JPH08184965A - Radiation-sensitive resin composition - Google Patents

Abstract

PURPOSE: To obtain a positive or negative radiation-sensitive resin compsn. which is useful as a chemically amplifying resist showing an excellent balance in characteristics such as coating property, sensitivity, resolution, stability of a pattern under conditions of exposure and baking, by incorporating a specified compd. having excellent solubility with various kinds of solvents and with various kinds of resin. CONSTITUTION: This compsn. contains at least one kind of N,N'-bis(sulfonyloxy)- bis(dicarboximide) compd. expressed by formula I or II, and (a) resin containing groups which can be dissociated with acid or (b) alkali-soluble resin, and a solubility controlling agent. In formula, R<1> is a quadrivalent hydrocarbon residue, R<2> and R<3> may be same or different and are univalent aliphatic, alicyclic or aromatic groups, X is -CO- or -COO-Y-OCO-, Y is an alkylene group or alkylene group containing a N-sulfonyloxy dicarboximide group.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention contains an N, N'-bis (sulfonyloxy) -bis (dicarboximide) compound and is useful for microfabrication using various radiations such as far ultraviolet rays such as excimer laser. The present invention relates to a positive or negative radiation-sensitive resin composition suitable as a chemically amplified resist.

[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 far-infrared rays such as a bright line spectrum of a mercury lamp (wavelength 254 nm), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), X-ray such as synchrotron radiation, electron beam, 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 am not completely satisfied. Therefore, a “chemically amplified resist” has been developed and is attracting attention as a resist suitable for deep ultraviolet rays such as excimer laser. This chemically amplified 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 catalytic action of the acid. This improves the sensitivity of the resist. For example, JP-A-59
-45439 discloses a resist comprising a resin protected by a t-butyl group or a t-butoxycarbonyl group and an acid former, and JP-A-60-52845 discloses a resin protected by a silyl group and an acid former. And a resist comprising an acetal group-containing resin and an acid forming agent are disclosed in Japanese Patent Application Laid-Open No. 25850/1990, and many reports have been made on chemically amplified resists. However, in these chemically amplified resists, onium salts are generally used as an acid forming agent, but these onium salts are liable to cause uneven coating due to poor solubility in a solvent or compatibility with a resin. However, there is a problem in that the sensitivity is low, and the sensitivity is low. Further, in the patterning process, if the temperature of the heat treatment after exposure (hereinafter referred to as "post-exposure baking") is increased in order to improve the apparent sensitivity. There is also a problem in the stability of the pattern shape with respect to the post-exposure baking conditions such as deformation of the pattern shape. Further, JP-A-3-206458 discloses a positive type radiation sensitive resin composition using a mono (sulfonyloxyimide) compound as an acid forming agent, and the compound has good solubility. However, this composition is also unsatisfactory in terms of resolution, stability of the pattern shape against the conditions of baking after exposure.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides an N, N'-bis (sulfonyloxy) -bis (dicarboximide) as an acid forming agent, which has excellent solubility in various solvents and compatibility with various resins. Contains compounds, coating properties, sensitivity,
It is an object of the present invention to provide a positive or negative type radiation sensitive resin composition which is useful as a chemically amplified resist having an excellent property balance such as resolution and stability of pattern shape with respect to post-exposure baking conditions.

[0004]

According to the present invention, the above-mentioned problems are as follows: (A) N, N'-represented by the following formula (1) or (2):
Bis (sulfonyloxy) -bis (dicarboximide)
At least one compound, and (B) (a) an alkali-insoluble or sparingly-soluble resin protected with an acid-dissociable group, which becomes an alkali-soluble resin when the acid-dissociable group dissociates (hereinafter , "Acid-dissociable group-containing resin"), or (b) an alkali-soluble resin, and the property of controlling the alkali solubility of the alkali-soluble resin, and is decomposed in the presence of an acid to give the alkali-soluble resin. It is characterized by containing a compound (hereinafter, referred to as "dissolution control agent") which exhibits an action of reducing or eliminating the action of controlling the alkali solubility of the resin or promoting the action of the alkali solubility of the alkali-soluble resin. And a positive radiation-sensitive resin composition (hereinafter referred to as “first invention”).

[0005]

[Chemical 1]

[0006]

Embedded image

(In the formulas (1) and (2), R ¹ is 4
Represents a valent hydrocarbon residue, R ² and R ^{3, which} may be the same or different from each other, represent an aliphatic, alicyclic or aromatic monovalent group, and X represents -CO- or -COO- Y-OCO-, wherein Y represents an alkylene group or an N-sulfonyloxydicarboximide group-containing alkylene group. ]

According to the present invention, the above-mentioned problems are, secondly,
(A) N, N′− represented by the above formula (1) or (2)
Bis (sulfonyloxy) -bis (dicarboximide)
At least one compound, (C) an alkali-soluble resin,
And (D) a compound capable of crosslinking the alkali-soluble resin in the presence of an acid (hereinafter, referred to as "crosslinking agent"), a negative radiation-sensitive resin composition (hereinafter, referred to as "second Invention ”).

