JPH0827094A - Novel onium salt and radiation-sensitive resin composition containing the same - Google Patents

Abstract

PURPOSE:To obtain a novel onium salt which is useful as a resin additive because it is excellent in solubility in solvents, compatibility with resins, thus can improve the application properties of resin composition for chemical amplification type resists as well as the stability of pattern shapes. CONSTITUTION:This onium salt is expressed by formula I [X is an aromatic group or an alkyl; Y is a difunctional organic group; Z is a difunctional organic group forming a heterocyclic ring structure together with I; A is -CH2-, -CHF-; B is -O-, a group of the formula: -Ar- (Ar is phenylene); a, b are each 0-2; c, g are each 0, 1; e is 5-40; a+b+2c=2] or formula II (Z is a difunctional organic group forming a heterocyclic ring structure together with S; a, b are each 0-3; f is e; a+b+2c= 3), for example, benzyl-4-hydroxy-phenylmethylsulfonium perflorooctylsulfonate. A diaryliodonium salt of formula I is obtained by reaction of an aryl compound with KIO3 in the presence of acetic anhydride and conc. sulfuric acid followed by anion-exchange with a sulfonic acid or sulfonate.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel onium salt and a positive type resist containing the onium salt, which is particularly suitable as a chemically amplified resist useful for microfabrication using various radiations such as far ultraviolet rays such as excimer laser. Alternatively, it relates to a negative-type radiation-sensitive resin composition.

[0002]

2. Description of the Related Art In the field of microfabrication represented by the manufacture of integrated circuit elements, miniaturization of the processing size in lithography is progressing in order to obtain higher integration, and in recent years, the size of 0.5 μm or less has been achieved. There is a need for a technique capable of performing fine processing with good reproducibility. Therefore, it is necessary to accurately form a pattern of 0.5 μm or less by a resist patterning process used for microfabrication.
It is extremely difficult to form a fine pattern of 0.5 μm or less with high precision by the method using 0 nm) or near ultraviolet rays (wavelength 400 to 300 nm). Therefore, utilization of radiation having a shorter wavelength (wavelength of 300 nm or less) is being studied. Examples of such short-wavelength radiation include deep line spectra of mercury lamps (wavelength 254 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 148 nm), X-rays such as synchrotron radiation, electron beams, etc. The charged particle beam of US Pat. No. 4,968,629 is used, and in particular, lithography using an excimer laser is drawing attention because of its high output and high efficiency. The resist used in this lithography is required to be capable of forming a fine pattern of 0.5 μm or less with high sensitivity and high resolution by an excimer laser with good reproducibility. Conventional resists have these required characteristics. I could not say that I was satisfied. Therefore, a “chemically amplified resist” is attracting attention as a resist suitable for deep ultraviolet rays such as excimer laser. This resist contains a radiation-sensitive acid forming agent (hereinafter, referred to as "acid forming agent") that forms an acid by irradiation with radiation (hereinafter, referred to as "exposure"), and the resist acts by the catalytic action of the acid. It improves the sensitivity. For example, JP-A-59-45439 discloses a resist comprising a resin protected by a t-butyl group or t-butoxycarbonyl group and an acid former, and JP-A-60-52845 discloses a resist protected by a silyl group. A resist comprising a resin and an acid forming agent, and further JP-A-2-25
No. 850 discloses a resist containing an acetal group-containing resin, and many reports have been made on a chemically amplified resist. However, in these chemically amplified resists, onium salts are generally used as an acid forming agent, and since these onium salts have poor solubility in a solvent or compatibility with a resin, uneven coating is likely to occur, resulting in poor coating properties. However, there is a problem in that the sensitivity is low, and in the patterning process, if the temperature of the post-exposure heat treatment (hereinafter referred to as “post-exposure baking”) is increased to improve the apparent sensitivity, the pattern There was also a problem in the stability of the pattern shape such as the shape being deformed. For example, JP-A-5-222257 describes a negative resist using a sulfonium salt having a sulfonate anion containing a perfluoroalkyl group having 8 or less carbon atoms as an acid forming agent. It does not solve the above-mentioned problems relating to the coating property, the stability of the pattern shape, and the like for both the positive resist and the positive resist.

[0003]

DISCLOSURE OF THE INVENTION The present invention is directed to a novel onium salt having excellent solubility in a solvent and compatibility with a resin, and a pattern shape containing the onium salt, which is suitable for coating properties and post-exposure baking conditions. It is an object of the present invention to provide a positive or negative radiation-sensitive resin composition which is useful as a chemically amplified resist excellent in stability and the like.

[0004]

According to the present invention, the above-mentioned problems are first achieved by an onium salt represented by the following formula (1) or (2) (hereinafter referred to as "first invention"). To be done.

[0005]

[Chemical 1]

[In the formula (1), X is an aromatic organic group,
Represents a monovalent group selected from the group consisting of an alkyl group, a cycloalkyl group, an aralkyl group and a phenacyl group, and a plurality of Xs may be the same or different from each other; Y represents a divalent organic group; Y may be the same as or different from each other, Z is a divalent organic group forming an aliphatic or aromatic heterocyclic structure with the iodine atom in the formula (1), and a is 0 to 2 Is an integer of 0, b is an integer of 0 to 2, c is 0 or 1, but satisfies a + b + 2c = 2, A represents a -CH _2- , -CHF- or -CF ₂ -group, B is-
Indicates an O-, -Ar-, -Ar-O-, -O-Ar- or -O-Ar-O- group, Ar
Represents a phenylene group, a naphthylene group or an anthrylene group, e is an integer of 5 to 40, and g is 0 or 1. ]

[0007]

Embedded image

[In the formula (2), X is an aromatic organic group,
Represents a monovalent group selected from the group consisting of an alkyl group, a cycloalkyl group, an aralkyl group and a phenacyl group, and a plurality of Xs may be the same or different from each other; Y represents a divalent organic group; Y may be the same as or different from each other, Z represents a divalent organic group forming an aliphatic or aromatic heterocyclic structure with the sulfur atom in the formula (2), and a is 0 to 3 Is an integer, b is an integer of 0 to 3, c is 0 or 1, but satisfies a + b + 2c = 3, A represents a —CH ₂ —, —CHF— or —CF ₂ — group, and B represents Is-
Indicates an O-, -Ar-, -Ar-O-, -O-Ar- or -O-Ar-O- group, Ar
Represents a phenylene group, a naphthylene group or an anthrylene group, g is 0 or 1, f is an integer of 5 to 40, and when A is a -CF ₂ -group and g is 0, f is 7 to 40
Is an integer. ]

According to the present invention, the above-mentioned problems are, secondly,
(A) at least one of the onium salts represented by the above formula (1) or (2), and (B) (a) an alkali-insoluble or sparingly-soluble resin protected with an acid dissociable group, A resin that becomes alkali-soluble when the acid-dissociable group dissociates (hereinafter referred to as "acid-dissociable group-containing resin"), or (b) an alkali-soluble resin and a property of controlling alkali solubility of the alkali-soluble resin. A compound which is decomposed in the presence of an acid and reduces or eliminates the action of controlling the alkali solubility of the alkali-soluble resin, or expresses the action of promoting the alkali solubility of the alkali-soluble resin ( Hereinafter, it is achieved by a positive-type radiation-sensitive resin composition (hereinafter, referred to as "second invention") containing a "dissolution control agent".

