the lapse of exposure-PEB. An object of the present invention is to provide a chemically amplified positive photoresist composition having little change in performance.

[0010]

The object of the present invention is achieved by the following constitution. (1) It contains a resin represented by the following general formula (I) and / or a repeating structural unit represented by the following general formulas (A), (B) and (C), and is represented by the general formula (C) A resin having a cross-linked structure with a linking group represented by the general formula (D) in a repeating structural unit, a compound capable of generating an acid upon irradiation with actinic rays or radiation, and a compound represented by the following general formula (II) or general formula (III) A positive photoresist composition comprising a compound represented by the formula:

[0011]

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In the formulas (A), (B), (C) and (D), R
_X : hydrogen atom, methyl group Ra, Rb, Rd, Re, Rg, Rh: each independently a hydrogen atom, a linear alkyl group having 1 to 8 carbon atoms, 3 to 8 carbon atoms
Branched alkyl groups and cyclic alkyl groups having 3 to 6 carbon atoms (provided that Ra, Rb, Rd, Re, Rg, and Rh do not simultaneously represent a hydrogen atom. In addition, Ra and Rb, Ra and Rc,
Rd and Re or Rg and Rh may be bonded to each other to form a ring. ), Rc: linear alkyl group having 1 to 8 carbon atoms, 3 to 8 carbon atoms
Branched alkyl groups, cyclic alkyl groups having 3 to 6 carbon atoms,

[0013]

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Rf: linear alkylene group having 1 to 6 carbon atoms, branched alkylene group having 3 to 8 carbon atoms, 3 to 6 carbon atoms
Cyclic alkylene groups,

[0015]

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Ri and Rj each independently represent a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms. And the molar ratio of the repeating structural units represented by the formulas (A), (B) and (C) is 0.05 ≦ formula (B) / (formula (A) + formula (B) + formula (C) )) ≦ 0.90 0.001 ≦ Formula (C) / (Formula (A) + Formula (B) + Formula (C)) ≦ 0.20.

[0017]

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In the formula (I), R _X , Ra, Rb and Rc are
It is the same as the above. 1, m: l + m = 100 0.05 ≦ m / (l + m) ≦ 0.90

[0019]

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In the formulas (II) and (III), A is a hydrogen atom or a hydroxyl group, E and G are groups represented by the following,

[0021]

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R _{1 to} R ₄ each represent a hydrogen atom, -XR ₁₃
Or a halogen atom, R _{5 to} R ₆ : hydrogen atom, methyl group, ethyl group, haloalkyl group having 1 to 2 carbon atoms, R ₇ : hydrogen atom, methyl group, ethyl group, haloalkyl having 1 to 2 carbon atoms Groups, a to f and k to n: each an integer of 0 or 1 to 3; g to j: each of 0, 1 or 2, p: an integer of 1 to 3, D is a single bond, a carbonyl group, a sulfide group, or a sulfonyl A group, —C (R ₅ ) (R ₆ ) — or a group represented by the following:

[0023]

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R _{8 to} R ₁₂ each represent a hydrogen atom, —OH,
-CN, -COOH, -X-R ₁₃ or halogen atom, R _13: 1-8C alkyl group having a carbon, X: a single bond, -O -, - S -, - CO -, - OCO-,
Represents

(2) The general formula (I) described in the above (1)
And / or a repeating structure represented by the general formula (C), comprising a repeating structural unit represented by the general formula (A), (B) or (C) described in the above (1). In the unit, a resin having a cross-linking structure by the linking group represented by the general formula (D) described in the above (1), a compound generating an acid upon irradiation with actinic rays or radiation, and a group decomposable by the action of an acid are included A low-molecular-weight acid-decomposable dissolution-inhibiting compound having a molecular weight of 3,000 or less, whose solubility in an alkaline developer is increased by the action of an acid; and the compound represented by the general formula (II) described in (1) above.
Or, a positive photoresist composition comprising a compound represented by the general formula (III).

In the present invention, the sensitivity and resolution can be improved by adding a resin having a specific structure and a compound represented by the above general formula (II) or (III) to a chemically amplified positive photoresist composition. Exposure-PEB, which is a problem specific to chemically amplified positive photoresists
With the elapse of time, changes in resist performance such as T-top formation, DOF reduction, resolution degradation, and sensitivity reduction were successfully solved.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION

[I] a resin represented by the general formula (I) in the present invention,
And a repeating structural unit represented by the general formula (A), (B) or (C), wherein the repeating structural unit represented by the general formula (C) comprises a linking group represented by the general formula (D) Resin with cross-linked structure

The above general formulas (I) and (A) of the present invention
In (D) to (D), examples of the linear alkyl having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. 1-4 linear alkyl groups are preferred. Examples of the branched alkyl group having 3 to 8 carbon atoms include isopropyl, isobutyl, t-butyl, neopentyl, 2-methylbutyl, 3-methylpentyl, 2-ethylbutyl, and 1,1-dimethyl- Examples thereof include a 2-methylpropyl group, a 1-methylhexyl group, a 2-ethylpentyl group, a 2-ethyl-3-methylbutyl group, and a 2-ethylhexyl group, and a branched alkyl group having 3 to 5 carbon atoms is particularly preferable. . Examples of the cyclic alkyl group having 3 to 6 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group, and among them, a cyclopentyl group and a cyclohexyl group are preferable.
Ra and Rb, Ra and Rc, Rd and Re, or Rg and Rh
May be bonded to each other to form a ring, and the ring may be cyclopropyl, cyclobutyl, cyclopentyl,
Cyclohexyl and the like can be mentioned.

In Rf, a linear alkylene group having 1 to 6 carbon atoms, a branched alkylene group having 3 to 8 carbon atoms,
As the 6 to 6 cyclic alkylene groups, each having the above carbon number of 1
Examples thereof include divalent groups corresponding to the specific examples described above for a straight-chain alkyl group having 6 to 6 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, and a cyclic alkyl group having 3 to 6 carbon atoms.