The present invention will be described in detail below. This will clarify the purpose, structure and effect of the present invention. N, N'-bis (sulfonyloxy) -bis (dicarb
Ximido) compound The N, N'-bis (sulfonyloxy) -bis (dicarboximide) compound used as the component (A) of the first invention and the second invention is represented by the formula (1) or (2). To be done. In formulas (1) and (2), R ¹ represents a tetravalent hydrocarbon residue, and specific examples thereof include, for example,

[0010]

Embedded image ,

[0011]

[Chemical 4] ,

[0012]

Embedded image ,

[0013]

[Chemical 6] ,

[0014]

[Chemical 7]

And the like. Also, R ² and
R ^{3 s} may be the same as or different from each other and represent an aliphatic, alicyclic or aromatic monovalent group, and examples thereof include an alkyl group, a perhaloalkyl group, a cycloalkyl group and an aryl group. Specific examples of such R ² and R ³ include:

[0016]

Embedded image

[0017]

[Chemical 9]

[0018]

[Chemical 10]

[0019]

[Chemical 11]

And the like. Also, X is -CO-
Or -COO-Y-OCO-, where Y is an alkylene group or N
-A sulfonyloxydicarboximide group-containing alkylene group is shown. As an example of Y,

[0021]

[Chemical 12] (Here, n and m are integers of 1 to 10.)

[0022]

[Chemical 13] (Here, R ² has the same meaning as in formula (1).) And the like. Examples of such N, N′-bis (sulfonyloxy) -bis (dicarboximide) compounds include:

[0023]

Embedded image

[0024]

[Chemical 15]

[0025]

Embedded image

[0026]

[Chemical 17]

[0027]

Embedded image

[0028]

[Chemical 19]

[0029]

Embedded image

[0030]

[Chemical 21]

[0031]

[Chemical formula 22]

[0032]

[Chemical formula 23]

And the like. However, R ² and
R ³ has the same meaning as in formula (1). The N, N′-bis (sulfonyloxy) -bis (dicarboximide) compound is usually obtained by converting a dianhydride of a corresponding tetracarboxylic acid compound into hydroxylamine in the presence of a base such as sodium carbonate, ammonia or pyridine. React with the hydrochloride to give N,
It can be produced by obtaining an N′-dihydroxy-bis (dicarboximide) compound and then reacting it with a sulfonyl chloride compound such as alkylsulfonyl chloride in the presence of the above base. In this reaction, in order to improve the purity and yield of the obtained N, N′-bis (sulfonyloxy) -bis (dicarboximide) compound, the reaction conditions such as reaction temperature and reaction time are adjusted and appropriate purification is performed. Perform processing. N, N′-bis (sulfonyloxy) represented by the above formula (1) or formula (2)
-A bis (dicarboximide) compound is, for example, X-rays such as deep ultraviolet rays such as excimer laser and synchrotron radiation.
It has the property of forming an acid by being exposed to various kinds of radiation such as a charged particle beam such as an electron beam and an electron beam, and has excellent solubility in various solvents and compatibility with various resins. Therefore, the N, N′-bis (sulfonyloxy) -bis (dicarboximide) compound is used, for example, in combination with an acid-dissociable group-containing resin or an alkali-soluble resin to change the coatability and the post-exposure baking conditions. It is possible to provide a positive or negative radiation-sensitive resin composition which is useful as a chemically amplified resist excellent in stability of the pattern shape against the above. Further, the N, N′-bis (sulfonyloxy) -bis (dicarboximide) compound in the first invention and the second invention is used as a single compound represented by the above formula (1) or formula (2). Or, in equation (1) or equation (2)
At least ^{one of} R ¹ , R ² , R ³ , X and Y is different 2
It may be used as a mixture of two or more compounds, and further, one or more compounds represented by formula (1) and one or more compounds represented by formula (2) may be used in combination. .

Acid-Dissociable Group-Containing Resin The acid-dissociable group-containing resin used as the component (B) (a) of the first invention contains at least one acidic functional group such as phenolic hydroxyl group and carboxyl group. One or more kinds of acid dissociation capable of dissociating a hydrogen atom of an acidic functional group in a resin, for example, an alkali-soluble resin having repeating units represented by formulas (3) to (6) described below in the presence of an acid. It is an alkali-insoluble or sparingly alkali-soluble resin that is substituted with a functional group. 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-dissociable group-containing resin instead of the resist film is developed, 50% or more of the initial film thickness of the film remains after 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 acid-dissociable group-containing resin (the ratio of the number of acid-dissociable groups to the total number of acidic functional groups and acid-dissociable groups in the acid-dissociable group-containing resin) is
It cannot be unconditionally specified depending on the kind of the acid dissociable group and the kind of the alkali-soluble resin into which the acid dissociable group is introduced, but it is preferably 10 to 100%, more preferably 15 to 100%.
%, Particularly preferably 20 to 100%. 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 1.
50,000, more preferably 3,000-100,
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-labile group-containing resin is also
It 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, or the alkali of the alkali-soluble resin. It exhibits an action of promoting solubility, and is included in the category of the dissolution control agent in the components (B) and (B) of the first invention. In the first 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 components (B) and (B) of the first invention and as the component (C) of the second invention is a functional group having an affinity with an alkali developing solution. It is a resin that is soluble in an alkaline developer and has at least one acidic functional group such as a phenolic hydroxyl group and a carboxyl group.
Examples of such alkali-soluble resins include resins having one or more kinds of repeating units represented by the following formulas (3) to (6).

