JPH11327149A - Positive photoresist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent the thinning in a resist pattern and forming of T shape in the surface therein at a lapse of time after exposure by containing resin that has a basic nitrogen contained compound having a specified multi-ring structure and a specified compound generating acid when it is irradiated with active light. SOLUTION: This composition contains at least one kind of a basic nitrogen contained compound having a multi-ring structure represented by a formula I and a compound represented by formulae II, III generating acid with the reception of active light, and resin that is dissolved by the action of acid and increases its soluble characteristic in an alkaline developping solution. In the formulae, Y, Z are alkylene groups R1 -R27 are hydrogen atom, alkyl group, alkoxyl group and the like, X<-> is for example anion such as benzen sulfonate, naphtahalen sulfonate having at least one selected from among a group of alkyl group and alcoxy group having 8 or more carbon atoms.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

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

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

[0004] Examples of such a combination include a combination of a compound that generates an acid by photolysis with an acetal or an O, N-acetal compound (Japanese Patent Application Laid-Open No. 48-89003), a combination of an orthoester or an amide acetal compound ( Combination with a polymer having an acetal or ketal group in the main chain (JP-A-53-172014).
3429), a combination with an enol ether compound (JP-A-55-12995), a combination with an N-acyliminocarbonate compound (JP-A-55-126236),
Combination with a polymer having an orthoester group in the main chain (JP-A-56-17345), combination with a tertiary alkyl ester compound (JP-A-60-3625), combination with a silyl ester compound (JP-A-60-3625) Showa 60-10247
No.) and a combination with a silyl ether compound (Japanese Unexamined Patent Publication No.
0-37549, JP-A-60-112446) and the like. These have high photosensitivity because the quantum yield exceeds 1 in principle.

Similarly, systems which are stable under aging at room temperature, but are decomposed by heating in the presence of an acid and solubilized in alkali are disclosed in, for example, JP-A-59-45439, JP-A-60-3625, JP-A-62-2229242, JP-A-63-27829, JP-A-63-36240, JP-A-63-250542, Polym.Eng.Sce., Vol. 23, 101
2 (1983); ACS.Sym. 242, 11 (1984); Semicond
uctor World 1987, November, p. 91; Macromolecules, 2
Vol. 1, p. 1475 (1988); SPIE, vol. 920, p. 42 (1988);
Combination systems with esters or carbonate compounds of primary or secondary carbons (eg t-butyl, 2-cyclohexenyl). Since these systems also have high sensitivity and low absorption in the far ultraviolet region, they can be effective systems for shortening the light source wavelength capable of ultrafine processing.

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

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

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a resist pattern that is thinned over time before exposure to heat treatment without deteriorating the sensitivity or that the surface shape of the resist pattern is T-type (T-type). An object of the present invention is to provide a positive photosensitive composition which does not exhibit top).

[0009]

The present invention has been achieved by the following constitutions. (1) (a) a basic nitrogen-containing compound having a polycyclic structure represented by the following general formula (I); and (b) a compound represented by the following general formulas (II) to (IV) which generate an acid upon irradiation with actinic rays. A bodi-type photosensitive composition comprising at least one of the compounds represented by formula (C) and a resin having a group which is decomposed by the action of an acid and increases the solubility in an alkali developing solution.

[0010]

Embedded image

(In the formula (I), Y and Z may be the same or different, may contain a hetero atom, and represent a linear, branched or cyclic alkylene group which may be substituted.)

[0012]

Embedded image

(Wherein R₁~ R₃₇Is hydrogen atom, straight chain, minute
Branch, cyclic alkyl group, straight-chain, branched, cyclic alkoxy group,
A hydroxy group, a halogen atom, or -SR₃₈Table
You. R ₃₈Is R₁~ R₃₇Straight-chain, branched, or cyclic alkyl having the same meaning as
Represents an aryl group or an aryl group. X^-Is branched or annular
A group of alkyl and alkoxy groups having 8 or more carbon atoms
Having at least one group selected from among
Branched or cyclic alkyl groups having 4 to 7 carbon atoms and alcohols
Having at least two groups selected from the group of xyl groups
Or a linear, branched or cyclic C 1 -C 3
A group selected from the group consisting of an alkyl group and an alkoxy group
Benzenesulfonic acid having at least three naphthalenes
Sulfonic acid or anthracene sulfonic acid anion
Represent. Or an ester group, R₃₉—CO— group, R₄₀-C
ONH-group, R₄₁-NH- group, R₄₂-OCONH- group,
R₄₃-NHCOO- group, R₄₄—NHCONH— group, R ₄₅
-NHCSN- group, R₄₆-SO_TwoNH- group, and nitro
A group having at least one group selected from the group consisting of
Benzene sulfonic acid, naphthalene sulfonic acid or anato
Represents an anion of helix sulfonic acid. R₃₉~ R₄₆Is R₃₈
Linear, branched, or cyclic alkyl group or aryl group as defined above
Represents )

