TWI333126B - - Google Patents

Description

1333126 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 发明 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负 负In the microfabrication of various kinds of radiation such as rays, it is suitable to use a negative-type radiation-sensitive resin composition which is a useful type of resist. [Prior Art] In order to achieve higher integration in the field of microfabrication represented by the manufacture of integrated circuit components, it has recently been possible to use ArF-excited (wavelength 193 nm) and F2 excimer laser (wavelength 15 7 nm) to about 20 Onm. The lithographic technique of microfabrication ^ The radiation sensitive linear resin composition irradiated by such excimer laser has been developed to enhance the chemical effect caused by the component having an acid dissociable functional group and an acid generator irradiated with radiation. Reinforced Chemical Linear Resin Composition In the reinforced chemical-type radiation-sensitive resin, the negative-type radiation-sensitive resin composition is subjected to a crosslinking reaction by radiation, so that the dissolution rate for the developing solution is lowered. Conventionally, a negative-type radiation-sensitive resin composition is known as a negative-type resist having a (meth)acrylic acid derivative having a alicyclic group as a crosslinking site (Patent Document 1). However, when a photoresist is used and an integrated circuit is actually fabricated, it is particularly enhanced for the external line and the electric particle. * For the elemental laser or the like, it is suitable for many cases in which the acid-sensing radiation composition is formed. In the case of a radiation-sensitive linear composition in which a radiation-sensitive component, a film-forming resin component, or the like is dissolved in a solvent to form a photoresist solution, and the photoresist solution is applied to a substrate for processing. After the photoresist film is formed thereon, the photoresist film is irradiated with radiation through a predetermined mask, and developed to form a pattern suitable for microfabrication. At this time, since the shape of the pattern cross section (pattern cross-sectional shape) has a significant influence on the fineness of the micro-machining, it is preferable to use a rectangular shape in order to improve the fineness. [Patent Document 1] Japanese Laid-Open Patent Publication No. 2000-122288. However, the conventional chemically-resistant negative photoresist has a difference in dissolution rate with respect to the developing solution of the photoresist due to the difference between the radiation irradiating portion and the radiation non-irradiating portion. Large, so the resolution is low, and the shape of the head of the pattern is not rectangular and has a problem of rounding. Further, since the dissolution rate of the radiation non-irradiated portion is extremely high, the dissolution rate of the radiation irradiation portion is not sufficiently lowered, and the pattern is swollen by the developing liquid, and the problem of the meandering is caused. SUMMARY OF THE INVENTION The present invention has been made to solve such problems, and provides a negative-type radiation-sensitive resin composition using an ArF light source, which can be applied without problems in a conventional normal concentration developing solution, and is in a usual line/ In the space pattern, high development is displayed, and a rectangular photoresist pattern can be formed, which can reduce the defects of the photoresist pattern such as cross-linking (orange connection) after the development, and the sensitivity, the imaging property, the dimensional fidelity, and the like. It is excellent as a negative-type radiation-sensitive resin composition for enhancing chemical-type negative photoresist. The negative-type radiation-sensitive resin composition of the present invention is characterized by containing a repeating unit (1-1) represented by the following formula (1-1) and a repeating unit represented by the following formula (1_2) (I· 2) a copolymer resin (A), a radiation sensitive acid generator (B), and an acid crosslinking agent (C). R1 -^CH2_C· ch2-c- R1

OH c=o

O X1 —C / X2 (1-1)

z r4~^ τ , OH (1-2) In the above formula (1-1) and formula (1-2), R1 represents a hydrogen atom or a methyl group, and in the formula (1-1), X1 and X2 The hydrogen atom or the fluoroalkyl group is independently represented, and at least one of X1 and X2 represents a fluoroalkyl group, Y represents a divalent organic group, Z represents a di-tetravalent organic group, and T represents a single or carbon number. 1 to 3 of the divalent organic groups, and η is an integer representing 1 to 3. Further, the copolymer resin (yttrium) has a weight average molecular weight of 1, and 〇〇〇 to 50,000 in terms of polystyrene measured by gel permeation chromatography (GPC). The negative-type radiation-sensitive resin composition of the present invention is characterized by comprising the above-mentioned copolymer resin (Α), a radiation-sensitive linear acid generator (Β), an acid crosslinking agent (c), and an acid diffusion inhibitor (D). Further, the amount of the radiation-sensitive linear acid generator (yttrium) is preferably from 0 to 1 part by weight based on 100 parts by weight of the copolymer resin. Further, the radiation sensitive linear acid generator (B) is characterized by containing at least one acid generator selected from the following formula (2-1), formula (2-2) and formula (2-3).