[0036]

[Chemical formula 24] [In Formula (3), R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a hydroxyl group, a carboxyl group, a -R ⁶ COOH group, a -OR ⁶ CO group.
OH group or -OCOR ⁶ COOH group (however, R ⁶ represents-(CH) h-,
h is an integer of 1 to 4. } Is shown. ]

[0037]

[Chemical 25] [In the formula (4), R ⁷ represents a hydrogen atom or a methyl group. ]

[0038]

[Chemical formula 26]

[0039]

[Chemical 27] [In the formula (6), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² 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 (3) to (5), 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. Examples of such other repeating units include styrene, α-methylstyrene, maleic anhydride, (meth) acrylonitrile, crotonnitrile,
Malein nitrile, fumaro nitrile, mesacone nitrile, citracon nitrile, itacone nitrile, (meth)
Polymerizability of monomers having a polymerizable double bond such as acrylamide, crotonamide, maleamide, fumaramide, mesacone amide, citracone amide, itaconamide, vinylaniline, vinylpyridine, vinyl-ε-caprolactam, vinylpyrrolidone, vinylimidazole The unit in which the double bond part is cleaved can be mentioned. The alkali-soluble resin having the repeating units represented by the formulas (3) to (5) corresponds to, for example, one or more kinds of monomers corresponding to the repeating units of the formulas, and optionally to the other repeating units. It can be produced by (co) polymerization with a monomer. 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. It can be selected and carried out by an appropriate polymerization method such as bulk polymerization, solution polymerization, precipitation polymerization, emulsion polymerization, suspension polymerization and bulk-suspension polymerization. Further, the alkali-soluble resin having a repeating unit represented by the above formula (6) may be composed of only the repeating unit, but as long as the produced resin is soluble in an alkali developing solution, other It is possible to further have a repeating unit. Such an alkali-soluble resin has an acidity of one or more phenols corresponding to the repeating unit of the formula (6) and one or more aldehydes, optionally together with a polycondensation component capable of forming another repeating unit. It can be prepared by (co) polycondensation in an aqueous medium or a mixed medium of water and a hydrophilic solvent in the presence of a catalyst.
Here, as the phenols, for example, o-cresol, p-cresol, 2,3-xylenol, 2,4
-Xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol and the like, and the aldehydes include, for example, formaldehyde. , Trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde,
Examples include phenylacetaldehyde and the like. The content of the repeating units represented by the formulas (3) to (6) in the alkali-soluble resin cannot be unconditionally defined depending on the kind of the other repeating units contained, but
Preferably 10 to 100 mol%, more preferably 20
~ 100 mol%. Mw of the alkali-soluble resin is
The radiation-sensitive resin composition can be selected according to the desired characteristics, 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 (3) and (6), it can be used as a hydrogenated product. In this case, the hydrogenation rate is usually 70% or less, preferably 50% or less, and more preferably 40% or less of the carbon-carbon unsaturated bond contained in each repeating unit. If the hydrogenation rate exceeds 70%, the developing characteristics of the alkali-soluble resin with an alkali developing solution may deteriorate. In the first invention and the second 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 component (B) (b) of the first invention has a property of controlling the alkali solubility of the alkali-soluble resin, and is decomposed in the presence of an acid, It is a compound that 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.
Examples of such a dissolution control agent include compounds in which one or more kinds of acid dissociable groups capable of dissociating in the presence of the above-described acid are introduced into acidic functional groups such as phenolic hydroxyl group and carboxyl group. . Examples of such an acid dissociable group include, for example, the substituted methyl group, the 1-substituted ethyl group, the silyl group, the 1-branched alkyl group, the germyl group, the alkoxycarbonyl group, the acyl group, which are exemplified for the acid dissociable group-containing resin. The same groups as the acid dissociable group such as a cyclic acid dissociable group can be mentioned. The dissolution control agent may be a low molecular weight compound or a high molecular weight compound. Examples of the low molecular weight dissolution control agent include compounds represented by the following formulas (7) to (11).

[0041]

[Chemical 28] [In the formula (7), R ¹³ is a substituted methyl group, a 1-substituted ethyl group, a 1-branched alkyl group, a silyl group, a germyl group,
It represents an alkoxycarbonyl group, an acyl group or a cyclic acid dissociable group, and a plurality of R ^13's may be the same or different from each other, and R ¹⁴ 's represent an alkyl group having 1 to 4 carbon atoms, a phenyl group or a naphthyl group. A plurality of R ^{14 s} may be the same or different, p is an integer of 1 or more, q is an integer of 0 or more, and p + q ≦ 6. ]

[0042]

[Chemical 29] [In the formula (8), R ¹³ and R ¹⁴ have the same meanings as in the formula (7), and A is a single bond, —S—, —O—, —CO—, —COO—, —SO.
-, -SO _2- , -C (R ¹⁵ ) (R ¹⁶ )-or

[0043]

Embedded image (Wherein R ¹⁴ is the same as above and x is an integer of 0 to 4), and R ¹⁵ and R ¹⁶ may be the same or different from each other, and are a hydrogen atom or a C 1 to C 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. ]

[0044]

[Chemical 31] [In the formula (9), R ¹³ and R ¹⁴ have the same meanings as in the formula (7), R ¹⁷ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and p, q, r, s, t and u are integers of 0 or more, p + q ≦ 5, r + s ≦ 5, t + u ≦ 5
Therefore, p + r + t ≧ 1. ]

