WO2004074936A1 - Negative radiation-sensitive resin composition - Google Patents

Abstract

A negative radiation-sensitive resin composition that in the formation of line and space pattern, exhibits high resolution, being capable of forming rectangular resist patterns, and that reduces resist pattern defects such as bridging after development, excelling in sensitivity, developability, dimensional royalty, etc. The negative radiation-sensitive resin composition comprises a copolymer resin, the copolymer having (meth)acrylic acid repeating units having side chains wherein hydroxyl and fluoroalkyl are bonded to one carbon atom and (meth)acrylic acid repeating units having hydroxyls in the side chains thereof, a radiation-sensitive acid generator and an acid crosslinking agent.

Description

Technical Field The present invention relates to a negative-type radiation-sensitive resin composition, and particularly to deep ultraviolet rays such as a KrF excimer laser or an F excimer laser, X-rays such as synchrotron radiation, and the like. Chemical enhancement useful for micromachining using various radiations such as charged particle beams such as electron beams

 Light

The present invention relates to a negative-type radiation-sensitive resin composition that can be suitably used as a width-type resist. book

Background art

In the field of microfabrication represented by fabrication of integrated circuit devices, in order to achieve a higher degree of integration in recent A r F excimer laser one (wavelength 1 9 3 nm), F ₂ E key striped laser (wavelength 1 There is a need for a lithography technology capable of fine processing at a level of about 200 nm or less using (57 nm) or the like. As a radiation-sensitive resin composition suitable for irradiation with such an excimer laser, a chemical amplification by a component having an acid-dissociable functional group and an acid generator which is a component that generates an acid upon irradiation with radiation. Many chemical amplification type radiation-sensitive resin compositions utilizing the effect have been proposed. Among the chemically amplified radiation-sensitive resin compositions, the negative-type radiation-sensitive resin composition forms a pattern by reducing the dissolution rate in the developer by promoting the crosslinking reaction in the radiation-irradiated part. Let me.

 Conventionally, as a negative radiation-sensitive resin composition, a chemically amplified negative resist having a (meth) acrylate derivative having a dihydroxy alicyclic group as a crosslinking site has been known (Patent Document 1).

By the way, when actually manufacturing an integrated circuit using a resist, usually, a radiation-sensitive component, a film-forming resin component, and the like are dissolved in a solvent to prepare a radiation-sensitive resin composition as a resist solution. After applying the resist solution on a substrate to be processed to form a resist film, the resist film is irradiated with radiation through a predetermined mask and developed, thereby forming a pattern suitable for fine processing. Let it form. At that time putter The cross-sectional shape (pattern cross-sectional shape) has a significant effect on the precision of microfabrication, and a rectangular shape is preferred to improve the precision.

 [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-122288 (paragraph [0022]) However, a conventional chemically amplified negative resist dissolves between a radiation-irradiated part and a non-irradiated part in a developing solution of the resist. There is a problem that the resolution is low because the speed difference is not sufficiently large, and that the head shape of the pattern is not rectangular but rounded. Furthermore, since the dissolution rate of the non-irradiated part is extremely high, the dissolution rate of the irradiated part cannot be sufficiently reduced, and there is a problem that the pattern is swollen or meandered by the developer. , Disclosure of the invention

The present invention has been made to address such a problem, and can be applied as a negative-type radiation-sensitive resin composition using an ArF light source to a conventional normal concentration developer without any problem. The line 'and' space pattern shows high resolution and can form a rectangular resist pattern, reduces resist pattern defects such as bridging after development, and improves sensitivity, developability, and dimensions. An object of the present invention is to provide a negative radiation-sensitive resin composition suitable as a chemically amplified negative resist excellent in fidelity and the like. The negative-type radiation-sensitive resin composition of the present invention comprises a repeating unit (1-1) represented by the following formula (111) and a repeating unit (1-1) represented by the following formula (1-2). 2) A copolymer resin containing (A), a radiation-sensitive acid generator (B), and an acid crosslinking agent (C).

(1-1) (1-2) In the above formulas (11-1) and (-2), R ¹ represents a hydrogen atom or a methyl group, and in the formula (, X ¹ and X ² independently of each other A hydrogen atom or a fluoroalkyl group, and at least one of X ¹ and X ² represents a fluoroanolealkyl group, Y represents a divalent organic group, Z represents a divalent to tetravalent organic group, and T represents Represents a single bond or a divalent organic group having 1 to 3 carbon atoms, and n represents an integer of 1 to 3.

 Further, the copolymer resin (A) has a polystyrene equivalent weight average molecular weight of 1,000 to 50,000 as measured by gel permeation chromatography (GPC).

 The negative radiation-sensitive resin composition of the present invention contains an acid diffusion controller (D) together with the copolymer resin (A), the radiation-sensitive acid generator (B) and the acid crosslinking agent (C). It is characterized by.

 Further, the compounding amount of the radiation-sensitive acid generator (B) is 0.1 to 20 parts by weight with respect to 100 parts by weight of the copolymer resin (A).

The radiation-sensitive acid generator (B) must contain at least one acid generator selected from the following formulas (2-1), (2-2) and (2-3). Features.

In the above formulas (2-1), (2-2) and (2-3), X represents R ^{3 and} SO _s , and R ³ may be partially or completely fluorinated , Represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group, R ² represents a hydrogen atom, or an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and R ⁴ represents partially or completely fluorinated Represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group which may be substituted, U represents a divalent organic group, and R ⁵ and R ⁶ each independently represent a hydrogen atom, an aliphatic hydrocarbon group, Or an aromatic hydrocarbon group, m represents an integer of 0 to 3, and 11 represents an integer of 0 to 2.

 In addition, the radiation-sensitive acid generator (B) is preferably represented by the formula (2-3). The negative-type radiation-sensitive resin composition of the present invention is characterized in that the amount of the acid crosslinking agent (C) is 0.5 to 50 parts by weight based on 100 parts by weight of the copolymerized resin (A). . The resin component is dissolved in a solvent, and the total solid content concentration is 3 to 50% by weight.

 Here, the total solid content concentration is measured by drying about 1 g of a negative-type radiation-sensitive resin composition sample at 100 ° C. for 4 hours.

The above solvent is 2-hexanone, 2-heptanone, 2-octanone, cyclopentanone, cyclohexanone, propylene dalicol monomethinoleate enoleacetate, propylene dali cornole monoethinoleate enoleacetate, 2- Methyl hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-ethoxypropionate Butyl, ethyl ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycolone resin methisolate-tenor, ethylene glycolone resin, terephthalate, ethylene glycolone methylone oleate acetate , Ethylene glycolone monoethinoleate / rareate, propylene glycolone monomethinoleate, propylene glycolose monoethynoleate, n-butyl dihydrochloride, methylinopyruvate, methyl ethyl pyruvate, and ethyl ethylene glycol It is characterized in that it is at least one solvent selected from the group consisting of monomethinoleatenole, diethyleneglyconeleoneete / leitenole, and γ-lactose lactone.

 Further, the acid diffusion controller (D) is characterized by being represented by the following formula (4).

(4) In the above formula (4), R ²³ and R ^M independently represent a hydrogen atom or an alkyl group, or an alicyclic hydrocarbon group or an aromatic hydrocarbon group formed by bonding to each other. And R ²⁵ represents a hydrogen atom, an alkyl group, or a C (O) OR ²⁷ group, R ²⁷ represents an alkyl group, and R ²⁶ represents a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group, or an aromatic group. Represents a group hydrocarbon group. -The negative radiation-sensitive resin composition of the present invention comprises a repeating unit (1-1) represented by the formula (1-1) and a repeating unit (1-2) represented by the formula (1-2) It contains a copolymer resin (A), a radiation-sensitive acid generator (B), and an acid cross-linking agent (C). An 'and' space pattern can be formed, and defects such as undissolved residue at the lower part of the pattern and pleasing at the upper part of the pattern, which are considered to be caused by insufficient solubility of the unirradiated part in the developer, are considered. Can be suppressed. Further, it is possible to hold and control a rectangular pattern shape even in the fine region while suppressing pattern collapse in the fine region due to swelling. BEST MODE FOR CARRYING OUT THE INVENTION

 A conventional chemically amplified negative resist using an A r F light source imparts a dissolution rate to the unirradiated part by copolymerizing a repeating unit containing a carboxyl group. It is difficult to adjust because it tends to be fast, the resolution of the resist pattern is low, and the swelling is weak. For this reason, a negative-type radiation-sensitive resin composition suitable as a chemically amplified negative-type resist excellent in sensitivity, developability, dimensional fidelity, and the like has not yet been commercialized.

By using a copolymer containing a repeating unit (1-1) having at least one of X ¹ and X ² containing a fluoroalkyl group and a repeating unit (1-2), the repeating unit (1-1) It has been found that the dissolution rate of the unirradiated portion in the resist pattern can be easily adjusted by the action of the fluoroalkyl group. The present invention is based on such findings. The dissolution rate is measured by measuring the time required for the film thickness to decrease from an initial value to a predetermined value when the film is developed under a predetermined developing condition, and [(initial film thickness−predetermined film thickness) / Hour]. Each component constituting the negative radiation-sensitive resin composition will be described.

Copolymer resin (A):

 In the repeating unit (1-1) constituting the copolymer resin (A), Y represents a divalent organic group. Examples of the organic group include a linear, branched, or alicyclic hydrocarbon group.

 As the linear or branched hydrocarbon group, a hydrocarbon group having 1 to 12 carbon atoms is preferable, and specific examples thereof include divalent hydrocarbons derived from methane, ethane, propane, butane, and isobutane. Groups.

As the alicyclic hydrocarbon group, an alicyclic hydrocarbon group having 6 to 20 carbon atoms is preferable, and specific examples thereof include cyclohexane, bicyclo [2.2.1] heptane, and 2-methylbis [ 2.2. 1] heptane, Adamantan, tricyclo [5.2. 1.0 ^2'6] decane, tetracyclo [6. 2. 1. I 3 '6. 0 2 · 7] 2 -valent derived from dodecanoic An alicyclic hydrocarbon group is exemplified. Among the divalent organic group represented by Y, hexane propane, butane, isobutane, cyclohexane, 2-methyl bicyclo [2.2.1] heptane, tetracyclo ^{[6. 2. 1. I 3 · 6} . 0 ² ' ⁷ ] A divalent organic group derived from dodecane is preferred. In the repeating unit (1-1), the fluoroalkyl group is preferably a fluoroalkyl group having 1 to 4 carbon atoms, and specific examples thereof include a monofluoromethyl group, a difluoromethyl group, and a trifluoromethyl group. Among these, a trifluoromethyl group and the like are preferable. Furuoroarukiru group is at least one of X ¹ and X ^2, preferably X ¹ and X ² are Furuoroarukiru group. In the repeating unit (1-2), Ζ represents a divalent to tetravalent organic group. Examples of the organic group include a linear, branched, or alicyclic hydrocarbon group.

 As the linear or branched hydrocarbon group, a linear or branched hydrocarbon group having 1 to 12 carbon atoms is preferable, and specific examples are derived from methane, ethane, propane, butane, isobutane, and the like. And divalent to tetravalent hydrocarbon groups.

The alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 6 to 20 carbon atoms, and specific examples thereof include cyclohexane, bicyclo [2.2.1] heptane, adamantane, and tricyclo [5. 2.1.2 0 ² '6] decane, tetracyclo [6.2.1 1. include 1 ^3.6. 0 ^{2, 7]} 2-4 divalent alicyclic hydrocarbon group derived from dodecane.

 Among the divalent organic groups represented by Ζ, ethane, propane, isopropane, butane, isobutane, cyclohexane, bicyclo [2.2.1] heptane, tetracycline

[6.2.1.1 ". 0 ² ' ⁷ ] A bivalent to tetravalent organic group derived from dodecane is preferred. In the repeating unit (1-2), Τ represents a single bond or 2 to 3 carbon atoms. Represents a monovalent organic group, and specifically includes a divalent hydrocarbon group derived from a single bond, methane, ethane, propane, isopropane, etc. Among these, a single bond, a methylene group, an ethylene group Are preferred.

In the formula (1-2), η represents an integer of 1 to 3, and 1 or 2 is preferable. Examples of the monomer that gives the repeating unit (111) represented by the formula (1-1) include (meth) acrylic acid (1,1,1,1-trifluoro-2-trifluoromethyl-12-hydroxy) (Droxy-3-propyl) ester, (meth) acrylic acid (1,1,1,1-trifluoro-2--2-trifluoromethyl-2-hydroxy-4-butyl) ester,

(Meth) atalinoleic acid (1,1,1,1-trifnoreo-l-2-methynolele 2-methydroxy-5-pentyl) ester, (meth) acrylic acid (1,1,1-trif-lenoleol 2-2-trifluoromethylino 2- (hydroxy-1,4-pentynole) ester, (meth) acrylic acid 2 _ {[[5- (1 ,,,, 1'-trifluoro-2, _trifluoromethyl-1,2,1-hydroxy) propyl] [2.2.1] heptyl} ester, (meth) acrylic acid 3 _ {[8- (1,, 1 ', 1,1-trifluoro-2, -trifluoromethyl-2'-hydroxy) propyl] Bok Rashikuro ^{[6. 2. 1. ι 3 · 6} . ο 2 · 7] ( meth) acrylic acid esters such as dodecyl} ester like et be.

In the present invention, “(meth) acrylic acid” indicates both “methacrylic acid” and “acrylic acid”. Monomers that give the repeating unit (1-2) represented by the formula (1-2) include (meth) acrylic acid hydroxymethyl ester, (meth) acrylic acid 1-hydroxyethyl ester, and (meth) acrylic acid. ) Acrylic acid 2-hydroxyethyl ester, (meth) acrylic acid 1-hydroxypropyl ester, (meth) acrylic acid 2-hydroxypropyl ester, (meth) acrylic acid 3-hydroxypropyl ester (Meta) acrylic acid 3-hydroxyamantane 1-1-yl ester, (meth) acrylic acid 3,5-dihydroxydamantane 1-1-yl ester, (meth) acrylic acid 3,5, 7—Trihydroxydamantane-1-yl ester, (meth) acrylic acid 5-hydroxypropyl mouth [2.2.1] Heptane-12-yl ester, (meth) acrylic acid 5—hydroxy Xymethylbicyclo [2.2.1] heptane-2-yl ester, (meth) acrylic acid 5-hydroxymethyl bicyclo [2.2.1] heptane 1-2-methyl ester, (meth) acrylic acid 8-hydroxytetra Cyclo ^{[6. 2. 1. I · 6.} 0 2 '7] dodecane one 3- Iruesuteru, (meth) Ryo acrylic acid 8-hydroxymethyl-tetracyclo ^{[6. 2. 1. I 3' 6} . 0 2 ' ^7] dodecane Hanil 3- Iruesuteru, (meth) Akuriru acid 8 hydroxycarboxylic tetra consequent opening ^{[6. 2. 1. I 3 · 6} . 0 2 '7] dodecane one 3-methyl ester of (meth ) Acrylic acid esters. The copolymer resin (A) of the present invention may further contain other repeating units in addition to the repeating unit (1-1) and the repeating unit (1-2).

Examples of monomers that give other repeating units include (meth) acrylic acid, (meth) acrylic acid ruboxyl methyl ester, (meth) acrylic acid 1-2-carboxylethyl ester, and (meth) acrylic acid- 3-Carboxydamantane-1-yl ester, (meth) acrylic acid-5-potassylbicyclo [2.2.1] hept-12-yl ester, (meth) acrylic acid cyanomethyl ester, (meth) acrylic acid-1 2 —Cyanoethyl ester, (meth) acrylic acid-1-3-cyanoadamantane-1-ylestenole, (meth) acrylic acid-5-cyanovisic mouth [2.2.1.1] Heptoh-2-yl ester, (meth) acrylic acid methyl ester , (Meth) ethyl acrylate ester, (meth) adamantane adamantan-1-ester / ester, (meth) acrylic acid Bicyclo [2.2.1] hepter 2-yl ester, (meth) acrylic acid 1,7,7-dimethylbicyclo [2.2.1] Hepta 1-yl ester, (meth) acrylic acid tris [5 2 · 1.0 ² ' ⁶ ] Deca 8 -yl ester, (meth) acrylic acid-7-oxo-16-oxalic acid mouth [3.2.1 .1] Octa 14 -yl ester, (meth) acrylic acid-2- Ethoxycarbonyl 1 7-oxo-6-oxa-bicyclo [3.2.1] octa-4-yl ester, (meth) acrylic acid 12-oxotetrahydridopyran-14-yl ester, (meth) atalylic acid-4-methyl-2 —Oxotetrahydrodropyran-1-ylester, (meth) atalylic acid-5-oxotetrahydrofuran-13-yl ester, (meth) acrylic acid-12-oxooxotetrahydrofuran-13-yl ester, ( Data) Akuriru monobasic 5- O Kiso tetrahydrofuran one 2-Ino les methyl ester, (meth) Akuriru monobasic 3, 3-dimethyl-5- Okisotetorahi Dorofuran one 2- Examples thereof include methyl ester, N, N-dimethyl (meth) acrylamide, crotonamide, maleamide, fumaramide, mesaconamide, citraconamide and itaconamide. The copolymer resin (A) of the present invention is preferably composed of the above repeating unit (1-1) and the repeating unit (1-2), and the copolymer resin (A) contains at least one kind of each repeating unit. can do.

 The repeating unit (1-2) is preferably a combination of a repeating unit containing an alicyclic hydrocarbon group and a repeating unit containing no alicyclic hydrocarbon group as Z. The copolymer of the present invention comprises a repeating unit (111), a repeating unit containing an alicyclic hydrocarbon group and a repeating unit (1-2) comprising a repeating unit containing no alicyclic hydrocarbon group. Is preferable since a rectangular resist pattern can be formed without generating bridging defects. '

The mixing ratio of each repeating unit, based on all repeating units, the repeating units (1 one 1) force S 4 0-8 0 mole _^0/0, preferably 5 0-8 0 mole _^0/0; repeating unit (1 one 2) 5-6 0 mole _^0/0, preferably from 1 0 to 5 0 mol _^0/0. If the content of the repeating unit (1_1) is less than 40 mol%, the solubility in the developing solution tends to deteriorate. If the content of the repeating unit (111) exceeds 80 mol%, the radiation The solubility of the irradiated part is too high and tends to degrade resolution and swell.

If the content of the repeating unit (1-2) is less than 5 mol%, the degree of crosslinking in the irradiated part tends to be insufficient, and the resolution tends to deteriorate, and the content of the repeating unit (1-2) is 60%. If it exceeds mol%, the developability will decrease and the irradiated area will tend to swell. The copolymer resin (A) is prepared, for example, by mixing a mixture of monomers corresponding to each repeating unit with a radical polymerization initiator such as a hydroperoxide, a dialkylperoxide, a disilveroxide, or an azo compound. It can be produced by polymerizing in a suitable solvent in the presence of a chain transfer agent if necessary. Examples of the solvent used for the polymerization include cycloalkanes such as cyclohexane and cycloheptane; ethyl acetate, n-butyl acetate, i-butyl acetate, methyl propionate, propylene glycol monomethyl ether acetate, and the like. Saturated carboxylic acid esters; alkyl ratatones such as y_butyrolatatone; ethers such as tetrahydrofuran, dimethoxetane, and jetoxetane; alkyl ketones such as 2-butanone, 2-heptanone, and methyl isobutyl ketone Cycloalkyl ketones such as xanone; alcohols such as 2-propanol and propylene glycol monomethyl ether;

 These solvents can be used alone or in combination of two or more. The reaction temperature in the polymerization is usually 40 to 120 ° C, preferably 50 to 100 ° C, and the reaction time is usually 1 to 48 hours, preferably 1 to 24 hours. It is time. It is natural that the copolymer resin (A) has few impurities such as halogens and metals, but the residual monomer component is less than a predetermined value, for example, 0.1% by weight by I-IPLC. It is preferable to improve the sensitivity, resolution, process stability, pattern shape, and the like of the resist, and to provide a resist free from foreign substances in the liquid and the temporal change in sensitivity.

Examples of the method for purifying the copolymer resin (A) include the following methods. As a method for removing impurities such as metals, a method of adsorbing metals in a resin solution using a zeta potential filter or a method of washing a resin solution with an acidic aqueous solution of oxalic acid, sulfonic acid, or the like to make the metal chelate. And the like. Methods for removing residual monomers and oligomer components below a specified value include liquid-liquid extraction methods that remove residual monomer and oligomer components by washing with water and combining an appropriate solvent, and methods of removing specific molecular weight or less. A purification method in a solution state such as ultrafiltration that extracts and removes only the resin, and a method that removes residual monomers by coagulating the resin in the poor solvent by dropping the resin solution into the poor solvent. There are methods of purification in the solid state, such as precipitation and washing with a poorly filtered resin slurry. You can also combine these methods . The poor solvent used in the above-mentioned reprecipitation method depends on the physical properties of the resin to be purified and cannot be unequivocally exemplified. Where appropriate, poor solvents are selected.

• The weight average molecular weight in terms of polystyrene of the copolymer resin (A) determined by gel permeation chromatography (GPC) (hereinafter referred to as “Mw”) is from 1,000 to 50,000 in the present invention. And particularly preferably 4,000 to 40,000. In this case, if the Mw of the copolymer resin (A) is less than 1,000, there is a tendency that a sufficient dissolution inhibiting ability is not exhibited in the irradiated part and the resist does not function as a negative resist. The radiation-irradiated part has insufficient solubility in the developer and tends not to function as a negative resist. In addition, the dispersion defined by the ratio (Mw / Mn) between the Mw of the copolymer resin (A) and the number average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) (hereinafter referred to as “Μιι”). In the present invention, the degree is preferably from 1.00 to 5.00, particularly preferably from 1.25 to 2.25. When the degree of dispersion is 1 to 25 or less, the negative resist pattern tends to have a defect, and when it exceeds 5.00, the resolution of the negative resist tends to decrease.

 In the present invention, the copolymer resin (A) preferably has an "iMw" of 1,000 to 50,000 and a dispersity of 1.25 to 5.00.

 In the present invention, the copolymer resin (A) can be used alone or in combination of two or more. Radiation-sensitive acid generator (B):

 The radiation-sensitive acid generator (B), which can be used in combination with the copolymer resin (A), is a component that generates an acid upon irradiation with radiation.

The acid generator suitable in the present invention preferably contains at least one or more acid generators selected from the following formulas (2-1), (2-2), and (2-3). . In addition, these radiation-sensitive acid generators have a dissolution time of less than 7 minutes and a dissolution time of 7 minutes or more with the radiation-sensitive acid generator (B1), which is less than 7 minutes, according to the elution time measured by HPLC performed under specified conditions. It can be separated from the radiation-sensitive acid generator (B2), and its distinction was also attached to the specific examples below.

In the formula (2-1), the formula (2-2) and the formula (2-3), X— represents R ³ —S _{3 3} , and R ³ is partially or completely fluorinated. Represents a good carbonitride group. This hydrocarbon group represents a linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms, or an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 12 carbon atoms. n represents an integer of 0 to 2.

Specific examples of R ³ -S 0 ₃ include: nonafenoleolone n-butane / lefonic acid, perfunoleolol _1Ί- octanesnolefonic acid, 2- (bicyclo [2.2.1] heptoh-2-inole) 1: I, 1 Anions such as 2,2,2-tetrafunolene roetansnolefonic acid and camphorsnolefonic acid can be mentioned. In the formula (2-1), R ² is a hydrogen atom, a linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms, or an alicyclic hydrocarbon having 6 to 12 carbon atoms. Represents a group or an aromatic hydrocarbon group. Specific examples of R ² include a hydrogen atom, a methynole group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a cyclopentyl group, a cyclohexyl group, a bicyclo [2.2.1] heptyl group, Adamantyl group, Tricyclo [5. 2. 0 ² ' ⁶ ] decanyl group, tetracyclo [6.2.1. I ³ ' ⁶ .

0 ² ' ⁷ ] dodecanyl group and the like. Specific examples of the radiation-sensitive acid generator represented by the formula (2-1) include trifrenyls / levoninumonaphnoroleol n-butansnorefonate, trifreninoreth / levonipermnorphanololeol n-octansnorre Hornet, Tri-Feninoles / Rehonium 2-

(Bishik [2.2.1] hept-1-yl) 1-1,1,2,2-tetrafluroletanesulfonate, triphenylsnorrephonenum camphorsulfonet, and these are Applicable to radiation-sensitive acid generator (B1).

 In addition, 4-six mouth hexinorefenignoles / levonium nononaphnoleolone n-butanesnorefonate, 4-six mouth hexinorefefine / resifeninoresolenium perfluoronorethone n-octanes Norefonate, 4-cyclohexylolefeninoresulfinyl sulfonium 2- (bicyclo [2.2.1] hepto-2_yl) 1-1,1,2,2-tetrafuronolene , 4-cyclohexenolefeninoresulfinyl sulfo-dumcamphor sulfonate, which is a radiation-sensitive acid generator (B2).

 In addition, 4-t-butynolepheninolesifeninoles / levoninumnonaf / leoron n-butanesulfonate, 4-t-butylphenyldiphenylsulfonium perfulone-n-year-old tans.lufonate, 4 _ t Butynolepheni / Lezifeninoles / Reform 2— (Bishik mouth [2.2.1] Heptaw 2-yl) 1-1,1,2,2-Tetra phnoleone mouth ethanesnorefonate, 4-t Butynole And pheninolesulfeninolesulfonium camphorsulfonate, which corresponds to the radiation-sensitive acid generator (B 1). '

In addition, birds (41-t-butynolephenolone) sozolehoninimunonaphnoreolonate n-butane-norhenolate, tris (41-t-butynolephene-2 / re) sunorehonium-p-funoreleuro n-octane-norhenolate, birds (4_ t _Ptinolephen 2) Snorehonium 2— (Bisik mouth [2.2.1] Heptoe 2-yl) 1,1,1,2,2-te Trafluo mouth ethanesnorefonate, tri (4-t—ptinolefene) Nore) Snorreponidum camphor monosulfonate, which falls under the radiation-sensitive acid generator (B2). In the formula (2-2), R ⁴ represents a hydrocarbon group which may be partially or completely fluorinated. This hydrocarbon group represents a linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms, or an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 12 carbon atoms. U represents an oxygen atom, a sulfur atom, a sulfoxide group, a sulfonyl group, an oxysulfonyl group, a sulfonyloxy group, or the like. n represents an integer of 0 to 2.

Specific examples of R ⁴ include, as unfluorinated, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a cyclopentyl group, a cyclohexyl group, a bicyclo [2 . 2. 1] heptyl group, Adamanchiru group, tricyclo [5.2.2 1.0 ^{2 '6]} decanyl group, tetracyclo ^{[6 · 2. 1. I 3'} 6. ο 2 · 7] dodecanyl group, camphor group Examples of the fluorinated compound include a trifluoromethyl group, a nonafluoro-n-butyl group, a perfluoro-n-octyl group, and a 2- (bicyclic [2.2.1.1] hept-2-) Yl) — 1, 1, 2, 2-tetrafluoroethyl group and the like. Specific examples of the radiation-sensitive acid generator represented by the formula (2- 2), 4ι one Petit Noresu / Reho Nino reflex Eni Roh registration Hue Nino less Honoré Honi © Takeno naphthoquinone Bruno Leo row _n Butansunore Honeto, 4 one 11 Buchinoresu / Lefonylpheninoresiphenyls / lefonium perfulol n-octanesulfonate, 4-n-butyl / resul'honylphenyldiphenyl-2-norlesulfonium 2- (bicyclo [2.2.1] heptoh-2-ynole 1) 1,1,2,2-te Trafnoreo mouth ethanesnorefone 4-n-petit / resnorefoni / lefeninolesiphenylsulfoyum camphorsulfonate, which correspond to the radiation-sensitive acid generator (B1) I do.

In addition, 4-six-hexyl-resinole-honin-refenino-resin-II / resnor-le-ony-m-nonaf-nor-e-n-butane-s-nor-le-fonate Hemo-perf-norethone η-octane snorrephonate, 4-cyclohexyl hexenolesnorefonyl pheninolesiphenyleninolesulfonium 2- (bicyclo [2.2.1] hept-1-yl 1) 1,1,2,2-Tetra-funoroloethanesulfonate. 4 -Hexyl hexyl nolefonyl phenylinole phenyl sulfonium camphors norephonate, which falls under the radiation-sensitive acid generator (B1).

4-Nonaphnoleolone _n -butylsulfonyloxyphenyldiphenyls-norefonyumnonaphnoleolone _n -butanesnorlehonate, 4-nonaphnoleolone _n -butynolenolehoninoleoxy Pheninolesiphenylsnorrenodium perphnoleolone n-octanesulfonate, 4-nonaphneoleol n-butylsulfoninoleoxyphenol dipheninolesnorefonium 2- (bicyclo [2.2.1] hept 1 2-inole) 1 1, 1, 2,2,2-tetrafnoroleoloethanesnorefonate, 4-nonafnoroleol n-petit noresnorelephoninoleoxyfuheninolespheninoles / lefonym camphorsulfonate These correspond to the radiation-sensitive acid generator (B2).

In addition, 4-camphorsulfoninoleoxyphenyldiphenylsulfonimino funoroleol n-butanesnorefonate, 4-camphors / levoninoleoxyphenyl, 2-camphorsulfoninoleoxyphenyl diphenylphenylsulfonium perfluoronorethone Norefonate, 4-north arsenorhenoloxyfeni / rejifenii / resnorefonium 2- (Bisik mouth [2.2.1] Hept-1-2-yl) 1-1,1,2,2-Tetrafluo mouth ethanesulfone 1, 4-camphorsulfoninoleoxyphenyldiphenylsulfonium camphorsulfonate, which is a radiation-sensitive acid generator (B2). In addition, 4- (bicyclo [2,2.l] heptoh-2-yl) -1-1,1,2,2-tetrafurenole / ethylonyloxy / phenyl / dipheninolesulfoyumnona / funolole n-butanes / lephonate, 4 ― (Bicyclo [2.2.1] heptoe-2-inole) 1-1,1,2,2-tetrafluoronorethorinolesulfonyloxyphenyldiphenylsulfonium perfluoro-n-octanesnorlenate , 4-(Bisic mouth [2.2.1 · 1] hept-2-yl) — 1,1,2,2-tetrahnoleroethyl Chlorinolexinolexyphenyl-didiphenylsulfonium 2— ( Bicyclo [2.2.1] hept-1-yl) 1-1,1,2,2-tetrafluoroethanesulfonate, 4- 1 (bicyclo [2.2.1] hept-2-yl) 1-1 , 1,2,2-Tetrafluoro mouth ethinolesulfoninoleoxyphene / regifue Include Roh less Honoré Honi © insensitive Firth Honoré Honeto, it corresponds to the radiation-sensitive acid generator (B 2). In the formula (2-3), and R ⁶ independently represent a hydrogen atom or a hydrocarbon group. This hydrocarbon group represents a linear or branched aliphatic hydrocarbon group having 1 to 8 carbon atoms, or an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 12 carbon atoms. m represents an integer of 0 to 3, and n represents an integer of 0 to 2.

Specific examples of R ⁵ and R ⁶ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isoptyl group, a cyclopentyl group, a cyclohexyl group, a bicyclo [2.2.1] heptyl group , Adamanchiru group, tricyclo [5.2.2 1.0 ^{2 '6]} decanyl group, tetracyclo [6. 2.1.3 I ^{3' 6.} 0 ^{2 '7]} dodecanyl group and the like. Specific examples of the radiation-sensitive acid generator represented by the formula (2-3) include: 1- (4-n-butoxynaphthalene-1-inole) tetrahydrothiophene-dumnonafnorole-n-butanesnorrejo 1- (4-n-butoxynaphthalene 1-innole) tetrahi-drochiofujiemba-fluoro-n-octanesnolephonate, 1-1 (4-n-butoxynaphthalene-1-1-y / re) tetrahi Drochofenium 2-(Bisik mouth [2.2.1] hept-2-yl) — 1,1,2,2-tetraphnoleroethane sulfonate, 1- (4-n-butoxynaphthalene-1) 1-yl) tetrahydrothiophenedium camphorsulfonate, which is a radiation-sensitive acid generator (B1).

Also, 11- (3,5-dimethyl-4-hydroxy-phenyl) tetrahydro-drothiophenomnonafnoroleol n-butans-norefonate, 1-1- (3,5-dimethinolate 4-hydroxy-doxypheninole) tetrahydro-drothiophene Numperphnolelow n-octanesnorrephonate, 1- (3,5-dimethyl-4-hydroxyphene) tetrahydrodrothiophene 2- (bicyclo [2.2.1] heptoto-2 —Yl) 1,1,1,2,2-tetrafluoroethanesulfonate, 1- (3,5-dimethyl-4—hydroxyphenole) tetrahydrothiophenylcamphorsolenate, Corresponds to the radiation-sensitive acid generator (B1). —Acid generators represented by the formulas (2_1), (2-2) and (2-3) that can be used together with the acid generators suitable for the present invention are referred to as “other radiation-sensitive acid generators”. Notation, and specific examples thereof include diphenyododenim nonafluorate_n—butane norephonate, dipheninoleno-donium perphnoleolone n-otatansnorehonate. (Bissik mouth [2.2.1] hept-12-yl) 1-1,1,2,2-tetraphlorenoloethane sulphonate, diphenodorendumcanfasulfonate, and these are sensitive It falls under Radioactive Acid Generator (B1).

 In addition, bis (4-t-butynolefenerone) n-butane / lefonate, bis (4-t-butynolefenerole) n-octane-norhenolole Hornet, bis (4_t-butinorefenyl ') odonium 2- (bicyclo [2.2.1] heptoh-2-yl) 1,1,1,2,2-tetrafluoromouth ethanesnorefonate, bis (4-t-petit / refeninole) Eodonum camphor sulfonate, which falls under the radiation-sensitive acid generator (B2). N- (nonaf / leo-n-butanes-norefoni / reoxy) succinimide, N- (perphnole-one-n-octanes-norefoninoleoxy) succinimide, N_ [2— (bicyclo [2.2.1]] Hepto-2-yl) _ 1,1,2,2-tetraboronesulfonyloxy] succinimide, N- (camphorsulfonyloxy) succinimide, and these are radiation-sensitive acid generators ( This corresponds to B 1). '

N- (Nonaflu 'orol n-butane / levoni / reoxy) bicyclo [2.2.1] hept _ 5-ene _ 2,3-dicarpoximidide, N— (perfluoro-n-octane norefoni / reoxy) Bicyclo [2.2.1] heptose 5-ene-1,2,3-dicarboximide, N— [(-(bicyclo [2.2.1] heptoe-2-inole) 1-1,1,2,2 —Tetrafunoroloethanesnolehoninoleoxy] bicyclo [2.2.1] heptose 5 _2,3-dicarboximid, N— (camphors ruphonyloxy) bicyclo [2.2.1] heptone 5-ene-2,3-dicarboxyimides, which fall under the radiation-sensitive acid generator (B1). In the present invention, a radiation-sensitive acid generator (2-1), a radiation-sensitive acid generator (2-2), a radiation-sensitive acid generator (, 2_3) and other radiation-sensitive acid generators Collectively referred to as radiation-sensitive acid generator (B) "can be used alone or as a mixture of two or more.

 The amount of the radiation-sensitive acid generator (B) used is 0.1 to 20 parts by weight with respect to 100 parts by weight of the copolymer resin (A) from the viewpoint of ensuring the sensitivity and resolution as a resist. Parts, preferably 0.1 to 15 parts by weight. In this case, if the amount of the radiation-sensitive acid generator (B) used is less than 0.1 part by weight, sensitivity and developability tend to decrease, while if it exceeds 20 parts by weight, the transparency to radiation increases. As a result, the phenomenon of insolubilizing only the resist surface (dye-top phenomenon) tends to occur, which tends to make it difficult to obtain a resist 1 and a pattern. Acid crosslinking agent (C):

 The acid crosslinking agent (C) in the present invention cross-links the copolymer resin (A), which is a soluble resin, in the presence of, for example, an acid generated from the radiation-sensitive acid generator (B) upon irradiation with radiation. The type of the N- (alkoxymethyl ') glycol represented by the following formula (3-1) is not particularly limited as long as it can suppress the solubility in a developing solution. It preferably contains an acid crosslinking agent (C) represented by a peryl compound.

In the above formula (3-1), R ^{7 to} R ^1Q each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and an isopropyl group. Specific examples of the N- (alkoxymethyl) daricol peril compound represented by the formula (3-1) include N, N, N, N-tetra (methoxymethyl) glycol peryl, N, N, N, N-tetra (Ethoxymethyl) glyconoperyl, N, N, N, N-tetra (n-propoxymethyl) glycolperyl, N, N, N, N-tetra (i-propoxymethyl) glycolperinole, N, N , N, N-tetra (n-butoxymethyl) glycol peril, N, N, N, N-tetra "-butoxymethyl) daryl.cotyl, etc. In the present invention, the negative-type radiation-sensitive resin composition is , An acid crosslinking agent (hereinafter referred to as “other acid crosslinking agent”) other than the acid crosslinking agent (3-1). The other acid crosslinking agent is represented by the following formula (3-2). N- (alkoxymethyl) ゥ rare compound represented by the following formula (3-3 )), And N- (alkoxymethyl) amino compounds such as N- (alkoxymethyl) ethylene-perylene compounds represented by the following formula (3-4).

CH ₂ one ^{OR, s} H-2

CH ₂ one OR ¹⁷

R ¹⁹ 0

 (3-4)

The equation (3-2), - represents the (3 3) and the (3-4), R ^U to R ²² is from 1 to 4 carbon atoms independently of one another straight-chain or branched alkyl group. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. Specific examples of the N- (alkoxymethyl) rare compound represented by the above formula (3-2) include N, N-di (methoxymethyl) rare, N, N-di (ethoxymethyl) rare, N, N-di (n-propoxymethyl) rare, N, N-di (i-propoxymethyl) rare, N, N-di (n-butoxymethylinole) rare, N, N-di (t-butoxymethyl) rare No.

 Specific examples of the N- (alkoxymethyl) melamine compound represented by the above formula (3-3) include N, N, N, N, N, N-hexa (methoxymethyl) melamine, N, N , N, N, N, N—Hexa (ethoxymethyl) melamine, N, N, N, N, N, N—Hexa (n-propoxymethyl) melamine, N, N, N, N, N, N— Hexa (i-propoxymethyl) melamine, N, N, N, N, N, N-hexa (n-butoxymethyl) melamine, N, N, N, N, N, N-hexa (t-butoxy) Methyl) melamine and the like.

 Specific examples of the N- (alkoxymethyl) ethylene urea compound represented by the above formula (3-4) include N, N-di (methoxymethyl) -14,5-di (methoxymethyl) ethylene perylene. , N, N-di (ethoxymethyl) -4,5-di (ethoxymethyl) ethyleneperia, N, N-di (n-propoxymethyl) -1,4,5-di (n-propoxymethinole) ethyleneperia, N, N— Di (i-propoxymethyl) -4,5-di (i-propoxymethyl'methyl) ethylene perea, N, N-di (n-butoxymethinole) 1,4,5-di (n-butoxymethyl) ethylene perea, N , N-di (t-butoxymethyl) -14,5-di (t-butoxymethylmethyl) ethylene perylene and the like. In the present invention, the acid crosslinking agent (C) can be used alone or as a mixture of two or more. Particularly preferred is that the acid crosslinking agent (3-1) contains at least one or more acid crosslinking agents (3-1). It is preferable to appropriately contain an acid crosslinking agent.

In the present invention, the content of the acid crosslinking agent (C) is preferably from 0.5 to 50 parts by weight, based on 100 parts by weight of the copolymer resin (A) which is an alkali-soluble resin. Preferably it is 1 to 30 parts by weight, more preferably 2 to 20 parts by weight. If the amount of the acid crosslinking agent (C) is less than 0.5 part by weight, the amount of the acid crosslinking agent (C) in the alkali developing solution of the copolymer resin (A) is low. The insolubilizing effect, which lowers the solubility, is insufficient, the pattern swells and is chewy, the pattern is meandering, and the sensitivity tends to decrease significantly. On the other hand, when the amount exceeds 50 parts by weight, the heat resistance and transparency of the resist tend to be reduced, and a phenomenon that only the resist surface becomes insoluble tends to be observed. Acid diffusion controller (D)

 The negative-type radiation-sensitive resin composition of the present invention controls the diffusion phenomenon of the acid generated from the radiation-sensitive acid generator (B) in the resist film by irradiation with radiation, which is undesirable in the non-radiation irradiation region. It is preferable to add an acid diffusion controller having an action of suppressing a chemical reaction.

 The acid diffusion controller (D) is not particularly limited as long as it has a strong affinity for an acid. In the present invention, the acid diffusion controller contains at least one or more acid diffusion controllers represented by the following formula (4). Is preferred.

(4) In the above formula (4), R ²³ and R ²⁴ are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or R ²³ and R ²⁴ are Represents an alicyclic hydrocarbon group having 4 to 12 carbon atoms or an aromatic hydrocarbon group formed by bonding to

R ²⁵ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or one C (O) O ⁷ group.

R ²⁶ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or an alicyclic alicyclic hydrocarbon group or aromatic hydrocarbon having 6 to 12 carbon atoms. Represents a group. .

R ²⁷ represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. Examples of the linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms for R ²³ and R ²⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a cyclopentyl group, and a cycloalkyl group. A hexyl group; examples of the alicyclic hydrocarbon group or aromatic hydrocarbon group having 4 to 12 carbon atoms formed by bonding to each other include a pentyl group at a mouth, a hexyl group at a mouth, and a cyclohexyl group; Examples include a mouth heptyl group, a phenyl group and a naphthyl group, which may have a substituent.

Examples of the hydrogen atom or the linear, branched or cyclic alkyl group having 1 to 6 carbon atoms for R ²⁵ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butynole group, an isoptinol group, and a cyclopentyl group. group, Kishinore group to cycloalkyl is exemplified et be, or include one C (O) oR ²⁷ group.

In R ^26, it is a linear, branched or cyclic alkyl group of carbon number 1-6, hexyl methyl group, Echiru group, a propyl group, an isopropyl group, a butyl group, Isobuchi group, a cyclopentyl group, cyclohexylene Examples of the alicyclic alicyclic hydrocarbon group or aromatic hydrocarbon group having 6 to 12 carbon atoms include a cyclohexyl group, a cycloheptyl group, a phenyl group, and a naphthyl group. And, these may have a substituent.

Examples of the hydrogen atom or the linear, branched or cyclic alkyl group having 1 to 6 carbon atoms for R ²⁷ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a cyclopentyl group. And cyclohexyl groups. Specific examples of the acid diffusion controller represented by the above formula (4) include imidazole, 4-methinoreimidazole ', 1-pentinole 2-methinoreimidazole, 4-methyl-12-phenylenoleimidazonole, and Benzi Midazonole, 21-pheninolebenzimidazole, N-t-butoxycarbonylbenzimidazole, N-t-butoxyca-norepony- 2-methylbenzimidazole, N_t-butoxycarbovinyl 2- 2-phenylbenz Imidazole, 1-benzilimidazole, 1-methyl-2-phenylenbenzimidazonole, 1-benzinole-12-pheninolebenzimidazonole and the like. By adding such an acid diffusion controller, the storage stability of the resulting negative-type radiation-sensitive resin composition is further improved, the resolution as a resist is further improved, and the radiation-induced development processing is started. The line width of the resist pattern due to fluctuations in the lay-down time (PED) can be suppressed, and not only a composition with excellent process stability can be obtained, but also the solubility from the top to the bottom of the pattern can be improved. Variation can be suppressed, and in particular, unmelted residue at the bridging pattern lower part of the pattern upper part can be suppressed. Further, the negative-type radiation-sensitive resin composition of the present invention comprises an acid diffusion controller having a skeleton other than the acid diffusion controller represented by the above formula (4) (hereinafter referred to as “other acid diffusion controllers”). ) Can be contained.

 Examples of other acid diffusion controllers include “tertiary amine compounds”, “amide group-containing compounds”, “quaternary ammonium hydroxide compounds”, and “nitrogen-containing heterocyclic compounds”.

 Examples of the “tertiary amine compound” include triethylamine, tree 11-propylamine, tri-n-butylamine, tri-n-pentylamine, tree n-hexynoleamine, tree n-heptylamine, tri-n-octylamine, Tri (cyclo) alkylamines such as hexahexyldimethyl 'amine, dihexylhexylmethylamine and trihexylhexylbumin; aniline, N-methylaniline', N, N-dimethylaniline, 2-methylaniline, Aromatic amines such as 3-methylaniline, 4-methylaniline, 412troaniline, 2,6-dimethylaniline, and 2,6-diisopropylaniline; triethanolamine, N, N— Alkanolamines such as di (hydroxyxethyl) aniline; N, N, Ν ', Ν'-tetramethinolle Rangeamine, Ν, ,, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzenetetramethylenediamine, bis (2-dimethylamino) (Ethyl) ether, bis (2-ethylethylamino) ether and the like.

Examples of the “amide group-containing compound” include N-t-butoxycarboryl n-otatinoleamine, N-t-butoxycarbonyldicyclohexylamine, and N-t-butoxycarbonyldicyclohexylamine. 1-t-butoxycarbone 1-adaman, tilamine, N-t-butoxycarpo ninole N-methinole 1-1-adamantylamine, N, N-ge t-butoxy-canolepo enolate 1-adamantylamine, N , N-di-t-toxoxycanoleponinole N-methyl_1-adamantylamine, N-t-butoxycarbonyl-4,4, diaminodipheninolemethane, N, N, di-t- Butoxycanoleponinolehexamethylenediamine, N, N, N'N'-tetrabutoxycarbonylhexamethylenediamine, 1- (t-butoxycarbonyl) 1-2-pyrrolidinemethanol, t-butyl (tetrahydrodraw) 2-oxa-l-furanyl) caprate, N, N'-di-t-butoxycanoleponyl 4,4, diaminodiphenylmethane, N-t-butoxycarbonylbenz N-t-butoxycarbonyl group-containing amino compounds, such as midazole, N-t-butoxycarbonyl-1-2-methylenvenezimidazonole, N-t-butoxy force / reponinolei 2-pheninolebenzimidazole, and the like. Can be

 Examples of the “quaternary ammonium hydroxide compound” include tetra-n-propyl / leammonium hydroxide, tetra-n-butynoleammonium hydroxide and the like.

Examples of the “nitrogen-containing heterocyclic compound” include: pyridine, 2-methylpyridine, 4-methinolepyridine, 2-ethynolepyridine, 4-ethynoleviridine, 2-phenylpyridine, 4-phenynolepyridine, 2-methyl-14 Pyridines such as 1-phenylpyridine, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline, and acridine; piperazine, 11- (2-hydroxyshetyl) In addition to perazines such as perazine, pyrazine, pyrazonole, pyridazine, quinozalin, purine, pyrrolidine, piperidine, 3-piperidino 1,2-prono. Diol, morpholine, 4-methinoremo / rephorin, 1,4-dimethy / leviperazine, 1,4-diazabicyclo [2.2.2] octane and the like. Of these other acid diffusion controllers, tertiary amine compounds and Nt-butoxycarbonyl group-containing amino compounds are preferred. In the present invention, the acid diffusion controller (D) can be used alone or in combination of two or more. Particularly preferably, the acid diffusion controller represented by the formula (4) is used in a reduced amount. It is preferable to contain at least one of them, and to appropriately contain other acid diffusion controlling agents.

 The amount of the acid diffusion controller (D) is usually 15 parts by weight or less, preferably 10 parts by weight or less, more preferably 5 parts by weight, based on 100 parts by weight of the copolymer resin (A). It is below 5. In this case, if the amount of the acid diffusion controller (D) exceeds 15 parts by weight, the sensitivity as a resist tends to be significantly reduced. If the amount of the acid diffusion controlling agent is less than S 0 ..001 parts by weight, the pattern shape and dimensional fidelity as a resist may be reduced depending on the process conditions.

10 The negative type radiation-sensitive resin composition of the present invention may contain various additives such as a dissolution controlling agent, a dissolution accelerator, a surfactant, and a sensitizer.

 Dissolution control agent:

 When the solubility of the copolymer resin (A), which is an alkali-soluble resin, in an alkali developing solution is too high, the dissolution controlling agent controls the solubility of the copolymer resin (A) to appropriately control the dissolution rate of the resin during alkali development. It is a component having a reducing effect. As such a dissolution controlling agent, a dissolution controlling agent that does not chemically change in the steps of baking, irradiation of radiation, development and the like of a resist film is preferable.

 As the dissolution controlling agent, a saturated hydrocarbon, particularly a hydrocarbon having an alicyclic skeleton is preferable, and a compound which does not show solubility in an aqueous solution by itself is preferable. These dissolution control agents can be used alone or in combination of two or more.

 Dissolution accelerator: · If the solubility of the copolymer resin (A), which is a soluble resin in an alkaline developer, is too low, the solubility enhancer is used to increase the solubility of the resin (A). Is a component having an action of appropriately increasing the dissolution rate of As such a dissolution promoter 5, one that does not chemically change in the steps of baking, irradiation of radiation, development and the like of the resist film is preferable.

-As the dissolution promoter, saturated hydrocarbons, particularly hydrocarbons having an alicyclic skeleton are preferable, and compounds that exhibit solubility in water alone are preferable. These dissolution controlling agents can be used alone or in combination of two or more. The amount of the dissolution controlling agent or dissolution promoter to be added is generally 50 parts by weight or less, preferably 30 parts by weight or less, based on 100 parts by weight of the copolymer resin (A). In this case, if the amount of the dissolution controlling agent or the dissolution promoter exceeds 50 parts by weight, the heat resistance of the resist tends to decrease. Surfactant:

 The negative-working radiation-sensitive resin composition of the present invention may contain a surfactant having an effect of improving coatability, developability and the like.

 Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl / ether, polyoxyethylene oleyl ether, polyoxyethylene n-otatinole phenylinoleate ether, and polyoxyethylene n-noni. In addition to nonionic surfactants such as Noren feninoleatenore, polyethylene glycol resirelate, and polyethylene glycol distearate, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and Polyflow No. 75, No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), Megafax F171, F173 (Dainippon Ink Chemical Industry Co., Ltd.), Florado FC430, FC431 (Sumitomo Sleam Co., Ltd.), Asahigard AG 710, Sablon S — 38 2, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.). These surfactants can be used alone or in combination of two or more.

 The amount of the surfactant is usually not more than 2 parts by weight based on 100 parts by weight of the copolymer resin (A). Sensitizer:

The negative-type radiation-sensitive resin composition of the present invention may contain a sensitizer having an effect of improving sensitivity and the like. -Preferred sensitizers include, for example, carbazones, benzophenones, rose bengals, anthracenes, phenols and the like. These sensitizers can be used alone or in combination of two or more. The compounding amount of the sensitizer is preferably 50 parts by weight or less based on 100 parts by weight of the copolymer resin (A).

 Furthermore, examples of the additives other than those described above include an antihalation agent, an adhesion aid, a storage stabilizer, and an antifoaming agent. When used, the negative-type radiation-sensitive resin composition of the present invention was dissolved in a solvent so that the total solid content concentration was usually 3 to 50% by weight, preferably 5 to 25% by weight. Thereafter, for example, the composition is prepared as a composition solution by filtering with a filter having a pore size of about 200 nm.

Solvents used for preparing this composition solution include, for example, 2-hexanone, 2-heptanone, 2-octanone, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate, propylene glycol Monoethynoleate / Rareacetate, 2-Hydroxymethylpropionate, 2-Hydroxypropionate, 3-Ethylmethylpropionate, 3-Ethoxypropionate, Ethyleneglycolmonomethylether, Ethyleneglycol / Lemonethinoleether, Dethylene glycol dimethyl ether / ethylene glycol, ethylene glycol monomethyl ether ether acetate, ethylene glycol monomethyl ether oleate acetate, ethylene glycol monomethyl lemon ether acetate, propylene glycol alcohol monomer Butyl ether, propylene glycol monoethyl ether, n-butynole acid, methyl pyruvate, ethyl pyruvate, methylene glycol monomethyl ether, diethylene glycol monoethyl ether, y-butyrate ratatone, and the like. Solvents can be used alone or as a mixture of two or more types. Among the above examples, 2-heptanone, hexahexane, propylene glycol monomethinole ether acetate, 2-ethyl propionate , 3-ethoxyethyl propionate, propylene dalichol monomethyl ether, _γ -butyrate ratatone, and the like are particularly preferable. It preferably contains at least one teracetate, propylene dalycol monomethyl ether and the like. The negative radiation-sensitive resin composition of the present invention is particularly useful as a chemically amplified negative resist.

 In a chemically amplified negative resist, an electrophilic site is formed from an acid crosslinking agent (C) by the action of an acid generated from a radiation-sensitive acid generator (B) upon irradiation, and the electrophilic site is formed by a copolymer resin ( A) Electrophilic attack on a polar group, for example, a hydroxyl group, in A) causes a crosslinking reaction. As a result, the solubility of the irradiated portion of the resist in an alkali developing solution is reduced, and the unirradiated portion is dissolved and removed by an alkaline developer to obtain a negative resist pattern.

When forming a resist pattern from the negative-type radiation-sensitive resin composition of the present invention, the composition solution is applied to a silicon wafer by an appropriate application means such as spin coating, casting coating, roll coating, spray coating, or the like. A resist film is formed by applying the resist film on a substrate such as, for example, a heat treatment (hereinafter referred to as “PB”) is performed in advance, and then the resist film is irradiated with radiation so as to form a predetermined resist pattern. Irradiate. The radiation used in this case, for example, K r F Ekishimare The one (wavelength 2 4 8 nm), A r F excimer laser (wavelength 1 9 3 nm), F ₂ screeching laser (wavelength 1 5 7 nm) , EUV (extreme ultraviolet rays, wavelength 13 nm, etc.), and the ability to select and use far-ultraviolet rays such as ultraviolet rays, charged particle beams such as electron beams, and X-rays such as synchrotron radiation. Far ultraviolet rays and electron beams are preferred. The irradiation conditions such as the irradiation dose are appropriately selected according to the composition of the negative-type radiation-sensitive resin composition, the type of each additive, and the like.

In the present invention, in order to stably form a high-precision fine pattern, it is preferable to perform a heat treatment (hereinafter, referred to as “PEB”) after radiation irradiation. By this PEB, the crosslinking reaction in the irradiated part proceeds smoothly. The heating conditions for PEB vary depending on the composition of the negative radiation-sensitive resin composition, but are usually 30 to 200 ° C, preferably 50 to 170 ° C. In the present invention, in order to maximize the potential of the negative-type radiation-sensitive resin composition, a substrate used as disclosed in, for example, Japanese Patent Publication No. 6-124452, etc. An organic or inorganic antireflection film can be formed thereon, and in order to prevent the influence of basic impurities and the like contained in the environmental atmosphere, for example, Japanese Patent Application Laid-Open No. As disclosed in Japanese Unexamined Patent Publication (Kokai) No. HEI 10-301, a protective film can be provided on a resist film, or these techniques can be used in combination.

 Next, a predetermined resist pattern is formed by developing the resist film irradiated with the radiation. As the developer used for the development, for example, an alkaline aqueous solution in which tetramethylammonium hydroxide is dissolved is preferable. The concentration of the alkaline aqueous solution is usually 1 to 10% by weight, preferably 1 to 5% by weight. Further, an appropriate amount of a surfactant or the like can be added to a developer composed of an alkaline aqueous solution. After development with a developing solution composed of an alkaline aqueous solution, the film is generally washed with water and dried. Example

 Hereinafter, examples of the present invention will be described more specifically. Here, parts are by weight unless otherwise specified.

 Each measurement and evaluation in Examples and Comparative Examples was performed in the following manner.

 (1) Mw and Mw'ZM n:

Using Tosoh the Corp. GPC column _{(G 2 0 0 0 H XL} 2 _{present, G 3 0 0 0 H XL} 1 _{present, G 4 0 0 0 H XL} 1 present), flow rate 1.0 milli liters / min, The measurement was performed by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under the analysis conditions of elution solvent tetrahydrofuran and a column temperature of 40 ° C.

 (2) Sensitivity:

Using a substrate on which a ARC29A (Nissan Chemical Industries) film with a thickness of 78 nm was formed on the silicon wafer surface, each composition solution was applied on the substrate by spin coating, and then placed on a hot plate. A Nikon ArF excimer laser exposure system (optical conditions: NA = 0.55) was applied to a resist film with a thickness of 26.5 nm formed by performing PB at a temperature of 5 ° C for 90 seconds. , 2/3 A nnu 1 ar) Irradiation was performed through a phase shift mask (PSM mask) in which the portion that had transmitted the ArF laser 6% and the phase was inverted by 180 degrees. Thereafter, PEB was carried out at 105 ° C for 90 seconds, and then developed with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide at 25 ° C for 60 seconds, washed with water, dried, and then dried. A mold resist pattern was formed. At this time, the optimum radiation dose is defined as the radiation dose that forms a line-and-space pattern (1 L 1 S) with a line width of 140 nm in a one-to-one line width. did.

 (3) Resolution:

 The resolution of the smallest line 'and' space pattern resolved at the optimal radiation dose was defined as three levels: 140 nm, 130 nm, and 120 nm.

 (4) HPLC condition of acid generator:

Using an ODS column manufactured by G.Science, acetonitrile, ^κ water = 60/40 (weight ratio) to which 0.1% by weight of phosphoric acid was added to water was used as the eluent. Measured at 1.0 milliliter / minute. For detection, the maximum was measured by the area of the absorption at 220 nm. The radiation-sensitive acid generator having an elution time of less than Ί minutes is referred to as (B1), and the radiation-sensitive acid generator for 7 minutes or more is referred to as (B2).

 (5) Radiation transmittance:

 A resin solution prepared by dissolving the resin in propylene glycol monomethyl ether acetate (PGMEA) is applied on quartz glass by spin coating, and PB is applied on a hot plate at 105 ° C for 90 seconds. The radiation transmittance of a 265 nm-thick film was calculated from the absorbance at a wavelength of 193 iim measured for the resist film formed in this manner.

 (6) Remaining film ratio:

The thickness of the resist film formed by applying PB on the surface of a silicon wafer by spin coating and performing PB on a hot plate at a temperature of 105 ° C for 90 seconds is defined as A. Te 2. the tetramethylammonium two Umuhi Dorokishido aqueous 38 wt _^0/0, and developed for 60 seconds at 25 ° C, washed with water, when the thickness B of the resist film measured after dried, residual film ratio = (B / A) x 100. , · (7) Residual residue at the bottom of the pattern

 In some cases, the bottom of the pattern may show an extreme skirting shape due to the balance between the solubility of the resin and the solubility after crosslinking. Cross-section SEM observation determined by visual observation that no footing was observed, 〇, and that footing was observed but the substrate was resolved to △, footing was observed. In addition, those that have not been resolved up to the substrate are indicated by “X”.

 (8) Bridging at the top of the pattern:

 Depending on the balance between the solubility of the resin and the solubility after crosslinking, bridging may be observed at the top of the pattern. According to the visual judgment by cross-sectional SEM observation, `` ン グ j, '' for those with no pledges, `` △ '' for those with remnants of pledges but not the gap between the patterns, Those that can clearly show the skew between the patterns are indicated by “X”. Synthesis example

 (S1-1) (S1-2) (S1-3)

Methacrylic acid (1,1,1,1-trifluoro-2, trifluoromethyl-1,2-hydroxy-1,4-pentynole) in a 100-milliliter three-necked flask Estenolle (S1—1) 5.42 g (70 mole _^0/0), methacrylic acid (3-hydroxycarboxylic § Dammann single 1_ I le) ester (S l- 2) 1. 24 g (20 mole _^0/0), methacrylic acid (1 over human Dorokishechiru) ester (S 1- 3) 0. 34 g (10 mole _^0/0) and 2-flop Robanoru 17. put and 86 g, after stirring and dissolving, nitrogen location 30 minutes at an internal temperature of 80 ° C Changed. Then, 0.09 g of 2,2-azobis (isobutyronitrile) was added thereto, and polymerization was carried out for 16 hours under a reflux condition under a nitrogen atmosphere. After completion of the polymerization, the polymerization solution is cooled to 30 ° C. or lower by water cooling, poured into 2200 g of n-hexane, and the precipitated white powder is filtered. The filtered white powder was washed with 55 g of n-hexane three times in a slurry state, filtered, and dried at 60 ° C for 17 hours to obtain a white powder copolymer resin. (5.67 g, 81% yield). This copolymer resin had Mw of 39,400 and Mw / Mn of 3.17. ^{According to 13} C-NMR measurement, the content of each of the repeating units (S l — l), (SI—2), and (SI—3) was 69.0: 20.1: 1.10 (mol ° / ₀ ). Was a copolymer of This copolymer resin is referred to as resin (A-1). The radiation transmittance of this resin (A-1) was 82.5%. Synthesis example 2

Methacrylic acid (1, 1, 1 one-Trifluoro-2-triflate Ruo Russia methyl one 2-arsenide Dorokishi one 4-pentyl) ester (S 1- 1) 1 1. 60 g (70 mole _^0/0), Metatarinore acid ( 3-Hydroxydamantane (11-yl) ester (S 1-2) 2.66 g (20 mol ⁰ ), methacrylic acid (1-hydroxyxethyl) ester (S

1 - 3) 0. 73 g (10 mole _^0/0) was dissolved in 2-heptanone 30 g, further 2,

Prepare a simple S solution containing 0.19 g of 2-azobis (isobutyronitrile '), and purge with nitrogen in a 100 ml three-necked flask charged with 15 g of 2-butanone for 30 minutes. After the nitrogen purge, the reactor was heated to an internal temperature of 80 ° C. while stirring, and the above-prepared monomer solution was added dropwise using a dropping funnel over 3 hours. The polymerization reaction was performed for 6 hours, with the start of the dropwise addition as the polymerization start time. After completion of the polymerization, the polymerization solution is cooled to 30 ° C or lower by water cooling, poured into 600 g of n-hexane, and the precipitated white powder is separated by filtration. The filtered white powder was washed twice with 60 g of n-hexane in a slurry, filtered, and dried at 60 ° C for 17 hours to obtain a white powder copolymer resin. (12.12 g, 80.8% yield). This copolymer resin had Mw of 14,600 and MwZMn of 2.05. ^{According to 13} C-NMR measurement, the content of each of the repeating units of (S l_ l), (SI-2) and (S 1-3) was 67. 2: 21.8: 11.0 (mol%). This copolymer resin is referred to as resin (A-2). The radiation transmittance of this resin (A-2) was 81.6%. Synthesis example 3

Methacrylic acid (1, 1, 1 one Torifuruoro one 2-triflate Honoré Oro methylate Honoré one 2-arsenide Dorokishi one 4-pentyl) ester (S 1- 1) 1 1. 60 g (70 mole _^0/0), Metakurinore acid (3-Hydroxydamantane 1-yl) Ester (S 1-2)

2. 66 g (20 mole _^0/0), methacrylic acid (1-arsenate Dorokishechiru) ester (S 1 3) 0. 73 g (10 mole _^0/0) was dissolved in 2-butanone 30 g, further 2 Prepare a monomer solution containing 0.37 g of 2,2-azobis (isobutyronitrile), and purge with nitrogen for 30 minutes into a 100-milliliter three-necked flask containing 15 g of 2-butanone. After the nitrogen purge, the reactor was heated to an internal temperature of 80 ° C. while stirring, and the above-prepared monomer solution was added dropwise using a dropping funnel over 3 hours. The polymerization reaction was carried out for 6 hours, with the start of the dropwise addition as the polymerization start time. After the polymerization, the polymerization solution is cooled with water. Cool to below C, pour it into 600 g of n-hexane, and filter out the precipitated white powder. The filtered white powder was washed twice with 60 g of n-hexane in a slurry form, filtered, and dried at 60 ° C for 17 hours to obtain a copolymer resin as a white powder ( 12.24 g, yield 81.6%). This copolymer resin had Mw of 10,500 and Mw./Mn of 2.00. ^{According to 13} C-NMR measurement, the content of each of the repeating units (S 1-1), (S 1-2) and (S 1-3) was 68.3: 21.0: 10.7 (mol%). Was a copolymer of This copolymer resin is referred to as a resin (A-3). The radiation transmittance of this resin (A-3) was 80.6%. Synthesis example 4

Metakurinore acid (1, 1, 1 one-Trifluoro-2-triflate Ruo Russia methyl one 2- arsenide Dorokishi 4-pentyl) Esutenore (S 1- 1) 1 5. 47 g (70 mole _^0/0), methacrylic acid (3 —Hydroxydamantane 1-yl) Ester (S 1-2)

3. 55 g (20 mole _^0/0), methacrylic acid (1 over human Dorokishechiru) ester (S 1- 3) 0. 98 g (10 mole _^0/0) was dissolved in 2-butanone 40 g, further 2 , Prepare a monomer solution charged with 0.99 g of 2-azobis (isobutyronitrile), and purge with nitrogen for 30 minutes a 100-milliliter three-necked flask charged with 20 g of 2-butanone. After the nitrogen purge, the reactor was heated to an internal temperature of 80 ° C. while stirring, and the above-prepared monomer solution was added dropwise over 3 hours using a dropping funnel. The polymerization reaction was carried out for 6 hours, with the start of the dropwise addition as the polymerization start time. After completion of the polymerization, the polymerization solution is cooled with water to 30 ° C or lower, poured into 800 g of n-hexane, and the precipitated white powder is filtered off. The filtered white powder was washed twice with 80 g of n-hexane in a slurry form, filtered, and dried at 60 ° C for 17 hours to obtain a white powdered resin (14. 92 g, yield 74.6 ° /.). This copolymer resin had Mw of 6,600 and Mw / Mn of 1.88. ^{According to 13} C-NMR measurement, the content of each of the repeating units (S 1-1), (S 1-2), and (S 1-3) was 66.6: 23.1: 10.4 (mol%). Was a copolymer of This copolymer resin is referred to as a resin (A-4). The radiation transmittance of this resin (A-4) was 76.4%. Synthesis example 5

Methacryloleic acid (1,1,1,1-trifluoro-2-trifluoromethyl-12-hydroxy-14-pentyl) Estenole (S l-l) 15.47 g (70 mol%), methacrylic acid (3- hydroxycarboxylic § Dammann single 1-I le) ester (S 1- 2) 3. 55 g (20 mole _^0/0), Metatariru acid (1 over human Dorokishechiru) ester (S 1 - 3) 0. 98 g ( 10 mol%) in 40 g of 2-butanone, prepare a monomer solution containing 1.48 g of 2,2-azobis (isobutyronitrile), and add 100 g of 20 g of 2-butanone. Purge the three-necked flask with nitrogen for 30 minutes. After the nitrogen purge, the reactor was heated to an internal temperature of 80 ° C. while stirring, and the above-prepared monomer solution was added dropwise using a dropping funnel over 3 hours. The polymerization reaction was carried out for 6 hours, with the start of the dropwise addition as the polymerization start time. After completion of the polymerization, the polymerization solution is cooled with water to 30 ° C or lower, poured into 800 g of n-hexane, and the precipitated white powder is filtered off. The filtered white powder was washed twice with 80 g of n-hexane in a slurry form, filtered, and dried at 60 ° C for 17 hours to obtain a white powdered resin (1). 5.92 g, yield 79.6%). This copolymer resin has a Mw of 4, 30 Mw / Mn was 1.60. ^{By 13} C-NMR measurement, the content of each of the repeating units (SI-1), (SI-2), and (S1-3) was found to be 67.5: 22.2: 10.3 (mol%). ). This copolymer resin is referred to as a resin (A-5). The radiation transmittance of this fat (A-5) was 76.2%. '' Synthesis example 6

Metatarinore acid (1, 1, 1 one-Trifluoro-2-triflate Honoré Oro methylate Honoré _ 2- arsenide Dorokishi 4 one Penchinore) Esutenore (S 1- 1) 1 3. 5 6 g (6 0 Monore _^0/0), methacrylic acid (3-hydroxycarboxylic § Dammann single 1 one I le) ester (S 1 - 2) 5. 44 g (3 0 mole _^0/0), methacrylic acid (1 over human Dorokishechiru) Esutenore (S

1-3) Dissolve 1.0 g (10 mol ⁰ /.) In 40 g of 2-butanone, and add

A monomer solution containing 1.43 g of 2-azobis (isobutyronitrile) and 0.31 g of n-dodecanethiol was prepared, and 100 g of 100 g of a monomer solution containing 20 g of 2-butanone was prepared. The three-necked flask is purged with nitrogen for 30 minutes. After the nitrogen purge, the reactor was heated to an internal temperature of 80 ° C. while stirring, and the above-prepared monomer solution was added dropwise using a dropping funnel over 3 hours. The polymerization reaction was carried out for 6 hours, with the start of the dropwise addition as the polymerization start time. After completion of the polymerization, the polymerization solution is cooled to 30 ° C. or lower by cooling with water, poured into 800 g of η-hexane, and the precipitated white powder is filtered. The filtered white powder was washed twice with 80 g of n-hexane in a slurry form, filtered, and dried at 60 ° C for 17 hours to obtain a white powder resin ( 15.92 g, yield 79.6%). This copolymer resin had Mw of 5,600 and Mw / Mn of 1.69. ^{According to 13} C-NMR measurement, the content of each of the repeating units (S 1-1), (S 1-2) and (S 1-3) was 67.0: 22.4: 10. 6 (mol%) was a copolymer. This copolymer resin is referred to as a resin (A-6). The radiation transmittance of this resin (A-6) was 75.6%. Examples 1 to 17 Various evaluations were made for each composition solution comprising the components shown in Table 1. Table 2 shows the evaluation results. The components other than the polymers (A-1) to (A-6) in Table 1 are as follows.

Radiation-sensitive acid generator (B)

B-1: 4-t-Ptinolepheninole dipheninolenesorenodium nonaphnoleolone n-butanesulfonate (HP LC elution time: 7.21 minutes)

 B—2: Trifenylsnorefonium 'nonafnoroleol n-butanesnorefonate (HPC LC elution time: 4.71 minutes)

 B-3: 4-six-hexyl hexinole honinolefe n-butane sulphine-n-butane sulphonate (HPLC elution time: 6.60 minutes)

B—4: 4 octane-fernose / reoxyphenyl + dipheninolenes / lenophenomna orolo- _n -butanesulfonate (HP LC elution time: 8.30 minutes)

B-5: 1- (4-n-butoxynaphthalene-11-yl) tetrahidrochiefuumnonafluoro-n-butanesulfonate (HP LC elution time: 7.32 min) Acid crosslinking agent (C)

 C—1: N, N, N, N—tetra (methoxymethyl) glycol peril

Acid diffusion controller (D)

 D— 1: Tetra (n-butyl) ammonium hydroxide

D—2: 2—Fenii / Le 'Benzimidazo / Le

Solvent (E)

E-1: Propylene Darico Monomethyl

Table 2

Industrial applicability

 The negative-working radiation-sensitive resin composition of the present invention will be used as a chemically amplified negative-working resist that is sensitive to actinic radiation, in particular, far-ultraviolet rays represented by an ArF excimer laser (wavelength: 193 nm). It can be used very suitably in the manufacture of semiconductor devices, which are expected to become more advanced.

Claims

The scope of the claims

1. a copolymer resin (A) containing a repeating unit (111) represented by the following formula (1-1) and a repeating unit (112) represented by the following formula (1-2); A negative-type radiation-sensitive resin composition comprising a radiation-sensitive acid generator (B) and an acid crosslinking agent (C).

 (1-1) (1-2)

In (the above formula (1 one 1) Oyopi formula (■ 2), R ¹ represents a hydrogen atom or a methyl group, in the formula (1-1), X ^L and X ² or a hydrogen atom independently of one another Represents a fluoroalkyl group, and at least one of X ¹ and X ² represents a fluoroalkyl group, Y represents a divalent organic group, Z represents a divalent to tetravalent organic group, and T represents a single bond or the number of carbon atoms. Represents a divalent organic group of 1 to 3, and n represents an integer of 1 to 3.)

2. The negative radiation sensitive material according to claim 1, wherein the copolymer resin (A) has a weight average molecular weight in terms of polystyrene of 1,000 to 50,000 as measured by gel permeation chromatography (GPC). Resin composition.

3. The method according to claim 1, further comprising an acid diffusion controller (D) together with the copolymer resin (A), the radiation-sensitive acid generator (B) and the acid crosslinking agent (C). Negative-type radiation-sensitive resin composition.

4. The composition according to claim 1, wherein the compounding amount of the radiation-sensitive acid generator (B) is 0.1 to 20 parts by weight based on 100 parts by weight of the copolymer resin (A). Negative-type radiation-sensitive resin composition.

5. The radiation-sensitive acid generator (B) contains at least one or more acid generators selected from the following formulas (2-1), (22) and (2-3). The negative-type radiation-sensitive resin composition according to claim 1, characterized in that:

In (the above formula (2 1), the formula (2-2) Oyopi formula (2 3), X- represents R ³ one S0 ₃ one, R ³ is partially or all fluorinated R ² represents a hydrogen atom or a hydrocarbon group, R ⁴ represents a hydrocarbon group which may be partially or completely fluorinated, and U represents a divalent hydrocarbon group. Represents an organic group, R ⁵ and R ⁶ independently represent a hydrogen atom or a hydrocarbon group, m represents an integer of 0 to 3, and n represents an integer of 0 to 2)

6. The negative-type radiation-sensitive resin composition according to claim 5, wherein the radiation-sensitive acid generator (B) is represented by the formula (2_3).

7. The negative mold according to claim 1, wherein the amount of the acid crosslinking agent (C) is 0.5 to 50 parts by weight based on 100 parts by weight of the copolymer resin (A). Radiation-sensitive 'resin composition.

8. The negative-type radiation-sensitive resin composition according to claim 1, wherein the resin component is dissolved in a solvent, and the total solid content concentration is 3 to 50% by weight.

9. The negative radiation-sensitive resin composition according to claim 8, wherein the solvent is at least one solvent selected from the following group.

 Solvent group: 21-hexanone, 21-heptanone, 2-octanone, cyclopentanone, hexahexanone, propylene glycol monomethizoleate enorea acetate, propylene glycol monoethyl ether acetate, 2-h Methyl droxypropionate, 2-ethylethyl propionate, · Methyl 3-ethoxypropionate, ethinole 3-ethoxypropionate, ethylene glycolone monomethyl ether, ethylene glycol mono / ethyl monoethyl ether, diethylene glycol 1 / resin methinooleate diethylene glycol getyl ether, ethylene glycol monomethyl ether oleate, ethylene glycol monoethyl enoate, enoleacetate, propylene glycol monomethyle, reether ', propylene glycol Ethers', acetic acid n- heptyl, methyl pyruvate, Echiru pyruvate, Jefferies Chi glycol mono methyl ether, diethylene glycol mono-E chill ether, gamma _ Buchirorata Bokun.

10. The negative radiation-sensitive resin composition according to claim 2, wherein the acid diffusion controller (D) is represented by the following formula (4).

(In the above formula (4), R ²³ ′ and R ²⁴ independently represent a hydrogen atom or an alkyl group, or an alicyclic hydrocarbon group or an aromatic hydrocarbon group formed by bonding to each other; ²⁵ represents a hydrogen atom, an alkyl group, or one C (O) OR ²⁷ group, R ²⁷ represents an alkyl group, and R ²⁶ represents a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group, or an aromatic group. Represents a hydrocarbon group.)