(2) (d) A low molecular weight dissolution inhibiting compound having a molecular weight of 3000 or less, which has a group decomposable by an acid and whose solubility in an alkali developing solution is increased by the action of an acid,
The positive photosensitive composition according to (1), further comprising: (3) (a) a basic nitrogen-containing compound having a polycyclic structure represented by the general formula (I) described in (1), and (b) an acid is generated by irradiation with an actinic ray described in (2). General formula (II)
At least one of the compounds represented by (IV) to (IV);
A low molecular weight dissolution inhibiting compound having a molecular weight of 3000 or less, which has a group decomposable by an acid and whose solubility in an alkaline developer is increased by the action of an acid; and (e) insoluble in water and soluble in an alkaline developer A hoji-type photosensitive composition comprising a resin. (4) (c) a resin having a group that is decomposed by the action of an acid and increases the solubility in an alkali developer is a resin containing a repeating structural unit represented by the following general formulas (IV) and (V): The positive photosensitive composition according to (1) or (2), wherein

[0015]

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 aralkyl group which may be substituted, and Z and L may combine to form a 5- or 6-membered ring.)

(5) (b) In the compounds of the general formulas (II) to (IV) which generate an acid upon irradiation with actinic rays, X ^- is a group of a branched or cyclic alkyl or alkoxy group having 8 or more carbon atoms. Or at least 2 groups selected from the group consisting of linear, branched or cyclic alkyl and alkoxy groups having 4 to 7 carbon atoms.
Or a linear, branched or cyclic carbon number of 1
(1) The positive electrode according to (1) to (4), which is an anion of benzenesulfonic acid having at least three groups selected from the group consisting of an alkyl group and an alkoxy group or having an ester group. -Type photosensitive composition.

The positive photosensitive composition of the present invention uses a compound represented by the above general formula (I) as a basic nitrogen compound to improve the line width by increasing the amount of addition in a chemically amplified resist. However, the problem of lowering the sensitivity was solved, and an excellent resist pattern was obtained.

[0019]

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

[I] Basic nitrogen-containing compound having a polycyclic structure (component (a)) The basic nitrogen-containing compound having a polycyclic structure of the present invention is represented by the above general formula (I), wherein Y and Z are Represents a linear, branched or cyclic alkylene group which may be the same or different, may contain a hetero atom, and may be substituted. Examples of the hetero atom include a nitrogen atom, a sulfur atom, and an oxygen atom.
The alkylene group preferably has 2 to 10 carbon atoms, and more preferably has 2 to 5 carbon atoms. Examples of the substituent of the alkylene group include an alkyl group having 1 to 6 carbon atoms, an aryl group,
In addition to the alkenyl group, a halogen atom and a halogen-substituted alkyl group are exemplified. Specific examples of the basic nitrogen-containing compound having a polycyclic structure of the present invention include the following compounds, but the present invention is not limited thereto.

[0021]

Embedded image

Among the compounds represented by the general formula (I), 1,8-diazabicyclo [5.4.0] undeca-
7-ene and 1,5-diazabicyclo [4.3.0] non-5-ene are particularly preferred.

The basic nitrogen-containing compounds of the present invention may be used alone or in combination of two or more. The amount of the basic nitrogen-containing compound to be used is generally 0.001 to 10 parts by weight, preferably 0.1 to 100 parts by weight, per 100 parts by weight of the photosensitive composition (excluding the solvent).
It is 01 to 5 parts by weight. If the amount is less than 0.001 part by weight, the effects of the present invention cannot be obtained. If the amount exceeds 10 parts by weight, sensitivity tends to decrease and developability of an exposed portion tends to deteriorate.

[II] Compounds represented by general formulas (II) to (IV) which generate an acid upon irradiation with actinic rays (component (b)): R ₁ to R ₁ in the above general formulas (II) to (IV) The linear or branched alkyl group for R ₄₆ may have a substituent,
Methyl group, ethyl group, propyl group, n-butyl group, se
Those having 1 to 4 carbon atoms such as a c-butyl group and a t-butyl group are exemplified. The cyclic alkyl group may have a substituent, a cyclopropyl group, a cyclopentyl group,
Those having 3 to 8 carbon atoms such as a cyclohexyl group are exemplified. Examples of the alkoxy group represented by R _{1 to} R ₃₇ include a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a t-butoxy group. One. Examples of the halogen atom for R _{1 to} R ₃₇ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the aryl group of R _{38 to} R ₄₆ include those having 6 to 14 carbon atoms which may have a substituent such as a phenyl group, a tolyl group, a methoxyphenyl group, and a naphthyl group. Preferably, these substituents have 1 to 1 carbon atoms.
4 alkoxy groups, halogen atoms (fluorine atom, chlorine atom, iodine atom), aryl group having 6 to 10 carbon atoms, alkenyl group having 2 to 6 carbon atoms, cyano group, hydroxy group, carboxy group, alkoxycarbonyl Group, nitro group and the like.