[0045]

Embedded image [In the formula (10), R ¹³ and R ¹⁴ are synonymous with the formula (7), A is synonymous with the formula (8), and R ¹⁷ is the formula (9).
R ¹⁷ present in plural numbers may be the same or different from each other, and p, q, r, s, t, u, v and w are 0.
With the above integers, p + q ≦ 5, r + s ≦ 5, t + u ≦ 5,
When v + w ≦ 5, p + r + t + v ≧ 1. ]

[0046]

[Chemical 33] [In the formula (11), R ¹³ and R ¹⁴ are synonymous with the formula (7), R ¹⁷ is synonymous with the formula (9), and p, q, r,
s, t, u, v, and w are integers of 0 or more, and p + q ≦
5, r + s ≦ 5, t + u ≦ 5, v + w ≦ 4, p + r +
t + v ≧ 1. In the first invention, a compound of the following formula (12) can be given as a specific example of a particularly preferable low molecular weight dissolution controlling agent.

[0047]

Embedded image

The above-mentioned resin containing an acid-dissociable group can be used as the polymer dissolution control agent. In the first invention, the dissolution controlling agent can be used either individually or in combination of two or more low molecular weight compounds and high molecular weight compounds (that is, acid dissociative group-containing resins). The compound and the polymer compound may be used in combination.

Crosslinking Agent The crosslinking agent used as the component (D) of the second invention is an acid,
For example, it is a compound capable of crosslinking an alkali-soluble resin in the presence of an acid generated by exposure. Examples of such a cross-linking agent include compounds having one or more kinds of substituents (hereinafter referred to as "cross-linkable substituents") having cross-linking reactivity with an alkali-soluble resin. Examples of the crosslinkable substituent include groups represented by the following formulas (13) to (17).

[0050]

Embedded image [In the formula (13), c is 1 or 2, and Q ¹ is
When c = 1, single bond, -O-, -S-, -COO- or -N
H-, or c = 2 represents a trivalent nitrogen atom, Q ² represents -O- or -S-, a is an integer of 0 to 3, b
Is an integer from 1 to 3 and a + b = 1 to 4. ]

[0051]

Embedded image [In the formula (14), Q ³ represents -O-, -COO- or -CO-, R ¹⁸ and R ¹⁹ may be the same or different from each other, and are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Indicates
R ²⁰ represents an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 14 carbon atoms,
d is an integer of 1 or more. ]

[0052]

Embedded image [In the formula (15), R ²¹ , R ²² and R ²³ may be the same or different from each other and each represent a hydrogen atom or a carbon number of 1 to 4
Is an alkyl group. ]

[0053]

[Chemical 38] [In the formula (16), R ¹⁸ and R ¹⁹ have the same meaning as in the formula (14), R ²⁴ and R ²⁵ may be the same or different from each other, and are an alkylol group or an alkoxyalkyl group having 1 to 5 carbon atoms. And e is an integer of 0 or more. ]

[0054]

[Chemical Formula 39] [In the formula (17), R ¹⁸ and R ¹⁹ have the same meanings as in the formula (14), and R ²⁶ has a hetero atom of any of an oxygen atom, a sulfur atom or a nitrogen atom, and forms a 3 to 8-membered ring. Is a divalent organic group, and d 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 melamine compound containing a methoxymethyl group include trade names of CYMEL300, CYMEL301,
There are CYMEL 303, CYMEL 305 (manufactured by Mitsui Cyanamid) and the like. As the cross-linking agent, a compound in which an acidic functional group in the alkali-soluble resin is further substituted with the cross-linking substituent to give properties as a cross-linking agent can also be suitably 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 1
It is 0 to 50 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 second invention, the crosslinking agent may be used alone or in combination of two or more kinds.

The blending ratio of each component constituting the positive-type radiation-sensitive resin composition of the first invention and the negative-type radiation-sensitive resin composition of the second 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 first invention, the compounding amount of the N, N′-bis (sulfonyloxy) -bis (dicarboximide) compound is such that the acid-labile group-containing resin or the alkali-soluble resin 100 is added. It is usually 0.05 to 20 parts by weight, preferably 0.1 to 15 parts by weight, and particularly preferably 0.5 to 10 parts by weight per part by weight. In this case, if the compounding amount of the N, N′-bis (sulfonyloxy) -bis (dicarboximide) compound is less than 0.05 parts by weight, the amount of acid formed by exposure will be small and the chemical change due to the acid will be reduced. It tends to be difficult to cause effectively,
On the other hand, if the amount exceeds 20 parts by weight, uneven coating at the time of coating the resist and scum at the time of development tend to occur.
In addition, the amount of the dissolution control agent is 10
It is usually 5 to 150 parts by weight, preferably 5 to 100 parts by weight, and particularly preferably 5 to 50 parts by weight per 0 parts by weight. In this case, if the content of the dissolution control agent is less than 5 parts by weight, the remaining film rate tends to decrease and the pattern tends to swell, and if it exceeds 150 parts by weight, the surface roughness and film strength of the film may be reduced. It tends to fall. More specifically, the mixing ratio of each component in the first invention is usually
[1-1] N, N′-bis (sulfonyloxy) -bis (dicarboximide) compound 0.05 to 20 parts by weight, and acid dissociable group-containing resin 100 parts by weight, or [1-
2] N, N′-bis (sulfonyloxy) -bis (dicarboximide) compound 0.05 to 20 parts by weight, 100 parts by weight of alkali-soluble resin and 5 to 150 parts by weight of a dissolution control agent, preferably [ 1-3] N, N′-bis (sulfonyloxy) -bis (dicarboximide) compound 0.1 to 15 parts by weight, and acid dissociable group-containing resin 10
0 parts by weight, or [1-4] N, N'-bis (sulfonyloxy) -bis (dicarboximide) compound 0.1
15 parts by weight, 100 parts by weight of alkali-soluble resin and 5 to 100 parts by weight of a dissolution control agent, and particularly preferably,
[1-5] N, N′-bis (sulfonyloxy) -bis (dicarboximide) compound 0.5 to 10 parts by weight, and acid dissociable group-containing resin 100 parts by weight, or [1-6]
0.5 to 10 parts by weight of an N, N'-bis (sulfonyloxy) -bis (dicarboximide) compound, 100 parts by weight of an alkali-soluble resin, and 5 to 50 parts by weight of a dissolution control agent.