According to the present invention, the above-mentioned problems are, thirdly,
(A) at least one of the onium salts represented by the formula (1) or (2), (C) an alkali-soluble resin, and (D) a compound capable of crosslinking the alkali-soluble resin in the presence of an acid (hereinafter , A "crosslinking agent") is contained in the negative radiation-sensitive resin composition (hereinafter referred to as "third invention").

The present invention will be described in detail below, which will clarify the purpose, constitution and effect of the present invention. Onium salt The onium salt that constitutes the first invention and is used as the component (A) in the second and third inventions is represented by the above formula (1) or (2). In formulas (1) and (2), the aromatic organic group represented by X is an organic group having an aromatic nucleus of a monocyclic or condensed ring carbocyclic structure or a monocyclic or condensed heterocyclic structure, and the aromatic nucleus is It means a group directly bonded to an iodine atom in the formula (1) or a sulfur atom in the formula (2). Examples of the aromatic nucleus in the aromatic organic group include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. These aromatic nuclei can also have a substituent at an appropriate position. As the substituent, an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, etc.),
An alkoxy group having 1 to 6 carbon atoms (for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group), a carbon number of 2 to 1
1 acyl group (eg, acetyl group, benzoyl group, etc.),
Acyloxy group having 2 to 11 carbon atoms (eg, acetyloxy group, benzoyloxy group, etc.), Aralkyl group having 7 to 20 carbon atoms (eg, benzyl group, diphenylmethyl group, phenylpropyl group, etc.), nitro group, cyano group, hydroxyl group ,
Examples thereof include a vinyl group, a butoxycarbonyloxy group, and a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.). Two or more kinds of these substituents may be present. Specific examples of the aromatic organic group include phenyl group, 4-methylphenyl group, 4-t-butylphenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 3,4-dimethoxyphenyl group and 2-benzoyl. Phenyl group, 4-acetyloxyphenyl group, 4
-Benzylphenyl group, 4-hydroxyphenyl group,
Examples thereof include a 3,5-dimethyl-4-hydroxyphenyl group, a naphthyl group, and an anthranyl group. Among these, preferable aromatic organic groups include phenyl group and 4
-Methylphenyl group, 4-t-butylphenyl group, 4-
Ethoxyphenyl group, 4-acetyloxyphenyl group,
4-hydroxyphenyl group etc. can be mentioned. X
Examples of the alkyl group include an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), and a preferable alkyl group is a methyl group, an ethyl group and the like. Examples of the cycloalkyl group of X include a cycloalkyl group having 3 to 8 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, etc.), and a preferable cycloalkyl group is a cyclohexyl group and the like. The aralkyl group for X is, for example, 7 to 7 carbon atoms.
20 aralkyl groups (eg benzyl group, naphthylmethyl group, anthranylmethyl group, diphenylmethyl group, etc.)
And these aralkyl groups can have a substituent at an appropriate position of the aromatic nucleus. As the substituent, the same substituents as those mentioned above for the aromatic organic group can be mentioned. Two or more kinds of these substituents may be present. Specific examples of the aralkyl group having or not having a substituent in the aromatic nucleus include benzyl group, 4-methylbenzyl group, 4-butylbenzyl group, 4-methoxybenzyl group, 4-acetyloxybenzyl group, 2- Examples thereof include a nitrobenzyl group, a 4-nitrobenzyl group, a 2,4-dinitrobenzyl group, a 4-cyanobenzyl group, a 4-hydroxybenzyl group, a 4-vinylbenzyl group, a naphthylmethyl group and an anthranylmethyl group. Of these, preferred aralkyl groups are benzyl group, 4-methoxybenzyl group, 2-nitrobenzyl group, 4-nitrobenzyl group, anthranylmethyl group and the like. Moreover, the divalent organic group of Y can be, for example, an arylene group, an alkylene group, a cycloalkylene group, an aralkylene group, or the like. Specific examples of these organic groups include phenylene group, naphthylene group, anthrylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, cyclohexylene group, xylylene group and the like. A xylylene group is preferred. The divalent organic group can have a substituent at an appropriate position. As the substituent, the same substituents as those mentioned above for the aromatic organic group can be mentioned. Two or more kinds of these substituents may be present. Further, Z is a divalent organic group forming an aliphatic or aromatic heterocyclic structure with the iodine atom in formula (1) or the sulfur atom in formula (2). Here, the term “aliphatic heterocyclic structure” means a 5- to 6-membered aliphatic cyclic structure, and the term “aromatic heterocyclic structure” means a divalent group containing at least one aromatic nucleus. A cyclic structure formed by binding the organic group of 1 to the iodine atom or the sulfur atom, wherein the cyclic structure is a 5- or 6-membered ring containing the iodine atom or the sulfur atom as a ring-constituting atom. Means 2 of Z
Examples of the valent organic group include-(CH ₂ ) ₅ -,-(CH ₂ ) ₆ -,-(CH
₂ ) _8- ,

[0012]

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[0013]

[Chemical 4] ,

[0014]

Embedded image ,

[0015]

[Chemical 6] ,

[0016]

[Chemical 7]

And the like. Preferred organic groups of _{these, - (CH 2) 5 -} , - (CH 2) 8 -,

[0018]

[Chemical 4]

Etc. In the formulas (1) and (2), a is an integer of 0 to 2 in the formula (1) and 0 in the formula (2).
Is an integer of 3 to 3, b is an integer of 0 to 2 in the formula (1),
In the formula (2), it is an integer of 0 to 3, and c is 0 or 1. a, b and c are a + b + 2c = 2 in the formula (1).
Is satisfied, and in Expression (2), a + b + 2c = 3 is satisfied.
Further, g is 0 or 1. All of the above numbers for a, b, c and g are preferably adopted. E in Formula (1) is an integer of 5 to 40, preferably 5 to 30, and more preferably 5 to 20. F in Formula (2) is an integer of 5 to 40, preferably 5 to 30, and more preferably 5 to 20. However, f
Is an integer of 7 to 40 when A is a —CF ₂ — group and g is 0, preferably 8 to 30, and more preferably 9 to 2.
0. Specific examples of the onium salt represented by the formula (1) include compounds represented by the following formulas (3) to (16).

[0020]

Embedded image ,

[0021]

[Chemical 9] ,

[0022]

[Chemical 10] ,

[0023]

[Chemical 11] ,

[0024]

[Chemical 12] ,

[0025]

[Chemical 13] ,

[0026]

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[0027]

[Chemical 15] ,

[0028]

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[0029]

[Chemical 17] ,

[0030]

Embedded image ,

[0031]

[Chemical 19] ,

[0032]

Embedded image ,

[0033]

[Chemical 21] .

Among the onium salts represented by the above formulas (3) to (16), preferred compounds are formulas (3), (5),
The compounds represented by (11), (12) and (15), and particularly preferred compounds are the compounds represented by formulas (3) and (5). Further, specific examples of the onium salt represented by the formula (2) include compounds represented by the following formulas (17) to (48).