The molar ratio of the repeating structural units represented by the general formulas (A), (B) and (C) is 0.05 ≦ the formula (B)
/ (Formula (A) + Formula (B) + Formula (C)) ≦ 0.90, preferably 0.10 ≦ Formula (B) / (Formula (A) + Formula (B) + Formula (C) ) ≦ 0.70, particularly preferably 0.2
0 ≦ Expression (B) / (Expression (A) + Expression (B) + Expression (C)) ≦
0.60. 0.001 ≦ Formula (C) / (Formula (A) + Formula (B) + Formula (C)) ≦ 0.20 is preferably 0.005 ≦ Formula (C) / (Formula (A) + (Formula (B) + Formula (C)) ≦ 0.15, particularly preferably 0.007 ≦ Formula (C) / (Formula (A) + Formula (B) + Formula (C)) ≦ 0.10
It is.

The repeating structural unit represented by the general formula (C) comprises a repeating structural unit represented by the general formula (A), (B) or (C). The weight average molecular weight of the resin having a crosslinked structure by a group is preferably 5,000 to 100,000, and more preferably 7000 to 50,000. The weight average molecular weight of the resin represented by the general formula (I) is 3000 to 5000
0 is preferable, and more preferably 5,000 to 30,000.

In the present invention, the resin represented by the general formula (C) contains a resin represented by the general formula (I) and / or a repeating structural unit represented by the general formulas (A), (B) and (C). The amount of the resin having a cross-linked structure represented by the general formula (D) in the repeating structural unit represented by the formula (D) in the composition is preferably 20% by weight to 99% by weight based on the total solid content. Is from 40% to 97% by weight.

Along with each resin of the present invention, the following [I
V], other resins such as the resin of [V] may be used in combination,
The resin of the present invention represented by the general formula (I) and / or the repeating structural unit represented by the general formulas (A), (B) and (C) is represented by the general formula (C) In the repeating structural unit, the proportion of the resin having a crosslinked structure by the linking group represented by the general formula (D) is from 20% by weight to 100% by weight, preferably from 40% by weight to 100% by weight, based on the total amount of the resin. is there.

[II] In the present invention, general formula (II) and
Compound represented by (III) In the compound represented by the general formulas (II) and (III) of the present invention, examples of the alkyl group for R ₁₃ include a methyl group, an ethyl group, a hydroxyethyl group, and a propyl group. , A hydroxypropyl group, an n-butyl group, an isobutyl group, a hexyl group, a 2-ethylhexyl group and the like, and an alkyl group having 1 to 8 carbon atoms, among which an alkyl group having 1 to 4 carbon atoms is particularly preferable. Examples of the halogen atom include a chlorine atom, a bromine atom, an iodine atom and a fluorine atom, and a chlorine atom and a bromine atom are particularly preferable. Examples of the haloalkyl group having 1 to 2 carbon atoms represented by R _{5 to} R ₇ include a chloromethyl group, a dichloromethyl group, a trichloromethyl group,
Bromomethyl group, dibromomethyl group, tribromomethyl group, chloroethyl group, dichloroethyl group, trichloroethyl group, bromoethyl group, but tribromoethyl group and the like, in particular a hydrogen atom and a methyl group as R ₅ to R ₇ preferable. X is a single bond, -O-, -S-, -CO
-, -OCO-, in which a single bond, -O-, -O
CO- is preferred.

The compound represented by the general formula (II) or (III) has an aromatic hydroxyl group in which the total number of carbon atoms in the molecule is 27 to 60 and the total number of aromatic hydroxyl groups is 2 to 10. Low molecular weight compounds are preferred. Among these compounds, compounds that increase the alkali dissolution rate of the alkali-soluble resin when added to the alkali-soluble resin are particularly desirable. If the compound has more than 60 carbon atoms, the effect of the present invention is reduced. If the diameter is smaller than 27, new disadvantages such as a decrease in heat resistance occur. In order to sufficiently exert the effects of the present invention, at least 2
It is necessary to have the number of hydroxyl groups,
Is exceeded, the effect of the present invention is reduced. In the present invention, specific examples of useful low molecular weight compounds having an aromatic hydroxyl group represented by the general formula (II) or (III) are shown below.
Of course, it is not limited to these.

[0036]

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[0037]

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[0038]

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[0039]

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[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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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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The preferable addition amount of the compounds represented by the general formulas (II) and (III) is 2 to 50% by weight, more preferably 3 to 30% by weight, and further preferably 3 to 30% by weight based on the resin.
１５15% by weight. With an addition amount exceeding 50% by weight,
A new disadvantage occurs in that the pattern is deformed during development. The compounds represented by the above general formulas (II) and (III)
Two or more kinds may be used as a mixture.

The general formula (II) or the general formula (III) of the present invention
The low molecular weight compound having an aromatic hydroxyl group represented by the following formula is disclosed in, for example, JP-A-2-28531, U.S. Pat. No. 4,916,621.
0, it can be easily synthesized by those skilled in the art with reference to the method described in European Patent No. 219294 and the like.