Next, in the negative-type radiation-sensitive resin composition of the second invention, N, N'-bis (sulfonyloxy)-
The compounding amount of the bis (dicarboximide) compound is usually 0.05 to 20 per 100 parts by weight of the alkali-soluble resin.
Parts by weight, preferably 0.1 to 15 parts by weight, particularly preferably 0.5 to 10 parts by weight. In this case, if the compounding amount of the N, N′-bis (sulfonyloxy) -bis (dicarboximide) compound is less than 0.05 parts by weight, the amount of acid formed by exposure will be small and the chemical change due to the acid will be reduced. When it is more than 20 parts by weight, uneven coating during resist coating and scum during development tend to occur. 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, based on 100 parts by weight of the alkali-soluble resin. In this case, 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.
If it exceeds 5 parts by weight, the developability tends to decrease. More specifically, the blending ratio of each component in the second invention is usually [2-1] N, N′-bis (sulfonyloxy) -bis (dicarboximide) compound 0.05 to 20.
Parts by weight, 100 parts by weight of the alkali-soluble resin and 5 to 95 parts by weight of the cross-linking agent, and preferably [2-2] N,
The N′-bis (sulfonyloxy) -bis (dicarboximide) compound is 0.1 to 15 parts by weight, the alkali-soluble resin is 100 parts by weight, and the crosslinking agent is 15 to 85 parts by weight, and particularly preferably [2-3]. N, N′-bis (sulfonyloxy) -bis (dicarboximide) compound 0.5 to 1
0 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 In the positive radiation-sensitive resin composition of the first invention and the negative radiation-sensitive resin composition of the second invention, if necessary, an acid diffusion controller, a surfactant and a sensitizer are added. Various additives such as agents can be blended. The acid diffusion control agent controls the diffusion phenomenon of the acid generated from the N, N′-bis (sulfonyloxy) -bis (dicarboximide) compound upon exposure in the resist film, and causes unfavorable chemistry in the unexposed area. It has the effect of suppressing the reaction. By using the acid diffusion control agent, it is possible to further improve the pattern shape, particularly the degree of eaves generation in the pattern upper layer portion, the dimensional fidelity to the mask dimension, and the like. As such an acid diffusion control agent, a nitrogen-containing organic compound whose basicity does not change by exposure or heating is preferable, and specific examples thereof include ammonia, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dibutylamine, Dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecyl Amine, aniline, N-methylaniline, N, N-dimethylaniline,
2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, 1-naphthylamine,
2-naphthylamine, diphenylamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, pyrrolidone, piperidine, imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, thiabendazole, pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 1-methyl-4-phenylpyridine, 2
-(1-ethylpropyl) pyridine, nicotinic acid amide, dibenzoylthiamine, riboflamine tetrabutyrate, 4,
4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl ) -2- (4-Aminophenyl) propane, 2
-(4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2-
(4-hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl)-
1-methylethyl] benzene, dimethyl succinate-1-
(2-hydroxyethyl) -4-hydroxy-2,2
6,6-Tetramethylpiperidine polycondensate, 2- (3,
5-di-t-butyl-4-hydroxybenzyl) -2-
Examples thereof include bis (1,2,2,6,6-pentamethyl-4-piperidiyl) n-butylmalonate.
These acid diffusion control agents can be used alone or in admixture of two or more. The compounding amount of the acid diffusion control agent is
It is usually 10 parts by weight or less, preferably 5 parts by weight or less, per 100 parts by weight of the acid-dissociable group-containing resin or the alkali-soluble resin. In this case, if the amount of the acid diffusion controller is more than 10 parts by weight, the sensitivity of the resist and the developability of the exposed area tend to decrease. 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),
Examples include each series such as 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). These surfactants may be used alone or in admixture of two or more. The compounding amount of the surfactant is 100 parts by weight of all the resin components in the resin composition, as an active ingredient of the surfactant.
Usually, it is 2 parts by weight or less. The sensitizer absorbs the energy of radiation and transfers the energy to the N, N′-bis (sulfonyloxy) -bis (dicarboximide) compound that is an acid forming agent, thereby generating an acid. It has the effect of increasing the amount, and has the effect of improving the apparent sensitivity of the radiation-sensitive resin composition. The sensitizer used is not particularly limited as long as it exhibits the above-mentioned action and effect, but when a preferable example thereof is given,
Examples include ketones, benzenes, acetophenones, benzophenones, naphthalenes, biacetyl, eosin, rose bengal, pyrenes, anthracenes, and phenothiazines. These sensitizers can be used alone or in admixture of two or more. The compounding amount of the sensitizer is
Usually 5 per 100 parts by weight of all resin components in the resin composition.
It is 0 part by weight or less, 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 radiation-sensitive resin composition of the first invention and the negative radiation-sensitive resin composition of the second 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 Resist from the positive-type radiation-sensitive resin composition of the first invention and the negative-type radiation-sensitive resin composition of the second invention (hereinafter, these are collectively referred to simply as “resin composition”). When forming a pattern, the composition solution prepared as described above 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. A resist film is formed by coating, and the resist film is exposed through a predetermined mask pattern. Radiation that can be used for exposure is the emission line spectrum of a mercury lamp (wavelength 254n
m), KrF excimer laser (wavelength 248 nm), ArF
Far-ultraviolet rays such as an excimer laser (wavelength 193 nm) are preferable, but charged particles such as X-rays such as synchrotron radiation and electron rays may be used depending on the type of N, N′-bis (sulfonyloxy) -bis (dicarboximide) compound. Other radiation, such as rays, can also be used. In addition, the exposure conditions such as the exposure amount are appropriately selected according to the compounding composition of the resin composition, the type 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 condition is usually 30 to 200 ° C., preferably 50 to 150 ° C., though it varies depending on the compounding composition of the resin composition, the kind 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; an alkaline compound such as 1,5-diazabicyclo- [4,3,0] -5-nonene is usually used in a concentration of 1 to 10% by weight, preferably 2 to 5% by weight. An alkaline aqueous solution dissolved in 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. When a developing solution composed of an alkaline aqueous solution is used, it is generally washed with water after development.