[0035]

[Chemical formula 22]

[0036]

[Chemical formula 23] ,

[0037]

[Chemical formula 24] ,

[0038]

[Chemical 25] ,

[0039]

[Chemical formula 26] ,

[0040]

[Chemical 27] ,

[0041]

[Chemical 28] ,

[0042]

[Chemical 29] ,

[0043]

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[0044]

[Chemical 31] ,

[0045]

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[0046]

[Chemical 33] ,

[0047]

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[0048]

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[0049]

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[0050]

Embedded image ,

[0051]

[Chemical 38] ,

[0052]

[Chemical Formula 39] ,

[0053]

[Chemical 40] ,

[0054]

Embedded image ,

[0055]

Embedded image ,

[0056]

[Chemical 43] ,

[0057]

[Chemical 44] ,

[0058]

Embedded image ,

[0059]

Embedded image ,

[0060]

[Chemical 47] ,

[0061]

Embedded image ,

[0062]

[Chemical 49] ,

[0063]

Embedded image ,

[0064]

[Chemical 51] ,

[0065]

Embedded image ,

[0066]

Embedded image ,

Among the onium salts represented by the formulas (17) to (48), preferred compounds are the formulas (17) and (1
8), (19), (20), (25), (26), (2
8), (33), (35), (36), (39), (4
1), (42), (45) and (46), and particularly preferred compounds are represented by formulas (17) and (2)
0), (25), (26), (33), (36), (3
The compounds represented by 9), (41) and (42). The onium salt of the first invention is described in the new experimental chemistry course (Maruzen), books such as Volume 14, Macromolecules, Vol.10, p.
1307, J. Organic Chemistry, Vol.33, p.2671, J. Polyme
r Science: Polymer Chemistry Edition, Vol.17, p.2877
In an aqueous solution of an onium salt synthesized by the method detailed in the above-mentioned report or in a solution of an organic solvent such as methanol, ethanol, or acetone, a specific sulfonic acid corresponding to the onium salt of the first invention (hereinafter, " It can be obtained by reacting with a specific sulfonic acid ") or a salt thereof (hereinafter, the specific sulfonic acid and the salt are collectively referred to as a" specific sulfonic acid (salt) ") and anion exchange.
In this case, the solution concentration of the onium salt used in the reaction is preferably as high as possible in order to obtain a high reaction yield. The specific sulfonic acid (salt) may be used as it is or may be used as a solution. Also in the case of a solution, it is preferable to increase the solution concentration of the specific sulfonic acid (salt). Usually, the anion exchange reaction proceeds by simply mixing and stirring both reaction components, and the onium salt of the first invention produced by the reaction is precipitated as crystals. An example of a typical synthesis method for the preferable onium salt in the first invention is shown below. (I) A diaryl iodonium salt is obtained by reacting an aryl compound such as benzene or toluene with potassium iodate in the presence of acetic anhydride and concentrated sulfuric acid, and then producing a specific sulfonic acid or its silver salt, sodium salt, or potassium salt. It can be obtained by anion exchange using an alkali metal salt such as a salt. (ii) The sulfonium salt is generally (ii-1) a method of performing anion exchange with a sulfonium salt having a halogen or the like as an anion using a specific sulfonic acid, or a silver salt thereof or the alkali metal salt. In addition to (ii-2) alkyl sulfides, aryl sulfides and other sulfide compounds, it can be obtained by reacting with a specific sulfonic acid ester. In the case of (ii-3) triarylsulfonium salts, Also preferred is the method of reacting an iodonium salt with a diaryl sulfide.

The onium salt represented by the formula (1) or (2) of the first invention is, for example, various ultraviolet ray such as excimer laser, X-ray such as synchrotron radiation, charged particle beam such as electron beam. It has the property of generating an acid when exposed to radiation, and has excellent solubility in various solvents and compatibility with various resins. Therefore, such an onium salt is useful as a resist excellent in coatability, stability of the pattern shape against the conditions of post-exposure baking, and the like, when used in combination with, for example, an acid-dissociable group-containing resin or an alkali-soluble resin, a positive type or A negative type radiation sensitive resin composition can be provided.

Next, the second invention contains the components (A) and (B) (a) or (b), and the third invention comprises the components (A), (C) and (D). Although contained, the component (A) in both inventions is used as a single compound represented by the above formula (1) or (2), or in the above formula (1) or (2). X, Y, Z,
It may be used as a mixture of two or more compounds in which any one or more of A, B, a, b, c, e or f and g is different, and further, a compound represented by the formula (1) You may use it as a mixture of 1 or more types of these, and 1 or more types of the compound represented by Formula (2). Acid dissociable group-containing resin The acid dissociable group-containing resin used in the second invention (component (B) (a)) is a resin containing at least one acidic functional group such as a phenolic hydroxyl group and a carboxyl group, For example, the hydrogen atom of the acidic functional group in the alkali-soluble resin having the repeating units represented by the formulas (49) to (52) described later,
A resin that is substituted with one or more acid-dissociable groups capable of dissociating in the presence of an acid and is itself insoluble or sparingly soluble in alkali. The term "alkali-insoluble or sparingly alkali-soluble" as used herein means an alkali development employed when forming a resist pattern from a resist film formed using a radiation-sensitive resin composition containing an acid dissociative group-containing resin. Under the conditions, when a film using only an acid-labile group-containing resin instead of the resist film is developed, 50% or more of the initial film thickness of the film remains after the development. Examples of the acid dissociable group include a substituted methyl group, a 1-substituted ethyl group, a 1-branched alkyl group, a silyl group, a germyl group, an alkoxycarbonyl group, an acyl group,
Examples thereof include cyclic acid-dissociable groups. Examples of the substituted methyl group include methoxymethyl group, methylthiomethyl group, ethoxymethyl group, ethylthiomethyl group, methoxyethoxymethyl group, benzyloxymethyl group, benzylthiomethyl group, phenacyl group, bromophenacyl group, methoxyphenacyl group. , A methylthiophenacyl group,
α-methylphenacyl group, cyclopropylmethyl group, benzyl group, diphenylmethyl group, triphenylmethyl group, bromobenzyl group, nitrobenzyl group, methoxybenzyl group, methylthiobenzyl group, ethoxybenzyl group, ethylthiobenzyl group, piperonyl Group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-
Propoxycarbonylmethyl group, isopropoxycarbonylmethyl group, n-butoxycarbonylmethyl group, t-
Examples thereof include butoxycarbonylmethyl group.
Examples of the 1-substituted ethyl group include 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1-diethoxyethyl group. Group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1,1-diphenoxyethyl group, 1-benzyloxyethyl group, 1-benzylthioethyl group, 1-cyclopropylethyl group, 1-
Phenylethyl group, 1,1-diphenylethyl group, 1-
Methoxycarbonylethyl group, 1-ethoxycarbonylethyl group, 1-n-propoxycarbonylethyl group, 1
Examples thereof include an isopropoxycarbonylethyl group, a 1-n-butoxycarbonylethyl group and a 1-t-butoxycarbonylethyl group. Examples of the 1-branched alkyl group include isopropyl group, sec-butyl group, t-butyl group, 1,1-dimethylpropyl group, 1-
Examples thereof include a methylbutyl group and a 1,1-dimethylbutyl group. Examples of the silyl group include trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, isopropyldimethylsilyl group, methyldiisopropylsilyl group, triisopropylsilyl group, t-butyldimethylsilyl group, di-t.
-Butylmethylsilyl group, tri-t-butylsilyl group,
Examples thereof include a phenyldimethylsilyl group, a methyldiphenylsilyl group and a triphenylsilyl group. Examples of the germyl group include a trimethylgermyl group,
Ethyldimethylgermyl group, methyldiethylgermyl group, triethylgermyl group, isopropyldimethylgermyl group, methyldiisopropylgermyl group, triisopropylgermyl group, t-butyldimethylgermyl group, di-t-butylmethylgel Examples thereof include a mil group, a tri-t-butylgermyl group, a phenyldimethylgermyl group, a methyldiphenylgermyl group and a triphenylgermyl group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, and a t-butoxycarbonyl group. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a heptanoyl group, a hexanoyl group, a valeryl group, a pivaloyl group, an isovaleryl group, a lauriloyl group, a myristoyl group, a palmitoyl group, a stearoyl group, an oxalyl group, a malonyl group, and a succinyl group. Group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacyl group, acryloyl group, propioloyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group,
Fumaroyl group, mesaconoyl group, camphoroyl group, benzoyl group, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, tenoyl group, nicotinoyl group, isonicotinoyl group , P-toluenesulfonyl group, mesyl group and the like. Examples of the cyclic acid dissociable group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group,
Cyclohexenyl group, 4-methoxycyclohexyl group,
Tetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group, tetrahydrothiofuranyl group, 3-bromotetrahydropyranyl group, 4-methoxytetrahydropyranyl group, 4-methoxytetrahydrothiopyranyl group, 3-tetrahydrothiophene -1,1-
Examples thereof include a dioxide group and the like. Among these acid dissociable groups, t-butyl group, benzyl group, t-butoxycarbonylmethyl group, t-butoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranyl group and tetrahydrothiofuranyl group. Is preferred.