In the general formulas (II) to (IV) used in the present invention,
The sulfonium and iodonium compounds represented are
Counter anion, X^-As a branched or cyclic carbon number of 8
Or more, preferably 10 or more alkyl groups or alkoxy
Having at least one or more linear groups, linear, branched or
Is a cyclic alkyl or alkoxy group having 4 to 7 carbon atoms
Having at least two or more, linear or branched
Or cyclic alkyl group having 1 to 3 carbon atoms or alkyl
Benzenesulfonic acid having at least three xy groups,
Naphthalenesulfonic acid or anthracenesulfonic acid
Has a nonion. Or an ester group, R₃₈-CO-
Group, R₃₉-CONH- group, R₄₀-NH- group, R₄₁-OC
ONH-group, R₄₂-NHCOO- group, R₄₃-NHCON
H-group, R ₄₄-NHCSN- group, R₄₅-SO_TwoNH-
Groups and at least one group selected from the group of nitro groups
Sulfonic acid, naphthalene sulfone, which also has one
It has an acid or an anthracene sulfonic acid anion.

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

From the viewpoint of suppressing a change in line width due to aging from exposure to post-heating, at least one group selected from the group consisting of a branched or cyclic alkyl group and an alkoxy group having 8 or more carbon atoms, or a linear or branched group Or a cyclic carbon number of 4 to
Has at least two groups selected from the group consisting of 7 alkyl groups and alkoxy groups, or has at least 3 groups selected from the group consisting of linear, branched or cyclic alkyl groups and alkoxy groups having 1 to 3 carbon atoms. The anion of benzenesulfonic acid having or having an ester group is most preferred.

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

Further, X ^- in the aromatic sulfonic acid represented by, in addition to the above specific substituent, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), C6-10
It may contain as substituents aryl groups, cyano groups, sulfide groups, hydroxy groups, carboxy groups, nitro groups and the like. Hereinafter, specific examples of these compounds are shown, but the present invention is not limited thereto.

[0030]

Embedded image

[0031]

Embedded image

[0032]

Embedded image

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

The component (b), for example, the compounds represented by the general formulas (II), (III) and (IV) can be used alone or in combination of two or more.
The component (b), for example, the general formula (II), the general formula (III)
) And the compound represented by the general formula (IV) can be prepared by the method described in US Pat. No. 3,734,928, Macromolec.
ules, vol. 10, 1307 (1977), Journal of Organic Chem
istry, vol. 55, 4222 (1990), J. Radiat. Curing, vo
l. It can be synthesized by using the method described in 5 (1), 2 (1978) or the like, and further exchanging the counter anion.
The content of the component (b), for example, the compound represented by the general formula (II), the general formula (III), or the general formula (IV) in the photosensitive composition is 0.1 to the solid content of the photosensitive composition. 1-20% by weight
Is suitable, preferably 0.5 to 10% by weight, more preferably 1 to 7% by weight.

[III] (b ') Other Photoacid Generating Compounds That Can Be Used in Combination In the photosensitive composition of the present invention, in addition to the above component (b) 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 (b ′)”) may be used in combination. The content of the component (b ′) which can be used in combination with the component (b) 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 cationic photopolymerization, 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, German Patent Nos. 2,904,626, 3,604,580, 3,60
No. 4,581, etc., sulfonium salt, JVCrivello eta
l, Macromorecules, 10 (6), 1307 (1977), JVCrivello 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), WJM
ijs et al, Coating Technol., 55 (697), 45 (1983), Akzo, H.
Adachi 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.

Further, a group that generates an acid by these lights,
Alternatively, a compound having a compound introduced into the main chain or side chain of a polymer, for example, MEWoodhouse et al., J. Am. Chem.
c., 104, 5586 (1982), SPPappas etal, J. Imaging Sc
i., 30 (5), 218 (1986), S. Kondo et al., Makromol.Chem., 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, German 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).

[0044]

Embedded image

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.

[0046]

Embedded image

[0047]

Embedded image

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

[0049]

Embedded image

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.

[0055]

Embedded image

[0056]

Embedded image

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]

Embedded image

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.

