JP3448790B2 - Radiation-sensitive resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a positive or negative resist which contains an organic compound having a thiosulfonate structure and is particularly suitable as a resist useful for fine processing using various radiations such as far ultraviolet rays such as excimer laser. 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, even in the resist used for fine processing, 0.5μ
It is necessary to form a pattern with a size of m or less with high precision, but with the conventional method using visible light (wavelength of 800 to 400 nm) or near ultraviolet light (wavelength of 400 to 300 nm), a fine pattern of 0.5 μm or less can be formed with high accuracy. Is extremely difficult to form. Therefore, shorter wavelength (wavelength 3
Utilization of radiation of (100 nm or less) has been earnestly studied.
Examples of such short-wavelength radiation include bright line spectra of mercury lamps (wavelength 254 nm), deep ultraviolet rays represented by KrF excimer laser (wavelength 248 nm), X-rays such as synchrotron radiation, and charged particle beams such as electron beams. Among them, lithography using an excimer laser is particularly attracting attention because of its high output and high efficiency characteristics. Therefore, it is necessary for a resist used for lithography to be able to form a fine pattern of 0.5 μm or less with high sensitivity, high resolution and good reproducibility by using an excimer laser. "Chemically amplified resist" has been proposed as a resist suitable for deep ultraviolet rays such as excimer laser. The chemically amplified resist uses a radiation-sensitive acid generator that produces an acid by irradiation with radiation (hereinafter referred to as “exposure”), and improves the sensitivity of the resist by the catalytic action of the acid. JP-A-59-45439 discloses a combination of a resin protected with a t-butyl group or a t-butoxycarbonyl group and a radiation-sensitive acid generator, and JP-A-60-52845 discloses a combination thereof. A combination of a resin protected with a silyl group and a radiation-sensitive acid generator,
Each is disclosed. In addition, many reports have been made on chemically amplified resists such as a resist containing a resin containing an acetal group and a radiation-sensitive acid generator (JP-A-2-25850). In the process of using these chemically amplified resists, post-exposure bake (hereinafter referred to as “PEB”) is generally performed in order to make the catalytic action of the acid generated by exposure more effective. However, due to the length of time from exposure to PEB, an abnormality (Post Exposure Time Delay; hereinafter referred to as “PED”) such as variation of the line width of the obtained pattern or distortion of the pattern shape occurs. However, there was a problem in the process stability of the resist against PED.

[0003]

SUMMARY OF THE INVENTION The present invention is applicable to exposure to P
Without PED depending on the time to EB, P
It is an object of the present invention to provide a positive or negative radiation-sensitive resin composition which is excellent in process stability against ED and is also excellent in sensitivity, resolution, pattern shape, residual film rate and the like.

[0004]

According to the present invention, the above-mentioned problems are, firstly, (A) a thiosulfonate compound represented by the following formula (1) or formula (2):

[0005]

[Chemical 1]

[0006]

[Chemical 2]

[In the formulas (1) and (2), X and Y may be the same or different from each other, and may be substituted, a monovalent acyclic hydrocarbon group, a cycloalkyl group,
1 having an aryl group, an aralkyl group or a hetero atom
Represents another valent organic group, and in the formula (2), Z is-(C
H ₂ ) n- (where n is an integer of 0 to 6),-(CH ₂ ) mC (= O)-
(CH ₂ ) m- (where m is an integer from 0 to ₂ ) and-(CH ₂ ) m-
It represents at least one divalent group selected from the group of C (= N ₂ )-(CH ₂ ) m- (where m is an integer of 0 to 2). And (B) (a) an alkali-insoluble or sparingly-soluble resin protected with an acid-dissociable group, which becomes alkali-soluble when the acid-dissociable group is dissociated (hereinafter, referred to as “acid dissociation”). Or (b) an alkali-soluble resin and an alkali solubility control agent (hereinafter, referred to as “first invention”), Achieved by

According to the present invention, the above-mentioned problems are, secondly,
(A) a thiosulfonate compound represented by the above 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 negative-type radiation-sensitive resin composition (hereinafter, referred to as "second invention") containing a "crosslinking agent").

The present invention will be described in detail below. This will clarify the purpose, structure and effect of the present invention. Thiosulfonate Compound The radiation-sensitive resin composition of the first invention and the second invention is characterized by containing the specific thiosulfonate compound represented by the formula (1) or (2). . The thiosulfonate compound undergoes a chemical change upon exposure to light,
It has an action of generating an acid. Hereinafter, the thiosulfonate compound will be described in detail. In the formula (1), the monovalent acyclic hydrocarbon group for X and Y is, for example, an alkyl group having 1 to 6 carbon atoms or 2 carbon atoms.
To alkenyl groups and C4 to C6 alkadienyl groups and the like, and these acyclic hydrocarbon groups may have one or more substituents at appropriate positions. Among the monovalent acyclic hydrocarbon groups, examples of the alkyl group having 1 to 6 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t -Butyl group, n-pentyl group, n-hexyl group and the like can be mentioned. Examples of the alkenyl group having 2 to 6 carbon atoms include CH ₂ = CH-, CH ₂ = CHCH _2- , CH ₂ = C ( CH ₃ )-, CH ₂ = CHCH ₂ CH _2-
, CH ₂ = C (CH ₃ ) CH _2- , CH ₃ CH = CHCH _2- , CH ₂ = CH ₂ CH ₂ CH ₂ CH _2-
, CH ₂ ═C (CH ₃ ) CH ₂ CH ₂ —, CH ₂ ═CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ — and the like, and examples of the alkadienyl group having 4 to 6 carbon atoms include CH ₂ = CHCH = CH-, CH ₂ = CHCH = CHCH _2- , CH ₂ = C (CH ₃ ) CH = CH-,
CH ₂ = CHCH ₂ CH = CH-, CH ₂ = CHCH = CHCH ₂ CH _2-, and the like can be mentioned. Examples of the substituent for the monovalent acyclic hydrocarbon include, for example, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), amino group,
Examples thereof include a dialkylamino group, an acetamino group, an acyl group, an acyloxo group, an alkylthio group, an arylthio group, a nitro group, a cyano group and an arylsulfonyl group. Examples of the monovalent acyclic hydrocarbon group having a substituent include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a 1-fluoroethyl group, and a 1-fluoropropyl group. Group, 1-fluorobutyl group, 1-chloroethyl group, 1-chloropropyl group, 1-chlorobutyl group, 1
-Aminoethyl group, 2-aminoethyl group, 1-dimethylaminoethyl group, 2-dimethylaminoethyl group, 1-acetaminoethyl group, 2-acetaminoethyl group, acetylmethyl group, 1-phenylthioethyl group, Examples thereof include a 2-phenylthioethyl group, a 1-nitroethyl group, a 2-nitroethyl group, a 1-cyanoethyl group, a 2-cyanoethyl group, a phenylsulfonylmethyl group and a di (phenylsulfonyl) methyl group. Among the monovalent acyclic hydrocarbon group and the substituted monovalent acyclic hydrocarbon group, methyl group, ethyl group, trifluoromethyl group, trichloromethyl group, 2-dimethylaminoethyl group, acetylmethyl A group, a di (phenylsulfonyl) methyl group and the like are preferable.