The introduction rate of the acid-dissociable group in the resin containing an acid-dissociable group (the ratio of the number of acid-dissociable groups to the total number of acidic functional groups and acid-dissociable groups in the resin containing an acid-dissociable group) is Although it cannot be specified unconditionally depending on the type of acid dissociable group or alkali-soluble resin, it is preferably 10 to 100%, more preferably 15 to 100%, particularly preferably 20 to 100%.
Is. The polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") of the acid dissociable group-containing resin measured by gel permeation chromatography is preferably 1,000 to 150,000, more preferably 3 ,.
000 to 100,000. The acid-dissociable group-containing resin can be produced, for example, by introducing at least one acid-dissociable group into a previously produced alkali-soluble resin, and a monomer having at least one acid-dissociable group can be produced. (Co) polymerization of, a (co) polycondensation of a polycondensation component having one or more acid dissociable groups, and the like. The acid-dissociable group-containing resin also has the property of controlling the alkali solubility of the alkali-soluble resin and is decomposed in the presence of an acid to reduce or eliminate the action of controlling the alkali solubility of the alkali-soluble resin. Alternatively, it exerts an action of promoting the alkali solubility of the alkali-soluble resin and falls within the scope of the dissolution control agent in the components (B) and (B) of the second invention. In the second invention, the acid-labile group-containing resin may be used alone or in combination of two or more.

Alkali-Soluble Resin The alkali-soluble resin used in the second invention (component (B) (b)) and the third invention (component (C)) is
It is a resin soluble in an alkali developing solution, which has at least one functional group having an affinity with the alkali developing solution, such as a phenolic hydroxyl group and a carboxyl group. Examples of the alkali-soluble resin include the following formulas (49) to (52)
A resin having one or more kinds of repeating units represented by

[0072]

[Chemical 54]

[In the formula (49), R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydroxyl group, a carboxyl group, or -R ³
COOH group, -OR ³ COOH group or -OCOR ³ COOH group (however, R ³ is-
(CH) _h- , where h is an integer of 1 to 4. } Is shown. ]

[0074]

[Chemical 55]

[In the formula (50), R ¹ represents a hydrogen atom or a methyl group. ]

[0076]

[Chemical 56]

[0077]

[Chemical 57]

[In the formula (52), R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different from each other and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. When the alkali-soluble resin has repeating units represented by the above formulas (49) to (51), it may be composed of only these repeating units, but the produced resin is soluble in an alkali developing solution. To some extent, it may further have other repeating units. Such other repeating units include, for example, styrene, α-methylstyrene, maleic anhydride, (meth) acrylonitrile, crotonnitrile, maleinnitrile, fumaronitrile, mesaconnitrile, citraconnitrile, itaconenitrile, (meth) acrylamide, crotonamide. , Maleinamide, fumaramide, mesacone amide, citraconamide, itacone amide, vinylaniline, vinylpyridine, vinyl-ε-caprolactam, vinylpyrrolidone,
An example is a unit in which the polymerizable double bond portion of a monomer having a polymerizable double bond such as vinylimidazole is cleaved. The alkali-soluble resin having the repeating units represented by the formulas (49) to (51) includes, for example, one or more kinds of monomers corresponding to the repeating units represented by the formulas, and optionally other repeating units described above. It can be produced by (co) polymerizing with a monomer corresponding to. In these (co) polymerizations, a polymerization initiator or a polymerization catalyst such as a radical polymerization initiator, an anionic polymerization catalyst, a coordinated anionic polymerization catalyst, or a cationic polymerization catalyst may be appropriately used depending on the type of monomer, reaction medium, etc. Selected, bulk polymerization, solution polymerization, precipitation polymerization,
It can be carried out by an appropriate polymerization method such as emulsion polymerization, suspension polymerization, and bulk-suspension polymerization. Also, the above formula (52)
Alkali-soluble resin having a repeating unit represented by,
Although it can be composed of only the repeating unit, it may further have other repeating units as long as the resin produced is soluble in the alkali developing solution. Such an alkali-soluble resin is a polycondensate capable of forming one or more phenols corresponding to the repeating unit represented by the formula (52) and one or more aldehydes, and optionally forming another repeating unit. It can be produced by (co) polycondensation with the components in an aqueous medium or a mixed medium of water and a hydrophilic solvent in the presence of an acidic catalyst. Here, examples of the phenols include o-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol,
2,5-xylenol, 3,4-xylenol, 3,5
-Xylenol, 2,3,5-trimethylphenol,
Examples of the aldehydes include 3,4,5-trimethylphenol and the like, and examples of the aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde and phenylacetaldehyde. The content of the repeating units represented by the formulas (49) to (52) in the alkali-soluble resin cannot be unconditionally defined depending on the kind of the other repeating units contained, but is preferably 1
It is 0 to 100 mol%, more preferably 20 to 100 mol%. The Mw of the alkali-soluble resin can be selected according to the desired characteristics of the radiation-sensitive resin composition, but it is preferably 1,000 to 150,000, more preferably 3,
000 to 100,000. When the alkali-soluble resin has a repeating unit containing a carbon-carbon unsaturated bond as represented by formulas (49) and (52), it can be used as a hydrogenated product. In this case, the hydrogenation rate is usually 70% or less, preferably 50% or less, more preferably 70% or less of the carbon-carbon unsaturated bond contained in the repeating units represented by the formulas (49) and (52). It is 40% or less. If the hydrogenation rate exceeds 70%, the developing characteristics of the alkali-soluble resin with an alkali developing solution may deteriorate. In the second invention and the third invention, the alkali-soluble resins may be used alone or in combination of two or more.

Dissolution Control Agent The dissolution control agent used in the second invention (component (B) (b)) is, for example, a dissociation into an acidic functional group such as a phenolic hydroxyl group or a carboxyl group in the presence of the above-mentioned acid. The compound which introduce | transduced the 1 or more types of acid dissociable group which can be mentioned can be mentioned. Examples of such an acid dissociable group include the substituted methyl group described in the section of the above-mentioned acid dissociable group-containing resin, 1-
Examples thereof include those similar to acid-dissociable groups such as a substituted ethyl group, silyl group, 1-branched alkyl group, germyl group, alkoxycarbonyl group, acyl group and cyclic acid-dissociable group. The dissolution control agent may be a low molecular weight compound or a high molecular weight compound. Examples of the low molecular weight compound include compounds represented by the following formula (53)
The compounds represented by (57) to (57) can be mentioned.