In the above formula (2-1) 'formula (2-2) and formula (2-3), X - represents R3-SO_, and R3 represents an aliphatic hydrocarbon group or aromatic which may also be partially or fully fluorinated. a hydrocarbon group, R2 represents a hydrogen atom, or an aliphatic hydrocarbon group or an aromatic hydrocarbon group, R4 represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group which may be partially or wholly fluorinated, U represents a divalent organic group, and R5 and R6 are Each of them independently represents a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group, m is an integer representing 0 to 3, and η is an integer representing 0 to 2. Further, in particular, the radiation sensitive linear acid generator (?) is characterized by the formula (2-3). The negative-type radiation-sensitive resin composition of the present invention is such that the compounding amount of the acid crosslinking agent (c) is 〇·5 to 50 parts by weight based on 1 part by weight of the copolymer resin (Α). Further, the 'tree resin component is characterized by being dissolved in a solvent and having a total solid content concentration of 3 to 50% by weight. Here, the measurement of the total solid concentration is carried out by subjecting the negative-type radiation-sensitive resin composition sample to about 1 g at 10 (drying for 4 hours). The above solvent is 2-hexanone, 2-heptanone, 2- Octanone, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 2-hydroxyformate, ethyl 2-hydroxypropionate, methyl 3-ethoxypropionate, 3 -ethyl ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diglyme, diethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate Selecting at least one solvent from the group consisting of ester, propylene glycol monomethyl ether, propylene glycol monoethyl ether, n-butyl acetate, methyl pyruvate, ethyl pyruvate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether and r-butyrolactone group Further, the 'acid diffusion inhibitor (D) is characterized by the following formula (4).

In the above formula (4), R23 and R24 each independently represent a hydrogen atom or an alkyl group, or are bonded to each other to form an alicyclic hydrocarbon group or an aromatic hydrocarbon group, and R25 represents a hydrogen atom, a hospital group, or a -C(O) group. 〇R27 group, R27 represents an alkyl group 'R26 represents a hydrogen atom, an alkyl group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. The negative-type radiation-sensitive resin composition of the present invention contains a copolymer resin containing a repeating unit (1-1) represented by the formula (1333126 1-1) and a repeating unit (1 _2 ) represented by the formula (1-2). (A), and the radiation-sensitive linear acid generator (B) and the acid crosslinking agent (C), even if applied to an alkaline developing solution of a usual concentration, a normal line/space pattern can be formed and suppressed The defect represented by the dissolution residue under the pattern and the bridging above the pattern caused by insufficient solubility of the developing liquid by the radiation-irradiated portion occurs. Further, it is also possible to suppress the pattern collapse of the fine regions caused by the swelling, and to maintain the rectangular pattern shape even in the fine regions. The best mode of the invention uses the previously enhanced chemically-type negative photoresist of the ArF light source to provide a dissolution rate of the radiation-unirradiated portion by copolymerizing a repeating unit containing a carboxyl group, and at this time, since the dissolution rate is apt to become fast, Therefore, the adjustment is difficult, and the resolution of the photoresist pattern is low, and it is easy to swell. Therefore, an appropriate negative-type radiation-sensitive resin composition which is excellent in sensitivity, development, dimensional fidelity, etc., which enhances the