[0061]

Embedded image

[0062]

Embedded image

[0063]

Embedded image

[0064]

Embedded image

[IV] (c) A resin having a group that decomposes under the action of an acid to increase the solubility in an alkaline developer (hereinafter, also simply referred to as “component (c)”). Examples of the resin having a group capable of decomposing with an acid used in (1) and increasing the solubility in an alkaline developer (also referred to as a group decomposable with an acid) include a main chain or a side chain of the resin or a main chain and a side chain Resin having acid-decomposable groups on both chains. Among them, a resin having a group which can be decomposed by an acid in a side chain is more preferable. A preferred group capable of being decomposed by an acid is -COOA
^0, a -O-B ⁰ group, the group further comprising them,
-R ⁰ -COOA ^0, or group represented by -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, when the group decomposable by these acids is bonded as a side chain, the base resin may have -OH or -COOH, preferably -R ⁰ -COOH or -A _r -OH group on the side chain. 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 capable of being decomposed by an acid used in the present invention are shown below, but the present invention is not limited thereto.

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

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

[0073]

Embedded image

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

The resin containing a repeating structural unit represented by the above general formulas (V) and (VI) may contain a structural unit derived from another monomer. 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 (V) and (VI) and the structural units of the other monomers is represented by the molar ratio [(V) + (V
I)] / [Other monomer components] = 100/0 to 50/5
0, 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 (V) and (VI) include:
The following are mentioned.

[0081]

Embedded image

[0082]

Embedded image

[0083]

Embedded image

[0084]

Embedded image

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.

[0087]

Embedded image

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

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

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

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

When the acid-decomposable dissolution-inhibiting compound has three or more, preferably four or more acid-decomposable groups, and also when it has two acid-decomposable groups, the acid-decomposable groups are mutually fixed. 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.

[0093]

Embedded image

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

More preferably, JP-A-1-289946.
JP-A-3-128959, JP-A-3-15885
5, JP-A-3-179353, JP-A-3-2002
No. 51, JP-A-3-200252, JP-A-3-200
255, JP-A-3-259149, JP-A-3-27
9958, JP-A-4-1650, JP-A-4-112
No. 60, JP-A-4-12356, 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 [V]
III].

[0101]

Embedded image

[0102]

Embedded image

[0103]

Embedded image

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

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

[0106]

Embedded image

[0107] Here, G = 2 to 6, provided that at least one alkyl group among when G = 2 is ^{R 150, R 151, R 150} , R 151: the same or different, a hydrogen atom, an alkyl group, an alkoxy Group, —OH, —COOH, —CN, a halogen atom, —R ¹⁵² —COOR ¹⁵³ or —R ¹⁵⁴
—OH, R ¹⁵² , R ¹⁵⁴ : alkylene group, R ¹⁵³ : hydrogen atom, alkyl group, aryl group or aralkyl group, R ⁹⁹ , R ^{103 to} R ¹⁰⁷ , R ¹⁰⁹ , R ^{111 to} R ¹¹⁸ , R
^{128 to} R ¹²⁹ , R ^{131 to} R ¹³⁴ , R ¹³⁸ , R ¹³⁹ : the same or different, hydrogen atom, hydroxyl group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, aralkyl group, aralkyl An oxy group, a halogen atom, a nitro group, a carboxyl group, a cyano group, or -N ( ^R155 ) ( ^R156 ) ( ^R155 , ^R156 : H, an alkyl group, or an aryl group) ^R110 : a single bond, An alkylene group, or

[0108]

Embedded image

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

R ¹¹⁹ and R ^{120 are the} same or different and are each a methylene group, a lower alkyl-substituted methylene group, a halomethylene group, or a haloalkyl group, provided that the lower alkyl group is an alkyl group having 1 to 4 carbon atoms; R ¹²⁴ to R ^127: the same or different, a hydrogen atom or an alkyl group, R ¹³⁵ to R ^137: the same or different, a hydrogen atom, an alkyl group, an alkoxy group, an acyl group or an acyloxy group,, R ¹⁴⁶ to R ^149: Same or different, hydrogen atom, hydroxyl group, halogen atom, nitro group, cyano group, carbonyl group, alkyl group, alkoxy group, alkoxycarbonyl group, aralkyl group, aralkyloxy group, acyl group, acyloxy group, alkenyl group, alkenyloxy Group, aryl group, aryloxy group, or aryloxycarbonyl group, provided that And each of the four substituents having the same symbol may not be the same group. Z, B: a single bond or —O—, A: a methylene group, a lower alkyl-substituted methylene group, a halomethylene group, or a haloalkyl group; a to v, c1 to r1: when plural, the groups in () may be the same or different; a to q, s, t, v, g1 to i1, k1 to m1, o1, q1: 0 or 1-5
An integer of r, u, w, x, y, z, c1 to f1, p1, r1: 0 or an integer of 1 to 4, j1, n1, z1, a2, b2, c2, d2: 0 or 1 to 3 An integer of at least one of a2, c2, d2 is 1 or more; (a + b), (e + f + g), (k + l + m), (q + r + s), (c1 + d1), (g1 + h1 + i1 + j
1), (o1 + p1) ≧ 2, (j1 + n1) ≦ 3, (r + u), (c1 + e1), (d1 + f1), (p1 + r1) ≦ 4, (a + c) , (b + d), (e + h), (f + i), (g + j), (k + n), (l + o), (m + p), (q
+ t), (s + v), (g1 + k1), (h1 + l1), (i1 + m1), (o1 + q1) ≦ 5.