[0080]

Embedded image

[In the formula (53), R ⁹ represents a substituted methyl group, a 1-substituted ethyl group, a 1-branched alkyl group, a silyl group, a germyl group, an alkoxycarbonyl group, an acyl group or a cyclic acid-dissociable group. R ⁹ present in plural numbers may be the same or different from each other, and R ¹⁰ represents an alkyl group having 1 to 4 carbon atoms, a phenyl group or a naphthyl group, and plural numbers are present.
R ^{10 s} may be the same as or different from each other, p is an integer of 1 or more, q is an integer of 0 or more, and p + q ≦ 6. ]

[0082]

Embedded image

[In the formula (54), R ⁹ and R ¹⁰ have the same meanings as in the formula (53), and A is a single bond, —S—, —O—, —CO.
-, -COO-, -SO-, -SO _2- , -C (R ¹¹ ) (R ¹² )-or

Embedded image (Wherein R ¹⁰ is the same as above and x is an integer of 0 to 4), and R ¹¹ and R ¹² may be the same or different from each other, and are a hydrogen atom or a carbon number of 1 to 6 It represents an alkyl group, an acyl group having 2 to 11 carbon atoms, a phenyl group or a naphthyl group, p, q, r and s are integers of 0 or more, and p + q
≦ 5, r + s ≦ 5, p + r ≧ 1. ]

[0084]

[Chemical formula 61]

[In the formula (55), R ⁹ and R ¹⁰ have the same meanings as in the formula (53), R ¹³ is a hydrogen atom, and has 1 to 4 carbon atoms.
Represents an alkyl group or a phenyl group of p, q, r,
s, t and u are integers of 0 or more, p + q ≦ 5, r + s
≦ 5, t + u ≦ 5, and p + r + t ≧ 1. ]

[0086]

Embedded image

[In formula (56), R ⁹ and R ¹⁰ have the same meanings as in formula (53), A has the same meaning as in formula (54),
R ¹³ has the same meaning as in formula (55), and a plurality of R ^13's may be the same or different from each other, and p, q, r, s, t,
u, v and w are integers of 0 or more, p + q ≦ 5, r + s
≦ 5, t + u ≦ 5, v + w ≦ 5, p + r + t + v ≧ 1
Is. ]

[0088]

[Chemical formula 63]

[In the formula (57), R ⁹ and R ¹⁰ have the same meaning as in the formula (53), R ¹³ has the same meaning as in the formula (55),
A plurality of R ^13's may be the same or different from each other,
p, q, r, s, t, u, v and w are integers of 0 or more, p + q ≦ 5, r + s ≦ 5, t + u ≦ 5, v + w ≦ 4
And p + r + t + v ≧ 1. In the second invention, a compound of the following formula (58) can be mentioned as a specific example of a particularly preferable low molecular weight dissolution control agent.

[0090]

[Chemical 64]

The above-mentioned resin containing an acid-dissociative group can be used as a polymer dissolution control agent. Second
In the invention, the dissolution control agent is a low molecular weight compound or a high molecular weight compound (that is, an acid-labile group-containing resin),
Can be used alone or in combination of two or more,
Further, a low molecular compound and a high molecular compound can be used in combination.

Crosslinking Agent The crosslinking agent used in the third invention (component (D)) is
It is a compound capable of crosslinking an alkali-soluble resin in the presence of an acid generated by exposure. As such a cross-linking agent,
For example, a compound having one or more kinds of substituents having cross-linking reactivity with an alkali-soluble resin (hereinafter referred to as “cross-linking substituent”) can be mentioned. Examples of the crosslinkable substituent include groups represented by the following formulas (59) to (63).

[0093]

Embedded image

[In the formula (59), n is 1 or 2, and Q ¹ is a single bond, —O—, —S—, or —COO when n = 1.
-Or -NH-, or when n = 2, it represents a trivalent nitrogen atom, Q ² represents -O- or -S-, and i is 0 to
An integer of 3, j is an integer of 1 to 3, and i + j = 1 to 4. ]

[0095]

[Chemical formula 66]

[In the formula (60), Q ³ is -O-, -COO-
Or -CO-, R ¹⁴ and R ¹⁵ may be the same or different from each other and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹⁶ is an alkyl group having 1 to 5 carbon atoms, or a carbon number. 6
To an aryl group having 12 to 12 or an aralkyl group having 7 to 14 carbon atoms, and k is an integer of 1 or more. ]

[0097]

Embedded image

[In the formula (61), R ¹⁷ , R ¹⁸ and
R ¹⁹ may be the same as or different from each other and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

[0099]

[Chemical 68]

[In the formula (62), R ¹⁴ and R ¹⁵ have the same meanings as in the formula (60), R ²⁰ and R ²¹ may be the same or different from each other, and are an alkylol group having 1 to 5 carbon atoms or It represents an alkoxyalkyl group, and k ¹ is an integer of 0 or more. ]

[0101]

[Chemical 69]

[In the formula (63), R ¹⁴ and R ¹⁵ have the same meanings as in the formula (60), and R ²² has a hetero atom of any one of an oxygen atom, a sulfur atom or a nitrogen atom, and has 3 to 8 members. It represents a divalent organic group forming a ring, and k is an integer of 1 or more. ) Specific examples of such crosslinkable substituents include glycidyl ether groups, glycidyl ester groups, glycidylamino groups, methoxymethyl groups, ethoxymethyl groups, benzyloxymethyl groups, dimethylaminomethyl groups, diethylaminomethyl groups, dimethylol. Examples thereof include an aminomethyl group, a diethylolaminomethyl group, a morpholinomethyl group, an acetoxymethyl group, a benzoyloxymethyl group, a formyl group, an acetyl group, a vinyl group and an isopropenyl group. Examples of the compound having a crosslinkable substituent include a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol S epoxy compound, a novolac resin epoxy compound, a resole resin epoxy compound, and a poly (hydroxystyrene) epoxy. Compound, methylol group-containing melamine compound, methylol group-containing benzoguanamine compound, methylol group-containing urea compound, methylol group-containing phenol compound, alkoxyalkyl group-containing melamine compound, alkoxyalkyl group-containing benzoguanamine compound, alkoxyalkyl group-containing urea compound, alkoxyalkyl group Containing phenolic compound, carboxymethyl group-containing melamine compound,
Examples thereof include a carboxymethyl group-containing benzoguanamine compound, a carboxymethyl group-containing urea compound, and a carboxymethyl group-containing phenol compound. Of these compounds having a crosslinkable substituent, a methylol group-containing phenol compound, a methoxymethyl group-containing melamine compound, a methoxymethyl group-containing phenol compound and an acetoxymethyl group-containing phenol compound are preferable, and a methoxymethyl group-containing melamine compound is more preferable. Is. Specific examples of the methoxymethyl group-containing melamine compound include trade names of CYMEL300, CYMEL301, and C.
There are YMEL303, CYMEL305 (manufactured by Mitsui Cyanamid) and the like. As the cross-linking agent, further, the acidic functional group in the alkali-soluble resin is substituted with the cross-linkable substituent,
A compound having a property as a crosslinking agent can also be preferably used. The introduction rate of the crosslinkable functional group in that case cannot be specified unconditionally depending on the type of the crosslinkable functional group or the alkali-soluble resin, but is usually 5 to 60 mol% with respect to the total acidic functional groups in the alkali-soluble resin. , Preferably 10-5
It is 0 mol%, more preferably 15 to 40 mol%.
If the introduction rate of the crosslinkable functional group is less than 5 mol%, the remaining film rate tends to decrease, and the pattern may meander or swell, and if it exceeds 60 mol%, the developability tends to deteriorate. is there. In the third invention, the crosslinking agent is used alone or
A mixture of two or more species can be used.