[0060]

EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited to these examples. 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 consisting of the N, N'-bis (sulfonyloxy) -bis (dicarboximide) compound and other components shown in Table 1 was visually observed to confirm that N, N'-bis (sulfonyl) When the (oxy) -bis (dicarboximide) compound was completely dissolved and there was no turbidity, the solubility was considered good. N shown in coatability Table 1, N'-bis (sulfonyloxy) - bis (dicarboximide) compounds and other each composition solution consisting of components, was spin-coated on a silicon wafer was formed by baking the resist The coating film was visually observed, and when coating unevenness, cloudiness and foreign matter were not observed and the surface was smooth, the coating property was considered good. Pattern shape A resist pattern formed on a silicon wafer using each composition solution consisting of an N, N′-bis (sulfonyloxy) -bis (dicarboximide) compound and other components shown in Table 1 was scanned by an electron scanning method. It was observed with a microscope and evaluated based on the cross-sectional shapes (a) and (b) shown in FIG. (I)
In the case of (2), the pattern shape is good, and in the case of (B),
The pattern shape was determined to be defective.

N, N′-bis (sulfonyloxy) -bi
Synthesis of su (dicarboximide) compound Synthesis example 1 33 g of pyromellitic dianhydride was added to tetrahydrofuran 3
It was dissolved in a mixed solvent of 0 ml and 30 ml of water, mixed with an aqueous solution of 20.5 g of sodium carbonate and 26.3 g of hydroxylamine hydrochloride, refluxed for 1 hour, and left overnight. Then, the precipitated crystals were filtered and dried to obtain a bis (hydroxyimide) compound. 10 g of this bis (hydroxyimide) compound and 4 g of pyridine were dissolved in 200 ml of dichloromethane,
After cooling to 1, trifluoromethanesulfonic anhydride 1
3.5 g was added dropwise over 0.5 hour. Then, the mixture was allowed to stand for 8 hours, washed three times with 400 ml of water each time, and then the solvent was distilled off. Then recrystallize with acetone,

[0062]

[Chemical 40]

11.5 g of the compound represented by This compound is referred to as an acid former a. Synthesis Example 2 A bis (hydroxyimide) compound was obtained in the same manner as in Synthesis Example 1 except that 63 g of ethylene glycol-bis (trimellitic anhydride) ester was used instead of 33 g of pyromellitic anhydride. 13.2 g of this bis (hydroxyimide) compound and 18 g of camphorsulfonyl chloride were dissolved in 400 ml of dichloromethane and cooled to 0 ° C., then 8 g of triethylamine was added.
It was added dropwise over 0.5 hour. Then, the mixture was allowed to stand for 6 hours, washed three times with 400 ml of water each time, and then the solvent was distilled off. Then recrystallize with hexane / acetone mixed solvent,

[0064]

Embedded image

19.5 g of the compound represented by This compound is referred to as an acid former b. Synthesis Example 3 Instead of 33 g of pyromellitic anhydride, 2-ethyl-
A bis (hydroxyimide) compound was obtained in the same manner as in Synthesis Example 1 except that 42 g of 1-methylcyclohexene-5,6,1 ′, 2′-tetracarboxylic acid anhydride was used.
7.95 g of this bis (hydroxyimide) compound and 4.9 g of butanesulfonyl chloride were mixed with dichloromethane 2
After dissolving in 00 ml and cooling to 0 ° C., 3.52 g of triethylamine was added dropwise over 0.5 hour. Then, the mixture was allowed to stand for 6 hours, washed three times with 400 ml of water each time, and then the solvent was distilled off. Then recrystallize with hexane,