[0111]

Embedded image

[0112]

Embedded image

[0113]

Embedded image

Specific examples of preferred compound skeletons are shown below.

[0115]

Embedded image

[0116]

Embedded image

[0117]

Embedded image

[0118]

Embedded image

[0119]

Embedded image

[0120]

Embedded image

[0121]

Embedded image

[0122]

Embedded image

[0123]

Embedded image

[0124]

Embedded image

[0125]

Embedded image

[0126]

Embedded image

[0127]

Embedded image

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

[0129]

Embedded image

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

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

[VI] (e) Resin Insoluble in Water and Soluble in Alkaline Developing Solution The composition of the present invention is used for controlling alkali solubility.
A resin that is insoluble in water and soluble in an alkali developer (hereinafter, also simply referred to as “component (e)”) can be contained. This resin has substantially no acid-decomposable groups. (E)
As the component, for example, novolak resin, hydrogenated novolak resin, acetone-pyrogallol resin, o-polyhydroxystyrene, m-polyhydroxystyrene, p-polyhydroxystyrene, hydrogenated polyhydroxystyrene,
Halogen or alkyl-substituted polyhydroxystyrene, hydroxystyrene-N-substituted maleimide copolymer, o / p- and m / p-hydroxystyrene copolymer, part of O- to hydroxyl group of polyhydroxystyrene
Alkyl compounds (for example, 5 to 30 mol% of O-methyl compound, O- (1-methoxy) ethyl compound, O- (1-ethoxy) ethyl compound, O-2-tetrahydropyranyl compound, O- (t- Butoxycarbonyl) methylated product) or O-acylated product (for example, 5 to 30 mol% 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.

The weight average molecular weight of the novolak resin is 1,
It is preferably in the range of 000 to 30,000.
If it is less than 1,000, the film loss of the unexposed portion after development is large, and if it exceeds 30,000, the developing speed is reduced. Particularly preferred is the range of 2,000 to 20,000. In addition, the weight average molecular weight of the polyhydroxystyrene other than the novolak resin, its derivative, and the copolymer is 2,000 or more, preferably 5,000 to 20,000.
0, more preferably 8,000 to 100,000. Further, from the viewpoint of improving the heat resistance of the resist film, it is preferably 10,000 or more. Here, the weight average molecular weight is defined as a value in terms of polystyrene by gel permeation chromatography. In the present invention, these alkali-soluble resins may be used as a mixture of two or more kinds. The amount of the alkali-soluble resin to be used is 40 to 97% by weight, preferably 60 to 90% by weight, based on the total weight of the photosensitive composition (excluding the solvent).

[VII] Other components used in the present invention The positive photosensitive composition of the present invention may further contain, if necessary, a dye, a pigment, a plasticizer, a surfactant, a photosensitizer, and a developing agent. A compound having two or more phenolic OH groups for promoting the solubility in a liquid may be contained.

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

The preferred addition amount of this phenol compound is 2 to 50% by weight, more preferably 5 to 30% by weight, based on the alkali-soluble resin. 50% by weight
If the addition amount exceeds the above range, the development residue becomes worse and a new defect that the pattern is deformed at the time of development occurs, which is not preferable.

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

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

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, by adding a spectral sensitizer as described below to sensitize the photosensitive composition of the present invention to a longer wavelength region than the far ultraviolet where the photoacid generator used does not have absorption, the photosensitive composition of the present invention is obtained. Sensitivity can be given to i or g rays. Suitable spectral sensitizers include, specifically, benzophenone, p,
p'-tetramethyldiaminobenzophenone, p, p '
-Tetraethylethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin,
Cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene,
Benzoquinone, 2-chloro-4-nitroaniline, N-
Acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone 1,2-benzanthraquinone, 3- Methyl-1,3-diaza-1,
9-benzanthrone, dibenzalacetone, 1,2-
Naphthoquinone, 3,3′-carbonyl-bis (5,7-
Dimethoxycarbonylcoumarin) and coronene, but are not limited thereto. Further, these spectral sensitizers can also be used as a light absorbing agent for far ultraviolet light of a light source. In this case, the light absorbing agent exerts the effect of improving the standing wave by reducing the reflected light from the substrate and reducing the influence of multiple reflection in the resist film.