The mixing ratio of each component constituting the positive type radiation sensitive resin composition of the second invention and the negative type radiation sensitive resin composition of the third invention can be selected according to the desired characteristics of the resist. The preferred blending ratio is as follows. First, in the positive-type radiation-sensitive resin composition of the second invention, the amount of the onium salt to be compounded is usually 0. 0 per 100 parts by weight of the acid-dissociable group-containing resin or the alkali-soluble resin.
05 to 20 parts by weight, preferably 0.1 to 15 parts by weight, particularly preferably 0.5 to 15 parts by weight. If the amount of the onium salt is less than 0.05 parts by weight, the amount of acid formed by exposure tends to be small, and it tends to be difficult to effectively cause a chemical change due to the acid. Unevenness in the application of the toner and scum during the development tend to occur. The amount of the dissolution control agent is usually 100 parts by weight of the alkali-soluble resin.
5 to 150 parts by weight, preferably 5 to 100 parts by weight, particularly preferably 5 to 50 parts by weight. If the content of the dissolution control agent is less than 5 parts by weight, the residual film rate tends to decrease and the pattern tends to swell, while if it exceeds 150 parts by weight, the film surface becomes rough and the film strength decreases. Tends to be easier. More specifically, the mixing ratio of each component in the second invention is preferably [1-1] onium salt 0.05.
To 20 parts by weight, and 100 parts by weight of the acid-dissociable group-containing resin, or 0.05 to 20 parts by weight of the [1-2] onium salt, 100 parts by weight of the alkali-soluble resin, and 5 to 150 parts by weight of the dissolution control agent, More preferably, [1-
3] 0.1 to 15 parts by weight of an onium salt and 100 parts by weight of an acid dissociable group-containing resin, or [1-4] 0.1 to 15 parts by weight of an onium salt, 100 parts by weight of an alkali-soluble resin, and a dissolution control agent 5 To 100 parts by weight, particularly preferably 0.5 to 15 parts by weight of [1-5] onium salt, and 100 parts by weight of acid-labile group-containing resin, or [1-6].
Onium salt 0.5 to 15 parts by weight, alkali-soluble resin 1
00 parts by weight and 5 to 50 parts by weight of a dissolution control agent.

Next, in the negative-type radiation-sensitive resin composition of the third invention, the amount of the onium salt is usually 0.05 to 20 parts by weight, preferably 0.1 to 100 parts by weight of the alkali-soluble resin. ˜15 parts by weight, particularly preferably 0.5 to 10 parts by weight. The onium salt content is 0.
If it is less than 05 parts by weight, the amount of acid formed by exposure is small, and it tends to be difficult to effectively cause a chemical change due to the acid. If it is more than 20 parts by weight, uneven coating at the time of applying a resist or Scum tends to occur during development. The amount of the cross-linking agent added is usually 5 to 95 parts by weight, preferably 15 to 85 parts by weight, and particularly preferably 20 to 75 parts by weight, per 100 parts by weight of the alkali-soluble resin.
Parts by weight. If the amount of the cross-linking agent is less than 5 parts by weight, the residual film rate tends to decrease, and the pattern tends to meander or swell, while if it exceeds 95 parts by weight, the developability tends to decrease. More specifically, the mixing ratio of each component in the third invention is preferably 0.05 to 20 parts by weight of a [2-1] onium salt, 100 parts by weight of an alkali-soluble resin, and 5 to 95 parts by weight of a crosslinking agent. And more preferably 0.1 to 15 parts by weight of [2-2] onium salt, 100 parts by weight of alkali-soluble resin and 15 to 85 parts by weight of cross-linking agent, and particularly preferably [2-3] onium salt 0. 0.5 to 10 parts by weight, 100 parts by weight of the alkali-soluble resin, and 20 to 75 parts by weight of the crosslinking agent.

Various Additives Various additives such as surfactants and sensitizers are added to the positive radiation-sensitive resin composition of the second invention and the negative radiation-sensitive resin composition of the third invention, if necessary. Agents can be added. The surfactant has an effect of improving the coating property, striation, developability and the like of the radiation sensitive resin composition. As such a surfactant, any of anionic type, cationic type, nonionic type and amphoteric type can be used, but a preferable surfactant is a nonionic type surfactant. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, and higher fatty acid diesters of polyethylene glycol, as well as KP (Shin-Etsu Chemical Co., Ltd.) , Polyflow (manufactured by Kyoeisha Yushi Kagaku Kogyo), F-top (manufactured by Tochem Products), Megafac (manufactured by Dainippon Ink and Chemicals), Florard (manufactured by Sumitomo 3M), Asahi Guard, Surflon (manufactured by Asahi Glass), etc. Can be mentioned.
These surfactants may be used alone or in admixture of two or more. The content of the surfactant is usually 2 parts by weight or less as an active ingredient of the surfactant per 100 parts by weight of all the resin components in the resin composition. The sensitizer has a function of absorbing the energy of radiation and transmitting the energy to the onium salt, thereby increasing the production amount of acid, thereby improving the apparent sensitivity of the radiation-sensitive resin composition. Has the effect of The sensitizer used is not particularly limited as long as it exhibits the above-mentioned action and effect, but preferred examples thereof include acetone, benzene, acetophenones, benzophenones, naphthalene compounds, biacetyl, eosin and rose bengal. , Pyrenes, anthracenes, phenothiazines and the like. These sensitizers can be used alone or in admixture of two or more. The compounding amount of the sensitizer is usually 50 parts by weight or less based on 100 parts by weight of all resin components in the resin composition,
It is preferably 30 parts by weight or less. In addition, by blending a dye or pigment, the latent image in the exposed area can be visualized and the effect of halation during exposure can be mitigated, and by blending an adhesion aid, the adhesion to the substrate can be improved. You can Further, other additives include antihalation agents, storage stabilizers, antifoaming agents, shape improving agents and the like.

Solvent The positive-working radiation-sensitive resin composition of the second invention and the negative-working radiation-sensitive resin composition of the third invention are
After being dissolved in a solvent so that the solid content concentration is, for example, 5 to 50% by weight, the solution is prepared as a composition solution by filtering with a filter having a pore size of about 0.2 μm. The solvent used in the preparation of the composition solution,
For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether. Ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, isopropenyl acetate, isopropenyl propionate, toluene, xylene, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone 4-heptanone, ethyl 2-hydroxypropionate, 2-hydroxy-2-methylpropionic acid ethyl, ethyl ethoxy acetate, hydroxyethyl acetate, 2-hydroxy-3-methylbutyric acid, 3-
Methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, propyl acetate, butyl acetate, methyl acetoacetate, Ethyl acetoacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide Etc. These solvents are used alone or in admixture of two or more. Further, the solvent, if necessary, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-
Nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate,
γ-butyrolactone, ethylene carbonate, propylene carbonate,
It is also possible to add one or more high boiling point solvents such as phenyl cellosolve acetate.