[0066]

Embedded image

9 g of the compound represented by This compound is referred to as an acid former c. Synthesis Example 4 Instead of 33 g of pyromellitic anhydride, 1-ethyl-
(1,2,3,4-tetrahydronaphthalene) -3,
A bis (hydroxyimide) compound was obtained in the same manner as in Synthesis Example 1 except that 46 g of 4,1 ′, 2′-tetracarboxylic acid anhydride was used. 15 g of this bis (hydroxyimide) compound and 9.5 g of p-toluenesulfonyl chloride
And are dissolved in 100 ml of dichloromethane and 0
After cooling to 0 ° C, 5.6 g of triethylamine was added to 0.
It dripped over 5 hours. Then leave for 6 hours, 10 times each
After washing with 0 ml of water three times, the solvent was distilled off. Then recrystallize with hexane,

[0068]

[Chemical 43]

11.2 g of the compound represented by This compound is referred to as an acid forming agent d. Synthesis Example 5 Instead of 33 g of pyromellitic anhydride, 2,3,5-
Tricarboxycyclopentyl-1-acetic acid dianhydride 46
A bis (hydroxyimide) compound was obtained in the same manner as in Synthesis Example 1 except that g was used. 10 g of this bis (hydroxyimide) compound and 5 g of ethanesulfonyl chloride were dissolved in 100 ml of dichloromethane, and the mixture was dissolved at 0 ° C.
After cooling to 3.7 g, triethylamine 3.7 g was added to 0.5
It dripped over time. Then leave for 6 hours, 100 each time
After washing 3 times with milliliters of water, the solvent was distilled off. Then recrystallize with hexane,

[0070]

[Chemical 44]

8.1 g of the compound represented by This compound is referred to as an acid former e. Synthesis of Acid-Dissociable Group-Containing Resin Synthesis Example 6 24 g of poly (hydroxystyrene) was dissolved in 96 ml of acetone, and then t-butyl bromoacetate was added.
g and potassium carbonate 7.6 g were added, and the mixture was reacted under reflux with stirring for 8 hours. Then, 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. The residue was redissolved in acetone and then dropped into water to remove the resin. Allowed to settle. The resin was dried overnight in a vacuum oven at 50 ° C. The obtained resin has Mw of 12000, and NMR
As a result of the measurement, it was found that 23% of the hydrogen atoms of the phenolic hydroxyl group had a structure in which t-butoxycarbonylmethyl group was substituted. This resin is called resin A. Synthesis Example 7 After dissolving 300 g of poly (hydroxystyrene) in 1200 ml of tetrahydrofuran, 650 g of triethylamine was added, and 200 g of di-t-butyl dicarbonate was added at 0 ° C. with stirring and reacted for 6 hours. Then, the reaction solution was dropped into water to precipitate a resin. This resin was dried overnight in a vacuum dryer at 50 ° C. to obtain an acid-labile group-containing resin. The obtained resin has Mw
Was 7,000, and as a result of NMR measurement, it had a structure in which 25% of the hydrogen atoms of the phenolic hydroxyl group were substituted with t-butoxycarbonyl groups. This resin is called resin B.

Synthesis of Alkali-Soluble Resin Synthesis Example 8 20% by weight of p-vinylphenol, 65% by weight of p-ethylphenol and 15% by weight of other components contained as impurities (breakdown: 10% by weight of water, 4% by weight of p-cresol) %, 1% by weight of phenol) 120 g of a mixture having the composition
Was mixed with 17 g of t-butyl acrylate and 50 g of propylene glycol monomethyl ether to give a uniform solution. After bubbling this solution for 30 minutes with nitrogen gas, 2,2'-azobis (4-methoxy-2,4-
Dimethyl valeronitrile) (1.9 g) was added, and while continuing the bubbling with nitrogen gas, the reaction liquid temperature was maintained at 40 ° C. for copolymerization for 7 hours. After completion of the polymerization, the reaction solution was mixed with a large amount of hexane to coagulate the produced copolymer. Then, the copolymer is redissolved in acetone, and then the procedure of coagulating with hexane again is repeated several times to completely remove the unreacted monomer, and dried at 50 ° C. under reduced pressure.
A white copolymer (yield 55%) was obtained. The obtained copolymer had a Mw of 31000, and as a result of NMR measurement, p
-The copolymerization molar ratio of vinylphenol and t-butyl acrylate was 60:40. This copolymer is referred to as resin C. Synthesis Example 9 67 g of p-isopropenylphenol and t-acrylic acid
After dissolving 64 g of butyl in 131 g of propylene glycol monomethyl ether, 8 g of azoisobutyronitrile was added, and polymerization was carried out at 60 ° C. for 10 hours in a nitrogen atmosphere. After completion of the polymerization, the reaction solution was dropped into 5 liters of hexane to coagulate the produced copolymer. After separating this copolymer, it was washed 5 times with 1 liter of hexane each time. Then, the copolymer was redissolved in acetone and then dropped into a large amount of water to be re-solidified to obtain 85 g of a white copolymer. The obtained copolymer had Mw of 12400 and N
As a result of the MR measurement, the copolymerization molar ratio of p-isopropenylphenol and t-butyl acrylate was 49.5: 50.
It was 5. This copolymer is referred to as resin D. Synthesis Example 10 A white copolymer 103 g was obtained in the same manner as in Synthesis Example 9, except that 84 g of p-vinylphenol and 74.4 g of di (t-butyl) fumarate were dissolved in 150 ml of dioxane. The copolymer obtained has an Mw of 2600.
0, and as a result of NMR measurement, the molar ratio of copolymerization of p-vinylphenol and di (t-butyl fumarate) was 69: 3.
It was 1. This copolymer is referred to as resin E.

Synthesis of Dissolution Control Agent Synthesis Example 11 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 generated precipitate was filtered, and the obtained solid was dried overnight in a vacuum dryer at 50 ° C. to obtain a dissolution control agent represented by the above formula (12).

Examples 1 to 7 and Comparative Examples 1 to 5 Solubility of each acid forming agent in a solution prepared by mixing the acid forming agent shown in Table 1 (addition amount is parts by weight) with the other components shown in Table 1. After evaluation, 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 was spin-coated on a silicon wafer and then baked at 100 ° C. for 2 minutes to form a resist film having a film thickness of about 1 μm. This resist film was exposed at a dose of 5 to 40 mJ / cm ² through a mask pattern using a KrF excimer laser irradiation device (MBK-400TL-N) manufactured by Admon Science. Then, after post-exposure baking at 100 ° C. for 2 minutes,
Development was performed for 1 minute at 25 ° C. using a 2.38 wt% tetramethylammonium hydroxide aqueous solution. After development, it was washed with water for 30 seconds to obtain a resist pattern. Table 1 shows the evaluation results of each example and each comparative example.

[0075]

[Table 1]

In the table, the components other than the acid formers a to e [N, N'-bis (sulfonyloxy) -bis (dicarboximide) compound] are as follows. Acid forming agent f: 1,2,3-tris (methylsulfonyloxy) benzene g: diphenyliodonium pyrenesulfonate h: m-nitrobenzylbenzenesulfonate i: triphenylsulfonium trifluoromethanesulfonate Other components : Resin A 100 parts by weight, diamino Diphenylmethane 1
Parts by weight, 460 parts by weight of methyl 3-methoxypurpionate. : 100 parts by weight of resin B, 1 diaminodiphenylmethane
Parts by weight, 500 parts of ethyl lactate. : Resin C 100 parts by weight, methyl 3-methoxypurpionate 450 parts by weight. : Resin D 100 parts by weight, Nicotinic acid amide 1 part by weight,
Propylene glycol monomethyl ether acetate 4
60 parts by weight. : 100 parts by weight of resin E, 315 parts by weight of ethyl lactate, 3
135 parts by weight of ethyl ethoxypropionate. : Poly (hydroxystyrene) (Mw = 8000) 1
00 parts by weight, trihexylamine 0.5 parts by weight, hexa (methoxymethyl) melamine 20 parts by weight, ethyl lactate 4
60 copies. : Poly (hydroxystyrene) (Mw = 12000)
100 parts by weight, nicotinamide 0.5 part by weight, tetra (methoxymethylol) urea 20 parts by weight, ethyl lactate 4
80 copies.

[0077]

EFFECT OF THE INVENTION N represented by the formula (1) or (2),
The positive-type radiation-sensitive resin composition and the negative-type radiation-sensitive resin composition of the present invention containing the N′-bis (sulfonyloxy) -bis (dicarboximide) compound have solubility in various solvents and various resins. Is excellent in compatibility, and has excellent characteristics balance such as resolution, sensitivity, stability of pattern shape against post-exposure baking conditions, and far-ultraviolet rays such as excimer laser, X-ray such as synchrotron radiation, and charging of electron beam. It can be applied to any of various types of radiation such as particle beams. Therefore, the positive-type radiation-sensitive resin composition and the negative-type radiation-sensitive resin composition of the present invention are extremely useful as a chemically amplified resist for semiconductor device production, which is 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 front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical indication location H01L 21/027 (72) Inventor Kimoto Yuuji 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd.

Claims (2)

[Claims] 1. (A) At least one N, N'-bis (sulfonyloxy) -bis (dicarboximide) compound represented by the following formula (1) or (2), and (B)
(A) an alkali-insoluble or sparingly alkali-soluble resin protected by an acid-dissociable group, which becomes alkali-soluble when the acid-dissociable group dissociates, or (b) an alkali-soluble resin, and the alkali It has the property of controlling the alkali solubility of the 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, or to dissolve the alkali soluble resin in the alkali. A positive-type radiation-sensitive resin composition, which comprises a compound exhibiting a property promoting action. 2. (A) At least one N, N′-bis (sulfonyloxy) -bis (dicarboximide) compound represented by the following formula (1) or (2), and (C) an alkali-soluble resin. And (D) a compound capable of cross-linking the alkali-soluble resin in the presence of an acid, a negative-type radiation-sensitive resin composition. Embedded image Embedded image (In the formulas (1) and (2), R ¹ represents a tetravalent hydrocarbon residue, R ² and R ³ may be the same or different from each other, and are aliphatic, alicyclic or aromatic 1 Represents a valent organic group, X represents -CO- or -COO-Y-OCO-, and Y represents an alkylene group or an N-sulfonyloxydicarboximide group-containing alkylene group.]