The photosensitive composition of the present invention is dissolved in a solvent capable of dissolving each of the above components and applied on a support. Examples of the solvent used herein include ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, and ethylene glycol monoethyl ether acetate. , Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate,
Ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

A surfactant may be added to the above solvents. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether,
Polyoxyethylene alkyl allyl ethers such as polyoxyethylene nonylphenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, Sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Surfactants such as polyoxyethylene sorbitan fatty acid esters such as acrylates and the like, F-top EF301, E 303, EF352 (manufactured by Shin Akita Kasei Co., Ltd.), Megafac F171, F173 (manufactured by Dainippon Ink Co., Ltd.), Flora - de FC430, FC43
1 (manufactured by Sumitomo 3M Limited), Asahi Guard AG71
0, Surflon S-382, SC101, SC102,
Fluorinated surfactants such as SC103, SC104, SC105 and SC106 (manufactured by Asahi Glass Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and acrylic or methacrylic (co) polymerized polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo KK) and the like. The amount of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solids in the composition of the present invention. These surfactants may be added alone or in some combination.

The above 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.

[0145]

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.

(A) Examples of the basic nitrogen-containing compound include the above-mentioned exemplified compounds (I-1), (I-2), (I-3) and (I-3).
-4) (Aldrich) was used.

(B) Synthesis of acid generating compound Synthesis of compound (II-1) 50 g of diphenylsulfoxide was dissolved in 800 ml of benzene, and 200 g of aluminum chloride was added thereto, followed by refluxing for 24 hours. The reaction solution was slowly poured into 2 liters of ice, and 400 ml of concentrated hydrochloric acid was added thereto, followed by heating at 70 ° C. for 10 minutes. This aqueous solution is treated with ethyl acetate 50
After washing with 0 ml and filtration, a solution prepared by dissolving 200 g of ammonium iodide in 400 ml of water was added. The precipitated powder was collected by filtration, washed with water, washed with ethyl acetate and dried to obtain 70 g of triphenylsulfonium iodide. 50 g of triphenylsulfonium iodide was dissolved in 300 ml of methanol, and 31 g of silver oxide was added thereto, followed by stirring for 4 hours. After filtering the reaction solution, 2,4,6-triisopropylbenzenesulfonic acid tetramethylammonium salt (2,4,6-triisopropylbenzenebenzenesulfonyl chloride is heated and reacted in tetramethylammonium hydroxide, water, and methanol) 45 g).
This solution was concentrated, and the resulting powder was sufficiently washed with water and recrystallized from ethyl acetate / acetone to give compound (II-1).
Was obtained in an amount of 50 g. Using a similar method, compound (II-
2) and (II-3) were synthesized.

Synthesis of Compound (II-4) 50 g of diphenyl sulfoxide and 45 g of diphenyl sulfide were added to methanesulfonic acid / diphosphorus pentoxide (10/1).
100 ml of the solution was added. After the exotherm subsided, the mixture was heated at 50 ° C. for 4 hours, and then the reaction solution was poured on ice. This aqueous solution was washed with toluene and filtered, and then a solution prepared by dissolving 200 g of ammonium iodide in 400 ml of water was added. The precipitated powder was collected by filtration and washed with water to obtain diphenyl (4-phenylthiophenyl) sulfonium iodide. This was salt-exchanged with 2-heptyloxycarbonylbenzenesulfonic acid (synthesized from o-sulfobenzoic anhydride and n-heptanol) in the same manner as in (II-1) to give compound (II-4). Compounds (III-1) and (III-2) were obtained by subjecting the corresponding sulfonic acid to salt exchange using the same method as (II-4).

Synthesis of Compound (IV-1) t-Amylbenzene 60 g, potassium iodate 39.5
g, 81 g of acetic anhydride and 170 ml of dichloromethane, and 66.8 g of concentrated sulfuric acid was slowly added dropwise thereto under ice-cooling. After stirring for 2 hours under ice cooling, the mixture was stirred at room temperature overnight. Water (50 ml) was added dropwise to the reaction mixture under ice-cooling, and the mixture was extracted with dichloromethane. The organic phase was washed with water, an aqueous solution of sodium hydrogen carbonate and water, and concentrated to obtain di-t-amylphenyliodonium sulfate. 10 g of this sulfate was added to an aqueous solution of 10 g of 2,4,6-triisopropylbenzenesulfonic acid tetramethylammonium salt, and the precipitated powder was collected by filtration and washed with water to obtain crude crystals. This is 2
-When recrystallized from propanol, compound (IV-1) is 5
g were obtained. Compound (IV-2) was obtained by using the same method as for compound (IV-1).