Formation of Resist Pattern When a resist pattern was formed from the positive radiation-sensitive resin composition of the second invention and the negative radiation-sensitive resin composition of the third invention, it was prepared as described above. The composition solution is applied onto a substrate such as a silicon wafer or a wafer covered with aluminum by a means such as spin coating, cast coating, or roll coating to form a resist film, and a predetermined mask pattern is formed. Through which the resist coating is exposed. The radiation that can be used at that time is the emission line spectrum of a mercury lamp (wavelength 254 nm),
Far-ultraviolet rays such as KrF excimer laser (wavelength 248 nm) and ArF excimer laser (wavelength 193 nm) are preferable, but radiation such as X-ray such as synchrotron radiation and charged particle beam such as electron beam is used depending on the kind of onium salt. You can also Further, the exposure conditions such as the radiation dose are appropriately selected according to the compounding composition of the resin composition, the kind of additives, and the like. After exposure, post-exposure baking is preferably performed in order to improve the apparent sensitivity of the resist. The heating conditions are the positive radiation-sensitive resin composition of the second invention and the third radiation-sensitive resin composition of the third invention.
The temperature is usually 30 to 200 ° C., preferably 50 to 150 ° C., though it varies depending on the composition of the negative radiation-sensitive resin composition of the invention, the type of additives and the like. Then, by developing with an alkaline developer, a predetermined resist pattern is formed. Examples of the alkaline developer include alkali metal hydroxides; ammonia water, alkylamines; alkanolamines; heterocyclic amines; tetraalkylammonium hydroxides; choline; 1,8-diazabicyclo- [5,4,4]. 0] -7-undecene; 1,5-diazabicyclo- [4,3,0] -5-nonene and other alkaline compounds are generally used in an amount of 1 to 10% by weight, preferably 2 to 5%.
An alkaline aqueous solution which is dissolved to have a concentration of wt% is used. These alkaline compounds can be used alone or in admixture of two or more. In addition, a proper amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the developer containing the alkaline aqueous solution. In addition, when using a developing solution composed of an alkaline aqueous solution as described above, generally,
After development, wash with water.

The second invention is characterized by containing the above-mentioned component (A) and the component (B) (a) or (B) (b). But -
When the onium salt having f of 5 or 6 is used in combination with the component (B) (a) or (B) (b) when g is 0 in the CF ₂ -group, coating property, exposure A positive-type radiation-sensitive resin composition having excellent pattern shape stability with respect to conditions for post-baking can be obtained. Also in such a positive-type radiation-sensitive resin composition, the blending ratio of each component is set to the above [1-
1] to [1-6] are preferable, and various additives such as the above-mentioned surfactants and sensitizers can be optionally mixed, and the preparation of the composition solution and the formation of the resist are It is carried out in the same manner as in the case of the second invention.

[0109]

The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. The Mw measurement and the resist evaluation in Examples and Comparative Examples were performed by the following methods. Mw Tosoh Corp. GPC column (G2000H _XL : 2 pieces,
G3000H _XL : 1 bottle, G4000H _XL : 1 bottle), using a flow rate of 1.0 ml / min, an elution solvent of tetrahydrofuran, and a column temperature of 40 ° C under the analytical conditions of gel permeation chromatography using monodisperse polystyrene as a standard. It was measured. Solubility The state of each composition solution containing the onium salt and other components shown in Table 1 was visually observed, and the case where the onium salt was completely dissolved and there was no turbidity was regarded as good solubility. Each composition solution consisting of onium salts and other components shown in coatability Table 1 was spin coated on a silicon wafer, the resist film after firing was visually observed, uneven coating, not observed haze and foreign matter, When the surface was smooth, the coating property was good. Pattern Shape A resist pattern formed on a silicon wafer using each composition solution containing an onium salt and other components shown in Table 1 was observed with a scanning electron microscope, and the cross-sectional shapes (a) and (b) shown in FIG. ). In the case of (a), the pattern shape was good, and in the case of (b), the pattern shape was bad.

Synthesis of Onium Salt Synthesis Example 1 An aqueous solution prepared by dissolving 21 g of benzyl-4-hydroxyphenyl-methylsulfonium chloride in 700 g of water was added.
An aqueous solution of 40 g of perfluorooctyl sulfonic acid dissolved in 500 g of water was added dropwise with stirring. After cooling for 24 hours, the deposited precipitate was filtered and washed with 400 g of water.
Washed twice. Then, the produced salt was dried under reduced pressure at 40 ° C. to quantitatively obtain benzyl-4-hydroxyphenyl-methylsulfonium perfluorooctylsulfonate. This compound is referred to as an onium salt (a). Synthesis Example 2 19 g of silver oxide was added to a solution of 16 g of triphenylsulfonium iodide in 200 g of methanol, and the mixture was stirred for 4 hours. 19 g of perfluorooctyl sulfonic acid was added to the filtered solution of silver iodide deposited by the reaction.
Was added dropwise to 100 g of methanol. After stirring for 2 hours, 1000 g of methanol was further added, and the deposited precipitate was extracted 3 times with 1000 g of ethyl acetate. Then, the solvent was distilled off under reduced pressure, and the resulting solid was dried at 40 °
After drying under reduced pressure at 20 g (74% yield) of triphenylsulfonium perfluoropentyl sulfonate was obtained. This compound is referred to as an onium salt (b). Synthesis Example 3 20 g of diphenyliodonium chloride was added to 1200 g of water.
A solution of 32 g of perfluorooctyl sulfonic acid dissolved in 100 g of water was added dropwise to the solution dissolved in g under stirring. After cooling for 24 hours, the deposited precipitate was filtered and washed with a small amount of water. Then, the precipitate was dried under reduced pressure at 40 ° C. to obtain 35 g (yield 70%) of diphenyliodonium doperfluorooctylsulfonate. This compound is referred to as an onium salt (c).

Synthesis of Acid-Dissociable Group-Containing Resin Synthesis Example 4 300 g of poly (hydroxystyrene) was added to dioxane 20
After dissolving in 00 ml, 200 g of hexamethyldisilazane was added, and the mixture was reacted at 90 ° C. for 6 hours with stirring. After the reaction was completed, the reaction solution was dropped into water, and the precipitated resin was dried overnight in a vacuum dryer at 50 ° C. to obtain an acid dissociable group-containing resin. The obtained resin had Mw of 7,000, and as a result of NMR measurement, it had a structure in which 50% of the hydrogen atoms of the phenolic hydroxyl group were replaced with trimethylsilyl groups. This resin is referred to as a resin (a). Synthesis Example 5 24 g of poly (hydroxystyrene) was dissolved in 96 ml of acetone, and then t-butyl bromoacetate was added.
g and 7.6 g of potassium carbonate were added, and the mixture was reacted for 8 hours under reflux with stirring. After the reaction was completed, the reaction solution was extracted with ethyl acetate, washed with a 5% by weight aqueous acetic acid solution and water, and then ethyl acetate and the like were distilled off under reduced pressure and propylene glycol monoethyl ether acetate was added repeatedly to exchange the solvent. Then, an acid dissociable group-containing resin solution was obtained. The obtained resin has Mw of 12000 and
As a result of R measurement, 23% of hydrogen atoms of phenolic hydroxyl group
Was a structure substituted with a t-butoxycarbonylmethyl group. This resin is referred to as resin (a-b). Synthesis Example 6 After dissolving 30 g of poly (hydroxystyrene) in 120 ml of tetrahydrofuran, 10 g of potassium t-butoxide was added, and then di-t- was added with stirring at 0 ° C.
Butyl dicarbonate (60 g) was added and the reaction was carried out for 4 hours. After the reaction was completed, the reaction solution was dropped into water, and the precipitated resin was dried overnight in a vacuum dryer at 50 ° C. to obtain an acid dissociable group-containing resin. The obtained resin has an Mw of 15,000.
As a result of NMR measurement, it was found that 29% of the hydrogen atoms of the phenolic hydroxyl group had a structure in which t-butoxycarbonyl group was substituted. This resin is resin (e-c)
And

Synthesis of Dissolution Control Agent Synthesis Example 7 1,1-bis (4-hydroxyphenyl) -1- [4 ′
15 g (0.035 mol) of-{1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane was dissolved in 200 g of tetrahydrofuran, and 36.5 g (0.21 mol) of di-t-butyl dicarbonate. And triethylamine (3.2 g, 0.032 mol) were added, and the mixture was reacted under reflux for 6 hours. Then the reaction solution was dropped into water,
The resulting precipitate was filtered, and the obtained solid was dried in a vacuum dryer at 50 ° C. overnight to obtain a dissolution control agent represented by the formula (58).