[III] Compound which decomposes upon irradiation with actinic rays or radiation to generate an acid (photoacid generator) As the photoacid generator, a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, Photochromic agents for colorants, photochromic agents,
Alternatively, a known compound that generates an acid by light and a mixture thereof used in a micro resist or the like 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. Pat.Nos. 4,069,055, 4,069,056, etc., phosphonium salts, JVCrivello et al., Macromorecules, 10 (6), 1307
(1977), Chem. & Eng. News, Nov. 28, p31 (1988), European Patent No. 104,143, U.S. Patent No. 339,049, No. 410,201.
No., JP-A-2-150,848, iodonium salts described in JP-A-2-296,514, etc., JVCrivello et al., Polymer J. 17,7
3 (1985), JVCrivello et al. J. Org.Chem., 43, 3055 (19
78), WRWatt et al, J. Polymer Sci., Polymer Chem. E
d., 22, 1789 (1984), JVCrivello etal, Polymer Bul
l., 14,279 (1985), JVCrivello etal, Macromorecules,
14 (5), 1141 (1981), JVCrivello etal, J. PolymerSc
i., Polymer Chem. Ed., 17, 2877 (1979), EP 370,6
No. 93, No. 3,902,114, No. 233,567, No. 297,443
Nos. 297,442; U.S. Pat.Nos. 4,933,377; 161,81
No. 1, 410,201, 339,049, 4,760,013,
Nos. 4,734,444 and 2,833,827, Dokoku Patent No. 2,904,62
Nos. 6, 3,604,580, 3,604,581, etc., sulfonium salts, JVCrivello et al., Macromorecules, 10
(6), 1307 (1977), JVCrivello etal, J. PolymerSci., P
olymer Chem.Ed., 17, 1047 (1979), etc., selenonium salts, CSwen et al., Teh, Proc. Conf. Rad. CuringASIA,
Onium salts such as arsonium salts described in p478 Tokyo, Oct (1988), etc., U.S. Pat.No. 3,905,815, JP-B-46-4605
No., JP-A-48-36281, JP-A-55-32070, JP-A-60-2
39736, JP-A-61-169835, JP-A-61-169837,
JP-A-62-58241, JP-A-62-212401, JP-A-63-702
No. 43, organic halogen compounds described in JP-A-63-298339, etc., K. Meier et al., J. Rad.Curing, 13 (4), 26 (1986), TP
Gilletal, Inorg.Chem., 19,3007 (1980), D. Astruc, Acc. C
hem. Res., 19 (12), 377 (1896), and organometallic / organic halides described in JP-A-2-14145, S. Hayase et al., JP
olymer Sci., 25, 753 (1987), E. Reichmanis et al., J. Phol
ymer Sci., Polymer Chem. Ed., 23, 1 (1985), QQZhueta
l, J. Photochem., 36, 85, 39, 317 (1987), B. Amitetal, Tetr
ahedron Lett., (24) 2205 (1973), DHR Barton et al., JC
hem Soc., 3571 (1965), PMCollins et al., J. Chem. SoC.,
Perkin I, 1695 (1975), M. Rudinstein et al, Tetrahedron
Lett., (17), 1445 (1975), JWWalker etal J. Am. Chem. S
oc., 110, 7170 (1988), SCBusman et al., J. Imaging Tech
nol., 11 (4), 191 (1985), HMHoulihan et al, Macormolec
ules, 21, 2001 (1988), PM Collins et al., J. Chem. Soc., Ch.
em. Commun., 532 (1972), S. Hayase et al, Macromolecules,
18,1799 (1985), E. Reichmanis et al., J. Electrochem. So
c., Solid State Sci.Technol., 130 (6), FMHoulihan e
tal, Macromolcules, 21, 2001 (1988), European Patent No. 0290,750
Nos. 046,083, 156,535, 271,851, 0,
U.S. Pat.Nos. 3,901,710 and 4,181,531
, A photoacid generator having an o-nitrobenzyl-type protecting group described in JP-A-60-198538, JP-A-53-133022, etc.
TUNOOKA etal, Polymer Preprints Japan, 35 (8), G. Bern
er etal, J.Rad.Curing, 13 (4), WJMijs etal, Coating
Technol., 55 (697), 45 (1983), Akzo, H. Adachi et al, Po
lymer Preprints, Japan, 37 (3), European Patent No. 0199,672,
No. 84515, No. 199,672, No. 044,115, No. 0101,122
Nos., U.S. Pat.Nos. 618,564, 4,371,605, 4,431,
No. 774, JP-A-64-18143, JP-A-2-245756, Japanese Patent Application No.
Compounds which generate sulfonic acid upon photolysis, such as iminosulfonates described in JP-A-3-140109, etc.
-166544 and the like.

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

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

Among the compounds capable of decomposing upon irradiation with actinic rays or radiation to generate an acid, those 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).

[0063]

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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
Show Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited thereto.

[0065]

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[0066]

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[0067]

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

[0069]

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In the formula, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. Here, 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,
And mercapto groups and halogen atoms.

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.

[0072] Z ^- represents a counter anion, CF ₃ SO ₃ ^-
And the like, such as perfluoroalkanesulfonic acid anions and pentafluorobenzenesulfonic acid anions.

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.

[0075]

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[0076]

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[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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The above onium salts represented by the general formulas (PAG3) and (PAG4) are known, for example, JWKnapcz
yk etal, J. Am. Chem. Soc., 91, 145 (1969), ALMaycoke
tal, J. Org.Chem., 35, 2532, (1970), E. Goethas et al, Bu
ll.Soc.Chem.Belg., 73,546, (1964), HM Leicester,
J. Ame. Chem. Soc., 51, 3587 (1929), JVCrivello etal,
J. Polym. Chem. Ed., 18,2677 (1980), U.S. Pat.
It can be synthesized by the methods described in JP-A Nos. 8 and 4,247,473 and JP-A-53-101,331.

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

[0085]

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

[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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The amount of the photoacid generator to be added is usually preferably from 0.001 to 40% by weight, more preferably from 0.01 to 40% by weight, based on the total weight of the resist composition (excluding the coating solvent). 20% by weight, more preferably 0.1%
-10% by weight.

[IV] Resin having a group which is decomposed by the action of an acid and increases the solubility in an alkali developer In the present invention, in addition to the resin of the above [I], it is decomposed by the action of an acid to A resin having a group that increases the solubility in a developer can be used. The resin having a group (group decomposable with an acid) that is decomposed by an acid used in the chemically amplified resist according to the present invention and increases solubility in an alkaline developer is a main chain or a side chain of the resin, or It is a resin having an acid-decomposable group in both the main chain and the side chain. Among them, a resin having a group which can be decomposed by an acid in a side chain is more preferable.

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

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

The alkali dissolution rate of these alkali-soluble resins was measured with a 0.261N tetramethylammonium hydroxide (TMAH) (23 ° C.) and measured at 170 ° C.
A / sec or more is preferable. Particularly preferably 330A
/ Sec or more (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, the transmittance at a wavelength of 248 nm with a thickness of 1 μm is 20 to 90%. From this perspective,
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-acylated product, styrene -Hydroxystyrene copolymer, α
-Methylstyrene-hydroxystyrene copolymer and hydrogenated novolak resin.

The resin having an acid-decomposable group for use 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 to these.

[0099]

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[0100]

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[0101]

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[0102]

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The content of acid-decomposable groups is determined by the number of acid-decomposable groups (B) and the number of alkali-soluble groups not protected by acid-decomposable groups (S) in the resin. B /
It is represented by (B + S). The content is preferably 0.01 to
0.5, more preferably 0.05 to 0.40, and still more preferably 0.05 to 0.30. B / (B + S)>
A value of 0.5 is not preferred because it causes film shrinkage after PEB, poor adhesion to the substrate and scum. On the other hand, B / (B + S) <
A value of 0.01 is not preferable because standing waves may be remarkably left on the pattern side wall.