chemical-type negative-type photoresist, has not been commercialized so far. The action of a fluoroalkyl group via a repeating unit (1-1) by using a copolymer containing a repeating unit (1 -1 ) of a fluorine-containing alkyl group and a repeating unit (1 -2 ) containing at least one of X1 and X2 It was found that the dissolution rate of the unirradiated portion of the radiation can be adjusted in the photoresist pattern. The present invention is based on such findings. In addition, the term "dissolution rate" refers to the time when the film thickness at the time of image development is measured by a predetermined development condition is reduced from the initial enthalpy to the specified enthalpy, and is expressed by [(initial film thickness of a predetermined film thickness) / time] After that. -10- 1333126 A copolymer resin (A) constituting a negative-type radiation-sensitive resin composition: a repeating unit constituting the copolymer resin (A) (1-1 shows a divalent organic group. The organic group may be a linear or branched group Hydrocarbon group. The linear or branched hydrocarbon group has 1 to 12 carbon atoms. Specific examples thereof include divalent hydrocarbon groups derived from methane, ethane, propane and butyl. The alicyclic hydrocarbon group has 6 to 20 carbon atoms. Specific examples of the alicyclic ring may be exemplified by cyclohexane, bicyclo [2.2.1] heptane [2.2.1] heptane, adamantane, tricyclo[5.2.1.02'6] [6.2.1.13'6.02'7] a divalent alicyclic hydrocarbon group of dioxane. Among the divalent organic groups represented by Y, it is derived from propane, cyclohexane, 2-methylbicyclo[2.2.1]heptane, tetraoxane [6. dioxane The divalent organic group is preferred. The fluoroalkyl group is preferably a carbon number group in the repeating unit (1-1), and specific examples thereof include a monofluoromethyl group and a difluoromethyl group. Among them, a trifluoromethyl group or the like is used. Preferably, the fluoroalkyl group is X, and preferably X2 and X2 are fluoroalkyl groups. In the repeating unit (1-2), Z represents a 2-4 molecular group, which may be linear, branched, or Alicyclic hydrocarbon linear The branched hydrocarbon group is preferably a hydrocarbon group having 1 to 12 carbon atoms in a branched form, and specific examples thereof include components derived from methane. Among them, Y is a tabular or alicyclic hydrocarbon group, and an alkane or isobutane is preferable. The hydrocarbyl group is preferred, and it is 2-methylbicyclodecane, tetracyclobutane, isobutane 2.1.3, 6.02'7] ten to four gas bases, at least trifluoromethyl groups 1 and X2 The price is organic. Have a base. a linear quaternary - ethane, propane -11 - 1333126, butane, isobutane or the like of a quaternary to tetravalent hydrocarbon group. 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[5.2.1.02'6. a non-tetravalent alicyclic hydrocarbon group of decane, tetracyclo[6.2.1.13, 6.03,7]dodecane. The divalent organic group represented by Z is derived from ethane, propane, isopropanol, butane, isobutane, cyclohexane, bicyclo [2.2.1] heptane, tetracyclo[6.2, 1.13'6.02' 7] The di-tetravalent organic group of dodecane is preferred. In the repeating unit (1-2), T is a divalent organic group representing a single bond or a carbon number, and specific examples thereof include a divalent hydrocarbon group derived from a single bond, methane, acetonitrile, propane or isopropane. Among them, a single bond, a methylene group, an ethyl group or the like is preferred. Further, in the formula (1-2), η is an integer representing 1 to 3, and 1 or 2 is preferable. The monomer which provides the repeating unit (1 -1 ) represented by the formula (1 -1 ) may be exemplified by (meth)acrylic acid (1' 1' 1-trifluoro-2-trifluoromethyl-2-hydroxy-3-propanol). Ester), (meth)acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-alkyl-4-yl) ester, (meth)acrylic acid (丨' 