Examples of the cycloalkyl group of X and Y include cycloalkyl groups having 3 to 8 carbon atoms such as cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group. The group can also have one or more substituents at appropriate positions. Examples of the substituent for the cycloalkyl group include those similar to the substituent for the monovalent acyclic hydrocarbon group. Examples of the cycloalkyl group having a substituent include a 4-methylcyclohexyl group, 4-fluorocyclohexyl group, 2-chlorocyclohexyl group, 4-chlorocyclohexyl group, 4-
Examples thereof include bromocyclohexyl group and 4-nitrocyclohexyl group. Among the cycloalkyl groups, a cyclohexyl group, a 2-chlorocyclohexyl group,
A 4-chlorocyclohexyl group and the like are preferable. Moreover, examples of the aryl group of X and Y include a phenyl group, a biphenylyl group, a naphthyl group, an anthryl group, and a phenanthryl group. These aryl groups have one or more substituents at appropriate positions. You can also Examples of the substituent for the aryl group include a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, n-pentyl group,
C1-C6 alkyl group such as n-hexyl group; Halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; C1-C6 such as methoxy group, ethoxy group, propoxy group, butoxy group An alkoxyl group of: an acetyl group, a propionyl group, a butyryl group, a hexanoyl group, an octanoyl group, a benzoyl group, or another acyl group having 2 to 11 carbon atoms;
Acyloxy group having 2 to 11 carbon atoms such as acetyloxy group, propionyloxy group, butyryloxy group, hexanoyloxy group, octanoyloxy group, benzoyloxy group; benzyl group, diphenylmethyl group, 2-phenylethyl group, 3- Examples include aralkyl groups having 7 to 20 carbon atoms such as phenylpropyl group and 2-phenylpropyl group; nitro group; cyano group; hydroxyl group; vinyl group; acetamino group; butoxycarbonyloxy group. Examples of the aryl group having a substituent include a 4-methylphenyl group, a 4-t-butylphenyl group, 2,4,6
-Trimethylphenyl group, 2,4,6-triisopropylphenyl group, 4-fluorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, 4-methoxyphenyl group, 4-ethoxyphenyl group, 3,4-dimethoxy Phenyl group, 2-benzoylphenyl group, 4-acetyloxyphenyl group, 4-benzylphenyl group, 4-hydroxyphenyl group, 3,5-dimethyl-4-hydroxyphenyl group, 2-nitrophenyl group, 4-nitrophenyl Group, 2,4-dinitrophenyl group, 4-acetaminophenyl group and the like. Among the aryl groups, phenyl group, 4-methylphenyl group, 2,4,6-
Triisopropylphenyl group, 4-t-butylphenyl group, 4-fluorophenyl group, 4-chlorophenyl group, 4
-Bromophenyl group, 4-methoxyphenyl group, 2-nitrophenyl group, 4-nitrophenyl group and the like are preferable.

Examples of the aralkyl group of X and Y include benzyl group, diphenylmethyl group and 3,5-
Examples thereof include aralkyl groups having 7 to 20 carbon atoms such as diphenylbenzyl group, 2-phenylethyl group, 3-phenylpropyl group, naphthylmethyl group, and anthranylmethyl group. These aralkyl groups may be one kind at appropriate positions. It is also possible to have the above substituents. Examples of the substituent for the aralkyl group include the same substituents as those described for the aryl group. Examples of the aralkyl group having a substituent include 4-methylbenzyl group, 4-butylbenzyl group, 4-fluorobenzyl group, 4-methoxybenzyl group, 4-acetyloxybenzyl group, 2-nitrobenzyl group, 4- Examples thereof include a nitrobenzyl group, a 2,4-dinitrobenzyl group, a 4-cyanobenzyl group, a 4-hydroxybenzyl group and a 4-vinylbenzyl group. Among the aralkyl groups, a benzyl group, anthranylmethyl group, 4-fluorobenzyl group, 4-methoxybenzyl group, 2-nitrobenzyl group,
A 4-nitrobenzyl group and the like are preferable.

1 having a heteroatom of X and Y
Examples of other valent organic groups include a cyano group, a dimethylaminocarbonyl group, a 4-bromobenzoyl group, and a pyridinyl group.

Next, in the formula (2), examples of X and Y include the same groups as those mentioned for X and Y in the formula (1). Z is-(CH ₂ ) n
- (wherein, n represents 0-6 _{integer), - (CH 2) mC} (= O) - (C
H ₂ ) m- (where m is an integer from 0 to ₂ ) and-(CH ₂ ) mC
(= N ₂ )-(CH ₂ ) m- (where m is an integer of 0 to 2) is at least one divalent group, specifically,-(CH ₂ ). ₂ -,-(CH ₂ ) ₃ -,-(CH ₂ ) ₄ -,-(CH ₂ ) _6- , -C (= O)
-, -CH ₂ C (= O) CH ₂ -,-(CH ₂ ) ₂ C (= O) (CH ₂ ) _2- , -C (= N ₂ )
_{-, - CH 2 C (=} N 2) CH 2 -, - (CH 2) 2 C (= N 2) (CH 2) 2 - and the like. Of the above divalent groups,-(CH ₂ ) ₂ -,-(CH ₂ )
_{3 -, - (CH 2)} 2 C (= O) (CH 2) 2 -, - (CH 2) 2 C (= N 2) (CH 2) 2 - and the like are preferable.

Combination of X, Y and Z in the thiosulfonate compound represented by formula (1) or formula (2)
The example of [X: Y] or [X: Z: Y] will be described in more detail below. Here, the number before each substituent represents the position of the substituent. [X: corresponding to equation (1)
Y] includes [CH ₃ : CH ₃ ], [CH ₃ : CH ₃ CH ₂ ], [CH ₃ CH ₂ : CH
₃ ], [CH ₃ CH ₂ : CH ₃ CH ₂ ], [CH ₃ CH ₂ CH ₂ : CH ₃ CH ₂ CH ₂
], [CH ₃ (CH ₂ ) ₂ CH ₂ : CH ₃ (CH ₂ ) ₂ CH ₂ ], [CH ₃ (CH ₂ ) ₃
CH ₂ : CH ₃ (CH ₂ ) ₃ CH ₂ ], [CH ₃ : ClCH ₂ ], [CH ₃ CH
₂ : CH ₃ CH (Cl)], [CH ₃ CH ₂ CH ₂ : CH ₃ CH ₂ CH (Cl)], [C
_{F 3: CF 3], [} C 6 H 5: CH 3], [C 6 H 5: CH 3 CH 2],
_{[C 6 H 5: CF 3} ], [C 6 H 5: CH 3 C (= O) CH 2], [C 6 H 5:
_{(CH 3) 2 NCH 2 CH} 2], [4-CH 3 -C 6 H 4: CH 3], [4-CH 3 -C 6 H
₄ : CH ₃ CH ₂ ], [4-CH ₃ -C ₆ H ₄ : CF ₃ ], [4-CH ₃ -C ₆ H
₄ : CH ₃ C (= O) CH ₂ ], [4-CH ₃ -C ₆ H ₄ : (CH ₃ ) ₂ NCH ₂ CH
₂ ], [4-NO ₂ -C ₆ H ₄ : CH ₃ CH ₂ ], [4-FC ₆ H ₄ : CH ₃ CH ₂
CH ₂ ], [4-CH ₃ -C ₆ H ₄ : BrC ₆ H ₄ C (= O) CH ₂ ], [C ₆ H ₅ :
_{(C 6 H 5 -SO 2)} 2 CH],

[Cyclohexyl: cyclohexyl]
, [C ₆ H _{5: cyclohexyl], [C 6 H 5:} 2- chloro _{cyclohexyl], [4-CH 3 -C} 6 H 4: _{cyclohexyl], [4-CH 3 -C} 6 H 4: 2- chloro Cyclohexyl]
,

[C ₆ H ₅ : C ₆ H ₅ ], [C ₆ H ₅ : 4-CH ₃ -C ₆ H
₄ ], [C ₆ H ₅ : 4-Br-C ₆ H ₄ ], [C ₆ H ₅ : 2-NO ₂ -C ₆ H ₄ ]
, [C ₆ H ₅ : 4-NO ₂ -C ₆ H ₄ ], [C ₆ H ₅ : (NO ₂ ) ₂ C ₆ H ₃ ]
, [C ₆ H ₅ : 4-CH ₃ OC ₆ H ₄ ], [4-CH ₃ -C ₆ H ₄ : C ₆ H
₅ ], [4-CH ₃ -C ₆ H ₄ : 4-CH ₃ -C ₆ H ₄ ], [4-CH ₃ -C ₆ H ₄ :
2-FC ₆ H ₄ ], [4-CH ₃ -C ₆ H ₄ : 4-FC ₆ H ₄ ], [4-CH ₃ -C
₆ H ₄ : 4-Br-C ₆ H ₄ ], [4-FC ₆ H ₄ : C ₆ H ₅ ], [4-CH ₃ O-
C ₆ H ₄ : 4-CH ₃ OC ₆ H ₄ ], [4-NO ₂ -C ₆ H ₄ : 4-NO ₂ -C ₆ H ₄ ]
, [4-FC ₆ H ₄ : 4-FC ₆ H ₄ ], [4-Cl-C ₆ H ₄ : 4-Cl-C _{6
H 4], [(CH 3} ) 3 C 6 H 2: (CH 3) 3 C 6 H 2], [(iso-C 3 H 7) 3
_{C 6 H 2: (iso-} C 3 H 7) 3 C 6 H 2], [(NO 2) 2 C 6 H 3: (NO 2) 2 C 6 H
₃ ],

[C ₆ H ₅ : C ₆ H ₅ CH ₂ ], [4-CH ₃ -C ₆ H ₄ : C ₆ H
₅ CH ₂ ], [C ₆ H ₅ : C ₆ H ₅ CH ₂ CH ₂ ], [C ₆ H ₅ : NO ₂ C ₆ H ₄ CH
₂ ], [4-CH ₃ -C ₆ H ₄ : C ₆ H ₅ CH ₂ CH ₂ ], [4-CH ₃ -C ₆ H ₄ :
4-FC ₆ H ₄ CH ₂ ], [4-CH ₃ -C ₆ H ₄ : NO ₂ C ₆ H ₄ CH ₂ ], [C ₆
H ₅ : CN], [4-CH ₃ -C ₆ H ₄ : CN], [4-CH ₃ -C ₆ H ₄ :
(CH ₃ ) ₂ NC (= O)] and the like.

[X: Z: Y] corresponding to the formula (2) includes [CH ₃ : CH ₂ CH ₂ : CH ₃ ], [CH ₃ CH ₂ : CH ₂ CH ₂ : CH ₃ CH ₂
], [CF ₃ : CH ₂ CH ₂ : CF ₃ ], [Cyclohexyl: CH ₂
CH ₂ : cyclohexyl], [2-chlorocyclohexyl
: CH ₂ CH _2: 2- chloro cyclohexyl], [C ₆ H _5:
CH ₂ CH ₂ : C ₆ H ₅ ], [4-CH ₃ -C ₆ H ₄ : CH ₂ CH ₂ : 4-CH ₃ -C ₆
H ₄ ], [4-FC ₆ H ₄ : CH ₂ CH ₂ : 4-FC ₆ H ₄ ], [4-NO ₂ -C ₆
H ₄ : CH ₂ CH ₂ : 4-NO ₂ -C ₆ H ₄ ], [C ₆ H ₅ CH ₂ : CH ₂ CH ₂ : C
₆ H ₅ CH ₂ ], [CH ₃ : CH ₂ CH ₂ CH ₂ : CH ₃ ], [CF ₃ : CH ₂ C
H ₂ CH ₂ : CF ₃ ], [Cyclohexyl: CH ₂ CH ₂ CH ₂ : Cyclohexyl], [2-chlorocyclohexyl: CH ₂ CH
₂ CH ₂ : 2-chlorocyclohexyl], [C ₆ H ₅ : CH ₂ CH
₂ CH ₂ : C ₆ H ₅ ], [4-CH ₃ -C ₆ H ₄ : CH ₂ CH ₂ CH ₂ : 4-CH ₃ -C
₆ H ₄ ], [4-FC ₆ H ₄ : CH ₂ CH ₂ CH ₂ : 4-FC ₆ H ₄ ], [4-
NO ₂ -C ₆ H ₄ : CH ₂ CH ₂ CH ₂ : 4-NO ₂ -C ₆ H ₄ ], [C ₆ H ₅ CH ₂ :
CH ₂ CH ₂ CH ₂ : C ₆ H ₅ CH ₂ ],

[CH ₃ : CH ₂ CH ₂ C (= O) CH ₂ CH ₂ : CH ₃ ], [
CF ₃ : CH ₂ CH ₂ C (= O) CH ₂ CH ₂ : CF ₃ ], [2-chlorocyclohexyl: CH ₂ CH ₂ C (= O) CH ₂ CH ₂ : 2-chlorocyclohexyl], [cyclohexyl: CH ₂ CH ₂ C (= O) CH ₂ CH ₂ :
Cyclohexyl], [C ₆ H ₅ : CH ₂ CH ₂ C (= O) CH ₂ CH ₂ : C
₆ H ₅ ], [4-FC ₆ H ₄ : CH ₂ CH ₂ C (= O) CH ₂ CH ₂ : 4-FC ₆ H
₄ ], [4-NO ₂ -C ₆ H ₄ : CH ₂ CH ₂ C (= O) CH ₂ CH ₂ : 4-NO ₂ -C ₆ H
₄ ], [C ₆ H ₅ CH ₂ : CH ₂ CH ₂ C (= O) CH ₂ CH ₂ : C ₆ H ₅ CH ₂ ],
[CH ₃ : CH ₂ CH ₂ C (= N ₂ ) CH ₂ CH ₂ : CH ₃ ], [CH ₃ CH ₂ : CH ₂
CH ₂ C (= N ₂ ) CH ₂ CH ₂ : CH ₃ CH ₂ ], [CF ₃ : CH ₂ CH ₂ C (= N ₂ ) CH
₂ CH ₂ : CF ₃ ], [Cyclohexyl: CH ₂ CH ₂ C (= N ₂ ) CH ₂ CH
₂ : cyclohexyl], [2-chlorocyclohexyl:
CH ₂ CH ₂ C (= N ₂ ) CH ₂ CH ₂ : 2-chlorocyclohexyl],
[C ₆ H ₅ : CH ₂ CH ₂ C (= N ₂ ) CH ₂ CH ₂ : C ₆ H ₅ ], [4-FC ₆ H ₄ :
CH ₂ CH ₂ C (= N ₂ ) CH ₂ CH ₂ : 4-FC ₆ H ₄ ], [4-NO ₂ -C ₆ H ₄ : C
H ₂ CH ₂ C (= N ₂ ) CH ₂ CH ₂ : 4-NO ₂ -C ₆ H ₄ ], [C ₆ H ₅ CH ₂ : CH ₂ C
_{H 2 C (= N 2)} CH 2 CH 2: C 6 H 5 CH 2] , and the like.

Of these thiosulfonate compounds, preferred compounds are compounds represented by the following formulas (3) to (27).

[0021]

[Chemical 3]

[0022]

[Chemical 4]

[0023]

[Chemical 5]

[0024]

[Chemical 6]

[0025]

[Chemical 7]

[0026]

[Chemical 8]

[0027]

[Chemical 9]

[0028]

[Chemical 10]

[0029]

[Chemical 11]

[0030]

[Chemical 12]

[0031]

[Chemical 13]

[0032]

[Chemical 14]

[0033]

[Chemical 15]

[0034]

[Chemical 16]

[0035]

[Chemical 17]

[0036]

[Chemical 18]

[0037]

[Chemical 19]

[0038]

[Chemical 20]

[0039]

[Chemical 21]

[0040]

[Chemical formula 22]

[0041]

[Chemical formula 23]

[0042]

[Chemical formula 24]

[0043]

[Chemical 25]

[0044]

[Chemical formula 26]

[0045]

[Chemical 27]

Among the above-mentioned thiosulfonate compounds, particularly preferable compounds are formula (3), formula (8), formula (9),
Formula (10), Formula (11), Formula (12), Formula (16), Formula (17), Formula (18), Formula (20), Formula (21), Formula (22), Formula (23), etc. Is. In the first invention and the second invention, the thiosulfonate compounds may be used alone or in combination of two or more.

Acid-Dissociative Group-Containing Resin The acid-dissociating group-containing resin used in the first invention (component (B) (a)) means at least one acidic functional group such as phenolic hydroxyl group and carboxyl group. One or more kinds of resins capable of dissociating a hydrogen atom of an acidic functional group in a resin contained therein, for example, an alkali-soluble resin having repeating units represented by formulas (28) to (31) described below in the presence of an acid. It is an alkali-insoluble or sparingly alkali-soluble resin which is substituted with an acid-dissociable group and which is itself alkali-insoluble or sparingly soluble. 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, and a cyclic acid dissociable group. . Examples of the substituted methyl group include a methoxymethyl group, a methylthiomethyl group, an ethoxymethyl group, an ethylthiomethyl group,
Methoxyethoxymethyl group, benzyloxymethyl group,
Benzylthiomethyl group, phenacyl group, bromophenacyl group, methoxyphenacyl group, methylthiophenacyl group, α-methylphenacyl group, cyclopropylmethyl group, benzyl group, diphenylmethyl group, triphenylmethyl group, bromobenzyl group, nitro Benzyl group, methoxybenzyl group, methylthiobenzyl group, ethoxybenzyl group, ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n
-Propoxycarbonylmethyl group, isopropoxycarbonylmethyl group, n-butoxycarbonylmethyl group, t
-Butoxycarbonylmethyl group and the like can be mentioned. 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-isopropoxycarbonylethyl group, 1-n-
Examples thereof include butoxycarbonylethyl group and 1-t-butoxycarbonylethyl group. Examples of the 1-branched alkyl group include isopropyl group, s-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, methyldi-t- Butylsilyl 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, methyldi-t-butylgermyl group, Examples thereof include tri-t-butylgermyl group, phenyldimethylgermyl group, methyldiphenylgermyl group and 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 acetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, lauriloyl group, myristoyl group, palmitoyl group, stearoyl group, oxalyl group, malonyl group, 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, 1-methoxyethyl group, 1-ethoxyethyl group, trimethylsilyl group, t-butoxycarbonyl group, t-butoxycarbonylmethyl group, tetrahydropyranyl group, A tetrahydrofuranyl group, a tetrahydrothiopyranyl group, a tetrahydrothiofuranyl group and the like are preferable.

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 However, it cannot be unconditionally specified depending on the type of the acid-dissociable group and the alkali-soluble resin into which the group is introduced, but preferably 10 to 10
It is 0%, more preferably 15 to 100%. Also,
The polystyrene-equivalent weight 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,
It is 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 at least one monomer having an acid-dissociable group. (Co) polymerization, and (co) polycondensation of one or more polycondensation components having an acid dissociable group. As the acid dissociable group-containing resin in the first invention, a resin in which a part of hydrogen atoms of a hydroxyl group in poly (hydroxystyrene) is substituted with the acid dissociable group, hydroxystyrene and / or hydroxy-
A resin in which a part or all of the hydrogen atoms of the hydroxyl group and / or the hydrogen atoms of the hydroxycarbonyl group in the copolymer of α-methylstyrene and (meth) acrylic acid are substituted with the acid dissociable group is preferable. The acid-labile group-containing resin is
Further, it has a 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 effect of controlling the alkali solubility of the alkali-soluble resin, or It has an action of promoting alkali solubility and is included in the category of the alkali solubility 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 first invention (component (B) (b)) and the second invention (component (C)) is a functional group having an affinity with an alkali developer, such as phenol. It is a resin that is soluble in an alkaline developer and has at least one acidic functional group such as a neutral hydroxyl group and a carboxyl group. Examples of the alkali-soluble resin include addition polymerization resins having one or more repeating units represented by the following formulas (28) to (30),
Examples thereof include polycondensation resins having at least one repeating unit represented by the following formula (31).

[0050]

[Chemical 28]

[In the formula (28), 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) g-, where g is an integer from 1 to 4. } Is shown. ]

[0052]

[Chemical 29]

[In the formula (29), R ¹ represents a hydrogen atom or a methyl group. ]

[0054]

[Chemical 30]

[0055]

[Chemical 31]

[In the formula (31), 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 is an addition polymerization resin, it may be composed of only the repeating units represented by the above formulas (28) to (30), but as long as the produced resin is soluble in an alkali developing solution. May further have other repeating units. Examples of such other repeating units include styrene, α-methylstyrene, maleic anhydride,
(Meth) acrylonitrile, crotonnitrile, malein nitrile, fumaronitrile, mesacone nitrile, citracone nitrile, itacone nitrile, (meth) acrylamide, crotonamide, maleamide, fumaramide, mesaconamide, citracone amide, itacone amide, vinylaniline, vinyl pyridine, Examples thereof include units in which the polymerizable double bond portion of a monomer having a polymerizable double bond such as vinyl-ε-caprolactam, vinylpyrrolidone and vinylimidazole is cleaved. The addition polymerization resin may include, for example, one or more kinds of monomers corresponding to the repeating units represented by the formulas (28) to (30), optionally together with a monomer corresponding to the other repeating units, ( It can be produced by co-polymerization. These (co)
Polymerization is carried out by appropriately selecting a polymerization initiator or a polymerization catalyst such as a radical polymerization initiator, an anion polymerization catalyst, a coordinated anion polymerization catalyst, or a cationic polymerization catalyst according to the type of the monomer, the reaction medium, etc. It can be carried out by an appropriate polymerization method such as solution polymerization, precipitation polymerization, emulsion polymerization, suspension polymerization and bulk-suspension polymerization. Further, when the alkali-soluble resin is a polycondensation resin, it may be composed of only the repeating unit represented by the above formula (31), but as long as the produced resin is soluble in an alkali developing solution, other It is also possible to further have a repeating unit of. Such a polycondensation resin contains at least one phenol corresponding to the repeating unit represented by the formula (31) and at least one aldehyde.
It can be produced by (co) polycondensation in an aqueous medium or a mixed medium of water and a hydrophilic solvent in the presence of an acidic catalyst, optionally together with a polycondensation component capable of forming another repeating unit. 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-
Examples of the aldehyde include trimethylphenol, and examples of the aldehydes include formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, and phenylacetaldehyde. The content of the repeating units represented by the formulas (28) to (31) in the alkali-soluble resin cannot be unconditionally defined depending on the kind of the other repeating units contained, but is preferably 10 to 100.
Mol%, more preferably 20 to 100 mol%.
The Mw of the alkali-soluble resin varies depending on the desired properties of the radiation-sensitive resin composition, but it is preferably 1,000-.
150,000, more preferably 3,000 to 10
It is 10,000. The alkali-soluble resin has the formula (2
When it has a repeating unit containing a carbon-carbon unsaturated bond as represented by 8) or (31), 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 the carbon-carbon unsaturated bond contained in the repeating unit represented by the formula (28) or (31). 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. As the alkali-soluble resin in the first invention and the second invention, particularly, poly (hydroxystyrene), a copolymer of hydroxystyrene and hydroxy-α-methylstyrene, a copolymer of hydroxystyrene and styrene, etc. are main components. Resins that In the first invention and the second invention, the alkali-soluble resins may be used alone or in combination of two or more.

Alkali Solubility Control Agent Next, as the alkali solubility control agent used in the component (B) (b) of the first invention, for example, the presence of an acid in an acidic functional group such as a phenolic hydroxyl group or a carboxyl group. One or more substituents capable of dissociating under the following (hereinafter, referred to as “acid-dissociable substituent”)
Say. The compound which introduce | transduced) can be mentioned. Examples of such an acid-dissociable substituent include, for example, the substituted methyl group, 1-substituted ethyl group, silyl group, 1-branched alkyl group, germyl group, alkoxycarbonyl group described in the section of the acid-dissociable group-containing resin, Examples thereof include the same acid dissociable groups as acyl groups and cyclic acid dissociable groups. The alkali solubility control agent may be a low molecular weight compound or a high molecular weight compound, and specific examples of the low molecular weight compound include the following formula (32).
To (36) can be mentioned.

[0058]

[Chemical 32]

[In the formula (32), R ⁹ is a substituted methyl group, 1-substituted ethyl group, 1-branched alkyl group, silyl group, germyl group, alkoxycarbonyl group, acyl group or cyclic acid-dissociable group. R ⁹ is an acid-dissociable group and a plurality of R ⁹ may be the same or different from each other, R ¹⁰ is an alkyl group having 1 to 4 carbon atoms, a phenyl group or a naphthyl group, and a plurality of R ¹⁰ are mutually present. They 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 ≦
It is 6. ]

[0060]

[Chemical 33]

[In the formula (33), R ⁹ and R ¹⁰ have the same meanings as in the formula (32), and A is a single bond, —S—, —O—, —CO.
-, -COO-, -SO-, -SO _2- , -C (R ¹¹ ) (R ¹² )-or

[0062]

[Chemical 34]

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

[0064]

[Chemical 35]

[In the formula (34), R ⁹ and R ¹⁰ have the same meanings as in the formula (32), and R ¹³ is a hydrogen atom or a carbon number of 1 to 4.
Represents an alkyl group or a phenyl group of p, q, r,
s, t, and u are each an integer of 0 or more, and p + q ≦
5, r + s ≦ 5, t + u ≦ 5, and p + r + t ≧ 1. ]

[0066]

[Chemical 36]

[In the formula (35), R ⁹ and R ¹⁰ have the same meaning as in the formula (32), A has the same meaning as in the formula (33),
R ¹³ has the same meaning as in formula (34), 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 each an integer of 0 or more, and p + q ≦
5, r + s ≦ 5, t + u ≦ 5, v + w ≦ 5, p + r + t
+ V ≧ 1. ]

[0068]

[Chemical 37]

[In the formula (36), R ⁹ and R ¹⁰ have the same meaning as in the formula (32), R ¹³ has the same meaning as in the formula (34), and a plurality of R ^{13 s} may be the same or different from each other. Well, p, q, r, s, t, u, v and w are each 0
With the above integers, p + q ≦ 5, r + s ≦ 5, t + u ≦ 5,
v + w ≦ 4 and p + r + t + v ≧ 1. The acid dissociable group-containing resin described above can be used as the polymer alkali solubility control agent. As the alkali solubility control agent in the first invention, compounds represented by the following formulas (37) and (38) are particularly preferable.

[0070]

[Chemical 38]

[0071]

[Chemical Formula 39]

In the first invention, the alkali solubility control agent may be used alone or in combination of two or more kinds of each of the low molecular weight compound and the high molecular weight compound (that is, the resin having an acid dissociable group). Also, a low molecular weight compound and a high molecular weight compound can be used in combination.

Crosslinking Agent The crosslinking agent (D) used in the second invention is a compound capable of crosslinking an alkali-soluble resin in the presence of an acid, for example, an acid generated by exposure. As such a cross-linking agent, for example, one or more kinds of substituents having cross-linking reactivity with an alkali-soluble resin (hereinafter referred to as "cross-linking substituents").
A compound having Examples of the crosslinkable substituent include groups represented by the following formulas (39) to (43).

[0074]

[Chemical 40]

[In the formula (39), k is 1 or 2, and Q ¹ is a single bond, -O-, -S-, -COO when k = 1.
-Or -NH-, or when k = 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. ]

[0076]

[Chemical 41]

[In the formula (40), 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, 6
-12 is an aryl group or a C7-14 aralkyl group, and y is an integer of 1 or more. ]

[0078]

[Chemical 42]

[In the formula (41), R ¹⁷ , R ¹⁸ and
R ^19's may be the same or different from each other and represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

[0080]

[Chemical 43]

[In the formula (42), R ¹⁴ and R ¹⁵ have the same meanings as in the formula (40), R ²⁰ and R ²¹ may be the same or different from each other, and are each an alkylol group having 1 to 5 carbon atoms. Where y is an integer of 1 or more. ]

[0082]

[Chemical 44]

[In the formula (43), R ¹⁴ and R ¹⁵ have the same meanings as in the formula (40), 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 y 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 resin, carboxymethyl group-containing benzoguanamine resin, carboxymethyl group-containing urea resin, Rubokishimechiru group containing phenol resins, carboxymethyl group-containing melamine compounds, carboxymethyl group-containing benzoguanamine compounds, carboxymethyl group-containing urea compounds, mention may be made of carboxymethyl group-containing phenol compounds and the like. 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, a methoxymethyl group-containing glycoluril compound, a methoxymethyl group-containing urea compound and an acetoxymethyl group A phenol compound containing is preferable, and a methoxymethyl group-containing melamine compound (for example, hexamethoxymethylmelamine), a methoxymethyl group-containing glycoluril compound, and a methoxymethyl group-containing urea compound are more preferable. The melamine compound containing a methoxymethyl group is CYME
L300, CYMEL301, CYMEL303, CY
With product names such as MEL305 (Mitsui Cyanamid),
The methoxymethyl group-containing glycoluril compound is CYM
With product names such as EL1174 (Mitsui Cyanamid),
The methoxymethyl group-containing urea compound is commercially available under the trade name of MX290 (manufactured by Sanwa Chemical Co., Ltd.). As the cross-linking agent, a compound in which the cross-linkable substituent is introduced into the acidic functional group in the alkali-soluble resin to impart the property as a cross-linking agent can also be suitably used. The introduction rate of the crosslinkable functional group in that case cannot be unconditionally defined depending on the type of the alkali-soluble resin into which the crosslinkable functional group or the group is introduced, but with respect to all acidic functional groups in the alkali-soluble resin, it is usually , 5 to 60 mol%, preferably 10 to 50 mol%, and 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. As the crosslinking agent in the second invention, a methoxymethyl group-containing compound, such as tetramethoxymethylurea or tetramethoxymethylglycoluril, is particularly preferable. In the second invention, the crosslinking agent may be used alone or in combination of two or more kinds.

The mixing 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 varies depending on the desired characteristics of the resist, but is preferable. The mixing ratio is as follows. First, in the positive-type radiation-sensitive resin composition of the first invention,
The compounding amount of the thiosulfonate compound is usually 0.001 to 70 parts by weight, preferably 0.01 to 5 parts by weight, per 100 parts by weight of the acid-dissociable group-containing resin or the alkali-soluble resin.
0 parts by weight, particularly preferably 0.1 to 20 parts by weight.
When the blending amount of the thiosulfonate compound is less than 0.001 part by weight, the effect of suppressing the fluctuation of the line width and the effect of suppressing the distortion of the pattern shape when the time from exposure to PEB changes, tend to decrease. If it exceeds the weight part, the coating property of the resist and the pattern shape tend to deteriorate. The amount of the alkali-solubility-controlling agent to be added is usually 5 to 150 per 100 parts by weight of the alkali-soluble resin.
Parts by weight, preferably 5 to 100 parts by weight, particularly preferably 5 to 50 parts by weight. If the compounding amount of the alkali solubility control agent is less than 5 parts by weight, the residual film rate tends to decrease and the pattern swelling tends to occur. If it exceeds 150 parts by weight, the film surface becomes rough and the film strength decreases. Tends to come. More specifically, the mixing ratio of each component in the first invention is preferably 0.001 to 70 parts by weight of [1-1] thiosulfonate compound and 100 parts by weight of an acid-labile group-containing resin, or [1-2] Thiosulfonate compound 0.001 to 70 parts by weight, alkali soluble resin 100 parts by weight and alkali solubility control agent 5 to 150 parts by weight, and more preferably [1-3] thiosulfonate. 0.01 to 50 parts by weight of a sulfonate compound, and 100 parts by weight of an acid-dissociable group-containing resin, or 0.01 to 50 parts by weight of a [1-4] thiosulfonate compound, 100 parts by weight of an alkali-soluble resin and alkali solubility Control agent 5-10
0 parts by weight, particularly preferably 0.1 to 20 parts by weight of [1-5] thiosulfonate compound and 100 parts by weight of acid dissociable group-containing resin, or [1-6] thiosulfonate compound. 0.1 to 20 parts by weight, 100 parts by weight of alkali-soluble resin, and 5 to 50 parts by weight of alkali solubility control agent.

Next, in the negative-type radiation-sensitive resin composition of the second invention, the compounding amount of the thiosulfonate compound is
Usually, 0.0 per 100 parts by weight of the alkali-soluble resin.
01 to 70 parts by weight, preferably 0.01 to 50 parts by weight,
It is particularly preferably 0.1 to 20 parts by weight. When the compounding amount of the thiosulfonate compound is less than 0.001 part by weight,
When the time from exposure to PEB changes, the effect of suppressing line width fluctuations and the effect of suppressing pattern shape distortion tend to decrease, and when it exceeds 70 parts by weight, resist coatability and pattern shape are deteriorated. Tends to be easier. Moreover, the compounding quantity of a crosslinking agent is 5-95 weight part normally per 100 weight part of alkali-soluble resin, Preferably it is 15-8.
5 parts by weight, particularly preferably 20 to 75 parts by weight. If the compounding amount of the cross-linking agent is less than 5 parts by weight, the residual film rate tends to decrease, and the pattern may meander or swell, and if it exceeds 95 parts by weight, the developability tends to decrease.
More specifically, the mixing ratio of each component in the second invention is preferably [2-1] thiosulfonate compound 0.001 to 70 parts by weight, alkali-soluble resin 100 parts by weight, and crosslinking agent 5 to 95. Parts by weight, more preferably [2-2] thiosulfonate compound 0.01 to
50 parts by weight, 100 parts by weight of alkali-soluble resin and 15 to 85 parts by weight of a cross-linking agent, and particularly preferably [2-
3] 0.1 to 20 parts by weight of thiosulfonate compound, 100 parts by weight of alkali-soluble resin, and 20 to 75 cross-linking agent
Parts by weight.

In the positive-type radiation-sensitive resin composition of the first invention and the negative-type radiation-sensitive resin composition of the second invention, if necessary, a radiation-sensitive acid generator other than the thiosulfonate compound is used. (Hereinafter, referred to as "acid generator"), various additives such as an acid diffusion controller, a surfactant and a sensitizer can be blended. Further, in particular, an alkali-soluble resin and / or an alkali-solubility controlling agent is further added to the positive radiation-sensitive resin composition of the first invention containing the thiosulfonate compound and the acid-dissociable group-containing resin. be able to. Examples of the acid generator include onium salt compounds, halogen-containing compounds, sulfone compounds, sulfonic acid ester compounds, quinonediazide compounds, sulfonimide compounds, diazomethane compounds, and the like. Examples of these acid generators are shown below. Onium salt compounds Examples of onium salt compounds include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, ammonium salts, pyridinium salts and the like.
Specific examples of the onium salt compound include diphenyliodonium triflate, diphenyliodonium pyrenesulfonate, diphenyliodonium dodecylbenzenesulfonate, triphenylsulfonium triflate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium hexafluoroantimonate, triphenylsulfonium naphthalene. Examples thereof include sulfonate and (hydroxyphenyl) benzylmethylsulfonium toluenesulfonate. Halogen-containing compound Examples of the halogen-containing compound include a haloalkyl group-containing hydrocarbon compound and a haloalkyl group-containing heterocyclic compound. Specific examples of the halogen-containing compound include phenyl-bis (trichloromethyl) -s-
(Poly) trichloromethyl-s-triazine derivatives such as triazine, methoxyphenyl-bis (trichloromethyl) -s-triazine, naphthyl-bis (trichloromethyl) -s-triazine, and 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane etc. can be mentioned. Sulfone compound Examples of the sulfone compound include β-ketosulfone and β
-Sulfonyl sulfone, these α-diazo compounds and the like can be mentioned. Specific examples of the sulfone compound include phenacylphenyl sulfone, mesitylphenacyl sulfone, bis (phenylsulfonyl) methane, 4-trisphenacyl sulfone and the like. Examples of the sulfonic acid ester compound sulfonic acid ester compound include alkyl sulfonic acid ester, haloalkyl sulfonic acid ester,
Aryl sulfonate, imino sulfonate, etc. can be mentioned. Specific examples of the sulfonic acid ester compound include benzoin tosylate, pyrogallol tris triflate, pyrogallol methanesulfonic acid triester, and nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, and particularly pyrogallol methane. Sulfonic acid triesters are preferred.

Quinonediazide Compound Examples of the quinonediazide compound include 1,2-quinonediazidesulfonic acid ester compounds of polyhydroxy compounds, diazobenzoquinone compounds, diazonaphthoquinone compounds and the like. Examples of the quinonediazide compound include 1,2-benzoquinonediazide-4-
Compounds having a 1,2-quinonediazidesulfonyl group such as a sulfonyl group, a 1,2-naphthoquinonediazide-4-sulfonyl group, a 1,2-naphthoquinonediazide-5-sulfonyl group, a 1,2-naphthoquinonediazide-6-sulfonyl group And the like, particularly 1,2-naphthoquinonediazide-4-sulfonyl group and / or 1,2
A compound having a naphthoquinonediazide-5-sulfonyl group and the like are preferable. Specific examples of such quinonediazide compounds include 1,2-quinonediazide sulfonic acid of (poly) hydroxyphenyl aryl ketone such as 2,3,4-trihydroxybenzophenone and 2,3,4,4′-tetrahydroxybenzophenone. Esters; 1,2 of bis [(poly) hydroxyphenyl] alkane such as bis (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) methane, and 2,2-bis (4-hydroxyphenyl) propane. -Quinonediazide sulfonic acid esters; 4,4 ', 4 "-trihydroxytriphenylmethane, 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- [4- {1- (4-hydroxyphenyl)
1,2-quinonediazide sulfonic acid esters of (poly) hydroxytriphenylalkane such as -1-methylethyl} phenyl] ethane; 2,4,4-trimethyl-
2 ', 4', 7-trihydroxy-2-phenylflavan, 2,4,4-trimethyl-2 ', 4', 5 ', 6
Examples thereof include 1,2-quinonediazidesulfonic acid esters of (poly) hydroxyphenylflavan such as 7-pentahydroxy-2-phenylflavan. Among these quinonediazide compounds, preferred compounds are 1,1-bis (4-hydroxyphenyl) -1-
Examples thereof include 1,2-naphthoquinonediazide-4-sulfonic acid ester of [4- {1- (4-hydroxyphenyl) -1-methylethyl} phenyl] ethane. Sulfonimide compound As the sulfonimide compound, for example, the following formula (44)
The compound represented by can be mentioned.

[0088]

[Chemical formula 45]

[In the formula (44), Q ⁴ represents a divalent group such as an alkylene group, an arylene group or an alkoxylene group, and R ²³ represents an alkyl group, an aryl group, a halogen-substituted alkyl group, a halogen-substituted aryl group or the like. Represents a monovalent group of. ] Specific examples of such a sulfonimide compound include N
-(Trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] Hept-5
-Ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (tri Fluoromethylsulfonyloxy)
Bicyclo [2.2.1] heptane-5,6-oxy-
2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (campanylsulfonyloxy) succinimide, N- (campanylsulfonyloxy) phthalimide, N- (campanylsulfonyloxy) diphenylmaleimide , N-
(Campanylsulfonyloxy) bicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide, N
-(Campanylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (campanylsulfonyloxy) bicyclo [2.2.1] heptane -5,6-oxy-2,
3-dicarboximide, N- (camphanylsulfonyloxy) naphthylimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) phthalimide, N- (4-methylphenylsulfonyloxy) ) Diphenylmaleimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) -7-oxa Bicyclo [2.2.1] hept-5-
Ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N
-(4-methylphenylsulfonyloxy) naphthylimide, N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N-
(2-trifluoromethylphenylsulfonyloxy)
Diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2
-Trifluoromethylphenylsulfonyloxy) -7
-Oxabicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.
1] Heptane-5,6-oxy-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) naphthylimide and the like. Examples of the diazomethane compound As the diazomethane compound, a compound represented by the following formula (45) can be given.

[0090]

[Chemical formula 46]

[In the formula (45), R ²⁴ and R ²⁵ may be the same as or different from each other, and each represent a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group. Specific examples of such a diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, methylsulfonyl-p-toluene. Sulfonyldiazomethane, 1-cyclohexylsulfonyl-1- (1,1-dimethylethylsulfonyl)
Examples thereof include diazomethane and bis (1,1-dimethylethylsulfonyl) diazomethane. Among the acid generators, preferred compounds are onium salt compounds,
Halogen-containing compound, sulfonate compound,
Sulfonimide compounds and diazomethane compounds, especially triphenylsulfonium triflate, pyrogallol methanesulfonic acid triester, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide, N
-(Camphanylsulfonyloxy) bicyclo [2.
2.1] hept-5-ene-2,3-dicarboximide, bis (cyclohexylsulfonyl) diazomethane,
2- (4-Methoxy-1-naphthyl) -4,6-bis (trichloromethyl) -s-triazine and the like are preferable.
In the present invention, the acid generator may be used alone or in combination of two or more. The amount of the acid generator used in the present invention is appropriately selected according to the type of each acid generator, but the acid dissociable group-containing resin or alkali-soluble resin 1
The amount is preferably 20 parts by weight or less, particularly preferably 15 parts by weight or less, per 00 parts by weight. The amount of acid generator used is 2
If it exceeds 0 parts by weight, application unevenness may occur when applying the resin composition, or scum may occur during development.

The acid diffusion control agent controls the diffusion phenomenon of the acid generated from the acid generator in the resist film by exposure, and suppresses an undesired chemical reaction in the unexposed area. Is a component to be blended with. By using such an acid diffusion control agent, it is possible to further improve the shape of the pattern to be formed, particularly the eaves generation in the upper layer portion of the pattern, the dimensional fidelity to the mask dimension, and the like. As the acid diffusion control agent, for example, a nitrogen compound that can retain basicity after exposure or after heating can be preferably used. Specific examples of such nitrogen compounds include ammonia, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, 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, benzimidazole, thiabendazole, pyridine, 2-methylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-
Phenylpyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, 2-benzylpyridine, nicotinic acid amide, dibenzoylthiamine, tetrabutyric acid riboflamine, 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
Examples thereof include-(4-aminophenyl) -1-methylethyl] benzene. Among these acid diffusion control agents, particularly tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, benzimidazole, 4-phenylpyridine,
4,4'-diaminodiphenyl ether, nicotinic acid amide and the like are preferable. The acid diffusion control agent may be used alone or in combination of two or more. The amount of the acid diffusion controller mixed varies depending on the type, combination with the thiosulfonate compound and / or acid generator, etc.
Usually 1 per 100 parts by weight of all resin components in the resin composition.
It is 0 part by weight or less, preferably 5 parts by weight or less. If the blending amount of the acid diffusion controller exceeds 10 parts by weight, the sensitivity 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, cationic, nonionic or amphoteric surfactants can be used, but the preferred surfactant is a nonionic 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 (Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), Ftop (Tochem Products Co., Ltd.), Megafac (Dainippon Ink and Chemicals Co., Ltd.), Florard (Sumitomo 3M Co., Ltd.),
Asahi guard, Surflon (manufactured by Asahi Glass) and other series 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 thiosulfonate compound and / or the acid generator, thereby increasing the amount of acid produced. It has the effect of improving the apparent sensitivity of the resin composition. Preferred examples of the sensitizer used include acetophenones, benzophenones, naphthalenes, biacetyl, eosin, rose bengal, pyrene, 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, preferably 30 parts by weight or less, per 100 parts by weight of all the resin components in the resin composition. Also, by blending a dye or pigment,
The latent image in the exposed area can be visualized to alleviate the effect of halation during exposure, and the adhesion to the substrate can be improved by incorporating an adhesion aid. Further, as other additives, antihalation agents, storage stabilizers, defoamers, shape improvers, and the like, specifically 4-hydroxy-4′-
Examples thereof include methyl chalcone.

The positive-type radiation-sensitive resin composition of the first invention and the negative-type radiation-sensitive resin composition of the second invention are used in a solvent so that the solid concentration becomes, for example, 5 to 50% by weight. After being dissolved, it is prepared as a composition solution by, for example, filtering with a filter having a pore size of about 0.2 μm. Examples of the solvent include ethers,
Esters, ether esters, ketones, ketone esters, amides, amide esters, lactams,
Lactones, (halogenated) hydrocarbons and the like can be mentioned, and more specifically, for example, ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers,
Acetic acid esters, hydroxyacetic acid esters, lactic acid esters, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether acetates, alkoxy acetic acid esters, (non) cyclic ketones, acetoacetic acid esters, pyruvic acid esters , Propionic acid esters, N, N-dialkylformamides, N, N-dialkylacetamides, N-
Examples thereof include alkylpyrrolidones, γ-lactones, (halogenated) aliphatic hydrocarbons, and (halogenated) aromatic hydrocarbons. Specific examples of the solvent, 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 acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, isopropenyl acetate, isopropenyl propionate, toluene, xylene, methyl ethyl ketone, cyclohexanone, 2-hepta Down,
3-heptanone, 4-heptanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutylacetate, 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, Mention may be made of methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like. You can Among these solvents, 2-hydroxypropionic acid esters, 3-alkoxypropionic acid esters, propylene glycol monoalkyl ether acetates and the like are preferable. The said solvent is used individually or in mixture of 2 or more types. 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, One or more high boiling point solvents such as benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate may be added.

When forming a resist pattern from the positive radiation-sensitive resin composition of the first invention and the negative radiation-sensitive resin composition of the second invention, the composition solution prepared as described above is used. A spin coating, a cast coating, a roll coating or the like is applied to a substrate such as a silicon wafer or a wafer coated with aluminum to form a resist coating, and the resist is applied through a predetermined mask pattern. Expose the coating. The radiation that can be used at that time is the emission line spectrum (wavelength 25
4 nm), KrF excimer laser (wavelength 248 nm),
Far-ultraviolet rays such as ArF excimer laser (wavelength 193 nm) are preferable, but X such as synchrotron radiation may be generated depending on the kind of thiosulfonate compound and / or acid generator.
A charged particle beam such as a beam or an electron beam can also be used.
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, PE is used to improve the apparent sensitivity of the resist.
It is preferable to perform B. The heating conditions vary depending on the composition of the positive radiation-sensitive resin composition of the first invention and the negative radiation-sensitive resin composition of the second invention, the type of additives, etc. Preferably 50 to 1
It is 50 ° C. Then, by developing with an alkaline developer, a predetermined resist pattern is formed. Examples of the alkaline developer include alkali metal hydroxide, aqueous ammonia, alkylamines, alkanolamines,
Heterocyclic amines, tetraalkylammonium hydroxides, choline, 1,8-diazabicyclo [5.4.
0] -7-undecene, 1,5-diazabicyclo [4.
3.0] -5-nonene and other alkaline compounds are usually
An alkaline aqueous solution which is dissolved to have a concentration of 1 to 10% by weight, preferably 2 to 5% by weight is used. A particularly preferred alkaline developer is an aqueous solution of tetraalkylammonium hydroxides. The alkaline compounds may 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.

[0095]

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. Here, evaluation of each resist was implemented in the following manner. A resist film formed on a sensitive silicon wafer was exposed at different exposure doses, immediately post-exposure baked, then alkali-developed, washed with water and dried to form a resist pattern having a line width of 0. The exposure amount for forming a line-and-space pattern (1L1S) of 5 μm with a line width of 1: 1 was taken as the optimum exposure amount, and this optimum exposure amount was taken as the sensitivity. Resolution The minimum dimension (μm) of the resist pattern resolved when exposed with the optimum exposure amount was defined as the resolution. Pattern shape 1L1 with a line width of 0.5μm formed on a silicon wafer
The dimension La of the lower side and the dimension Lb of the upper side of the S-shaped cross section were measured with a scanning electron microscope to satisfy 0.85≤Lb / La≤1, and the pattern scribing near the substrate A pattern having no eaves in the upper layer portion was defined as "good" in pattern shape, and a pattern not satisfying at least one of these conditions was defined as "defective". Residual film ratio The residual film ratio was defined as the ratio (%) of the thickness after development to the thickness before development of the resist pattern that was resolved when exposed at the optimum exposure amount. Process stability against PED A resist pattern in the case where a resist film formed on a silicon wafer is exposed at different exposure amounts, and then immediately post-exposure bake and alkali development are performed, and the post-exposure 1
With respect to the resist pattern in the case where the resist pattern was left for a time and subjected to post-exposure bake and alkali development, each minimum exposure amount (E
Th) was evaluated by an optical microscope, and the smaller the difference in Eth between immediately after exposure and after 1 hour, the better the process stability against PED. However, the evaluation result of the pattern shape was also added to the final evaluation of the process stability against PED.

Each component used in each example and comparative example is
It is as follows. [I] Positive-type radiation-sensitive resin composition (first invention) -thiosulfonate compound-The thiosulfonate compounds used in the examples were mainly commercial products (for example, manufactured by Aldrich and Vader). However, the compound which is not commercially available is a known synthetic method, for example, the method described in Chapter 5 of “Organic Sulfur Chemistry (Synthesis)” edited by Shigeru Ohbiki (Tokyo Kagaku Dojin, 1982) (desired substituents). Reactions of Sulfonyl Halides and Thiols in Alkaline Solution, Condensation Reactions of Thiosulfonates with Alkyl Halides, Condensation Reactions of Sulfenyl Chloride with Sulfinic Acid, Condensation Reactions of Disulfide with Sulfinic Acid, Thiol Compounds N ₂ O ₄ oxidation reaction or diflufide electrophilic oxidation reaction). The thiosulfonate compound of each example is as follows. (A-1) S-phenyl-benzenethiosulfonate [Formula (10)] (A-2) S-cyclohexyl-cyclohexanethiosulfonate [Formula (8)] (A-3) S-benzyl-4 -Toluenethiosulfonate [Formula (16)] (A-4) S-Methyl-methanethiosulfonate [Formula (3)] (A-5) Ethylenedithiotosylate [Formula (22)] (A- 6) Trimethylene dithiotosylate [Formula (2
3)]-Acid-dissociative group-containing resin- (B-1) A resin (Mw = 9000) in which 26% of hydrogen atoms of the phenolic hydroxyl group of poly (hydroxystyrene) are substituted with t-butoxycarbonyl group. (B-2) A resin (Mw = 20,000) in which 25% of the hydrogen atoms of the phenolic hydroxyl group of poly (hydroxystyrene) are substituted with t-butoxycarbonylmethyl groups. (B-3) Copolymer of hydroxy-α-methylstyrene and t-butyl acrylate (copolymerization molar ratio = 5: 5,
Mw = 12,000). -Alkali-soluble resin- (B-4) Poly (p-hydroxystyrene) (Mw =
7,500). -Alkali solubility control agent- (b-1) Formula (37)

[0097]

[Chemical 38]

(B-2) Formula (38)

[0099]

[Chemical Formula 39]

-Other Components-As the acid generator, triphenylsulfonium trifluoromethanesulfonate (α-1), N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene -2,3-Dicarboximide (α-2) or pyrogallol methanesulfonic acid triester (α-
3) was used, tributylamine (β-1), nicotinic acid amide (β-2) or benzimidazole (β-3) was used as the acid diffusion controller, and ethyl 2-hydroxypropionate was used as the solvent. .

[II] Negative radiation-sensitive resin composition (second
Invention) -Thiosulfonate compound- [I] The same compounds as those used in the positive radiation-sensitive resin composition were used. -Alkali-soluble resin- (C-1) Poly (p-hydroxystyrene) (Mw =
7,500). (C-2) A copolymer of p-hydroxystyrene and styrene (copolymerization molar ratio = 7: 3, Mw = 7,000) was used. -Crosslinking agent- (D-1) Tetramethoxymethylurea (trade name MX2
90, manufactured by Sanwa Chemical). (D-2) Tetramethoxymethyloluril (trade name C
(YMEL1174, manufactured by Mitsui Cyanamid). -Other components-As an acid generator, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-
2,3-Dicarboximide (α-2) or pyrogallol methanesulfonic acid triester (α-3) was used, and ethyl 2-hydroxypropionate was used as a solvent.

Examples 1 to 32, Comparative Examples 1 to 8 Table 1 (Positive radiation sensitive resin composition) and Table 2 (Negative radiation sensitive resin composition) (however, parts are based on weight). The respective components shown were mixed to form a uniform solution, which was then filtered through a membrane filter having a pore size of 0.2 μm to prepare a composition solution. This composition solution was spin-coated on a silicon wafer and then prebaked at 90 ° C. for 120 seconds to form a resist film having a film thickness of 1.0 μm. KrF made by Admon Science Co., Ltd.
Excimer laser irradiation device (trade name MBK-400TL
-N), an excimer laser with a wavelength of 248 nm,
The exposure amount was changed through the mask pattern. After the exposure, PEB was performed at 110 ° C. for 60 seconds. Then 2.
Using a 38 wt% tetramethylammonium hydroxide aqueous solution as a developing solution, development was performed at 23 ° C. for 60 seconds, followed by washing with water for 30 seconds and drying to form a resist pattern. Table 3 shows the evaluation results of each Example and Comparative Example.
(Evaluation of resist performance of positive radiation-sensitive resin composition) and Table 4 (Evaluation of resist performance of negative radiation-sensitive resin composition).

[0103]

[Table 1]

[0104]

[Table 2]

[0105]

[Table 3]

[0106]

[Table 4]

[0107]

The radiation-sensitive resin composition of the present invention is excellent not only in process stability against PED, but also in sensitivity, resolution, pattern shape and residual film rate.
Moreover, the radiation-sensitive resin composition contains far ultraviolet rays, X-rays,
It can be applied to various kinds of radiation such as a charged particle beam. Therefore, the positive-working radiation-sensitive resin composition and the negative-working radiation-sensitive resin composition of the present invention are extremely useful particularly as a resist for semiconductor device production, which is expected to be further miniaturized in the future.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mikio Yamachika 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) Reference JP-A-7-209797 (JP, A) JP-A 5-313371 (JP, A) JP-A-3-28849 (JP, A) JP-A-58-17132 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F 7/004 -7/18 CAPLUS (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A thiosulfonate compound represented by the following formula (1) or formula (2): [Chemical 2] [In the formulas (1) and (2), X and Y may be the same or different from each other, and may be substituted, a monovalent acyclic hydrocarbon group, a cycloalkyl group, an aryl group,
An aralkyl group or another monovalent organic group having a hetero atom is shown, and in the formula (2), Z is-(CH ₂ ) n- (where n is an integer of 0 to 6),-(CH ₂ ). mC (= O)-(CH ₂ ) m- (where m is an integer from 0 to ₂ ) and-(CH ₂ ) mC (= N ₂ )-(CH ₂ ).
At least one divalent group selected from the group of m- (where m is an integer of 0 to 2) is shown. ], 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 an alkali-soluble resin A positive radiation-sensitive resin composition comprising a control agent. 2. A thiosulfonate compound represented by formula (1) or formula (2) according to claim 1, (C) an alkali-soluble resin, and (D) an alkali-soluble compound in the presence of an acid. A negative radiation-sensitive resin composition comprising a compound capable of crosslinking a resin.