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

It is preferable to mix an acid-decomposable low-molecular-weight dissolution-inhibiting compound described later with the above-mentioned photoacid generator and a resin having an acid-decomposable group.

[V] Alkali-Soluble Resin Used in the Present Invention In the present invention, it is preferable to use a resin that is insoluble in water and soluble in an aqueous alkali solution (hereinafter, also referred to as an alkali-soluble resin). Examples of the alkali-soluble resin used in the present invention include novolak resin, hydrogenated novolak resin, acetone-pyrogallol resin, o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene, hydrogenated polyhydroxystyrene, and halogen. Or an alkyl-substituted polyhydroxystyrene, a hydroxystyrene-N-substituted maleimide copolymer, o /
p- and m / p-hydroxystyrene copolymers, partially O-alkylated compounds based on hydroxyl groups of polyhydroxystyrene (for example, 5 to 30 mol% of O-methylated products, O-
(1-methoxy) ethylated product, O- (1-ethoxy) ethylated product, O-2-tetrahydropyranylated product, O-
(T-butoxycarbonyl) methylated compound) or O
-Acylated products (e.g., 5 to 30 mol% o-acetylated product, O- (t-butoxy) carbonylated product, etc.), styrene-maleic anhydride copolymer, styrene-hydroxystyrene copolymer, α-methylstyrene -Hydroxystyrene copolymer, carboxyl group-containing methacrylic resin and derivatives thereof, but are not limited thereto. Particularly preferred alkali-soluble resins are novolak resins and o-polyhydroxystyrene,
-Polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrene, partially O-alkylated or O-acylated product of polyhydroxystyrene, styrene-hydroxystyrene copolymer, α- It is a methylstyrene-hydroxystyrene copolymer. The novolak resin is obtained by subjecting a given monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

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

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

The novolak resin thus obtained preferably has a weight average molecular weight in the range of 1,000 to 30,000. If it is less than 1,000, the film loss of the unexposed portion after development is large, and if it exceeds 30,000, the developing speed is reduced. Particularly preferred are 2,000-20,
000. In addition, the weight average molecular weight of the polyhydroxystyrene other than the novolak resin, its derivative, and the copolymer is 2,000 or more, preferably 5,000.
~ 200,000, more preferably 10,000-1000
00. Further, from the viewpoint of improving the heat resistance of the resist film, 25,000 or more is preferable. here,
The weight average molecular weight is defined as a value in terms of polystyrene by gel permeation chromatography.

[VI] Low-molecular acid-decomposable dissolution inhibiting compound used in the present invention In the present invention, it is preferable to use a low-molecular acid-decomposable dissolution-inhibiting compound. The acid-decomposable dissolution inhibiting compound used in the present invention has at least two acid-decomposable groups in its structure, and at the position where the distance between the acid-decomposable groups is farthest away, the acid-decomposable group Is a compound having at least 8 bonding atoms excluding. In the present invention, the acid-decomposable dissolution-inhibiting compound preferably has at least two groups capable of being decomposed by an acid in its structure, and at the position where the distance between the acid-decomposable groups is farthest away, the acid-decomposable group A compound having at least 10, preferably at least 11, and more preferably at least 12 bonding atoms excluding the above, or a position where the distance between the acid-decomposable groups is the longest, having at least three acid-decomposable groups Is a compound having at least 9, preferably at least 10, and more preferably at least 11 bonding atoms excluding an acid-decomposable group. or,
The preferred upper limit of the number of the bonding atoms is 50, more preferably 30. In the present invention, when the acid-decomposable dissolution-inhibiting compound has three or more, preferably four or more acid-decomposable groups, and even when the compound has two acid-decomposable groups, the acid-decomposable groups are mutually present. If the distance is more than a certain distance, the dissolution inhibiting property with respect to the resin is remarkably improved. In addition,
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.

[0111]

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

In a preferred embodiment of the present invention,
A group which can be decomposed by⁰, -OB⁰
As a group containing a group, -R⁰-COO-A⁰Or -A
r-OB⁰The group shown by these is mentioned. Where A
⁰Is -C (R⁰¹) (R⁰²) (R⁰³), -Si (R⁰¹)
(R⁰²) (R ⁰³) Or -C (R⁰⁴) (R⁰⁵) -O-
R⁰⁶Represents a group. B⁰Is A⁰Or -CO-OA⁰Base
Show. R⁰¹, R⁰², R⁰³, R⁰⁴And R⁰⁵Are the same
May be different from each other, and may include a hydrogen atom, an alkyl group,
Represents a chloroalkyl, alkenyl, or aryl group
Then R⁰⁶Represents an alkyl group or an aryl group. However
Then R⁰¹~ R⁰³At least two are groups other than hydrogen atoms
And R⁰¹~ R⁰³, And R⁰⁴~ R⁰⁶Two of
The groups may combine to form a ring. R⁰Has a substituent
Divalent or higher aliphatic or aromatic hydrocarbons
Represents a group, -Ar- has a monocyclic or polycyclic substituent
And a divalent or higher aromatic group which may be present.

Here, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group and a t-butyl group. Preferred are those having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group, and alkenyl groups 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,
Alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, aralkyl groups such as benzyl group, phenethyl group and cumyl group, aralkyloxy groups, and acyl groups such as formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group, and valeryl group. Group, an acyloxy group such as a butyryloxy group, the above alkenyl group, a vinyloxy group.
Examples thereof include an alkenyloxy group such as a propenyloxy group, an allyloxy group, and a butenyloxy group, an aryloxy group such as the above-described aryl group and phenoxy group, and an aryloxycarbonyl group such as a benzoyloxy group.

The group which can be decomposed by an acid is preferably a silyl ether group, a cumyl ester group, an acetal group, a tetrahydropyranyl ether group, an enol ether group, an enol ester group, a tertiary alkyl ether group or a tertiary alkyl group. Alkyl ester groups, tertiary alkyl carbonate groups and the like. More preferred are a tertiary alkyl ester group, a tertiary alkyl carbonate group, a cumyl ester group and a tetrahydropyranyl ether group.

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

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

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

[0119]

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[0120]

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[0121]

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[0122]

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

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

[0125]

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[0126] 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

[0127]

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

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

[0130]

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R ¹⁴⁴ and R ¹⁴⁵ may be the same or different and represent a hydrogen atom, a lower alkyl group, a lower haloalkyl group,
Or an aryl group, R ^{146 to} R ¹⁴⁹ : may be the same or different and 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, at least one of z1, a2, c2, d2 is 1 or more, y1: an integer of 3 to 8, (a + b), (e + f + g), (k + l + m), (q + r + s), (w + x + y), (c1 + d1), (g1 +
h1 + i1 + j1), (o1 + p1), (s1 + t1) ≧ 2, (j1 + n1) ≦ 3, (r + u), (w + z), (x + a1), (y + b1), (c1 + e1), (d1 + f1), (p1 + r1),
(t1 + v1), (x1 + w1) ≦ 4, provided that (w +
z), (x + a1) ≦ 5, (a + c), (b + d), (e + h), (f + i), (g + j), (k + n), (l + o), (m + p), (q
+ t), (s + v), (g1 + k1), (h1 + l1), (i1 + m1), (o1 + q1), (s1 + u1)
≦ 5.

[0132]

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[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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[0150]

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[0151]

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[0152]

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[0153]

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[0154]

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[0155]

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

[0157]

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

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

[VI] Other Components Used in the Present Invention The composition of the present invention may further contain a dye, a pigment, a plasticizer, a surfactant, a photosensitizer, an organic basic compound, and the like, if necessary. It can be contained.

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).

[0162]

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Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, and particularly preferred is a ring structure containing a substituted or unsubstituted amino group and a nitrogen atom. Or a compound having an alkylamino group. Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted imidazole,
Substituted or unsubstituted pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted Or, unsubstituted aminomorpholine, substituted or unsubstituted aminoalkylmorpholine and the like can be mentioned. Preferred substituents are an amino group,
An aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group, a hydroxyl group, and a cyano group. As particularly preferred compounds, guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-
Aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino -4-methylpyridine, 2-amino-5
-Methylpyridine, 2-amino-6-methylpyridine,
3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6 -Tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p- Tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline,
Examples include, but are not limited to, N-aminomorpholine and N- (2-aminoethyl) morpholine.

These nitrogen-containing basic compounds are used alone or in combination of two or more. The amount of the nitrogen basic compound used is based on 100 parts by weight of the composition (excluding the solvent).
Usually, 0.001 to 10 parts by weight, preferably 0.01 to 10 parts by weight
5 parts by weight. If the amount is less than 0.001 part by weight, the effect of the present invention is reduced. On the other hand, if it exceeds 10 parts by weight, the sensitivity tends to decrease and the developability of the unexposed part tends to deteriorate.

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

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

The photosensitive composition of the present invention is dissolved in a solvent capable of dissolving each of the above components, and coated on a support. As the solvent used here, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate,
Ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, 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-mentioned solvent. 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, 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 for the production of precision integrated circuit devices by an appropriate 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.

As the developer for the photosensitive composition of the present invention,
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.

[0171]

EXAMPLES The present invention will be described below with reference to examples, but the present invention should not be limited to these examples. [Synthesis example of resin represented by general formula (I)] 21 g of parahydroxystyrene and 11.5 g of t-butyl vinyl ether are dissolved in 100 ml of THF, and a THF solution of hydrochloric acid (1 g of hydrochloric acid / 99 g of THF) is added thereto. And stirred at room temperature for 24 hours. The reaction solution was poured into 3 liters of water, and the precipitated powder was collected by filtration and dried to obtain the desired product [P-3]. The protection rate was 60%.

[Synthesis Example of Resin Containing Monomers of General Formulas (A) to (C)] 21 g of parahydroxystyrene and 5.
8 g of t-butyl vinyl ether and 0.86 g of 2,2-bis (4-hydroxycyclohexyl) propane are dissolved in 100 ml of THF, and THF of hydrochloric acid is added thereto.
A dissolved acid (1 g of hydrochloric acid / 99 g of THF) was added, and the mixture was added at room temperature for 24 hours.
Stirred for hours. The reaction solution was poured into 3 liters of water, and the precipitated powder was collected by filtration and dried to obtain the desired product [P-8].
The protection rate was 30%. [P-1], [P
-2], [P-4], [P-5], [P-6], [P-
7], [P-9] and [P-10] were synthesized.

Synthesis of Low Molecular Weight Compound (1) 4 equipped with a stirrer, reflux condenser, thermometer and dropping device
188 g of phenol and 300 m of acetone in a one-necked flask
1, 100 mL of distilled water and 0.5 g of hydrochloric acid,
130 ml of an acetone solution of 34.8 g of 4'-propylenebis-2,6-bishydroxymethylphenol was added to 25
The mixture was added dropwise with stirring at 1 ° C for 1 hour. After raising the temperature of the reaction solution to reflux and reacting for further 10 hours, distilled water 400 ml
, And the mixture was stirred, and an aqueous solution of tetramethylammonium hydroxide was added dropwise until the pH reached 6, and the mixture was allowed to stand after stirring.
The upper layer separated into two layers is removed by decanting, and acetone 10
400 ml of 0 ml distilled water was added, and the mixture was stirred and allowed to stand. 3-4
This operation was repeated twice, and the lower layer was separated and dried under reduced pressure.
4 g were obtained. When analyzed by GPC of a polystyrene standard, the purity was 90%.

Synthesis of low molecular weight compound (2) Synthesis was performed in the same manner as in Synthesis Example (1) except that 216 g of o-cresol was used instead of phenol. Analysis by GPC with polystyrene standards revealed a purity of 85%.

Synthesis of low molecular weight compound (3) In a three-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 34.2 g of bisphenol A, 73.2 g of 2,6-dimethylphenol, and 37% Marine aqueous solution
65 g, propylene glycol monomethyl ether 15
0 ml and 0.1 g of oxalic acid dihydrate were charged and reacted at 40 ° C. for 7 hours with stirring. The temperature was further raised to 100 ° C., and the reaction was performed for 4 hours. After the reaction, the system was cooled to room temperature, the reflux condenser was removed, and the pressure was reduced to 30 mmHg. Then, the temperature was gradually raised to 150 ° C. to remove water, solvent and unreacted monomer. When the obtained reaction product was analyzed by GPC of a polystyrene standard, it was a mixture containing hexanuclear bodies as a main component.

Synthesis of low molecular weight compound (9) Bisphenol S32.7 instead of bisphenol A
Synthesis was performed in the same manner as in Synthesis Example (3) except that g was used.
Analysis by GPC with polystyrene standards revealed a purity of 75%.

Synthesis of Low Molecular Weight Compound (6) The compound was synthesized in the same manner as in Synthesis Example (1) except that 216 g of m-cresol was used instead of phenol. Analysis by GPC with polystyrene standards revealed a purity of 78%.

Synthesis of low molecular weight compound (7) Instead of 2,6-dimethylphenol, phenol 2
The synthesis was carried out in the same manner as in Synthesis Example (3) except that 8.2 g and 36.6 g of 2,6-dimethylphenol were used. Analysis by GPC of polystyrene standard revealed that the mixture containing hexanuclear bodies as a main component had a purity of 62%.

Synthesis of low molecular weight compound (11) 4 equipped with a stirrer, reflux condenser, thermometer and dropping device
4,4 'dihydroxybenzophenone 2
7.8 g, 100 ml of methoxyethanol and 0.1 ml of hydrochloric acid.
1 g was charged, and a solution of 80 g of 4-hydroxymethyl-2,6-dimethylphenol in methoxyethanol was 230 m.
was added dropwise with stirring at 70 ° C. for 2 hours. 10 more
The temperature was raised to 0 ° C. and reacted for 4 hours. After the reaction, the system was cooled to room temperature, the reflux condenser was removed, and the pressure was reduced to 30 mmHg. Then, the temperature was gradually raised to 150 ° C. to remove water, solvent and impurities. The obtained reaction product was analyzed by GPC of polystyrene standard. As a result, it was found that the mixture mainly composed of hexanuclear bodies had a purity of 81%.

Synthesis of low molecular weight compound (17) Synthesis was performed in the same manner as in Synthesis Example (7) except that 65 g of 4-hydroxymethylphenol was used instead of 4-hydroxymethyl-2,6-dimethylphenol. did. Analysis by GPC with polystyrene standards revealed that the mixture containing hexanuclear bodies as a main component had a purity of 63%.

Synthesis of Low Molecular Weight Compound (30) In place of 27.8 g of 4,4'dihydroxybenzophenone, 32 g of 2,4,2 ', 4'tetrahydroxybenzophenone was added to 4-hydroxymethyl-2,6-dimethylpheno- 4-Hydroxymethyl-
Synthesis was performed in the same manner as in Synthesis Example (7) except that 40 g of 2,6-dimethylphenol was used. Polystyrene standard G
When analyzed by PC, the mixture containing tetranuclear as a main component had a purity of 61%.

Synthesis of low molecular weight compound (41) 116 g of phenol and 2.5 g of a 16% aqueous solution of methyl mercaptan sodium salt were placed in a flask equipped with a stirrer, reflux condenser, thermometer, dropping device and gas inlet tube. Hydrogen chloride gas was introduced while stirring at 40 ° C. to saturate the solution. Subsequently, a mixture of 19 g of p-isopropenylacetophenone and 19 g of phenol was added dropwise over 2 hours while introducing hydrogen chloride gas at 40 ° C. The reaction was carried out at 40 ° C. for 6 hours while introducing hydrogen chloride gas little by little. After the temperature was lowered to room temperature and allowed to stand overnight, 700 g of toluene and 360 g of a 3% aqueous sodium hydrogen carbonate solution were added, and the mixture was vigorously stirred at 80 ° C. for 30 minutes. After cooling to room temperature, the precipitated crystals were collected by filtration and washed with toluene and distilled water. After heating and dissolving in a mixed solvent of methyl isobutyl ketone-toluene, washing with distilled water, cooling, the crystals were collected by filtration and dried to obtain 41 g of white crystals having a melting point of 221-224 ° C. As a result of mass spectrometry, M ⁺ was 424.

Synthesis of Low Molecular Weight Compound (44) The reaction was carried out in the same manner as in Synthesis Example (10) except that m-isopropenylacetophenone was used instead of p-isopropenylacetophenone. 380 g of toluene was added to and dissolved in the reaction mixture, and a 3% aqueous sodium hydrogen carbonate solution was added thereto.
Subsequently, it was washed with a dilute aqueous solution of phosphoric acid. The solvent and unreacted phenol were distilled off by heating under reduced pressure, and recrystallized from toluene to obtain 42 g of white crystals having a melting point of 188-190 ° C. As a result of mass spectrometry, M ⁺ was 424.

Synthesis of low molecular weight compound (46) p-Isopropenyl acetophenone was used instead of m-isopropenyl acetophenone, and 1 was used instead of phenol.
The reaction and treatment were carried out in the same manner as in Synthesis Example (11) using 36go-cresol to give pale yellow crystals 4 having a melting point of 88-91 ° C.
1.5 g were obtained. However, decane was used as a recrystallization solvent. As a result of mass spectrometry, M ⁺ was 466.

[Synthesis Example 1 of Dissolution Inhibitor Compound] α,
α ′, α ″ -tris (4-hydroxyphenyl) -1,
20 g of 3,5-triisopropylbenzene was dissolved in 400 ml of tetrahydrofuran. Under a nitrogen atmosphere
14 g of potassium tert-butoxide was added, and after stirring at room temperature for 10 minutes, 29.2 g of di-tert-butyl dicarbonate was added. The reaction was allowed to proceed at room temperature for 3 hours, the reaction solution was poured into ice water, and the product was extracted with ethyl acetate. The ethyl acetate layer was further washed with water and dried, after which the solvent was distilled off. The obtained crystalline solid was recrystallized (diethyl ether) and dried to obtain 25.6 g of a compound example (31: R are all t-BOC groups).

[Synthesis Example 2 of Dissolution Inhibitor Compound] α,
α ′, α ″ -tris (4-hydroxyphenyl) -1,
20 g of 3,5-triisopropylbenzene was dissolved in 400 ml of diethyl ether. Under a nitrogen atmosphere,
31.6 g of 4-dihydro-2H-pyran and a catalytic amount of hydrochloric acid were added and reacted under reflux for 24 hours. After completion of the reaction, a small amount of sodium hydroxide was added and the mixture was filtered. The solvent of the filtrate was distilled off, and the obtained product was purified by column chromatography, dried, and the compound example (31: R was all T
HP group).

[Synthesis Example 3 of Dissolution Inhibitor Compound] α,
α ', α "-tris (4-hydroxyphenyl) -1,
19.2 g of 3,5-triisopropylbenzene (0.0
120 mol) of N, N-dimethylacetamide
21.2 g (0.15 mol) of potassium carbonate and 27.1 g (0.14 mol) of t-butyl bromoacetate were added to the solution, and the mixture was stirred at 120 ° C. for 7 hours. Thereafter, the reaction mixture was poured into 1.5 l of water, and extracted with ethyl acetate. After drying over magnesium sulfate, the extract was concentrated and purified by column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-hexane = 3/7 (volume ratio)). As a result, a pale yellow viscous solid was obtained. 30 g were obtained. According to NMR, this is a compound example (31: R is all —CH ₂ COOC ₄ H ₉
^t group).

[Synthesis Example 4 of Dissolution Inhibitor Compound] 1-
42.4 g (0.10 mol) of [α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene was added to N, N -Dissolved in 300 ml of dimethylacetamide, added with 49.5 g (0.35 mol) of potassium carbonate and 84.8 g (0.33 mol) of cumyl bromoacetate, and then stirred at 120 ° C for 7 hours. The reaction mixture was poured into 2 liters of ion-exchanged water, neutralized with acetic acid, and extracted with ethyl acetate.The ethyl acetate extract was concentrated and purified in the same manner as in Synthesis Example [3] to give Compound Example (18). : R
All -CH ₂ COOC is _{(CH 3) 2 C 6 H} 5 group) 70
g was obtained.

[Synthesis Example 5 of Dissolution Inhibitor Compound] α,
α, α ', α', α ", α" -hexakis (4-hydroxyphenyl) -1,3,5-triethylbenzene 14.3 g
(0.020 mol) of N, N-dimethylacetamide 1
In a 20 ml solution, 21.2 g (0.15 mol) of potassium carbonate and 27.1 g (0.14 mol) of t-butyl bromoacetate were added.
Mol) was added and the mixture was stirred at 120 ° C for 7 hours. Thereafter, the reaction mixture was poured into 1.5 l of water and extracted with ethyl acetate. After drying over magnesium sulfate, the extract was concentrated and purified by column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-hexane = 2/8 (volume ratio)), and as a result, a pale yellow powder was obtained. 24 g were obtained. N
According to MR, this is a compound example (62: R is all -CH ₂
—COO—C ₄ H ₉ ^t group).

[Synthesis Example 6 of Dissolution Inhibitor Compound] α,
α ', α "-tris (4-hydroxyphenyl) -1,
20 g of 3,5-triisopropylbenzene (0.042
Mol) was dissolved in 400 ml of tetrahydrofuran (THF). To this solution, 9.3 g (0.083 mol) of potassium t-butoxide was added under a nitrogen atmosphere, and the mixture was stirred at room temperature for 10 minutes, and then 19.5 g of di-t-butyl dicarbonate was added.
(0.087 mol) was added. The reaction was allowed to proceed at room temperature for 3 hours, the reaction solution was poured into ice water, and the product was extracted with ethyl acetate. The ethyl acetate extract is concentrated and subjected to column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-
Hexane = 1/5 (volume ratio))
7 g of compound examples (31: two Rs are t-BOC groups, one R is a hydrogen atom) were obtained.

[Synthesis Example 7 of Dissolution Inhibitor Compound] α,
α ', α "-tris (4-hydroxyphenyl) -1,
48.1 g of 3,5-triisopropylbenzene (0.1
0 mol) in 300 ml of dimethylacetamide,
To this, 22.1 g (0.16 mol) of potassium carbonate and 42.9 g (0.22 mol) of t-butyl bromoacetate were added. Then, it stirred at 120 degreeC for 5 hours. The reaction mixture was poured into 2 l of ion-exchanged water, neutralized with acetic acid, and extracted with ethyl acetate. The ethyl acetate extract is concentrated and subjected to column chromatography (carrier: silica gel, developing solvent: ethyl acetate / n-hexane = 1/5 (volume ratio))
)), The compound example (31: 2 R
It is _{-CH 2 -COO-C 4 H 9} t group, one R to give a hydrogen atom) 10 g.

[Synthesis Example 8 of Dissolution Inhibitor Compound] 44 g (0.10 mol) of the following compound (60 ′) was dissolved in 300 ml of N, N-dimethylacetamide, and 70.2 g (0.497 g) of potassium carbonate was added thereto. Mol), and bromoacetic acid t-
89.8 g (0.464 mol) of butyl were added. Thereafter, the mixture was stirred at 120 ° C. for 7 hours. Thereafter, the reaction mixture 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)), and as a result, 135 g of a pale yellow powder was obtained. I got According to NMR, this is a compound example (60: R is all —CH ₂ COO).
—C ₄ H ₉ ^t group).

[0193]

Embedded image

Examples 1 to 14 and Comparative Example 1 Resists were prepared using the resins and compounds of the present invention shown in the above synthesis examples. The prescription at that time is shown in Table 1 below.

[0195]

[Table 1]

The resins of the present invention used in Table 1 are shown below.

[0197]

Embedded image

[0198]

Embedded image

The abbreviations used in Table 1 represent the following contents. <Polymer> () indicates the molar ratio of PHS poly (p-hydroxystyrene) (weight average molecular weight 8,000) PHS / TBOMS p-hydroxystyrene / t-butoxycarbonylmethyloxystyrene copolymer (80/20) (weight average) (Molecular weight 20,000) PHS / St p-hydroxystyrene / styrene copolymer (85/15) (weight average molecular weight 35,000) PHS / AcST p-hydroxystyrene / p-acetoxystyrene copolymer (80/20) (weight average molecular weight 20,000) PHS / OHS p-hydroxystyrene / o-hydroxystyrene copolymer (80/20) (weight-average molecular weight 32,000) t-BOCS poly ^{(p-t-butoxycarbonyloxystyrene)} (weight average molecular weight 18,000) HQ hydroquinone

<Acid-decomposable group in dissolution inhibitor>

[0201]

Embedded image

[Preparation and Evaluation of Resist Composition] To each material shown in Table 1 was added 0.02 g of 4-dimethylaminopyridine, dissolved in 9.5 g of propylene glycol monomethyl ether acetate, and filtered through a 0.2 μm filter. Thus, a resist solution was prepared. This resist solution is applied on a silicon wafer using a spin coater,
The resist film was dried on a vacuum adsorption type hot plate at 110 ° C. for 90 seconds to obtain a resist film having a thickness of 0.83 μm. This resist film was exposed using a 248 nm KrF excimer laser stepper (NA = 0.42). Immediately after the exposure, each was heated for 60 seconds on a vacuum adsorption type hot plate at 100 ° C., immediately immersed in a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, rinsed with water for 30 seconds, and dried. The profile, sensitivity, and resolution of the pattern on the silicon wafer thus obtained were evaluated and compared as follows. The results are shown in Table 2 below.

Resist Profile (Exposure-PEB)
(After 30 minutes of aging), the presence or absence of T-top was evaluated. The evaluation criteria are shown below. ：: T-top was not observed at all. ×: T-top formation. Sensitivity was defined as the reciprocal of the exposure amount reproducing a 0.40 μm mask pattern. Indicated by value. The resolving power indicates a limit resolving power at an exposure amount for reproducing a 0.40 μm mask pattern. The resolving power represents the resolving power when heated (PEB) immediately after exposure and developed, and the resolving power in parentheses is 60 ° C. in a clean room after exposure.
It shows the resolving power in the case where the film was left standing for one minute, heated (PEB), and developed. Table 2 shows the results.

[0204]

[Table 2]

From the results shown in Table 2, the profile and the resolving power after the lapse of time between exposure and PEB were good, without formation of T-top and deterioration of the resolving power. Further, with respect to the sensitivity and the limiting resolution, better results were obtained for the composition of the present invention as to the limiting resolution as compared with Comparative Examples. In addition, the composition of the present invention obtained good results in which the DOF and the sensitivity did not decrease except for the formation of T-top over time.

[0206]

According to the present invention, it is possible to provide a chemically amplified positive photoresist composition having excellent sensitivity and resolving power and having little change in performance over time after exposure.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 25/18 H01L 21/30 502R

Claims (2)

[Claims] 1. A resin represented by the following general formula (I) and / or
Or a linking group containing a repeating structural unit represented by the following general formulas (A), (B) and (C), and a repeating group represented by the general formula (C) A resin having a crosslinked structure, a compound capable of generating an acid upon irradiation with actinic rays or radiation, and a compound represented by the following general formula (II) or (III): Composition. Embedded image In the formulas (A), (B), (C) and (D), R _x : hydrogen atom, methyl group Ra, Rb, Rd, Re, Rg, Rh: each independently a hydrogen atom, having 1 to 8 carbon atoms Linear alkyl group having 3 to 8 carbon atoms
Branched alkyl groups and cyclic alkyl groups having 3 to 6 carbon atoms (provided that Ra, Rb, Rd, Re, Rg, and Rh do not simultaneously represent a hydrogen atom. In addition, Ra and Rb, Ra and Rc,
Rd and Re or Rg and Rh may be bonded to each other to form a ring. ), Rc: linear alkyl group having 1 to 8 carbon atoms, 3 to 8 carbon atoms
Branched alkyl groups, cyclic alkyl groups having 3 to 6 carbon atoms, Rf: C1-C6 linear alkylene group, C3-C3
8 branched alkylene groups, a cyclic alkylene group having 3 to 6 carbon atoms, Ri and Rj each independently represent a hydrogen atom, a straight-chain alkyl group having 1 to 6 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, or a cyclic alkyl group having 3 to 6 carbon atoms; The content molar ratio of the repeating structural units represented by (A), (B), and (C) is 0.05 ≦ formula (B) / (formula (A) + formula (B) + formula (C)) ≦ 0.90 0.001 ≦ formula (C) / (formula (A) + formula (B) + formula (C)) ≦ 0.20. Embedded image In formula (I), R _X , Ra, Rb, and Rc have the same meanings as described above. 1, m: l + m = 100 0.05 ≦ m / (l + m) ≦ 0.90 Embedded image In the formulas (II) and (III), A: a hydrogen atom or a hydroxyl group; E, G: groups represented by the following, respectively: R ₁ to R _4: each a hydrogen atom, -X-R ₁₃ or halogen atom, R ₅ to R _6: each a hydrogen atom, a methyl group, an ethyl group, number 1-2 haloalkyl group carbon, R _7: a hydrogen atom , A methyl group, an ethyl group, a haloalkyl group having 1 to 2 carbon atoms, a to f and k to n: each an integer of 0 or 1 to 3, g to j: 0, 1, or 2, respectively; D is a single bond, a carbonyl group, a sulfide group, a sulfonyl group, —C (R ₅ ) (R ₆ ) — or a group represented by the following formula: R ₈ to R _12: each a hydrogen atom, -OH, -CN, -C
OOH, -X-R ₁₃ or halogen atom, R _13: alkyl group having 1 to 8 carbon atoms, X: a single bond, -O -, - S -, - CO -, - OCO-,
Represents 2. The resin represented by the general formula (I) according to claim 1, and / or the general formula (A) according to claim 1.
Including repeating structural units represented by (B) and (C),
A resin having a crosslinked structure with a linking group represented by the general formula (D) according to claim 1 in the repeating structural unit represented by the general formula (C), a compound capable of generating an acid upon irradiation with actinic rays or radiation. A low-molecular acid-decomposable dissolution-inhibiting compound having a molecular weight of 3000 or less, having a group decomposable by the action of an acid, and having an increased solubility in an alkaline developer by the action of an acid; (II) or the general formula (I
A positive photoresist composition comprising a compound represented by the formula (II):