JP2003057826A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an excellent photosensitive resin composition having sufficient transmittance when a source of light having <=160 nm wavelength, specifically F2 excimer laser light (157 nm) is used and ensuring small line edge roughness and small dependence on development time. SOLUTION: The photosensitive resin composition comprises a resin which is decomposed by the action of an acid having a specified structure to increase its solubility in an alkali developing solution, a compound which generates the acid represented by the formula A1 H when irradiated with active light or radiation, an ionic compound represented by the formula B<+> A2 <-> , a solvent and a surfactant, and the acid A1 H generated by irradiation with active light or radiation and the ionic compound B<+> A2 <-> carry out a salt exchange reaction represented by the formula A1 H+B<+> A2 <-> →B<+> A1 <-> +A2 H.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition suitable for use in microlithography processes such as manufacturing of ultra-LSIs and high-capacity microchips and other photofabrication processes. More specifically, the present invention relates to a positive resist composition capable of forming a highly refined pattern using vacuum ultraviolet light of 160 nm or less.

2. Description of the Related Art The degree of integration of integrated circuits is increasing more and more, and in the manufacture of semiconductor substrates such as VLSI, it has become necessary to process ultrafine patterns having a line width of less than quarter micron. It was As one of means for achieving a finer pattern, it is known to shorten the wavelength of an exposure light source used when forming a resist pattern.

For example, to manufacture a semiconductor device having an integration degree of up to 64 Mbits, up to now, the i-line (365n) of a high pressure mercury lamp has been used.
m) has been used as a light source. As a positive resist compatible with this light source, many compositions containing a novolac resin and a naphthoquinonediazide compound as a photosensitive material have been developed, and have achieved sufficient results in processing line widths up to about 0.3 μm. . Further, KrF excimer laser light (248 nm) has been adopted as an exposure light source instead of the i-line in the manufacture of a semiconductor device having an integration degree of 256 Mbits or more. Furthermore, for the purpose of manufacturing semiconductors with a degree of integration of 1 Gbit or more, the use of ArF excimer laser light (193 nm), which is a light source with a shorter wavelength in recent years, has a
The use of F2 excimer laser light (157 nm) for forming a pattern of m or less has been studied.

With the shortening of the wavelength of these light sources, the constituent components of the resist material and the compound structure thereof have changed greatly. As a resist composition for exposure by KrF excimer laser light, poly (hydroxystyrene) having a small absorption in the 248 nm region is used as a main skeleton and a resin protected with an acid decomposing group is used as a main component, and an acid is irradiated by irradiation with far ultraviolet light. A composition, which is a so-called chemically amplified resist, in which a generated compound (photo-acid generator) is combined has been developed.

In addition, ArF excimer laser light (193
As a resist composition for exposure, a chemically amplified resist using an acid-decomposable resin in which an alicyclic structure having no absorption at 193 nm is introduced in the main chain or side chain of a polymer has been developed.

With respect to F ₂ excimer laser light (157 nm), even the above alicyclic resin has large absorption in the 157 nm region, and it is proved that it is insufficient to obtain a target pattern of 0.1 μm or less. However, in contrast to this, the resin containing a fluorine atom (perfluoro structure) is 157n
Proc. SPIE. Vol.367 has sufficient transparency for m.
8. Reported on page 13 (1999), effective structure of fluororesin is Proc. SPIE. Vol. 3999. 330 (2000), 357 (2000), 365 (2000), WO-00. / 17712
No. 4, pp. 187-242, and studies on a resist composition containing a fluorine-containing resin have been made.

However, a resist composition containing a fluorine resin for F ₂ excimer laser light exposure has problems such as line edge roughness and development time dependency, and it has been desired to solve these problems. The line edge roughness means that, due to the characteristics of the resist, the edge of the resist line pattern and the substrate interface has a shape that irregularly fluctuates in the direction perpendicular to the line direction. When this pattern is observed from directly above, the edges look uneven (± several nm to several tens of nm). Since the unevenness is transferred to the substrate by the etching process, if the unevenness is large, the electrical characteristics will be deteriorated and the yield will be reduced. Further, the development time dependency means the degree of change in the pattern dimension due to the change in the development time. If the development time dependency is large, the dimensional uniformity within the wafer surface deteriorates, and the process controllability becomes difficult.

[0007]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to obtain a light of 160 nm or less, especially F ₂ excimer laser light (1
(57 nm) exposure light source, and to provide a suitable photosensitive resin composition. Specifically, it exhibits sufficient transmissivity when using a 157 nm light source, and has excellent line edge roughness and development time dependency. Another object of the present invention is to provide a photosensitive resin composition.

[0008]

Means for Solving the Problems The inventors of the present invention, as a result of diligent study in consideration of the above-mentioned various characteristics, have found that the object of the present invention can be successfully achieved by using the following specific composition. Has reached the present invention. That is, the present invention has the following configuration.

(1) (A) The following general formulas (I) and (I
I) and (VI) each having at least one repeating unit, which decomposes by the action of an acid and increases the solubility in an alkali developing solution, (B1) by irradiation with actinic rays or radiation, a compound represented by the general formula A ₁ a compound capable of generating an acid represented by H, (B2) the general formula B ⁺ a ₂ ^- ionic compound represented by in (C) a solvent, and (D) a photosensitive resin composition containing a surface active agent There, upon irradiation with actinic rays or radiation (B1) an acid generated by component a ₁ H and ionic compounds B ⁺ a ₂ ^- is ^{_{a 1 H + B + a 2}} - → B + a 1 - + a 2 H ( Here, H is a hydrogen atom, A ₁ is a residue obtained by removing a hydrogen atom from the acid A ₁ H, B ⁺ is a cation portion of the ionic compound, and A _{2 is}
^- represents an anion portion. A ₁ ^- is an anion derived from A ₁ ,
A ₂ represents a group derived from A ₂ ^— having a reduced ionicity due to the bond with a hydrogen atom ion. The photosensitive resin composition characterized by performing the salt exchange reaction represented by these.

[0010]

[Chemical 3]

In the general formulas (I), (II) and (VI),
R₁, R_Five, R_17aAnd R₁₇Are the same or different
Often, hydrogen atom, halogen atom, cyano group or substituent
It represents an alkyl group which may have. R₂, R₃, R₆Over
And R₇May be the same or different and may be a hydrogen atom,
Possess a rogen atom, cyano group, hydroxyl group or substituent
Optionally, an alkyl group, a cycloalkyl group, an
Coxy group, acyl group, acyloxy group, alkenyl group,
Represents a reel group or an aralkyl group. R₅₀~ R ₅₅Is
They may be the same or different and may be hydrogen atom, fluorine atom or
Represents an alkyl group which may have a substituent. However,
R₅₀~ R₅₅Of these, at least one is a fluorine atom or
At least one hydrogen atom is replaced by a fluorine atom
Represents a kill group. R_FourIs the following general formula (IV) or (V)
Represents the group of. R₁₈Is -C (R_18d) (R_18e)
(R_18f) Or -C (R_18d) (R_18e) (OR_{18 g}) Table
You R_18d~ R _{18 g}Can be the same or different, water
An alkyl group, optionally substituted with an atom or a substituent,
Chloroalkyl group, alkenyl group, aralkyl group or
Represents an aryl group. R_18d, R_18e, R_18fTwo of the
Is R_18d, R_18e, R_{18 g}Two of them combine to form a ring
You may.

[0012]

[Chemical 4]

In the general formula (IV), R ₁₁ , R ₁₂ and R
₁₃ represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group, which may be the same or different and may have a substituent. General formula (V)
R ₁₄ and R _{15, which} may be the same or different, each represent a hydrogen atom or an alkyl group which may have a substituent. R ₁₆ is an alkyl group which may have a substituent,
It represents a cycloalkyl group, an aralkyl group or an aryl group. Two of R _{14 to} R ₁₆ may combine with each other to form a ring.

(2) The component (B1) is a compound which generates an aliphatic or aromatic sulfonic acid substituted with at least one fluorine atom upon irradiation with actinic rays or radiation, and the component (B2) is a salt. By an exchange reaction, an aliphatic or aromatic sulfonic acid containing no fluorine atom,
Alternatively, the photosensitive resin composition as described in (1) above, which is an ionic compound that generates an aliphatic or aromatic carboxylic acid. (3) The component (B1) is a compound that generates a fluorine atom-free aliphatic or aromatic sulfonic acid upon irradiation with actinic rays or radiation, and the component (B2) is an aliphatic or aromatic compound produced by a salt exchange reaction. The photosensitive resin composition as described in (1) above, which is an ionic compound that generates an aromatic carboxylic acid. (4) The component (B1) is a compound which generates an aliphatic or aromatic carboxylic acid substituted with at least one fluorine atom upon irradiation with actinic rays or radiation,
The photosensitive resin composition as described in (1) above, wherein the component (B2) is an ionic compound which generates an aliphatic or aromatic carboxylic acid containing no fluorine atom by a salt exchange reaction.

Further, the following embodiments are preferable. (5) In the above general formula (VI), R ₁₈ is the following general formula (V
IA) is represented by the above (1) to
The photosensitive resin composition according to any one of (4).

[0016]

[Chemical 5]

In the general formula (VI-A), R _18a and R _18
18b may be the same or different and represents an alkyl group which may have a substituent. R _18c represents a cycloalkyl group which may have a substituent.

(6) In the general formula (VI), R ₁₈ is
The photosensitive resin composition according to any one of (1) to (5) above, which is represented by the following general formula (VI-B).

[0019]

[Chemical 6]

In the general formula (VI-B), R _18h represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group which may have a substituent. Z is
It represents an atomic group constituting a monocyclic or polycyclic alicyclic group together with the carbon atom in the general formula (VI-B).

(7) In the general formula (VI), R ₁₈ is
The photosensitive resin composition according to any one of (1) to (6) above, which is represented by the following general formula (VI-C).

[0022]

[Chemical 7]

In formula (VI-C), R _{18 '} represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group which may have a substituent.

(8) R in the general formula (I)₁, General formula
R of (II)_FiveAnd R in the general formula (VI) ₁₇At least
One of which is a trifluoromethyl group
The photosensitive resin composition according to any one of (1) to (7) above.
Stuff.

(9) The resin of (A) further has at least one repeating unit represented by the following general formula (III) or (VII), wherein (1) to
The photosensitive resin composition according to any one of (8).

[0026]

[Chemical 8]

In the general formula (III), R ₈ is a hydrogen atom,
It represents a halogen atom, a cyano group or an alkyl group which may have a substituent. R ₉ and R ₁₀ may be the same or different, and may have a hydrogen atom, a halogen atom, a cyano group or a substituent, an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, an acyloxy group, It represents an alkenyl group, an aryl group or an aralkyl group. In formula (VII), R ₁₉ and R _{20, which} may be the same or different, each represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group which may have a substituent. R ₂₁ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, or -D-CN group. D represents a single bond or a divalent linking group.

(10) The resin of (A) further has at least one repeating unit represented by the following general formulas (VIII) to (XVII), wherein (1) to (1)
The photosensitive resin composition according to any one of (9).

[0029]

[Chemical 9]

In the general formulas (VIII) to (XVII), R
_{twenty five}, R₂₆And R₂₇Can be the same or different, water
An elementary atom, a fluorine atom or an optionally substituted group,
Represents a alkyl group, a cycloalkyl group or an aryl group.
You R₂₈, R₂₉And R₃₀Can be the same or different
, Optionally substituted alkyl group, cycloalkyl group
It represents a alkyl group or an aryl group. Also, R_{twenty five}And R₂₆, R
₂₇And R₂₈, R₂₉And R₃₀And are linked together to form a ring
May be. R₃₁, R₃₅, R₃₇, R₄₀And R₄₄Is the same
May be different from each other and have a hydrogen atom or a substituent.
May be alkyl group, cycloalkyl group, acyl group
Specifically, it represents an alkoxycarbonyl group. R ₃₂, R₃₃, R
₃₄, R₄₁, R₄₂And R₄₃Can be the same or different
Even if it has a hydrogen atom, a halogen atom or a substituent
Represents an alkyl group or an alkoxy group. R₃₆Over
And R₃₉May be the same or different and may be a hydrogen atom,
Rogen atom, cyano group or an optionally substituted group
Represents a rukyl group. R₃₈May have a substituent,
Alkyl group, cycloalkyl group, aralkyl group or ari
Group. B₁And B₂Is a single bond or a divalent linking group
Represents B₃Represents a divalent linking group. n is 0 or 1
Represents

(11) The photosensitive resin composition as described in any of (1) to (10) above, which further comprises (D) a fluorine-based and / or silicon-based surfactant. (12) The photosensitive resin composition as described in any of (1) to (11) above, which further comprises a basic compound having a nitrogen atom as the (E) acid diffusion inhibitor. (13) The photosensitive resin composition as described in any of (1) to (12) above, which is for irradiation with F ₂ laser light having a wavelength of 157 nm.

[0032]

BEST MODE FOR CARRYING OUT THE INVENTION The compounds used in the present invention are described in detail below. [1] Resin (A) of the Present Invention The resin (A) of the present invention has the general formulas (I) and (I
A resin having at least one repeating unit represented by each of I) and (VI), which decomposes by the action of an acid and increases the solubility in an alkali developing solution. In the resin (A) of the present invention, R ₁₈ in the general formula (VI) is preferably represented by the above general formula (VI-A), (VI-B) or (VI-C). The resin (A) in the present invention further has the above general formulas (III) and (VII) to (XVI).
It may have at least one repeating unit represented by I).

In the general formulas (I), (II) and (VI),
R₁, R_Five, R_17aAnd R₁₇Are the same or different
Often, hydrogen atom, halogen atom, cyano group or substituent
It represents an alkyl group which may have. R₂, R₃, R₆Over
And R₇May be the same or different and may be a hydrogen atom,
Possess a rogen atom, cyano group, hydroxyl group or substituent
Optionally, an alkyl group, a cycloalkyl group, an
Coxy group, acyl group, acyloxy group, alkenyl group,
Represents a reel group or an aralkyl group. R₅₀~ R ₅₅Is
They may be the same or different and may be hydrogen atom, fluorine atom or
Represents an alkyl group which may have a substituent. However,
R₅₀~ R₅₅Of these, at least one is a fluorine atom or
At least one hydrogen atom is replaced by a fluorine atom
Represents a kill group. R_FourIs the following general formula (IV) or (V)
Represents the group of. R₁₈Is -C (R_18d) (R_18e)
(R_18f) Or -C (R_18d) (R_18e) (OR_{18 g}) Table
You R_18d~ R _{18 g}Can be the same or different, water
An alkyl group, optionally substituted with an atom or a substituent,
Chloroalkyl group, alkenyl group, aralkyl group or
Represents an aryl group. R_18d, R_18e, R_18fTwo of the
Is R_18d, R_18e, R_{18 g}Two of them combine to form a ring
You may.

In the general formula (IV), R ₁₁ , R ₁₂ and R
₁₃ represents an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group or an aryl group, which may be the same or different and may have a substituent. General formula (V)
R ₁₄ and R _{15, which} may be the same or different, each represent a hydrogen atom or an alkyl group which may have a substituent. R ₁₆ is an alkyl group which may have a substituent,
It represents a cycloalkyl group, an aralkyl group or an aryl group. Two of R _{14 to} R ₁₆ may combine with each other to form a ring.

In the general formula (VI-A), R _18a and R _18
18b may be the same or different and represents an alkyl group which may have a substituent. R _18c represents a cycloalkyl group which may have a substituent. General formula (VI-
In B), R _18h represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group, which may have a substituent. Z represents an atomic group forming a monocyclic or polycyclic alicyclic group together with the carbon atom in the general formula (VI-B). In general formula (VI-C), R _{18 ′} represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group, which may have a substituent.

In the general formula (III), R ₈ is a hydrogen atom,
It represents a halogen atom, a cyano group or an alkyl group which may have a substituent. R ₉ and R ₁₀ may be the same or different, and may have a hydrogen atom, a halogen atom, a cyano group or a substituent, an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, an acyloxy group, It represents an alkenyl group, an aryl group or an aralkyl group. In formula (VII), R ₁₉ and R _{20, which} may be the same or different, each represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group which may have a substituent. R ₂₁ represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, or -D-CN group. D represents a single bond or a divalent linking group.

In the general formulas (VIII) to (XVII), R
_{twenty five}, R₂₆And R₂₇Can be the same or different, water
An elementary atom, a fluorine atom or an optionally substituted group,
Represents a alkyl group, a cycloalkyl group or an aryl group.
You R₂₈, R₂₉And R₃₀Can be the same or different
, Optionally substituted alkyl group, cycloalkyl group
It represents a alkyl group or an aryl group. Also, R_{twenty five}And R₂₆, R
₂₇And R₂₈, R₂₉And R₃₀And are linked together to form a ring
May be. R₃₁, R₃₅, R₃₇, R₄₀And R₄₄Is the same
May be different from each other and have a hydrogen atom or a substituent.
May be alkyl group, cycloalkyl group, acyl group
Specifically, it represents an alkoxycarbonyl group. R ₃₂, R₃₃, R
₃₄, R₄₁, R₄₂And R₄₃Can be the same or different
Even if it has a hydrogen atom, a halogen atom or a substituent
Represents an alkyl group or an alkoxy group. R₃₆Over
And R₃₉May be the same or different and may be a hydrogen atom,
Rogen atom, cyano group or an optionally substituted group
Represents a rukyl group. R₃₈May have a substituent,
Alkyl group, cycloalkyl group, aralkyl group or ari
Group. B₁And B₂Is a single bond or a divalent linking group
Represents B₃Represents a divalent linking group. n is 0 or 1
Represents

Examples of the above alkyl group include linear and branched alkyl groups, for example, having 1 to 8 carbon atoms.
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, and octyl group. The cycloalkyl group may be monocyclic or polycyclic. The monocyclic type has 3 to 8 carbon atoms, and preferred examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
The polycyclic type has 6 to 20 carbon atoms and includes, for example, an adamantyl group, a norbornyl group, an isobornyl group,
Camphanyl group, dicyclopentyl group, a-pinel group,
Preferable examples include tricyclodecanyl group, tetracyclododecyl group, androstanyl group. still,
The cycloalkyl group is intended to include those in which a part of carbon atoms constituting the ring is substituted with a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom.

The aryl group has, for example, 6 to 1 carbon atoms.
5 aryl groups, specifically, a phenyl group,
Tolyl group, dimethylphenyl group, 2,4,6-trimethylphenyl group, naphthyl group, anthryl group, 9,10-
Preferred examples thereof include a dimethoxyanthryl group. The aralkyl group is, for example, an aralkyl group having a carbon number of 7 to 12, and specific examples thereof include a benzyl group, a phenethyl group and a naphthylmethyl group.

The alkenyl group has, for example, 2 to 2 carbon atoms.
8 alkenyl groups, specifically vinyl groups,
An allyl group, a butenyl group, and a cyclohexenyl group can be preferably mentioned. The alkoxy group is, for example, an alkoxy group having 1 to 8 carbon atoms, and specifically, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, a butoxy group, a pentoxy group, an allyloxy group, an octoxy group. A group and the like can be preferably mentioned.

The acyl group has, for example, 1 to 10 carbon atoms.
Specific examples of the acyl groups include formyl group, acetyl group, propanoyl group, butanoyl group, pivaloyl group, octanoyl group and benzoyl group. The acyloxy group has 2 to 1 carbon atoms.
Two acyloxy groups are preferable, and examples thereof include an acetoxy group, a propionyloxy group, and a benzoyloxy group. The alkynyl group is preferably an alkynyl group having 2 to 5 carbon atoms, and examples thereof include an ethynyl group, a propynyl group and a butynyl group. Examples of the alkoxycarbonyl group include t-butoxycarbonyl group and t-
Examples thereof include tertiary alkoxycarbonyl groups such as amyloxycarbonyl group and 1-methyl-1-cyclohexyloxycarbonyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

The divalent linking group means a divalent alkylene group, cycloalkylene group, alkenylene group or arylene group or -O-CO-R which may have a substituent.
_22a -,-CO-O- _R22b -,-CO-N ( _R22c )-
Represents _R22d- . R _22a, R _{22 b} and R _{22 d} may be the same or different, a single bond or an ether group, an ester group, which may have an amide group, a urethane group or a ureido group, a divalent alkylene group Represents a cycloalkylene group, an alkenylene group or an arylene group. R
_22c represents a hydrogen atom or an alkyl group, cycloalkyl group, aralkyl group or aryl group which may have a substituent.

Examples of the alkylene group include linear and branched alkylene groups. Examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group having 1 to 8 carbon atoms. There are things. Examples of the cycloalkylene group include those having 5 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group. As the alkenylene group, those having 2 to 6 carbon atoms such as an ethenylene group, a propenylene group and a butenylene group, which may have a substituent, can be mentioned. The arylene group is preferably an arylene group having a carbon number of 6 to 15, such as a phenylene group, a tolylene group and a naphthylene group which may have a substituent.

Two of R _{18d to} R _18f , R _18d , R _18e ,
The ring formed by combining two of R _18g , two of R _{14 to} R ₁₆ , R ₂₅ and R ₂₆ , R ₂₇ and R ₂₈ or R ₂₉ and R ₃₀ with each other is, for example, 3 to 8-membered ring, specifically, cyclopropane ring, cyclopentane ring, cyclohexane ring, tetramethylene oxide ring, pentamethylene oxide ring, hexamethylene oxide ring, furan ring, pyran ring, dioxonol ring, 1,3-dioxolane Examples include rings.

Z represents an atomic group constituting a monocyclic or polycyclic alicyclic group together with the carbon atom in the general formula (VI-B).
The monocyclic alicyclic group preferably has 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. As the polycyclic alicyclic group, those having 6 to 20 carbon atoms are preferable, and examples thereof include an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an α-pinel group, a tricyclodecanyl group, and tetracyclododecyl. Group, androstanyl group and the like.

The above alkyl group, cycloalkyl group, alkoxy group, acyl group, acyloxy group, alkynyl group,
The alkenyl group, aryl group, aralkyl group, alkoxycarbonyl group, alkylene group, cycloalkylene group, alkenylene group, arylene group and the like may have a substituent. Substituents substituted on these groups include those having active hydrogen such as amino group, amide group, ureido group, urethane group, hydroxyl group and carboxyl group, and halogen atoms (fluorine atom, chlorine atom, bromine atom, Iodine atom), alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, etc.), thioether group, acyl group (acetyl group, propanoyl group, benzoyl group, etc.), acyloxy group (acetoxy group, propanoyloxy group, benzoyl) Oxy group, etc.), alkoxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, etc.), alkyl group (methyl group, ethyl group,
Propyl group, butyl group), cycloalkyl group (cyclohexyl group), aryl group (phenyl group), cyano group, nitro group and the like.

In the present invention, at least one of R ₁ of general formula (I), R ₅ of general formula (II) and R ₁₇ of general formula (VI) is preferably a trifluoromethyl group.

Action of acid contained in the resin of the present invention (A)
Examples of the group that is decomposed by and shows alkali solubility include
-OC (R_18d) (R_18e) (R_18f), -OC (R
_18d) (R_18e) (OR_{18 g}), -O-COO-C
(R_18d) (R_18e) (R_18f), -OC (R₀₁) (R
₀₂) COO-C (R_18d) (R_18e) (R_18f), -CO
OC (R_18d) (R_18e) (R_18f), -COO-C
(R_18d) (R_18e) (OR_{18 g}) And the like. R_18d
~ R_{18 g}Is the same as defined above except for a hydrogen atom.
R₀₁, R ₀₂Has a hydrogen atom or a substituent shown above.
Optional alkyl group, cycloalkyl group, alkene
Represents an alkyl group, an aralkyl group or an aryl group.

A preferred specific example is a t-butyl group,
t-amyl group, 1-alkyl-1-cyclohexyl group,
2-alkyl-2-adamantyl group, 2-adamantyl-2-propyl group, 2- (4-methylcyclohexyl)
Ether group or ester group of tertiary alkyl group such as 2-propyl group, acetal group or acetal ester group such as 1-alkoxy-1-ethoxy group, tetrahydropyranyl group, t-alkyl carbonate group, t-alkylcarbonyl A methoxy group and the like are preferable. More preferably, it is an acetal group such as a 1-alkoxy-1-ethoxy group or a tetrahydropyranyl group. In the case of an acetal group, the acid decomposability is large, the range of selection of the acid generating compound to be used in combination is widened, and it is effective in terms of the improvement of sensitivity, performance fluctuation with the elapse of time after exposure and heating. Particularly preferred is an acetal group containing an alkoxy group derived from the above perfluoroalkyl group as the 1-alkoxy component of the acetal group. In this case, the transmittance of short-wave exposure light (for example, 157 nm of F ₂ excimer laser light) can be further improved.

The content of the repeating unit represented by the general formula (I) in the resin (A) is generally 5 to 80 mol%, preferably 7 to 75 mol%, more preferably 10 to
Used in the range of 70 mol%. The content of the repeating unit represented by the general formula (II) in the resin (A) is generally 5 to 80 mol%, preferably 7 to 70 mol%, more preferably 10 to 65 mol%. To be done. The content of the repeating unit represented by the general formula (VI) in the resin (A) is generally 1 to 70 mol%, preferably 1 to 65 mol%, more preferably 5 to 60 mol%. used. The content of the repeating unit represented by the general formula (III) is generally 1 to 4 in the resin (A).
It is used in an amount of 0 mol%, preferably 3 to 35 mol%, more preferably 5 to 30 mol%. General formula (VII)
The content of the repeating unit represented by is generally 1 to 40 mol%, preferably 3 to 35 mol%, more preferably 5 to 30 mol% in the resin (A). The content of the repeating units represented by the general formulas (VIII) to (X) is generally 1 to 40 in the resin (A).
Mol%, preferably 3 to 35 mol%, more preferably 5
It is used in the range of ˜30 mol%. General formula (XI)-
The content of the repeating unit represented by (XIII) in the resin (A) is generally 1 to 40 mol%, preferably 3 to 35 mol%, more preferably 5 to 30 mol%. It The content of the repeating unit represented by the general formula (XIV) is generally 1 to 4 in the resin (A).
It is used in an amount of 0 mol%, preferably 3 to 35 mol%, more preferably 5 to 30 mol%. The content of the repeating unit represented by the general formula (XV) in the resin (A) is generally 1 to 40 mol%, preferably 3 to 35 mol%, more preferably 5 to 30 mol%. used. The content of the repeating unit represented by the general formula (XVI) is generally 1 to 40 mol% in the resin (A),
It is preferably used in the range of 3 to 35 mol%, more preferably 5 to 30 mol%. The content of the repeating unit represented by the general formula (XVII) in the resin (A) is generally 1 to 40 mol%, preferably 3 to 35 mol%, more preferably 5 to 30 mol%. used.

The resin of the present invention (A) may be copolymerized with other polymerizable monomers in addition to the above repeating structural units for the purpose of further improving the performance of the photosensitive resin of the present invention. .

Copolymerizable monomers that can be used include those shown below. For example, addition-polymerizable unsaturated bonds selected from acrylic acid esters, acrylamides, methacrylic acid esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic acid esters, etc. other than the above It is a compound having one.

Specifically, for example, acrylic acid esters such as alkyl (wherein the alkyl group has 1 to 1 carbon atoms).
0 is preferred) Acrylate (eg, methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate 2,
2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, glycidyl acrylate, benzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, etc.) Aryl acrylate (eg phenyl acrylate etc.);

Methacrylic acid esters, for example, alkyl (alkyl groups preferably having 1 to 10 carbon atoms) methacrylate (for example, methyl methacrylate,
Ethylmethacrylate, propylmethacrylate, isopropylmethacrylate, amylmethacrylate, hexylmethacrylate, cyclohexylmethacrylate,
Benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate,
5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc., aryl methacrylate (for example, phenyl methacrylate) , Cresyl methacrylate, naphthyl methacrylate, etc.);

Acrylamides such as acrylamide, N-alkylacrylamide, and the like (alkyl groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, t-butyl, and heptyl. Group, octyl group, cyclohexyl group, benzyl group, hydroxyethyl group, benzyl group, etc.), N-arylacrylamide (as the aryl group, for example, phenyl group, tolyl group, nitrophenyl group, naphthyl group,
There are cyanophenyl group, hydroxyphenyl group, carboxyphenyl group and the like. ), N, N-dialkylacrylamide (the alkyl group has 1 to 10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, cyclohexyl group, etc.), N, N-diarylacrylamide (an aryl group includes, for example, a phenyl group), N-methyl-N-phenylacrylamide, N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide, etc. ;

Methacrylamides, such as methacrylamide, N-alkylmethacrylamides (wherein the alkyl group is one having 1 to 10 carbon atoms, such as methyl group, ethyl group, t-butyl group, ethylhexyl group, hydroxyethyl group). Group, cyclohexyl group, etc.), N
-Aryl methacrylamide (an aryl group includes a phenyl group, etc.), N, N-dialkyl methacrylamide (an alkyl group includes an ethyl group, a propyl group, a butyl group, etc.), N, N-diaryl. Methacrylamide (such as a phenyl group as an aryl group), N-hydroxyethyl-N-methylmethacrylamide, N-methyl-N-phenylmethacrylamide, N-ethyl-N-phenylmethacrylamide, etc .;
Allyl compounds, such as allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate), allyloxyethanol Such;

Vinyl ethers such as alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether,
Ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, Tetrahydrofurfuryl vinyl ether, etc.), vinyl aryl ether (eg vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-
2,4-dichlorophenyl ether, vinyl naphthyl ether, vinyl anthranyl ether, etc.);

Vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barrate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate. , Vinyl phenylacetate, vinyl acetoacetate, vinyl lactate, vinyl-β-
Phenyl butyrate, vinyl cyclohexyl carboxylate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate, etc .;

Styrenes such as styrene, alkylstyrenes (eg methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethyl). Styrene, trifluoromethylstyrene, ethoxymethylstyrene, acetoxymethylstyrene, etc.), alkoxystyrene (eg, methoxystyrene, 4-methoxy-3-methylstyrene, dimethoxystyrene, etc.), halogen styrene (eg, chlorostyrene, dichlorostyrene). , Trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromstyrene, dibromostyrene, iodostyrene, fluoros Ren, trifluoromethyl styrene, 2
-Bromo-4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene, etc.), carboxystyrene, vinylnaphthalene;

Crotonic acid esters, for example, alkyl crotonic acid (eg, butyl crotonic acid, hexyl crotonic acid, glycerin monocrotonate, etc.); Dialkyl itaconic acid (eg, dimethyl itaconic acid, diethyl itaconic acid, dibutyl itaconic acid, etc.) ); Dialkyl esters of maleic acid or fumaric acid (eg,
Dimethyl maleate, dibutyl fumarate, etc.) and the like. In addition, any addition-polymerizable unsaturated compound that is generally copolymerizable may be used.

Specific examples of the repeating structural unit represented by formula (I) are shown below, but the invention is not limited thereto.

[0062]

[Chemical 10]

[0063]

[Chemical 11]

[0064]

[Chemical 12]

[0065]

[Chemical 13]

[0066]

[Chemical 14]

[0067]

[Chemical 15]

[0068]

[Chemical 16]

[0069]

[Chemical 17]

Specific examples of the repeating structural unit represented by the general formula (II) are shown below, but the invention is not limited thereto.

[0071]

[Chemical 18]

[0072]

[Chemical 19]

[0073]

[Chemical 20]

[0074]

[Chemical 21]

Specific examples of the repeating structural unit represented by the general formula (III) are shown below, but the invention is not limited thereto.

[0076]

[Chemical formula 22]

Specific examples of the repeating structural unit represented by the general formula (VII) are shown below, but the invention is not limited thereto.

[0078]

[Chemical formula 23]

In the following, general formulas (VIII) to (XII
Specific examples of the repeating structural unit represented by I) are shown below, but the invention is not limited thereto.

[0080]

[Chemical formula 24]

[0081]

[Chemical 25]

[0082]

[Chemical formula 26]

[0083]

[Chemical 27]

In the following, general formulas (VI) and (XVII)
Specific examples of the repeating structural unit represented by are shown below, but the present invention is not limited thereto.

[0085]

[Chemical 28]

[0086]

[Chemical 29]

[0087]

[Chemical 30]

[0088]

[Chemical 31]

[0089]

[Chemical 32]

[0090]

[Chemical 33]

[0091]

[Chemical 34]

[0092]

[Chemical 35]

Specific examples of the repeating structural unit represented by formula (XV) include the repeating structural unit formed by the vinyl ethers.

The repeating structural units shown in the above specific examples may be used alone or in combination of two or more. The preferred molecular weight of the resin (A) of the present invention having the repeating structural unit is 1,000 to 2 on a weight average basis.
0,000, and more preferably 3,000 to 2
Used in the range of 10,000. Molecular weight distribution is 1-10
And preferably in the range of 1 to 3, more preferably 1 to 2. The smaller the molecular weight distribution,
The resolution, the resist shape, and the side wall of the resist pattern are smooth, and the roughness is excellent. The addition amount of the resin (A) of the present invention is generally in the range of 50 to 99.5% by weight, preferably 60 to 98% by weight, more preferably 65 to 95% by weight, based on the total solid content of the composition. Used in.

[2] B1 and B2 Components The photosensitive resin composition of the present invention comprises actinic rays or radiation,
Especially by the irradiation of F ₂ excimer laser ^{_{light, A 1 H + B + A}} 2 - → B + A 1 - + A 2 may represented by salt exchange reaction with H, the acid represented by the general formula A ₁ H generating a compound (B1 component) and the general formula B ⁺ a ₂ ^-
And an ionic compound (B2 component) represented by
Here, H represents a hydrogen atom, and A ₁ represents a residue obtained by removing a hydrogen atom from an acid generated by irradiation with actinic rays or radiation. B ⁺ represents a cation portion and A ₂ ⁻ represents an anion portion in the ionic compound. A ₁ ^- is an anion, A ₂ derived from A ₁ is A ₂ ionic drops by binding with the hydrogen atoms ion ^- represents a group derived from a. The acid represented by the general formula A ₁ H generated by irradiation with actinic rays or radiation is usually an organic acid and functions as a proton donor. In general formula B ⁺ A ₂ ^- the ionic compound represented by the onium salt is preferred. The strong acid generated by the irradiation of actinic rays or radiation is replaced by weak acid through the salt exchange reaction, and the contrast of the strong acid concentration distribution near the interface (low energy dose irradiation area) between the irradiated / irradiated areas of active light or radiation is low. Can be increased.

A compound (B1 component) which generates an acid represented by the general formula A ₁ H upon irradiation with actinic rays or radiation,
The formula B ⁺ A ₂ ^- in the ionic compound represented by (B2 component), which generally is used as the compound capable of generating an acid (photoacid generator) upon irradiation with actinic rays or radiation You can choose from. That is, a photo-initiator for photo-cationic polymerization, a photo-initiator for photo-radical polymerization, a photo-decoloring agent for dyes, a photo-discoloring agent, or known light (UV rays of 400 to 200 nm, far UV rays, particularly preferably g rays, h rays, i rays, K
rF excimer laser light), ArF excimer laser light, F ₂ excimer laser light, compounds that generate an acid by electron beam, X-ray, molecular beam or ion beam, and mixtures thereof can be appropriately selected and used.

Examples of such a compound include S.
I. Schlesinger, Photogr. Sci. Eng., 18, 387 (197
4), TS Bal et al, Polymer, 21, 423 (1980) and other diazonium salts, U.S. Pat.Nos. 4,069,055 and 4,06.
9,056, Re 27,992, ammonium salts described in JP-A-3-140140, DC Necker et al, Macromolecul
es, 17, 2468 (1984), CS Wen et al, Teh, Proc. Co
nf.Rad. Curing ASIA, p478 Tokyo, Oct (1988), U.S. Pat.
1307 (1977), Chem. & Eng. News, Nov. 28, p31 (198
8), European Patent Nos. 104,143, 339,049, and 410,201.
JP-A No. 2-150848, JP-A No. 2-296514, etc., iodonium salts, JV Crivello et al, Polymer J. 1
7, 73 (1985), JV Crivello et al., J.Org. Chem.,
43, 3055 (1978), WR Watt et al, J. Polymer Sci.,
Polymer Chem. Ed., 22, 1789 (1984), JV Crivello
et al, Polymer Bull., 14, 279 (1985), JV Crivell
o et al, Macromorecules, 14 (5), 1141 (1981), JV
Crivello et al, J. Polymer Sci., Polymer Chem. E
d., 17, 2877 (1979), European Patent No. 370,693, and 161,811.
No. 410, No. 410, 201, No. 339,049, No. 233,567, No. 297, 4
No. 43, No. 297,442, U.S. Patent No. 4,933,377, No. 3,902,
No. 114, No. 4,760,013, No. 4,734,444, No. 2,833,827
Patent No. 2,904,626, No. 3,604,580, No. 3,604,
Sulfonium salts described in No. 581, etc., JV Crivello et a
l, Macromorecules, 10 (6), 1307 (1977), JV Crivel
lo et al, J. Polymer Sci., Polymer Chem. Ed., 17,
1047 (1979) and other selenonium salts, CS Wen et a
l, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo,
Onium salts such as arsonium salts described in Oct (1988),
U.S. Pat.No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Laid-Open No. 48-3
6281, JP-A-55-32070, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241
JP-A-62-212401, JP-A-63-70243, JP-A-63-
Organic halogen compounds described in No. 298339, K. Meier et.
al, J. Rad. Curing, 13 (4), 26 (1986), TP Gill et
al, Inorg. Chem., 19, 3007 (1980), D. Astruc, Acc.
Chem. Res., 19 (12), 377 (1896), Japanese Patent Application Laid-Open No. H2-161445, organometallic / organic halides, S. Hayase et a
l, J. Polymer Sci., 25, 753 (1987), E. Reichmanis et
al, J. Pholymer Sci., Polymer Chem. Ed., 23, 1 (19
85), QQ Zhuetal, J. Photochem., 36, 85, 39, 317
(1987), B. Amit et al, Tetrahedron Lett., (24) 2205.
(1973), DHR Barton et al, J. Chem Soc., 3571.
(1965), PM Collins et al, J. Chem. Soc., Perkin.
I, 1695 (1975), M. Rudinstein et al, Tetrahedron L
ett., (17), 1445 (1975), JW Walker et al, J. Am.
Chem. Soc., 110, 7170 (1988), SC Busman et al,
J. Imaging Technol., 11 (4), 191 (1985), HM Houlih
an et al, Macromolecules, 21, 2001 (1988), PMCol
lins et al, J. Chem. Soc., Chem. Commun., 532 (197
2), S. Hayase et al, Macromolecules, 18, 1799 (198
5), E. Reichmanis et al, J. Electrochem. Soc., Sol
id State Sci. Technol., 130 (6), FM Houlihan et
al, Macromolcules, 21, 2001 (1988), European Patent 0290,7
50, 046,083, 156,535, 271,851, 0,3
88,343, U.S. Pat.
et al, Polymer Preprints Japan, 35 (8), G. Berneret
al, J. Rad. Curing, 13 (4), WJ Mijs et al, Coa
ting Technol., 55 (697), 45 (1983), Akzo, H. Adachi e
t al, Polymer Preprints, Japan, 37 (3), European Patent No. 0
No. 199,672, No. 84515, No. 044,115, No. 618,564, No.
0101,122, U.S. Pat.Nos. 4,371,605 and 4,431,774
JP-A-64-18143, JP-A-2-245756, JP-A-3-14
Compounds which generate sulfonic acid by photolysis represented by iminosulfonates described in JP-A No. 61-166.
Examples thereof include disulfone compounds described in No. 544 and the like.

As the combination of the B1 component and the B2 component, the following combinations can be preferably mentioned.

The component B1 is a compound which generates an aliphatic or aromatic sulfonic acid substituted with at least one fluorine atom upon irradiation with actinic rays or radiation, and the component B2 does not contain a fluorine atom as an anion. A combination which is an ionic compound having an aliphatic or aromatic sulfonic acid or an aliphatic or aromatic carboxylic acid which may have a fluorine atom.

The component B1 is a compound which generates an aliphatic or aromatic sulfonic acid containing no fluorine atom upon irradiation with actinic rays or radiation, and the component B2 may have a fluorine atom as an anion. A combination that is an ionic compound having an aliphatic or aromatic carboxylic acid.

The component B1 is a compound which generates an aliphatic or aromatic carboxylic acid substituted with at least one fluorine atom upon irradiation with actinic rays or radiation, and does not contain a fluorine atom as an anion as the component B2. A combination that is an ionic compound having an aliphatic or aromatic carboxylic acid.

[A] A compound capable of generating a fluorine-containing sulfonic acid upon irradiation with actinic rays or radiation (and an ionic compound having a fluorine-containing sulfonic acid as an anion)
Will be described.

For example, an iodonium salt represented by the following general formula (PAG3) or a sulfonium salt represented by the following general formula (PAG4) can be mentioned.

[0104]

[Chemical 36]

In the formula, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. R ²⁰³ , R ²⁰⁴ , R
²⁰⁵ each independently represents a substituted or unsubstituted alkyl group or aryl group. Z ⁻ represents a sulfonate anion having at least one fluorine atom. Also, two of R ²⁰³ , R ²⁰⁴ , and R ²⁰⁵ and Ar ¹ and Ar ²
May be bonded via their respective single bonds or substituents.

The aryl group as Ar ¹ , Ar ² , R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ preferably has 6 to 14 carbon atoms.
The aryl group and the alkyl group are preferably an alkyl group having 1 to 8 carbon atoms. Preferred substituents include
For an aryl group, an alkoxy group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 9 carbon atoms, an alkylcarbonylamino group having 2 to 9 carbon atoms, a nitro group, a carboxyl group , A hydroxy group, a halogen atom and a phenylthio group, and for an alkyl group, an alkoxy group having 1 to 8 carbon atoms, an aryl group having 5 to 14 carbon atoms, an arylcarbonyl group having 6 to 15 carbon atoms, a carboxyl group and halogen. Atoms can be mentioned.

The sulfonate anion of Z ⁻ preferably has at least one fluorine atom and has 1 carbon atom.
Examples thereof include aliphatic hydrocarbons having 20 to 20 carbon atoms and aromatic hydrocarbons having 5 to 20 carbon atoms. These may have a substituent, and the substituent has, for example, 1 to 10 carbon atoms.
An optionally substituted fluorine-containing alkoxy group having 2 to 2 carbon atoms
Examples thereof include an optionally substituted fluorine-containing alkoxycarbonyl group, a phenylamino group, a phenylcarbonyl group, a halogen atom and a hydroxyl group. Further examples of the aromatic hydrocarbon include an alkyl group having 1 to 15 carbon atoms. Incidentally, regarding the aliphatic sulfonate anion, in particular, an anion having a fluorine atom on the α carbon atom of the sulfonic acid has a high acid strength, and tends to easily undergo salt exchange with an anion having no fluorine atom. is there. Further, perfluoroaliphatic sulfonic acid has higher acid strength.

Specific examples will be given below, but the present invention is not limited thereto.

[0109]

[Chemical 37]

[0110]

[Chemical 38]

[0111]

[Chemical Formula 39]

[0112]

[Chemical 40]

[0113]

[Chemical 41]

[0114]

[Chemical 42]

[0115]

[Chemical 43]

[0116]

[Chemical 44]

[0117]

[Chemical formula 45]

[0118]

[Chemical formula 46]

[0119]

[Chemical 47]

[B] Examples of the compound generating a fluorine-free sulfonic acid upon irradiation with actinic rays or radiation and the ionic compound having a fluorine-free sulfonic acid as an anion include, for example, the above general formulas (PAG3) and (PA).
Examples of G4) include iodonium salts and sulfonium salts in which Z ⁻ is a sulfonate anion having no fluorine atom.

Specific examples thereof include, but are not limited to, the compounds shown below.

[0122]

[Chemical 48]

[0123]

[Chemical 49]

[0124]

[Chemical 50]

[0125]

[Chemical 51]

[0126]

[Chemical 52]

[0127]

[Chemical 53]

[0128]

[Chemical 54]

[0129]

[Chemical 55]

Further, a disulfone derivative represented by the following general formula (PAG5) or an iminosulfonate derivative represented by the general formula (PAG6) can be given.

[0131]

[Chemical 56]

In the formula, Ar³, Ar^FourReplace each independently
Or an unsubstituted aryl group. R ²⁰⁶Is replaced or
An unsubstituted alkyl group and an aryl group are shown. If A is replaced
Or unsubstituted alkylene group, alkenylene group, aryle
Group.

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

[0134]

[Chemical 57]

[0135]

[Chemical 58]

[0136]

[Chemical 59]

[0137]

[Chemical 60]

Further, a diazodisulfone derivative represented by the following general formula (PAG7) can be given.

[0139]

[Chemical formula 61]

In the formula, R represents a linear, branched or cyclic alkyl group or an aryl group which may be substituted.

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

[0142]

[Chemical formula 62]

The compounds described in the above [a] and [b] can be synthesized by reacting an aromatic compound with a periodate and subjecting the obtained iodonium salt to salt exchange with the corresponding sulfonic acid. is there. Alternatively, it can be synthesized by reacting an aryl Grignard reagent such as aryl magnesium bromide with a substituted or unsubstituted phenyl sulfoxide, and subjecting the obtained triarylsulfonium halide to salt exchange with the corresponding sulfonic acid. Further, a method of condensing and salt-exchange of a substituted or unsubstituted phenyl sulfoxide and the corresponding aromatic compound with an acid catalyst such as methanesulfonic acid / diphosphorus pentoxide or aluminum chloride, and a method of diaryl iodonium salt and diaryl sulfide with copper acetate. It can be synthesized by a method such as condensation and salt exchange using a catalyst such as. The salt exchange can also be performed by a method of once converting to a halide salt and then converting to a sulfonate by using a silver reagent such as silver oxide, or by using an ion exchange resin. The sulfonic acid or sulfonate used for the salt exchange may be a commercially available product, or may be obtained by hydrolysis of a commercially available sulfonic acid halide.

[C] A compound that generates a fluorine-containing carboxylic acid upon irradiation with actinic rays or radiation and an ionic compound that has a fluorine-containing carboxylic acid as an anion will be described.

Examples of the fluorine-substituted aliphatic carboxylic acid include acetic acid, propionic acid, n-butyric acid, isobutyric acid, valerianic acid, trimethylacetic acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, Examples thereof include fluorine-substituted products of aliphatic carboxylic acids such as myristic acid, palmitic acid, stearic acid, undecanoic acid, dodecanoic acid and tridecanoic acid. These may have a hydroxyl group, an alkoxy group, or a halogen atom as a substituent. Further, it is preferable that the aliphatic chain contains a linking group such as an oxygen atom, a sulfur atom, a carbonyl group, a carboxyl group or a sulfonyl group. Examples of preferable fluorine-substituted aliphatic carboxylic acid include those represented by the following general formula. _{L- (CH 2) p (CF} 2) q (CH 2) r-COOH general formula, L is a hydrogen atom or a fluorine atom. p and r each independently represent an integer of 0 to 15, and q represents an integer of 1 to 15. The hydrogen atom or the fluorine atom of the alkyl chain in this general formula is an alkyl group optionally substituted by a fluorine atom (preferably having a carbon number of 1 to 5) or an alkoxy group optionally substituted by a fluorine atom (preferably a carbon atom). Number 1
~ 5) or may be substituted with a hydroxyl group. The above-mentioned fluorine-substituted aliphatic carboxylic acid is preferably a fluorine-substituted saturated aliphatic carboxylic acid having 2 to 20 carbon atoms, and more preferably 4 to 20 carbon atoms. By setting the carbon number to 4 or more, the diffusibility of the generated carboxylic acid decomposability is lowered, and the line width change due to the passage of time from exposure to post-heating can be further suppressed. Above all,
A fluorine-substituted product of a linear or branched saturated aliphatic carboxylic acid having 4 to 18 carbon atoms is preferable.

The fluorine-substituted aromatic carboxylic acid has 7 to 20 carbon atoms, and more preferably 7 carbon atoms.
It is preferably a fluorine-substituted aromatic carboxylic acid having a molecular weight of 15 to 15, more preferably 7 to 11. Specifically, benzoic acid, substituted benzoic acid, naphthoic acid, substituted naphthoic acid, anthracenecarboxylic acid, substituted anthracenecarboxylic acid (wherein the substituent is an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, an aryl group, an acyl group). Group, an acyloxy group, a nitro group, an alkylthio group, an arylthio group), and the like, and a fluorine-substituted product of an aromatic carboxylic acid. Among them, benzoic acid and fluorine-substituted products of substituted benzoic acid are preferable.

The aliphatic or aromatic carboxylic acid substituted with a fluorine atom is one in which one or more hydrogen atoms existing in the skeleton other than the carboxyl group are substituted with a fluorine atom, and particularly preferably the carboxyl group. Is an aliphatic or aromatic carboxylic acid (perfluoro saturated aliphatic carboxylic acid or perfluoroaromatic carboxylic acid) in which all hydrogen atoms existing in the skeleton other than are substituted with fluorine atoms. Thereby, the sensitivity is further improved. Regarding the aliphatic carboxylate anion,
The anion having a fluorine atom on the α carbon atom of the carboxylic acid has high acid strength and tends to easily undergo salt exchange with the carboxylic acid anion having no fluorine atom. Further, perfluoroaliphatic sulfonic acid has higher acid strength.

Preferably, an onium salt compound (sulfonium salt, iodonium salt, etc.) having an anion of an aliphatic or aromatic carboxylic acid substituted with a fluorine atom as a counter anion, or an imide having a carboxylic acid ester group is preferable. Examples thereof include a carboxylate compound and a nitrobenzyl ester compound. More preferably, the compounds represented by the above general formulas (I) to (III) can be mentioned. As a result, the sensitivity, resolution and exposure margin are further improved. By irradiating this compound with actinic rays or radiation, the compounds of the general formulas (I) to (II
X of I) ^- at least one saturated aliphatic or aromatic carboxylic acid substituted with fluorine atoms corresponding to occur, to function as a photoacid generator.

[0149]

[Chemical formula 63]

(In the above formula, R ₁ ~ R ₃₇ are each independently
Hydrogen atom, straight chain, branched or cyclic alkyl group, straight chain,
It represents a branched or cyclic alkoxy group, a hydroxy group, a halogen atom, or a —S—R ₃₈ group. Here, R ₃₈ represents a linear, branched, or cyclic alkyl group or aryl group. X
^- is an anion of at least one aliphatic or aromatic carboxylic acid substituted with a fluorine atom. ) X ⁻ is preferably an anion of perfluoroaliphatic carboxylic acid or perfluoroaromatic carboxylic acid,
Particularly preferred is an anion of a fluorine-substituted alkylcarboxylic acid having 4 or more carbon atoms.

R _{1 to} R in the general formulas (I) to (III)
The linear or branched alkyl group of ₃₈ may have a substituent and has 1 carbon atom such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group or t-butyl group.
Up to four. As the cyclic alkyl group,
Examples thereof include those having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group which may have a substituent. As the alkoxy group for R _{1 to} R ₃₇ ,
Methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-
Examples thereof include those having 1 to 4 carbon atoms such as butoxy group and t-butoxy group. Examples of the halogen atom of 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 include those having 6 to 14 carbon atoms such as phenyl group, tolyl group, methoxyphenyl group and naphthyl group. The aryl group may have a substituent. As these substituents, preferably,
Alkoxy group having 1 to 4 carbon atoms, halogen atom (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,
Examples thereof include a nitro group.

General formulas (I) to (II used in the present invention
The iodonium compound or sulfonium compound represented by I) has at least 1 as its counter anion X ^−.
It has an anion of a saturated aliphatic or aromatic carboxylic acid substituted with one fluorine atom. These anions are anions (—COO ⁻ ) from which a hydrogen atom of the carboxylic acid (—COOH) has been desorbed.

Specific examples will be shown below, but the present invention is not limited thereto. Specific examples (I-1f) to (I to 36f) of the photo-acid generator represented by the general formula (I):

[0154]

[Chemical 64]

[0155]

[Chemical 65]

[0156]

[Chemical formula 66]

[0157]

[Chemical formula 67]

[0158]

[Chemical 68]

Specific examples (II-1f) to (II to 67f) of the photoacid generator represented by the general formula (II):

[Chemical 69]

[0160]

[Chemical 70]

[0161]

[Chemical 71]

[0162]

[Chemical 72]

[0163]

[Chemical formula 73]

[0164]

[Chemical 74]

[0165]

[Chemical 75]

[0166]

[Chemical 76]

[0167]

[Chemical 77]

Specific examples (III-1f) to (III to 4f) of the photoacid generator represented by the general formula (III):

[0169]

[Chemical 78]

Specific examples of other photoacid generators (IV-1f)
~ (V ~ 4f):

[0171]

[Chemical 79]

The compound represented by the above general formula (I) can be synthesized by reacting an aromatic compound with a periodate and subjecting the obtained iodonium salt to salt exchange with a corresponding carboxylic acid. . General formula (II), general formula (III)
The compound represented by can be synthesized by, for example, reacting an aryl Grignard reagent such as aryl magnesium bromide with a substituted or unsubstituted phenyl sulfoxide, and subjecting the obtained triarylsulfonium halide to salt exchange with a corresponding carboxylic acid. Further, a method of condensing and salt-exchange of a substituted or unsubstituted phenyl sulfoxide and the corresponding aromatic compound with an acid catalyst such as methanesulfonic acid / diphosphorus pentoxide or aluminum chloride, and a method of diaryl iodonium salt and diaryl sulfide with copper acetate. It can be synthesized by a method such as condensation and salt exchange using a catalyst such as. The salt exchange can also be performed by a method of once converting to a halide salt and then converting to a carboxylate using a silver reagent such as silver oxide, or by using an ion exchange resin.
The carboxylic acid or carboxylic acid salt used for salt exchange may be a commercially available one, or may be obtained by hydrolysis of a commercially available carboxylic acid halide.

As the fluorine-substituted carboxylic acid as the anion moiety, one derived from a fluoroaliphatic compound produced by the telomerization method (also called telomer method) or the oligomerization method (also called oligomer method) is used. Those that have been used are also preferable. Regarding the production method of these fluoroaliphatic compounds, for example,
117-11 of "Synthesis and Function of Fluorine Compound" (Supervised by Nobuo Ishikawa, Issued: CMC, 1987)
See page 8 and "Chemistry of Organic Fluorine Compo
unds II "(Monograph 187, Ed by Milos Hudlicky and
Attila E. Pavlath, American Chemical Society 199
5) pp. 747-752. The telomerization method is a method of synthesizing a telomer by radically polymerizing a fluorine-containing vinyl compound such as tetrafluoroethylene with an alkyl halide having a large chain transfer constant such as iodide as a telogen (example in Scheme-1. showed that). In the synthesis by the telomer method, a mixture of a plurality of compounds having different carbon chain lengths can be obtained, and this mixture may be used as it is or may be purified before use.

[D] Specific examples of the compound generating a fluorine-free carboxylic acid upon irradiation with actinic rays or radiation and the ionic compound having a fluorine-free carboxylic acid as an anion are mentioned, but the invention is not limited thereto.

Examples thereof include compounds represented by the following general formulas (AI) to (AV).

[0176]

[Chemical 80]

In the above formula, R _{301 to} R ₃₃₇ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group,
Linear, branched or cyclic alkoxy group, hydroxy group,
It represents a halogen atom or a —S—R ₀ group. R ₀ is a straight chain,
Represents a branched, cyclic alkyl group or aryl group. Ra,
Rb's each independently represent a hydrogen atom, a nitro group, a halogen atom, or an optionally substituted alkyl group or alkoxy group. Rc and Rd are each independently a halogen atom,
It represents an alkyl group or an aryl group which may have a substituent. Rc and Rd may combine to form an aromatic ring, a monocyclic or polycyclic cyclic hydrocarbon (these rings may contain an oxygen atom and a nitrogen atom). Y ₁ , Y ₂
Represents a carbon atom, and the Y ₁ -Y ₂ bond may be a single bond or a double bond. The above X ⁻ represents an anion of the carboxylic acid compound represented by the following formula. X ₁ and X ₂ are
Each independently represents a compound in which a carboxylic acid compound represented by the following formula becomes an ester group at the carboxyl group portion.

[0178]

[Chemical 81]

[0179]

[Chemical formula 82]

In the above formula, R ₃₃₈ is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms (wherein the chain of the alkyl group may contain an oxygen atom or a nitrogen atom). A linear, branched or cyclic alkenyl group having 1 to 20 carbon atoms, a linear, branched or cyclic alkynyl group having 1 to 20 carbon atoms, a linear or branched chain having 1 to 20 carbon atoms, or Cyclic alkoxyl group, a group in which at least a part of hydrogen atoms of the alkyl group are substituted with a halogen atom and / or a hydroxyl group, and a group in which at least a part of hydrogen atoms of the alkenyl group are substituted with a halogen atom and / or a hydroxyl group. Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Here, examples of the substituent of the aryl group include an alkyl group, a nitro group, a hydroxyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group, and a halogen atom.

R ₃₃₉ is a single bond or has 1 to 2 carbon atoms.
A straight-chain, branched or cyclic alkylene group having 0 (here, an oxygen atom or a nitrogen atom may be contained in the chain of the alkylene group), a straight-chain, branched or cyclic having 1 to 20 carbon atoms Alkenylene group, a group in which at least a part of hydrogen atoms of the alkylene group is substituted with a halogen atom and / or a hydroxyl group, a group in which at least a part of hydrogen atoms of the alkenylene group is substituted with a halogen atom, or a carbon number of 2 It indicates 20 alkoxide alkylene group, R _338, R ₃₃₉ existing in plural numbers may be the same or different from each other.

R ₃₄₀ represents a hydroxyl group or a halogen atom, and a plurality of R _{340 s} may be the same or different from each other. m, n, p and q are each independently an integer of 0 to 3, and m + n ≦ 5 and p + q ≦ 5. z is 0 or 1.

In the above general formulas (AI) to (AV),
As the straight chain or branched alkyl group for R _{301 to} R ₃₃₇ , Ra, Rb, Rc, Rd, and R ₀ , a methyl group, an ethyl group, a propyl group, an n-butyl group, which may have a substituent,
1 to 4 carbon atoms such as sec-butyl group and t-butyl group
There are individual ones. Examples of the cyclic alkyl group include those having a carbon number of 3 to 8, such as cyclopropyl group, cyclopentyl group and cyclohexyl group, which may have a substituent. The alkoxy group of R _{301 to} R ₃₃₇ , Ra, and Rb has a carbon number such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, and t-butoxy group. One to four can be mentioned. R _{301 to} R ₃₃₇ , Ra,
Examples of the halogen atom of Rb, Rc, and Rd include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the aryl group of R ₀ , Rc, and Rd 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. These substituents preferably have 1 to 1 carbon atoms.
4 alkoxy groups, halogen atom (fluorine atom, chlorine atom, iodine atom), aryl group having 6 to 10 carbon atoms, alkenyl group having 2 to 6 carbon atoms, cyano group, hydroxy group, carboxy group, alkoxycarbonyl Group, nitro group and the like.

The aromatic ring, monocyclic or polycyclic cyclic hydrocarbon formed by combining Rc and Rd (which may contain an oxygen atom or a nitrogen atom) includes
Benzene structure, naphthalene structure, cyclohexane structure,
Examples thereof include a norbornene structure and an oxabicyclo structure.

General formulas (AI) to (A) used in the present invention
Sulfonium represented III), or an iodonium compound, its counter anion X ^- is the above formula (C1) ~ (C
At least one of the carboxylic acid compounds represented by 10)
Including those in which the carboxyl group (—COOH) of the seed compound becomes an anion (—COO ⁻ ). The compounds represented by the general formulas (AIV) to (AV) used in the present invention have at least one of the carboxylic acid compounds represented by the above formulas (C1) to (C10) as the substituents X ₁ and X _2. The carboxyl group (-COOH) of the seed compound is an ester group (-CO
O-) is included in the substituent.

A linear, branched or cyclic alkyl group having 1 to 30 carbon atoms for R ₃₃₈ (wherein the chain of the alkyl group may contain an oxygen atom or a nitrogen atom)
Examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, dodecyl, 1-ethoxyethyl, adamantyl and the like. 1 to 2 carbon atoms
Examples of the linear, branched or cyclic alkenyl group of 0 include ethenyl, propenyl, isopropenyl, cyclohexene and the like. As the linear, branched or cyclic alkynyl group having 1 to 20 carbon atoms, acetylene,
Propylene and the like can be mentioned. Examples of the linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, propyloxy, butoxy, cyclohexyloxy, isobutoxy and dodecyloxy. Examples of the substituted or unsubstituted aryl group having 6 to 20 carbon atoms include phenyl, naphthyl and anthranyl. The substituent of the aryl group is an alkyl group,
Examples thereof include a nitro group, a hydroxyl group, an alkoxy group, an acyl group, an alkoxycarbonyl group and a halogen atom.

As the linear, branched or cyclic alkylene group having 1 to 20 carbon atoms in R ₃₃₉ (here, an oxygen atom or a nitrogen atom may be contained in the chain of the alkylene group), Examples thereof include methylene, ethylene, propylene, butylene, isobutylene, ethoxyethylene and cyclohexylene. As the linear, branched or cyclic alkenylene group having 1 to 20 carbon atoms, vinylene,
Arylene etc. are mentioned.

Although specific examples are shown, the present invention is not limited to these.

[0189]

[Chemical 83]

[0190]

[Chemical 84]

[0191]

[Chemical 85]

[0192]

[Chemical 86]

[0193]

[Chemical 87]

The above photoacid generator, that is, the compound represented by the general formula (A
The compounds represented by formula (I), general formula (AII) and general formula (AIII) are described in US Pat. No. 3,734,928, Macromolecules, vol. 10, 1307 (1977), Journ.
al of Organic Chemistry, vol.55, 4222 (1990), J. Ra
It can be synthesized by using the method described in diat. Curing, vol. 5 (1), 2 (1978) or the like and further exchanging the counter anion. The compounds represented by the general formulas (AIV) and (AV) are prepared by reacting an N-hydroxyimide compound with a carboxylic acid chloride under basic conditions or by reacting nitrobenzyl alcohol with a carboxylic acid chloride under basic conditions. It is obtained by

The weight ratio of the added amounts of the B1 component and the B2 component is
Usually 1/1 to 50/1, preferably 1/1 to 10/1,
Particularly preferably, it is 2/1 to 5/1. B1 component and B2
The total amount of the components is usually 0.5-based on the total solid content of the composition.
20% by weight, preferably 0.75 to 15% by weight, more preferably 1 to 10% by weight. B1 component and B
The two components may each contain a plurality of types.

[3] Solvent (Component C) The composition of the present invention is dissolved in a solvent capable of dissolving the above components and coated on a support. As the solvent used here,
1-methoxy-2-propanol acetate, 1-methoxy-2-propanol, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone, γ
-Butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate , Methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and 1 -Methoxy-
2-Propanol acetate and 1-methoxy-2-propanol are particularly preferable. These solvents may be used alone or as a mixture.

[4] Surfactant (Component D) The photosensitive resin composition of the present invention contains a surfactant, and particularly preferably contains a fluorine-based and / or silicon-based surfactant. That is, the photosensitive resin composition of the present invention particularly preferably contains a fluorine-containing surfactant, a silicon-containing surfactant, or a surfactant containing both a fluorine atom and a silicon atom, or two or more kinds thereof. can do. Addition of these fluorine-based and / or silicon-based surfactants is effective in suppressing development defects and improving coatability.

Examples of these surfactants include those disclosed in
62-36663, JP-A-61-226746, JP-A-61-226745,
JP 62-170950 A, JP 63-34540 A, JP 7-23016 A
5, JP 8-62834A, JP 9-54432A, JP 9-598A
8, U.S. Pat.No. 5,405,720, U.S. Pat.No. 5,360,692, U.S. Pat.No. 5,528,981, U.S. Pat.No. 5,296,330, U.S. Pat.
U.S. Patent No. 5576143, U.S. Patent No. 5296143, U.S. Patent
5294511 and US Pat. No. 5,824,451 can be mentioned, and the following commercially available surfactants can be used as they are. Examples of such commercially available surfactants include F-top EF301, EF303, EF352 (Shin-Akita Kasei)
Fluoro FC430, 431 (Sumitomo 3M Limited)
Made), MegaFac F171, F173, F176, F189, R08 (made by Dainippon Ink and Chemicals), Asahi Guard AG710, Surflon S
-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.) and the like fluorine-based surfactants or silicon-based surfactants can be mentioned. . Also polysiloxane polymer KP
-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as the silicon-based surfactant.

The content of the surfactant is usually 0.001% by weight to 2% by weight, preferably 0.01% by weight to 1% by weight, based on the solid content in the composition of the present invention. These surfactants may be added alone or in some combinations.

[5] Acid Diffusion Inhibitor (E) Applicable to the Present Invention In the composition of the present invention, the performance variation (T-to-pattern of the pattern) after irradiation with actinic rays or radiation and before heat treatment is increased.
(P shape formation, sensitivity fluctuation, pattern line width fluctuation, etc.) and performance fluctuation with time after coating, and further, after irradiation with actinic rays or radiation, excessive diffusion of acid (deterioration of resolution) during heat treatment. Therefore, it is preferable to add an acid diffusion inhibitor. The acid diffusion inhibitor is an organic basic compound,
For example, an organic base compound containing basic nitrogen, and a compound having a pKa value of the conjugate acid of 4 or more is preferably used. Specifically, the structures of the following formulas (A) to (E) can be mentioned.

[0201]

[Chemical 88]

Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² may be the same or different and each is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, or 1 carbon atom. ~ 6 hydroxyalkyl group or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R is
²⁵¹ and R ²⁵² may combine with each other to form a ring. R
²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ^{256, which} may be the same or different, each represents an alkyl group having 1 to 6 carbon atoms. More preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, and particularly preferably both a substituted or unsubstituted amino group and a ring structure containing a nitrogen atom. It is a compound containing or a compound having an alkylamino group.

Preferred specific examples are substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazole, imidazole, Substituted or unsubstituted pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted Alternatively, unsubstituted aminomorpholine, substituted or unsubstituted aminoalkylmorpholine and the like can be mentioned. Preferred substituents are amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group. Is.

Particularly preferred compounds are guanidine,
1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2-phenylimidazole, 4,5-diphenylimidazole, 2 , 4,5-Triphenylimidazole, 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, N-aminomorpholine, N- (2-aminoethyl) morpholine and the like, but not limited thereto. These nitrogen-containing basic compounds may be used alone or in combination of two or more.

The ratio of the acid generator and the organic basic compound used in the composition is preferably (acid generator) / (organic basic compound) (molar ratio) = 2.5 to 300. If the molar ratio is less than 2.5, the sensitivity may be low and the resolution may be lowered. If the molar ratio is more than 300, the resist pattern may become thicker with the lapse of time after the post-exposure heat treatment, and the resolution may be lowered. . The (acid generator) / (organic basic compound) (molar ratio) is preferably 5.0 to 200, more preferably 7.0 to 150.

In the step of forming a pattern on the resist film in the production of precision integrated circuit devices, etc., the photosensitive film of the present invention is formed on a substrate (eg, silicon / silicon dioxide covering, glass substrate, transparent substrate such as ITO substrate). A resin composition,
Next, irradiation is performed using an actinic ray or radiation drawing device,
A good resist pattern can be formed by heating, developing, rinsing and drying.

The developer of the photosensitive resin composition of the present invention includes sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, inorganic alkalis such as aqueous ammonia, ethylamine, n-propylamine. Primary amines such as diethylamine, di-n-
Secondary amines such as butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanamine, quaternary compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline. Cyclic amines such as ammonium salts, pyrrole and piperidine,
Aqueous solutions of alkalis such as can be used. Furthermore, alcohols such as isopropyl alcohol and surfactants such as nonionic surfactants may be added to the aqueous solution of the above alkalis in appropriate amounts. Of these developers, quaternary ammonium salts are preferable, and tetramethylammonium hydroxide and choline are more preferable.

[0209]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the contents of the present invention are not limited thereto.

1. Synthesis Example 1 (Synthesis of Resin (2)) 4- (2-hydroxyhexafluoroisopropyl) styrene (manufactured by Central Glass Co., Ltd.), 4- (in a 100 ml three-necked flask equipped with a reflux tube and a nitrogen introduction tube. 1-
(Methoxyethoxy) styrene (manufactured by Tosoh Corporation) and 1-adamantane-1-methyl-ethylmethacrylate (manufactured by Daicel) were charged at a molar ratio of 50/40/10, and then tetrahydrofuran was added to the mixture to prepare a monomer concentration of 30% by weight. A total of 30 g of the reaction solution of was prepared. It was stirred and heated to 65 ° C. under a stream of nitrogen. Azo polymerization initiator V-65
(Manufactured by Wako Pure Chemical Industries, Ltd.) was added in an amount of 5.0 mol% with respect to the total number of moles of the three monomers, and the mixture was reacted for 8 hours while stirring under a nitrogen stream. Hexane 200 was added to the obtained reaction solution.
ml was added, the produced polymer was precipitated from the solution, and the unreacted monomer was separated and purified. The polymer composition determined from C ¹³ NMR was 51/39/10. When the obtained polymer was analyzed by GPC (in THF solvent, converted to standard polystyrene), the weight average molecular weight was 8,400,
Dispersion degree 2.20, molecular weight 1000 contained in polymer
The following proportion was 15% by weight. Similarly, the resins of the present invention shown in Table 1 were synthesized.

[0211]

[Table 1]

<Synthesis of triphenylsulfonium nonafluorobutane sulfonate (VII-4)> 20 g of triphenylsulfonium iodide was dissolved in 500 ml of methanol, 12.5 g of silver oxide was added thereto, and the mixture was stirred at room temperature for 4 hours. After the reaction solution was filtered to remove the silver compound, the solution was treated with nonafluorobutane sulfonic acid 14.9.
g was added and the solution was concentrated. To the obtained oily product, 300 ml of diisopropyl ether was added and sufficiently stirred, and then the procedure of removing the diisopropyl ether by decanting was performed.
Repeated times. The obtained oily substance was dried under reduced pressure to obtain 18 g of the desired product.

<Synthesis of triphenylsulfonium 4-dodecylbenzene sulfonate (PAG4-1)> 10 g of triphenylsulfonium iodide was added to 50 parts of methanol.
It was dissolved in 0 ml, 4.44 g of silver oxide was added thereto, and the mixture was stirred at room temperature for 4 hours. After the reaction solution was filtered to remove the silver compound, 4.67 g of 4-dodecylbenzene sulfonic acid was added to this solution, and this solution was concentrated. The operation of adding 300 ml of diisopropyl ether to the obtained oil and stirring the mixture sufficiently, and then removing the diisopropyl ether by decanting was repeated twice. The obtained oily substance was dried under reduced pressure to obtain 6 g of the desired product.

<Synthesis of triphenylsulfonium nonafluoropentanoate (II-4f)> 20 g of triphenylsulfonium iodide was dissolved in 500 ml of methanol, 12.5 g of silver oxide was added thereto, and the mixture was stirred at room temperature for 4 hours. After the reaction solution was filtered to remove the silver compound, 14.9 g of nonafluoropentanoic acid was added to this solution, and this solution was concentrated. The operation of adding 300 ml of diisopropyl ether to the obtained oily substance, stirring the mixture sufficiently, and then removing diisopropivir ether by decanting was repeated twice. When the obtained oily substance is dried under reduced pressure, the target substance is 1
8 g was obtained.

[Examples 1-28 and Comparative Examples 1 and 2] 1.2 g of A component and 0.024 g of B1 component shown in Table 2 below.
B2 component 0.006 g, D component 100 ppm (based on polymer solution), E component 0.0012 g, C component 19.6
The polymer solution dissolved in g was filtered through a 0.1 μm Teflon (registered trademark) filter to prepare a positive photoresist solution.

[0216]

[Table 2]

[0217]

[Table 3]

The contents of the symbols in Table 2 are as follows. N-1: Hexamethylenetetramine N-2: 1,5-diazabicyclo [4.3.0] -5-nonene N-3: 1,8-diazabicyclo [5.4.0] -7-undecene W-1 : Megafac F176 (manufactured by Dainippon Ink and Chemicals, Inc.) (fluorine-based) W-2: Megafacque R08 (manufactured by Dainippon Ink and Chemicals, Inc.) (fluorine and silicon-based) S-1: Ethyl lactate S -2: Propylene glycol monomethyl ether acetate S-3: Propylene glycol monomethyl ether The ratio of plural uses shown in Table 2 for each component is a weight ratio.

The positive photoresist solution prepared as described above was applied to an antireflection film (DUV42-6B) using a spin coater.
rewerScience. Inc.) coated evenly on a silicon wafer, and heated and dried at 120 ° C. for 60 seconds,
A positive photoresist film having a film thickness of 0.1 μm was formed.
This resist film is pattern-exposed using an F2 laser microstepper (NA = 0.60) using a line-and-space mask, and 110 ° C. immediately after the exposure.
Heated on a hot plate for 90 seconds. 2.38%
2 with tetramethylammonium hydroxide aqueous solution
It was developed for 30 seconds at 3 ° C., rinsed for 30 seconds in pure water, and then dried. The resist performance of the pattern on the silicon wafer thus obtained was evaluated by the following method.

The evaluation was performed as follows. [Line Edge Roughness] For the range of 5 μm edge in the longitudinal direction of the line pattern, measure the distance from the reference line where the edge should be SEM (S-88 manufactured by Hitachi Ltd.)
40), 50 points are measured, the standard deviation is calculated, and 3
σ was calculated. The smaller the value, the better the performance.

[Development Time Dependence] When the development time is set to 30 seconds, the development time is set to 9 at the exposure dose for reproducing the dimension of the 150 nm line-and-space mask pattern.
The dimension difference from 150 nm when the formation dimension of the same pattern when 0 second is lengthened is shown. The performance evaluation results are shown in Table 3.

[0222]

[Table 4]

From the results shown in Table 3, it is understood that the composition of the present invention has a small dependency on the line edge roughness and the development time and is excellent.

[0224]

According to the present invention, it is possible to provide a photosensitive resin composition in which the problems of line edge roughness and development time dependency are improved.

Claims (4)

[Claims] 1. (A) The following general formulas (I), (II) and
At least one repeating unit represented by (VI)
Having an acid, it decomposes due to the action of acid
Resins that increase solubility, (B1) actinic rays or radiation
Of the general formula A₁Generation of acid represented by H
Compound, (B2) general formula B⁺A₂ ^-Ionic compound represented by
Containing a compound, (C) solvent, and (D) surfactant
Resin composition, which is exposed to actinic rays or radiation.
Acid A generated by component (B1)₁H and ionic compound
Object B⁺A₂ ^-But A₁H + B⁺A₂ ^-  → B⁺A₁ ^- + A₂H (However, H is a hydrogen atom, A₁Is acid A₁Remove hydrogen atom from H
Residue, B⁺Is the cation part of the ionic compound, A₂
^-Represents an anion part. A₁ ^-Is A₁Anion derived from
A₂Has reduced ionicity due to binding with hydrogen ion
A₂ ^-Represents a group derived from. ) The salt exchange reaction
A photosensitive resin composition characterized in that it is carried out. [Chemical 1] R in the general formulas (I), (II) and (VI)₁, R_Five, R
_17aAnd R₁₇Can be the same or different and
Child, a halogen atom, a cyano group or a substituent
Represents a good alkyl group. R₂, R₃, R₆And R₇Is the same
Or they may be different, such as hydrogen atom, halogen atom,
May have an ano group, a hydroxyl group or a substituent
Alkyl group, cycloalkyl group, alkoxy group,
Sil group, acyloxy group, alkenyl group, aryl group
Represents an aralkyl group. R₅₀~ R ₅₅Is the same but different
May have a hydrogen atom, a fluorine atom or a substituent.
Represents an optionally substituted alkyl group. However, R₅₀~ R₅₅of
At least one of them is a fluorine atom or at least one
Represents an alkyl group in which a hydrogen atom of is substituted with a fluorine atom.
You R_FourRepresents a group of the following general formula (IV) or (V)
You R₁₈Is -C (R_18d) (R_18e) (R_18f) Or −
C (R_18d) (R_18e) (OR_{18 g}) Represents. R_18d~ R
_{18 g}May be the same or different and may be a hydrogen atom or
Alkyl group, cycloalkyl, which may have a substituent
Group, alkenyl group, aralkyl group or aryl group
Represent R_18d, R_18e, R_18f2 of or R_18d, R
_18e, R_{18 g}Two of them may combine to form a ring. [Chemical 2] R in the general formula (IV)₁₁, R₁₂And R₁₃Is the same but different
An alkyl group which may have a substituent or may have a substituent.
Group, cycloalkyl group, alkenyl group, aralkyl group
Alternatively, it represents an aryl group. R in the general formula (V)₁₄And R₁₅
May be the same or different and each represents a hydrogen atom or a substituent.
Represents an alkyl group which may have. R₁₆Is a substituent
Which may have an alkyl group, a cycloalkyl group,
Represents an aralkyl group or an aryl group. R₁₄~ R₁₆of
Two of them may combine to form a ring. 2. The component (B1) is a compound which generates an aliphatic or aromatic sulfonic acid substituted with at least one fluorine atom upon irradiation with actinic rays or radiation, and the component (B2) is salt exchange. Depending on the reaction, an aliphatic or aromatic sulfonic acid containing no fluorine atom, or
The photosensitive resin composition according to claim 1, which is an ionic compound that generates an aliphatic or aromatic carboxylic acid. 3. The component (B1) is a compound capable of generating a fluorine atom-free aliphatic or aromatic sulfonic acid upon irradiation with actinic rays or radiation, and the component (B2) is a compound which undergoes a salt exchange reaction to produce a fatty acid. The photosensitive resin composition according to claim 1, which is an ionic compound that generates a carboxylic acid of a group or an aromatic. 4. The component (B1) is a compound which generates an aliphatic or aromatic carboxylic acid substituted with at least one fluorine atom upon irradiation with actinic rays or radiation, and the component (B2) is salt exchange. The photosensitive resin composition according to claim 1, which is an ionic compound that generates an aliphatic or aromatic carboxylic acid containing no fluorine atom by a reaction.