Examples 1 to 7 and Comparative Examples 1 to 6 For each solution prepared by mixing 5 parts of the onium salt shown in Table 1 (based on weight; the same applies hereinafter) with the other components shown in Table 1, After the solubility was evaluated, each solution was subjected to microfiltration with a membrane filter having a pore size of 0.2 μm to remove foreign matters, to prepare a composition solution. Then, each composition solution is spin-coated on a silicon wafer, and then 100 ° C.
By baking for 2 minutes, a resist film having a film thickness of about 1 mm was formed. This resist coating is manufactured by Admon Science
KrF excimer laser irradiation device (MBK-400TL-
N) and through a mask pattern, 5-40 mJ / cm
Exposure was at a dose of ² . Then, post-exposure baking was performed at 100 ° C. for 2 minutes, and development was performed for 1 minute at 25 ° C. with a 2.38 wt% tetramethylammonium hydroxide aqueous solution.
After development, it was washed with water for 30 seconds to obtain a resist pattern. Examples 8 to 10 For each solution obtained by mixing the onium salt and other components shown in Table 1, the solubility of the onium salt was evaluated in the same manner as in Examples 1 to 7. Then, in the same manner as in Examples 1 to 7, a resist film having a film thickness of about 1 mm is formed, and an electron beam drawing apparatus (ELS330 manufactured by Elionix Co., Ltd.) is formed on the resist film.
0) was used and the exposure was performed at an accelerating voltage of 20 Kv and a dose of 1 to ²⁰ μC / cm ² . After exposure, a resist pattern was obtained in the same manner as in Examples 1-7. Table 1 shows the evaluation results of each example and each comparative example.

[0114]

[Table 1]

In the table, onium salts (a) of the first invention
Each component other than (c) is as follows. Onium salt triphenylsulfonium trifluoromethanesulfonate. Diphenyliodonium tetrafluoroborate. Triphenylsulfonium hexafluorophosphate. Other component resin (a-a) 100 parts, diaminodiphenylmethane 1 part, ethyl lactate 600 parts. Resin (i-b) 100 parts, diaminodiphenylmethane 1 part, ethyl lactate 420 parts, ethyl 3-ethoxypropionate 180 parts. Resin (a-c) 100 parts, propylene glycol monomethyl ether acetate 600 parts. Poly (hydroxystyrene) (Mw = 12000)
100 parts, hexamethoxymethylmelamine 20 parts, 1,1 '
-Bis (4-chlorophenyl) -2,2,2-trichloroethane 5 parts, methyl 3-methoxypropionate 620 parts. Poly (hydroxystyrene) (Mw = 22000)
100 parts, dissolution control agent (formula (58)) 30 parts, ethyl lactate 430 parts, butyl acetate 170 parts.

[0116]

The onium salt of the first invention has excellent solubility in various solvents used in the radiation-sensitive resin composition and compatibility with various resins, and can provide a composition solution having excellent coatability. it can. Further, both the positive-type radiation-sensitive resin composition of the second invention and the negative-type radiation-sensitive resin composition of the third invention are excellent in coatability, stability of pattern shape with respect to post-exposure baking conditions, and the excimer. It can be applied to any of various kinds of radiation such as deep ultraviolet rays such as laser, X-ray such as synchrotron radiation, and charged particle beam such as electron beam. Therefore, these positive-type or negative-type radiation-sensitive resin compositions are extremely useful especially as resists for manufacturing semiconductor devices, which are expected to be further miniaturized in the future.

[Brief description of drawings]

FIG. 1 is a diagram illustrating a cross-sectional shape of a resist pattern and evaluation criteria of a pattern shape.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08K 5/37 KBS 5/42 KBU C08L 101/00 G03F 7/004 503

Claims (3)

[Claims] 1. An onium salt represented by the following formula (1) or (2): Embedded image [In Formula (1), X is an aromatic organic group, an alkyl group,
A monovalent group selected from the group consisting of a cycloalkyl group, an aralkyl group and a phenacyl group, a plurality of Xs present may be the same or different from each other, and Y represents a divalent organic group,
A plurality of Y may be the same or different from each other, Z is a divalent organic group forming an aliphatic or aromatic heterocyclic structure with the iodine atom in the formula (1), and a is 0
Is an integer of 2 to 2, b is an integer of 0 to 2, c is 0 or 1, but satisfies a + b + 2c = 2, and A is -CH.
_2- , -CHF- or -CF ₂ -group, B is -O-, -Ar-, -A
rO-, -O-Ar- or -O-Ar-O- group, Ar represents phenylene group, naphthylene group or anthrylene group, and e is 5
Is an integer of ˜40 and g is 0 or 1. ] [Chemical 2] [In the formula (2), X is an aromatic organic group, an alkyl group,
A monovalent group selected from the group consisting of a cycloalkyl group, an aralkyl group and a phenacyl group, a plurality of Xs present may be the same or different from each other, and Y represents a divalent organic group,
A plurality of Ys may be the same or different from each other, Z is a divalent organic group forming an aliphatic or aromatic heterocyclic structure with the sulfur atom in the formula (2), and a is 0 to 0.
Is an integer of 3, b is an integer of 0 to 3, c is 0 or 1, but satisfies a + b + 2c = 3, and A is -CH.
_2- , -CHF- or -CF ₂ -group, B is -O-, -Ar-, -A
represents an rO-, -O-Ar- or -O-Ar-O- group, Ar represents a phenylene group, a naphthylene group or an anthrylene group, and g is 0.
Or 1 and f is an integer of 5 to 40, but A is -C
F ₂ - when g is 0 in group, f represents an integer of 7 to 40. ] 2. (A) At least one of the onium salts according to claim 1, and (B) (a) an alkali-insoluble or sparingly-soluble resin protected with an acid-dissociable group, wherein the acid A resin that becomes alkali-soluble when the dissociable group dissociates, or (b) has a property of controlling the alkali solubility of the alkali-soluble resin and the alkali-soluble resin, and is decomposed in the presence of an acid to give the alkali-soluble resin. A positive-type radiation-sensitive resin composition comprising a compound that reduces or eliminates the action of controlling the alkali solubility of the resin, or expresses the action of promoting the alkali solubility of the alkali-soluble resin. 3. (A) At least one of the onium salts according to claim 1, (C) an alkali-soluble resin, and (D) a compound capable of crosslinking the alkali-soluble resin in the presence of an acid. A negative-type radiation-sensitive resin composition comprising: