JPH11153870A - Positive photosensitive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition having a large difference in the dissolution rate of the unexposed part and that of the exposed part and superior in resolution in minute pattern and small in decrease of film thickness in the unexposed part and free from deterioration of sensitivity by incorporating a resin having iodonium salts to be allowed to generate an acid by irradiation with activating rays or radiation and groups capable of increasing solubility in an alkaline developing upon decomposition by action of the acid. SOLUTION: This composition contains the resin having iodonium salts with >=2 iodonium structures in the molecule and capable of generating an acid by irradiation with activated rays or radiation, and groups for increasing solubility in the alkaline developing solution. This iodonium salt is selected from the compounds represented by formulae I and II in which (n) is 1 or 2; X is an optionally substituted straight or branched alkyl or optionally substituted aryl or optionally substituted hetero-aryl or optionally substituted aralkyl group; A is a divalent organic group; B is a trivalent organic group; and R1 is a univalent organic group.

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.

[0007] In any system, the basic performance required of a chemically amplified positive resist is that the solubility is sufficiently inhibited unless exposed to light, and the presence of acid as a result of exposure. The dissolution inhibiting ability is lost, and the dissolution rate is increased. If this performance is sufficiently satisfied, the difference between the dissolution rates of the two is naturally increased to improve the resolving power, prevent the dissolution loss (film loss) of the unexposed portion, and increase the precision of the pattern shape. From this viewpoint, regarding the resin having a group which is decomposed by the reaction with an acid and becomes alkali-soluble, a resin having a t-butoxy group as an acid labile group (DA Conlon et al., Macromolecules, 22, 22, 509) Page (1
989)), resins with terahydropyranyl ether groups as acid labile groups (Hayashi et al., ACS Polymer Materia1 Science
and Engineering 61, 417 (1989)), Resins having trimethylsilyl ether groups as acid labile groups (Murata et al.,
J. Photopolymer Science and Technology, Vol. 5, p. 79 (1
992)), a resin having a carboxylic acid ester group as an acid labile group (Horibe et al., Proceedings, SP1E, No. 2483, p. 61 (1992)).
Although many studies and applications have been made, such as 5)), at present, the difference in dissolution rate between exposed and unexposed areas is still not sufficient, and further improvement is desired.

[0008]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a large difference in dissolution rate between an exposed portion and an unexposed portion,
An object of the present invention is to provide a chemically amplified positive photosensitive composition which is excellent in resolution of a fine pattern, has a small film loss in an unexposed portion, and does not cause a decrease in sensitivity.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies while paying attention to the above-mentioned properties, and as a result, have found that the object of the present invention is achieved by using a specific compound which generates an acid by actinic rays. I found it. That is, the present invention has the following configuration. (1) (a) an iodonium salt having two or more iodonium structures in one molecule and generating an acid upon irradiation with actinic rays or radiation; and (b) decomposing by the action of an acid, and A bodiary photosensitive composition comprising a resin having a group that increases solubility. (2) (c) a molecular weight of 3 having a group decomposable by an acid and having an increased solubility in an alkaline developer due to the action of an acid;
The positive photosensitive composition according to the above (1), further comprising a low molecular weight dissolution inhibiting compound having a molecular weight of 000 or less.

(3) (a) an iodonium salt having two or more iodonium structures in one molecule and generating an acid upon irradiation with actinic rays or radiation, (c) a group having a group decomposable by an acid, and an alkali A hoji type containing a low molecular weight dissolution inhibiting compound having a molecular weight of 3,000 or less, whose solubility in a developer is increased by the action of an acid, and (d) a resin insoluble in water and soluble in an alkali developer. Photosensitive composition. (4) The (a) iodonium salt having two or more iodonium structures in one molecule and generating an acid upon irradiation with actinic rays or radiation is represented by the following general formulas (I) and (II)
The positive photosensitive composition according to any one of the above (1) to (3), which is at least one selected from the group of compounds represented by

[0011]

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In the above formula, n represents 1 or 2. X represents a linear, branched or cyclic alkyl group which may be substituted, an aryl group which may be substituted, a heteroaryl group which may be substituted, or an aralkyl group which may be substituted; And a plurality of Xs in the same molecule may be the same or different. A represents a divalent organic group. B is 3
It shows a valent organic group. R ₁ represents a monovalent organic group. Also,
X and A or B may combine to form a ring together with I ⁺ . (5) (b) a resin having a group that is decomposed by the action of an acid and increases the solubility in an alkaline developer is a resin containing a repeating structural unit represented by the following general formulas (IV) and (V): The positive photosensitive composition as described in (1) or (2) above.

[0013]

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In the above formula, L is a hydrogen atom, a straight-chain, branched,
Alternatively, it represents a cyclic alkyl group or an aralkyl group which may be substituted. Z represents a linear, branched or cyclic alkyl group or an optionally substituted aralkyl group. Further, Z and L may combine to form a 5- or 6-membered ring.

The positive photosensitive composition of the present invention uses a compound having two or more iodonium structures in one molecule as a photoacid generator, whereby the photoacid generator has a cross-linking type interaction with the resin. It is considered that a large dissolution inhibiting effect is obtained. On the other hand, in the exposed portion, the dissolution inhibiting effect is canceled by the photolysis of the iodonium salt, and as a result, the sensitivity does not decrease. Therefore, according to the present invention, the dissolution rate difference between the unexposed and exposed portions is increased,
As a result, the resolution of a fine pattern is improved, and an excellent resist pattern with less film loss in an unexposed portion is provided.

[0016]

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] (a) An iodonium salt having two or more iodonium structures in one molecule and generating an acid upon irradiation with actinic rays or radiation (hereinafter, also simply referred to as “component (a)”) In the above, the iodonium structure means an iodonium cation structure having two substituents. In one molecule of the component (a) in the present invention, preferably 2 or more and 4
Hereinafter, more preferably, it has a 2-3 iodonium structure.

Preferred examples of the component (a) include, but are not limited to, the compounds represented by formulas (I) to (II). In the general formulas (I) and (II), n represents 1 or 2. X is the same or different, and may be a substituted, linear, branched or cyclic alkyl group, preferably an alkyl group having 1 to 12 carbon atoms;
An optionally substituted aryl group, preferably having 6 carbon atoms
To 14 optionally substituted aryl groups; optionally substituted heteroaryl groups, preferably having 5 to 1 carbon atoms
An optionally substituted heteroaryl group; or an optionally substituted aralkyl group, preferably having 7 carbon atoms
Represents 10 to 10 optionally substituted aralkyl groups.

A is a divalent organic group, preferably an optionally substituted arylene group, an optionally substituted heteroarylene group, an optionally substituted linear, branched or cyclic alkylene group; An aralkylene group which may be substituted, or a divalent organic group having two or more of these groups, and at least one of these groups may be combined with -O-, -S
-, -C (= O)-, -NH-, -S (= O) (= O)
And-represents a divalent organic group in which at least one of -S (= O)-is combined.

B is a trivalent organic group, preferably an optionally substituted arylene group, an optionally substituted heteroarylene group, an optionally substituted linear, branched or cyclic alkylene group; An aralkylene group which may be substituted, or a trivalent organic group having two or more of these groups, and at least one of these groups and -O-, -S
-, -C (= O)-, -NH-, -S (= O) (= O)
And a trivalent organic group in which at least one of-, -S (= O)-is combined. R ₁ has the same meaning as the monovalent organic group, preferably the substituent described for X above.

In X, A, B and R ₁ , preferred further substituents of the above groups include a halogen atom; a linear, branched, or cyclic alkyl group; a linear, branched, or cyclic alkoxy group; Oxy group; acyl group; formyl group;
Nitro group; acylamino group; sulfonylamino group; aryl group; alkoxydicarbonyl group; aralkyl group; In the above, the carbon number does not include the carbon atom of the substituent.

Specific examples of the above groups for X and R ₁ are as follows:
It is as follows. Alkyl group; methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, dodecyl, etc. it can. Aryl group; phenyl group, naphthyl group, anthryl group and the like.

Heteroaryl group; the following formulas (A1) to (A)
In the structure shown in 4), a monovalent group can be used.

[0024]

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Here, X is an oxygen atom, a sulfur atom or-
NH-, Y₁~ Y₆Is -CH = or-
N = Y in formula (A3)₁~ Y₆Few of
At least one represents -N =. Y₇~ Y₁₄Is -CH
= Or -N =, and Y ₇~ Y₁₄At least
One represents -N =. Aralkyl group; benzyl group, phenethyl group, etc.
Can be.

In the general formula (I) or the general formula (II),
More preferred as X is a phenyl group. R ₁
Is more preferably a phenyl group.

Specific examples of the divalent or trivalent organic group represented by A and B include the following. Arylene group; phenylene group, naphthylene group, anthrylene group and the like. Heteroarylene group: a heteroarylene group which is a divalent group in the structures represented by the above formulas (A1) to (A4). Alkylene group; ethylene group, 1,4-butylene group, 1,
Examples thereof include straight-chain, branched and cyclic ones having 1 to 10 carbon atoms such as a 4-cyclohexylene group. Aralkylene group; toluylene group, xylylene group, phenethylene group and the like.

Specific examples of the compounds represented by formulas (I) and (II) are shown below. In the following specific examples, the compound of (I-number) is a specific example of general formula (I), and (II-number)
Is a specific example of the general formula (II).

[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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The component (a), for example, the compounds represented by the general formulas (I) and (II) can be used alone or in combination of two or more. The component (a),
For example, the compounds represented by the general formulas (I) and (II) can be prepared by the method described in US Pat. No. 3,734,928 or the method described in Macromolecules, vol. 10, 1307 (1977). And by exchanging the counter anion. The content of the component (a), for example, the compound represented by the general formula (I) or (II) in the photosensitive composition is 0.1 to 2 with respect to the solid content of the photosensitive composition.
0% by weight is suitable, preferably 0.5 to 10% by weight, more preferably 1 to 7% by weight.

[II] (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 is 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), WRW
att etal, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1
984), JVCrivello etal, Polymer Bull., 14,279 (198
5), JVCrivello etal, Macromorecules, 14 (5), 1141 (19
81), JVCrivello etal, J. PolymerSci., Polymer Che
m.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, Dokoku 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 et
al, J. PolymerSci., Polymer Chem. Ed., 17,1047 (1979)
Selenonium salts, CSwen et al, Teh, Proc.Co
Onium salts such as arsonium salts described in nf.Rad.Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.
No., 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, 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), organometallics / organic halides described in JP-A-2-14145, S. Hayase et al., J. Polymer Sci. ., 25,753 (1987), ER
eichmanis etal, J.Pholymer Sci., Polymer Chem.Ed., 2
3,1 (1985), QQ Zhu et al., J. Photochem., 36, 85, 39, 317 (1
987), B. Amit etal, Tetrahedron Lett., (24) 2205 (197
3), DHR Barton et al., J. Chem Soc., 3571 (1965), PM
Collins et al., J. Chem.SoC., Perkin I, 1695 (1975), M. Rud
instein etal, Tetrahedron Lett., (17), 1445 (1975), J.
W. Walker et al. J. Am. Chem. Soc., 110, 7170 (1988), SCBu
sman et al, J. Imaging Technol., 11 (4), 191 (1985), HMH
oulihan etal, Macormolecules, 21, 2001 (1988), PMColl
ins etal, J. Chem. Soc., Chem. Commun., 532 (1972), S. Haya
se etal, Macromolecules, 18, 1799 (1985), E. Reichmanis
etal, J.Electrochem.Soc., SolidState Sci.Technol., 13
0 (6), FMHoulihan et al., Macromolcules, 21, 2001 (198
8), European Patent Nos. 0290,750, 046,083, 156,535
No. 271,851, No. 0,388,343, U.S. Pat.No. 3,901,7
No. 10, 4,181,531, JP-A-60-198538, JP-A-53-1
Photoacid generator having an o-nitrobenzyl-type protecting group described in No. 33022, M. TUNOOKA et al., Polymer Preprints Ja
pan, 35 (8), G. Berner et al., J. Rad. Curing, 13 (4), WJMij
s etal, Coating Technol., 55 (697), 45 (1983), Akzo, H.Ad
achi etal, Polymer Preprints, Japan, 37 (3), European Patent Nos. 0199,672, 84515, 199,672, 044,115
Nos. 0101,122; U.S. Pat.Nos. 618,564; 4,371,605
No. 4,431,774, JP-A-64-18143, JP-A-2-24575
No. 6, iminosulfone described in Japanese Patent Application No. 3-140109, etc.
And disulfone compounds described in JP-A-61-166544 and the like.

A group which 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., 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.
No. 49,137, Dokoku Patent No. 3914407, JP-A-63-26653,
JP-A-55-164824, JP-A-62-69263, JP-A-63-1460
Compounds described in JP-A-38-163452, JP-A-63-163452, JP-A-62-153853, 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),
Compounds that generate an acid by light described in DHR Barton et al., J. Chem. Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, and EP 126,712 can also be used.

Among the compounds which can be used together and decompose upon irradiation with actinic rays or radiation to generate an acid, 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).

[0041]

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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.

[0043]

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[0044]

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[0045]

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

[0047]

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

R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group or aryl group. Preferably, an aryl group having 6 to 14 carbon atoms, 1 to 8 carbon atoms
And substituted derivatives thereof. Preferred substituents 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 ^-, SiF₆
^2-, ClO_Four ^-, CF_ThreeSO_Three ^-Perfluoroal such as
Cansulfonate anion, pentafluorobenzene sulfone
Phonate anion, naphthalene-1-sulfonic acid anion
Polynuclear aromatic sulfonic acid anions such as anthraquino
Sulfonic acid anions, sulfonic acid group-containing dyes, etc.
However, the present invention is not limited thereto.

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.

[0053]

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[0054]

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[0055]

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[0056]

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The above 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, J.Po
Chem. Ed., 18,2677 (1980), U.S. Pat. Nos. 2,807,648 and 4,247,473, and JP-A-53-101,331.

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

[0059]

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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.

[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[III] (b) Resin having a group which is decomposed by the action of an acid and increases the solubility in an alkali 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 alkali 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 of the resin. 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 -A _r -O-B ^0. Here, A ⁰ is -C (R ⁰¹ ) (R ⁰² ) (R
^{03), - Si (R 01} ) (R 02) (R 0 3) or -C
It represents a (R ⁰⁴ ) (R ⁰⁵ ) -OR ⁰⁶ group. B ⁰ indicates the A ⁰ or -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, as a base resin when the groups decomposable by these acids are bonded as a side chain, the side chain may be -OH or -COOH, preferably -R ⁰ -COOH or -A _r -OH group. It is an alkali-soluble resin having. 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) (23 ° C.) and measured at 170 ° 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 these viewpoints, 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 to these.

[0072]

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[0073]

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[0074]

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[0075]

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The content of acid-decomposable groups is determined by the number of acid-decomposable groups in the resin (B) and the number of alkali-soluble groups not protected by acid-decomposable groups (S). B /
It is represented by (B + S). The content is preferably 0.01 to
0.7, more preferably 0.05 to 0.50, and still more preferably 0.10 to 0.50. B / (B + S)>
A value of 0.7 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.

In the present invention, as the resin having an acid-decomposable group, a resin containing a repeating structural unit represented by the above general formula (IV) or (V) is preferable. Thereby, it has a high resolution and the performance change over time from exposure to heating is reduced. Examples of the alkyl group in L and Z in the general formula (IV) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a pentyl group, a cyclopentyl group, a hexyl group, and a cyclohexyl group. Straight-chain, branched or cyclic ones having 1 to 20 carbon atoms such as a group, octyl group and dodecyl group. Preferred substituents of the alkyl group include an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acylamino group, and a sulfonylamino 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, and a sulfonylamino group.

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, and 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 contain 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.

[0083]

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[0084]

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[0085]

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[0086]

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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 at 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.

[0089]

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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, and if it exceeds 300,000, the dissolution rate of the resin itself in alkali becomes slow and the sensitivity is lowered. 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.

[IV] (c) Low-molecular acid-decomposable dissolution-inhibiting compound The photosensitive composition of the present invention comprises (c) a low-molecular acid-decomposable-dissolution-inhibiting compound (hereinafter, also simply referred to as “component (c)”). May be contained. The component (c) 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 (c) 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 (c), 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. 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.

[0095]

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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, the group containing an -O-B ⁰ group, -R ⁰ -COO-A
^0, or group represented by -Ar-O-B ^0. 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 a hydrogen atom, and two groups of R ^{01 to} R ⁰³ and R ^{04 to} R ⁰⁶ are bonded to form a ring. Is also 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 having 2 to 2 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group. Preferably, the aryl group has 6 to 1 carbon atoms such as phenyl, xylyl, toluyl, cumenyl, naphthyl and anthracenyl.
Four are preferred. Further, as a substituent, a hydroxyl group,
Halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, the above alkyl group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, s
an alkoxy group such as an ec-butoxy group and a t-butoxy group,
Alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, aralkyl groups such as benzyl group, phenethyl group and cumyl group, aralkyloxy groups, acyl groups such as formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group, and valeryl group. Group, an acyloxy group such as a butyryloxy group, the above alkenyl group, a vinyloxy group.
Examples thereof include an alkenyloxy group such as a propenyloxy group, an allyloxy group, and a butenyloxy group, an aryloxy group such as the above-described aryl group and phenoxy group, and an aryloxycarbonyl group such as a benzoyloxy group.

The 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 (c) is preferably selected from those disclosed in
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 is used.
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, the following general formulas [I] to [X]
VI].

[0103]

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[0104]

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[0105]

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[0106]

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Here, R¹⁰¹, R¹⁰², R¹⁰⁸, R¹³⁰: Same or different,
Hydrogen atom, -R⁰-COO-C (R⁰¹) (R⁰²)
(R⁰³) Or -CO-OC (R⁰¹) (R⁰²)
(R ⁰³) Where R⁰, R⁰¹, R⁰²And R⁰³The definition of
Same as above.

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

[0109]

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[0110] 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
^{121 to} R ¹²³ , R ^{128 to} R ¹²⁹ , R ^{131 to} R ¹³⁴ , R
^{138 to} R ¹⁴¹ and R ^{143 are the} same or different and each represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, a halogen atom, a nitro group,
Carboxyl group, cyano group, or -N ( ^R155 )
(R ¹⁵⁶ ) (R ¹⁵⁵ , R ¹⁵⁶ : H, alkyl group or aryl group) R ¹¹⁰ : single bond, alkylene group, or

[0111]

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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 ^142: a hydrogen atom, ^{-R 0 -COO-C (R 01} )
( ^R02 ) ( ^R03 ) or -CO-OC ( ^R01 ) ( ^R02 )
(R ⁰³ ), or

[0114]

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R ¹⁴⁴ and R ^{145 are the} same or different and are a hydrogen atom, a lower alkyl group, a lower haloalkyl group or an aryl group; R ^{146 to} R ^{149 are the} same or different and are a hydrogen atom, a hydroxyl group, a halogen atom or a nitro group , A cyano group, a carbonyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aralkyl group, an aralkyloxy group, an acyl group, an acyloxy group, an alkenyl group, an alkenyloxy group, an aryl group, an aryloxy group, or an aryloxycarbonyl group. However, the substituents of the same four symbols may not be the same group, Y: —CO—, or —SO ₂ —, Z, B: single bond, or —O—, A: methylene group, A lower alkyl-substituted methylene group, a halomethylene group, or a haloalkyl group, E: a single bond or an oxymethylene group, a z, a1 to y1: 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, s1, u1: 0 or an integer of 1 to 5, r, u, w, x, y, z, a1 to f1, p1, r1, t1, v1 to 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, except for the general formula [V], where (w + z), (x + a1) ≦ 5, (a + c), (b + d), ( e + h), (f + i), (g + j), (k + n), (l + o), (m + p), (q
+ t), (s + v), (g1 + k1), (h1 + l1), (i1 + m1), (o1 + q1), (s1 + u1)
≦ 5.

[0116]

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[0117]

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[0118]

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[0119]

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Specific examples of preferred compound skeletons are shown below.

[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0136]

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[0137]

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[0138]

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[0139]

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

[0141]

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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 to be 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.

[V] (d) 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 (d)”) can be contained. This resin has substantially no acid-decomposable groups. (D)
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% 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 and o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene and copolymers thereof, alkyl-substituted polyhydroxystyrene, partial O-alkylation of polyhydroxystyrene, Or an O-acylated product, a styrene-hydroxystyrene copolymer, or an α-methylstyrene-hydroxystyrene copolymer. The novolak resin is obtained by subjecting a given monomer as a main component to addition condensation with an aldehyde in the presence of an acidic catalyst.

Examples of the predetermined monomer include phenol and 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
Hydroxyaromatic compounds such as -chlorophenol, p-chlorophenol, o-chlorophenol, dihydroxybiphenyl, bisphenol A, phenylphenol, resorcinol, and naphthol can be used alone or in combination of two or more, but are not limited thereto. Not something.

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 8,000 to 10,000
0. 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% based on the total weight of the photosensitive composition (excluding the solvent).
９７97% by weight, preferably 60-90% by weight.

[VI] 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 an organic base. And a compound having two or more phenolic OH groups that promote solubility in a developing solution.

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 preferred addition amount of the 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, European Patent 219294, and the like. ,
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 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).

[0154]

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

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

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

Further, a spectral sensitizer as described below is added to sensitize the photosensitive composition of the present invention to a longer wavelength region than far ultraviolet where the photoacid generator used has no absorption. Sensitivity can be given to 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 in which each of the above components is dissolved, and coated on a support. Examples of the solvent used herein include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, and ethylene glycol monoethyl ether acetate. , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate,
Ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

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 photosensitive composition is applied on a substrate (eg, silicon / silicon dioxide coating) 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.

Examples of the developer for the photosensitive composition of the present invention include:
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Inorganic alkalis such as sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, and triethylamine and methyldiethylamine Use alkaline aqueous solutions such as triamines, alcoholamines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and pichelidine. be able to. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution.

[0163]

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.

[Synthesis of Iodonium Salt] Synthesis Example 1 (Synthesis of Component (a): Compound Example (I-2)) 25.1 g of phenyliodosohydroxytosylate (6
4 mmol), 4.4 g (25.6) of diphenyl ether.
mmol) and 200 ml of acetic anhydride.
C., and 18 g of concentrated sulfuric acid was added dropwise over 1 hour. The reaction solution was left to return to room temperature overnight, cooled to 0 ° C., and 200 ml of distilled water was added dropwise thereto. The solution was extracted with dichloromethane, and the organic phase was washed with water, dried and concentrated to obtain Compound Example (I-2). Similarly, diacetoxyiodobenzene is used in place of phenyliodosohydroxytosylate, reacted with the corresponding aromatic compound to form bisiodonium sulfate, and then salt-exchanged with the corresponding sulfonic acid to give a compound example ( I-
3) to (I-7) and (I-10) to (I-12) can be obtained. For other compounds, an iodine-substituted aromatic compound is converted into a diacetoxyiodide compound, and then reacted with the corresponding aromatic compound to form bisiodonium sulfate. Then, the compound is subjected to salt exchange with the corresponding sulfonic acid. I-8) and (I-13) to (I-23) can be obtained.

[Resin Synthesis Example] (Resin Synthesis Example 1) PHS / iBES: P-hydroxystyrene / P- (1
-Iso-butoxyethoxystyrene copolymer (60 /
Synthesis of poly-p-hydroxystyrene (VP-800 manufactured by Nippon Soda)
0, weight average molecular weight 11000) 500 g of dehydrated THF
Dissolved in 2000 ml. 176 g of iso-butyl vinyl ether and 0.15 g of dehydrated p-toluenesulfonic acid were added to this solution, and the mixture was stirred at room temperature for 10 hours. After adding 16 g of triethylamine to the reaction solution, the mixture was poured into a solution of 40 liters of ion-exchanged water, and the precipitated powder was collected by filtration, washed with water,
When dried, p-hydroxystyrene / p- (1-iso
-Butoxyethoxy) styrene copolymer (60/40)
I got

(Resin Synthesis Example 2) PHS / iBESB: P-hydroxystyrene / P-
Synthesis of (1-iso-butoxyethoxy) styrene copolymer (70/30: molar ratio, partially crosslinked type) Poly p-hydroxystyrene (VP-800 manufactured by Nippon Soda)
0, weight average molecular weight 11000) 500 g of dehydrated THF
Dissolved in 2000 ml. 166 g of iso-butyl vinyl ether, 40 g of 2,2-bis (4-hydroxycyclohexyl) propane and 0.15 g of dehydrated p-toluenesulfonic acid were added to this solution, and the mixture was stirred at room temperature for 10 hours. After adding 16 g of triethylamine to the reaction solution, the mixture was poured into 40 liters / solution of ion-exchanged water, and the precipitated powder was collected by filtration, washed with water and dried to obtain p-hydroxystyrene / p-hydroxystyrene.
A (1-iso-butoxyethoxy) styrene copolymer (70/30, partially crosslinked) was obtained.

(Synthesis Example 3 of Resin) PHS / THPS: p-hydroxystyrene / p- (2
-Tetrahydropyranyloxy) styrene copolymer (6
Synthesis Example 1 except that 2,3-dihydro-4H-pyran was used in place of the iso-butyl vinyl ether of Synthesis Example 1.
P-hydroxystyrene / p- (2-tetrahydropyranyloxy) styrene copolymer (60/4
0) was obtained.

(Resin Synthesis Example 4) PHS / tBOCS: P-hydroxystyrene / P-
Synthesis of (t-butyloxycarbonyloxy) styrene copolymer (60/40) Poly p-hydroxystyrene (VP-800 manufactured by Nippon Soda)
0, weight average molecular weight 11,000) was dissolved in 40 ml of pyridine, and di-t-butyl dicarbonate (1.
28 g were added. After reacting at room temperature for 3 hours, the mixture was added to a solution of 1 liter of ion-exchanged water / 20 g of concentrated hydrochloric acid. The precipitated powder was filtered, washed with water, and dried to obtain a p-hydroxystyrene / p- (t-butyloxycarbonyloxy) styrene copolymer (60/40).

(Synthesis example 5 of resin) PHS / EES: P-hydroxystyrene / P- (1-
Synthesis of ethoxyethoxy) styrene copolymer (55/45: molar ratio, partially cross-linked) Using ethyl vinyl ether instead of t-butyl vinyl ether, p-hydroxystyrene / p- (1-Ethoxyethoxy) styrene copolymer (55/45, partially crosslinked) was obtained.

(Synthesis Example 6 of Resin) PHS / tBCMO: p-hydroxystyrene / p-
Synthesis of (t-butoxycarbonylmethyloxy) styrene copolymer (65/35: molar ratio) Poly p-hydroxystyrene (VP-800 manufactured by Nippon Soda)
0, weight average molecular weight 11000) 50 g, potassium carbonate 25.2 g and N, N-dimethylacetamide 300 ml
Was added and stirred at room temperature for 30 minutes. To this solution, 32.4 g of t-butyl bromoacetate was added and reacted at 120 ° C. for 5 hours. After allowing to cool to room temperature, the mixture was poured into 2 L of distilled water, and a 1N aqueous hydrochloric acid solution was added thereto to make the mixture neutral. The obtained viscous solid was washed with water and dried to obtain p-hydroxystyrene / p- (t
(-Butoxycarbonylmethyloxy) styrene copolymer (65/35) was obtained. PHS / iBES / AS: P-hydroxystyrene / P
-(1-iso-butoxyethoxystyrene / P-acetoxystyrene copolymer (70/20/10: molar ratio)
Was synthesized using the same method. Weight average molecular weight 12000

[Synthesis of Dissolution Inhibitor Compound] (Synthesis Example 1 of Dissolution Inhibitor Compound: Synthesis of Compound Example 31) α, α ′, α ″ -tris (4-hydroxyphenyl)
20 g of -1,3,5-triisopropylbenzene was dissolved in 400 ml of tetrahydrofuran. 14 g of potassium tert-butoxide was added to this solution under a nitrogen atmosphere, and the mixture was stirred at room temperature for 10 minutes, and then 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, and the compound example (31: R was all t
-BOC group) 25.6 g were obtained.

(Synthesis Example 2 of Dissolution Inhibitor Compound: Synthesis of Compound Example 18) 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- [α ′, α′-bis ( 4 "
-Hydroxyphenyl) ethyl] benzene 42.4 g
(0.10 mol) in N, N-dimethylacetamide 30
09.5 ml, and potassium carbonate 49.5 g (0.
35 mol), and 84.8 g of cumyl bromoacetate
(0.33 mol) was added. Then, at 120 ° C, 7
Stirred for 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 was concentrated and purified in the same manner as in Synthesis Example-3.
Compound Example (18: R are all -CH ₂ COOC (CH ₃₎
70 g of ₂ C ₆ H ₅ groups) were obtained.

(Synthesis Example 3 of Dissolution Inhibitor Compound: Compound)
Synthesis of 60) 1,3,3,5-tetrakis- (4-hydrido)
Roxyphenyl) pentane in 44 g of N, N-dimethyla
Dissolve in 250 ml of Cetamide and add potassium carbonate
70.7 g and then 90.3 g of t-butyl bromoacetate
The mixture was stirred at 120 ° C. for 7 hours. Ionize the reaction mixture
The mixture was poured into 2 l of exchanged water, and the obtained viscous material was washed with water. this
Was purified by column chromatography to give Compound Example 6.
0 (R is all -CH _TwoCOOC_FourH₉(T)) is 87
g were obtained.

(Synthesis Example 4 of Dissolution Inhibitor Compound: Synthesis of Compound Example 62) α, α, α ′, α ′, α ″, α ″,-Hexakis (4-hydroxyphenyl) -1,3,5 20 g of triethylbenzene in 400 ml of diethyl ether
Was dissolved. Under a nitrogen atmosphere, 42.4 g of 3,4-dihydro-2H-pyran and a catalytic amount of hydrochloric acid were added to this solution,
Refluxed for 24 hours. After the completion of the reaction, a small amount of sodium hydroxide was added, followed by filtration. The filtrate was concentrated and purified by column chromatography to obtain 55.3 g of Compound Example 62 (R is all THP groups).

(Examples 1 to 10 and Comparative Examples 1 to 3) Resists were prepared using the compounds shown in the above Synthesis Examples. The prescription at that time is shown in Table 1 below.

[0176]

[Table 1]

The abbreviations used in Table 1 represent the following contents. <Polymer> () is the molar ratio PHS / iBES p-hydroxystyrene / p- (1-iso-butoxyethoxystyrene copolymer (60/40) Weight average molecular weight 12000 PHS / iBESB p-hydroxystyrene / p- ( 1-iso-butoxyethoxy) styrene copolymer (70/30 partially crosslinked) Weight average molecular weight 96,000 PHS / EES p-hydroxystyrene / p- (1-ethoxyethoxy) styrene copolymer (55/45) Weight average Molecular weight 13,000 PHS / THPS p-hydroxystyrene / p- (2-tetrahydropyranyloxy) styrene copolymer (60/40) Weight average molecular weight 12000 PHS / tBOCS p-hydroxystyrene / p- (t-butyloxycarbonyloxy) Styrene copolymer (6 / 40) Weight average molecular weight 12000 PHS / tBCMO p-hydroxystyrene / p- (t-butoxycarbonylmethyloxy) styrene copolymer (65/35) Weight average molecular weight 13000 PHS / St p-hydroxystyrene / styrene copolymer (85/15) weight average molecular weight 51000 PHS / iBES / AS P-hydroxystyrene / P- (1-iso-butoxyethoxystyrene / P-acetoxystyrene copolymer (70/20/10) weight average molecular weight 12000 <dissolution Acid decomposable group in inhibitor and compounds (A), (B), (C) for comparative examples>

[0178]

Embedded image

[0179]

Embedded image

[Preparation and Evaluation of Photosensitive Composition] Each material shown in Table 1 was dissolved in 9.5 g of propylene glycol monomethyl ether acetate, and filtered with a 0.1 μm filter to prepare a resist solution. The resist solution was applied on a silicon wafer using a spin coater, and dried on a vacuum suction type hot plate at 90 ° C. for 60 seconds to obtain a resist film having a thickness of 0.76 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 90 seconds on a vacuum adsorption type hot plate at 110 ° 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, resolution, and film loss of the pattern on the silicon wafer thus obtained were evaluated and compared as described below. The results are shown in Table 1 above.

[Sensitivity] The sensitivity was defined as an exposure amount for reproducing a master pattern of 0.40 μm. [Resolving power] The resolving power indicates a limit resolving power at an exposure amount for reproducing a 0.40 μm master pattern. [Film loss] was calculated as described in Table 1.

From the results shown in Table 1, the positive type photosensitive composition of the present invention has high sensitivity and high resolution, and the film loss of the resist film in the unexposed portion is remarkably small as compared with Comparative Examples 1 to 3. It can be seen that this is an excellent photosensitive composition.

[0183]

According to the present invention, an acid generator having two or more iodonium salt structures interacts with a binder in a cross-linking manner, so that an acid generator having a larger iodonium salt structure than the one having only one iodonium salt structure in a molecule can be obtained. A blocking effect is obtained. On the other hand, in the exposed portion, the dissolution inhibiting effect is released by the photolysis of the iodonium salt. As a result, the dissolution rate of the unexposed portion in the developing solution can be reduced without lowering the sensitivity, and the film loss of the unexposed portion can be suppressed. Further, the difference in solubility between the unexposed portion and the exposed portion in the developing solution is increased, and a high resolution is obtained.

Claims (5)

[Claims] (A) an iodonium structure in one molecule
Characterized by containing an iodonium salt which generates an acid upon irradiation with actinic rays or radiation, and (b) a resin having a group which is decomposed by the action of an acid to increase the solubility in an alkaline developer. Bodi type photosensitive composition. (C) having a group decomposable by an acid, wherein the solubility in an alkali developer is increased by the action of an acid;
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. 3. (a) Two iodonium structures in one molecule
An iodonium salt capable of generating an acid upon irradiation with actinic rays or radiation, (c) having a group decomposable by an acid, and having a solubility in an alkaline developer increased by the action of an acid, a molecular weight of 3000 or less And (d) a resin which is insoluble in water and soluble in an alkali developing solution. 4. The (a) iodonium salt having two or more iodonium structures in one molecule and generating an acid upon irradiation with actinic rays or radiation is represented by the following general formulas (I) and (II): The positive photosensitive composition according to any one of claims 1 to 3, wherein the composition is at least one selected from the group of compounds shown below. Embedded image In the above formula, n represents 1 or 2. X represents a linear, branched or cyclic alkyl group which may be substituted, an aryl group which may be substituted, a heteroaryl group which may be substituted, or an aralkyl group which may be substituted; And a plurality of Xs in the same molecule may be the same or different. A represents a divalent organic group. B represents a trivalent organic group. R ₁ represents a monovalent organic group. Further, X and A or B may be bonded to form a ring together with I ⁺ . 5. The resin (b) having a group capable of decomposing by the action of an acid to increase the solubility in an alkaline developer contains a repeating structural unit represented by the following general formulas (IV) and (V): The positive photosensitive composition according to claim 1, which is a resin. Embedded image In the above formula, L represents a hydrogen atom, a linear, branched, or cyclic alkyl group, or an optionally substituted aralkyl group. Z represents a linear, branched or cyclic alkyl group or an optionally substituted aralkyl group.
Further, Z and L may combine to form a 5- or 6-membered ring.