1,;! ·Trifluoro-2-trifluoromethyl-2-hydroxy-5-pentyl)ester, (meth)acrylic acid (1,1, fluorene-trifluoro-2-trifluoromethyl-2-hydroxy-4- Pentyl)ester, (meth)acrylic acid 2. {[5-(1',1',1'-trifluoro-2,-trifluoromethyl-2,-hydroxy)propyl]bicyclo[2.2_1] Heptyl}ester, (meth)acrylic acid 3_{[8_(1,,Γ,ι,_trifluoro-2'-trifluoromethyl-21-hydroxy)propyl]tetracyclo[6·2·1· 13,6·〇2,7] 12 yards} vinegar and other (methyl) propane smoldering wake up. -12- 1333126 Further, "(meth)acrylic acid" in the present invention means both "(meth)acrylic acid" and "acrylic acid". The monomer which provides the repeating unit (1-2) represented by the formula (1-2) may, for example, be hydroxymethyl (meth) acrylate, bismuth (methyl) acrylate 经 _ acetonitrile, (meth) acrylate 2 - Hydroxyethyl ester, bis(methyl)propanoate 丨 _ propyl vinegar, 2-hydroxypropyl (meth) acrylate, (methyl) propylene citrate 3 · propyl vinegar, 3-hydroxy ketamine (meth) acrylate Alkenyl 1-yl ester, 3,5-dihydroxyadamantan-1-yl (meth)acrylate, 3'5,7-tri-hydroxydendan-1-yl, (meth)propanoic acid, (Meth)acrylic acid 5-carbylbicyclo[2·2·1]heptan-2-yl ester '(meth)acrylic acid 5-hydroxymethylbicyclo[2·2·1] Gengyuan·2· vinegar , (meth)acrylic acid 5-oxomethylbicyclo[2·2·1] Gengyuan-2·methyl ketone, (meth)acrylic acid 8-hydroxytetracyclo[6.2.1.13'6.〇2'7 ]Dodecyl-3-yl ester, (meth)acrylic acid 8·hydroxymethyltetracyclo t6.2·1.1.3·6.02·7]12th hospital·3_yl ester, (meth)acrylic acid 8- (Meth) acrylate such as hydroxytetracyclo[6.H·13'6.〇2,7]dodecane·3_methyl ester. The copolymer resin (A) of the present invention may contain other repeating units in addition to the above repeating unit (1-1) and repeating unit (1-2). Examples of the monomer which provides another repeating unit include (meth)acrylic acid, carboxymethyl (meth)acrylate, 2-carboxyethyl (meth)acrylate, and 3-carboxyadamantane-1 (meth)acrylate. -yl ester, 5-(carboxy)bicyclo[2.2.1]hept-2-yl (meth)acrylate cyanomethyl (meth) acrylate, 2-cyanoethyl (meth) acrylate, (methyl) Acrylic acid-3·cyanoadamantan-1-yl ester, 5-(cyanobicyclo)[2.2.1]hept-2-yl (meth)acrylate, methyl (meth)acrylate, (methyl) Ethyl acrylate, (meth) propylene • 13- 1333126 acid Donkey Kong -1- vinegar, (methyl) acrylic acid bicyclo [2.2.1] hept-2-yl vinegar, (meth) acrylate-7, 7-Dimethylbicyclo[2.2.1]heptanyl vinegar, trimethyl [(methyl) acrylate] [5.2.1.02,6] 癸-8-yl ester, (meth)propanoic acid _ 7 -oxygen -6 -Naibicyclo[2.2.1]oct-4-yl vinegar, (methyl)propanoid acid-2-methoxycarbonyl '7.oxy-6-indole bicyclo[2.2.1]oct-4-yl ester , (meth)acrylic acid 2-methoxytetrahydropyran-4-yl ester, (meth)acrylic acid-4-methyl-2-oxytetramethyl sulfonium-4-yl vinegar, (methyl ) C Dilutic acid-5-oxytetraazin-3-yl ester '2-oxytetrahydrofuran-3-yl (meth)acrylate, 5-methoxytetrahydrofuran-2-yl (meth)acrylate Ester,-3,3-dimethyl-5-oxytetrahydrofuran-2-ylmethyl (meth)acrylate, N,N-di(methyl)propanol, crotonamide, Malayan Amine, fumarate, mesaconamine, citrate, itaconamide, and the like. The copolymer resin (A) of the present invention is preferably constituted by the above repeating unit (1-1) and the repeating unit (1-2), and the copolymer resin (A) is preferably one or more repeating units. Further, the repeating unit (1-2) is preferably a combination of a repeating unit containing an alicyclic hydrocarbon group and a repeating unit not containing an alicyclic hydrocarbon group. The copolymer of the present invention is a combination of a repeating unit (1-1), a repeating unit containing an alicyclic hydrocarbon group, and a repeating unit (1 - 2 ) which does not contain an alicyclic hydrocarbon group, since it does not occur. It is preferable to bridge the defects and form a rectangular photoresist pattern. The mixing ratio of each repeating unit is 40 to 80 mol%, preferably 50 to 80 mol%, in the repeating unit (1-1) with respect to the total repeating unit: the repeating unit (1-2) is 5 to 60 Ear %, preferably 10 to 50 mol%. Repeating the single -14-13333 bit (1 -1) content is less than 40 mol%', the solubility of the developing solution tends to deteriorate, and the repeating unit (1-1) content exceeds 80 m. %, the solubility of the radiation irradiation portion is too high, and the resolution is deteriorated and there is a tendency to swell. When the content of the repeating unit (1 - 2 ) is less than 5 mol %, the degree of crosslinking of the radiation irradiating portion is insufficient and the resolution is deteriorated, and the content of the repeating unit (1-2 ) exceeds 60 m. % shows a decrease in developability, and the radiation irradiation portion tends to swell. For the copolymer resin (A), for example, a radical polymerization initiator such as hydrogen peroxide, a dialkyl peroxide, a dioxonium peroxide or an azo compound may be used as the monomer mixture for each repeating unit, as needed. It can be produced by polymerizing in a suitable solvent in the presence of a chain shifting agent. Examples of the solvent used for the polymerization include cycloalkanes such as cyclohexane and cycloheptane; and saturation of ethyl acetate, n-butyl acetate, isobutyl acetate, methyl propionate, and propylene glycol monomethyl ether acetate. Carboxylic acid esters; alkyl lactones such as 7-butyrolactone; ethers such as tetrahydrofuran, dimethoxyethane, diethoxyethane, etc.; 2-butanone, 2-heptanone, An alkyl ketone such as methyl isobutyl ketone; a cycloalkyl ketone such as cyclohexanone; an alcohol such as 2-propanol 'propylene glycol monomethyl ether or the like. These solvents may be used alone or in combination of two or more. Further, the reaction temperature in the polymerization is usually from 40 to 120. (:, preferably 50 to 100 ° C, the reaction time is usually 丨 ~ 48 hours, preferably 1 to 24 hours 〇 copolymer resin (A) of course, halogen, metal and other impurities are preferred -15- 1333126, and the residual monomer and oligomer components are below the specified enthalpy, for example, 0.1% by weight of HPLC, etc., so that not only the sensitivity, resolution, step stability, pattern shape, etc. of the photoresist can be further improved, and The photoresist having a change in the amount of the foreign matter and the sensitivity in the absence of the liquid is provided. The method for purifying the copolymer resin (A) may, for example, be the following method. A method for removing impurities such as a metal may be a method of adsorbing a metal in a resin solution using a potential filter paper. And a method in which the resin solution is washed with an acidic aqueous solution such as oxalic acid or sulfonic acid, and the metal is in a state of being fitted and removed. Further, the method of removing the residual monomer and the oligomer component to a predetermined enthalpy is a combined water washing and A suitable solvent for removing various residual monomers and oligomer components, and extracting only substances having a specific molecular weight or less and purifying them in a solution state such as ultrafiltration. And a refining method in which a resin solution is dropped to a poor solvent to solidify the resin in a poor solvent, and a residual monomer or the like is removed, and a solid state in which the poor solvent of the resin slurry is removed by filtration is removed. These methods are combined. The poor solvent used in the above-described reprecipitation method is affected by the physical properties of the purified resin, etc., and cannot be exemplified. The poor solvent is appropriately selected. The copolymer resin (A) is converted into a gel by gel permeation chromatography (GPC). The weight average molecular weight of styrene (hereinafter referred to as "Mw") is preferably 1,000 to 50,000, particularly preferably 4,000 to 40,000 in the present invention. At this time, the Mw of the copolymer resin (A) is less than 1, In other words, the radiation