(C) Synthesis of Resin (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 40 liters of ion-exchanged water, and the precipitated powder was collected by filtration, washed with water and dried to obtain a p-hydroxystyrene / p- (1-iso-butoxyethoxy) styrene copolymer ( 60/40).

(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 of ion-exchanged water, and the precipitated powder was collected by filtration, washed with water and dried to obtain p-hydroxystyrene / p- (1-i
so-butoxyethoxy) styrene copolymer (70/3
0, partially crosslinked type).

(Resin Synthesis Example 3) 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 / iBES / AS: P-hydroxystyrene / P
-(1-iso-butoxyethoxystyrene / P-acetoxystyrene copolymer (70/20/10: molar ratio)
Synthesis of poly-p-hydroxystyrene (weight average molecular weight 110
00) 360 g, isobutyl vinyl ether 126.0
g was dissolved in 1800 ml of anhydrous THF, 0.1 g of p-toluenesulfonic acid was added, and the mixture was stirred at room temperature for 2 hours. To the reaction solution was added 40 g of pyridine, and then acetic anhydride 4 g.
2 g was added, and the mixture was stirred at room temperature for 2 hours. The reaction solution was poured into 3 liters of water, and the precipitated powder was collected by filtration, washed with water, and dried, and a p-hydroxystyrene / p- (i-butoxyethoxy) styrene / acetyloxystyrene copolymer (7
0/20/10) (weight average molecular weight 12,000).

(D) Synthesis of Dissolution Inhibitor Compound (Synthesis Example 1 of Dissolution Inhibitor Compound: Synthesis of Compound Example 16) 1- [α-methyl-α- (4′-hydroxyphenyl) ethyl] -4- [Α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene 42.4 g (0.10
Mol) was dissolved in 300 ml of N, N-dimethylacetamide, to which 49.5 g (0.35 mol) of potassium carbonate and 84.8 g (0.5 mol) of cumyl bromoacetate were added.
33 mol) was added. Thereafter, the mixture was stirred at 120 ° C. for 7 hours. The reaction mixture was poured into 2 l of ion-exchanged water, neutralized with acetic acid, and extracted with ethyl acetate. Concentration of the ethyl acetate extracts were purified in the same manner as in Synthesis Example -3, all compounds Example 16 (R is _{-CH 2 COOC (CH 3) 2} C 6 H
₅ g) 70 g were obtained.

(Synthesis Example 2 of Dissolution Inhibitor Compound: Compound)
Synthesis of 41) 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 4.
1 (R is all -CH _TwoCOOC_FourH₉(T)) is 87
g were obtained.

(Synthesis Example 3 of Dissolution Inhibitor Compound: Synthesis of Compound Example 43) 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 43 (R is all THP groups).

(Examples 1 to 8, 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.

[0160]

[Table 1]

The abbreviations used in Table 1 represent the following contents. <Polymer> In parentheses, the molar ratio is PHS / iBES p-hydroxystyrene / p-
(1-iso-butoxyethoxystyrene copolymer (6
0/40) 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 (55/4
5) Weight average molecular weight 13000 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 (60/40) Weight average molecular weight 12000 PHS / St p-hydroxystyrene / styrene copolymer (85/15) Weight average molecular weight 51000 PHS / iBES / AS P-hydroxy Styrene / P- (1-iso-butoxyethoxystyrene / P-acetoxystyrene copolymer (70/20/10) Weight average molecular weight 12000 <Acid decomposable group in dissolution inhibitor>

[0162]

Embedded image

<Compound (A) for Comparative Example> Triphenylsulfonium trifluoromethanesulfonate [Preparation and Evaluation of Photosensitive Composition]
It was dissolved in 5 g and filtered through a 0.1 μm filter to prepare a resist solution. This resist solution is applied on a silicon wafer by using a spin coater, and 90 ° C.
Drying was performed on a vacuum adsorption type hot plate for 60 seconds to obtain a resist film having a thickness of 0.76 μm. In this resist film,
248 nm KrF excimer laser stepper (NA =
Exposure was performed using 0.42). Immediately after the exposure, each was heated for 60 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, and resolution of the pattern on the silicon wafer thus obtained were evaluated and compared as follows. The results are shown in Table 1 above.

[Profile] The pattern on the silicon wafer thus obtained was observed with a scanning electron microscope to evaluate the resist profile. [Sensitivity] Sensitivity was defined as an exposure amount that reproduced a master pattern of 0.30 μm. [Resolving power] The resolving power indicates a limit resolving power at an exposure amount for reproducing a 0.30 μm master pattern.

Further, in the same manner, two hours after the exposure,
Heat as above and immediately with 2.38% aqueous tetramethylammonium hydroxide (TMAH)
It was immersed for 0 second, rinsed with water for 30 seconds and dried. The line width of the 0.30 μm mask pattern thus obtained was measured, and the rate of change from the value immediately after exposure was calculated. Table 1 shows the results.

From the results shown in Table 1, it can be seen that the positive photosensitive composition of the present invention has high sensitivity and high resolution, and is superior in sensitivity to Comparative Examples 1 to 3 with little change in line width. It turns out that it is a composition. The profiles of the resist patterns were all rectangular.

[0167]

EFFECTS OF THE INVENTION The chemically amplified positive photosensitive composition of the present invention provides a positive photosensitive composition having a good profile, high sensitivity and high resolution, and little change in performance over time after exposure. can do.

Claims (5)

[Claims] (A) a polycyclic compound represented by the following general formula (I)
A basic nitrogen-containing compound having a structure, (b) irradiation with actinic rays
In the following general formulas (II) to (IV) which generate an acid upon irradiation
Action of at least one of the compounds represented and (c) acid
Decomposes and increases solubility in alkaline developer
Characterized by containing a resin having a base group
Light composition. Embedded image(In the formula (I), Y and Z may be the same or different.
Straight chain, which may contain
Represents a branched or cyclic alkylene group. )(Where R₁~ R₃₇Is a hydrogen atom, linear, branched, or cyclic
Kill group, linear, branched, cyclic alkoxy group, hydroxy
Group, halogen atom, or -SR₃₈Represents a group. R ₃₈Is
Represents a linear, branched, or cyclic alkyl group or an aryl group.
X^-Is a branched or cyclic alkyl group having 8 or more carbon atoms.
And at least a group selected from the group of alkoxy groups
One, or a linear, branched or cyclic C 4-7
Groups selected from the group of alkyl and alkoxy groups
Or at least two, or linear, branched or
Cyclic alkyl groups having 1 to 3 carbon atoms and alkoxy groups
Benzene having at least three groups selected from the group
Sulfonic acid, naphthalenesulfonic acid or anthracene
Represents the anion of sulfonic acid. Or an ester group, R
₃₉—CO— group, R₄₀-CONH- group, R₄₁-NH- group,
R₄₂—OCONH— group, R₄₃-NHCOO- group, R₄₄−
NHCONH- group, R ₄₅-NHCSN- group, R₄₆-SO
_TwoA group selected from the group consisting of an NH- group and a nitro group
Benzenesulfonic acid having at least one naphthalene
The anion of sulfonic acid or anthracenesulfonic acid
Represent. R₃₉~ R₄₆Is a linear, branched, or cyclic alkyl group or
Represents an aryl group. ) (D) having a group decomposable by an acid, wherein the solubility in an alkaline 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 basic nitrogen-containing compound having a polycyclic structure represented by the general formula (I) according to claim 1;
An alkali developer having at least one of the compounds represented by the general formulas (II) to (IV), which generate an acid upon irradiation with actinic rays according to claim 1, and (d) having an acid-decomposable group, With a molecular weight of 3
A hodgi-type photosensitive composition comprising a low molecular weight dissolution inhibiting compound of 000 or less and (e) a resin which is insoluble in water and soluble in an alkali developing solution. 4. A resin having a group which decomposes under the action of an acid and increases the solubility in an alkali developer, comprises 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, an alkyl group on a linear, branched, or ring, or an aralkyl group which may be substituted. Z is a linear, branched, or cyclic alkyl group, or Represents an aralkyl group which may be substituted.
Further, Z and L may combine to form a 5- or 6-membered ring. ) 5. The compound of the general formulas (II) to (IV) which generates an acid upon irradiation with an actinic ray, wherein X ^- is a branched or cyclic alkyl or alkoxy group having 8 or more carbon atoms. It has at least one selected group, has at least two groups selected from the group consisting of linear, branched or cyclic alkyl and alkoxy groups having 4 to 7 carbon atoms, or has a linear, branched or cyclic carbon group. The positive electrode according to any one of claims 1 to 4, wherein the positive electrode is an anion of benzenesulfonic acid having at least three groups selected from the group consisting of an alkyl group and an alkoxy group having a number of 1 to 3, or having an ester group. -Type photosensitive composition.