irradiation unit cannot exhibit sufficient dissolving ability, and there is a tendency that it cannot be used as a negative photoresist function. On the other hand, if it exceeds 50,000, the radiation non-irradiated portion is for the alkaline developing solution. The solubility is not sufficient, and there is a tendency that it cannot be used as a negative-16-1333126 type photoresist function. ( Μη is more than a seed acid 2-application of the release body, the copolymer resin (A) Mw and according to the gel penetration Chromatography GPC) The degree of dispersion defined by the ratio (Mw/Mn) of the number average molecular weight (hereinafter referred to as "") of the polystyrene is preferably 1.00 to 5.00 in the present invention, and particularly preferably in the range of 1.25 to 2.25. When the dispersion is 1.25 or less, the negative resist pattern defect tends to occur, and if it is 5.00 or less, the resolution of the negative photoresist tends to decrease. In the present invention, the copolymer resin (A) has "Mw" 1. 00 0 to 5 0,000, and a range of dispersion of 1.25 to 5.00 is preferable. In the present invention, the copolymer resin (A) may be used singly or in combination of two or more. Radiation-sensitive linear acid generator (B): copolymerizable with the above The radiation sensitive linear agent (B) used in combination with the resin (A) is a component which generates an acid by irradiation with radiation. A suitable acid generator in the present invention is preferably an acid generator selected from at least one of the following formula (1), formula (2-2), and formula (2-3). Moreover, these radiation-sensitive linear acid generators are dissolution time measured by real HPLC according to specific conditions, and can be divided into radiation sensitizing agents (Β1) having a dissolution time of less than 7 minutes and a radiation ray having a dissolution time of 7 minutes or longer. Sexual acid generator (Β2), and this difference can also be accompanied by the following examples. 1333126

In the formula (2-1), the formula (2-2) and the formula (2-3), X - is a formula R3-S〇3_ 'R3 is a hydrocarbon group which may be partially or wholly fluorinated. The wall group is 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. η is an integer representing 1 to 2 & Specific examples of R3-S〇3_ include nonafluoro-n-butanesulfonic acid, total gas-octane sulfonic acid, and 2-(bicyclo[2.2.1]heptan-2-yl)-1,1,2 , an anion of 2-four gas, sulfonic acid, camphorsulfonic acid, and the like. In the formula (2-1), R2 is a hydrogen atom or a linear or branched aliphatic hydrocarbon group having 8 or more carbon atoms, or an aliphatic or aromatic hydrocarbon group having 6 to 12 carbon atoms. Specific examples of R2 include a hydrogen atom, a methyl group, a & 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, an adamantyl group, and the like. Tricyclic [5.2.1.02·6] fluorenyl, tetracyclic [6.2.1.1 3 6.02·7] dodecyl and the like. Specific examples of the radiation-sensitive linear acid generator represented by the formula (2·1) include -18 · 1333126 triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-orthoester, Triphenylphosphonium 2-(bicyclo[2.2.1]hept-2-yl)-1, 1, fluoroethanesulfonate, triphenyl camphorsulfonate, and its equivalent linear acid generator (B 1 ). Further, examples thereof include 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-decyl ester, 4-cyclohexylphenyldiphenylphosphonium perfluoro-n-octylsulfonate, and 4 phenyldiphenylphosphonium 2-( Bicyclo[2.2.1]hept-2-yl)-1,1,2 ethanesulfonate, 4-cyclohexylphenyldiphenyl campholesulfonate, inductively linear acid generator (B2). Further, it can be exemplified by 4-tert-butylphenyldiphenylsulfonium hexafluoro- ugly acid ester, 4-tert-butylphenyldiphenylphosphonium perfluorooctanesulfonate, butyltributyl phenyl diphenyl benzene. Base 2·(bicyclo[2.2.1]hept-2-yl)-1,2-tetrafluoroethanesulfonate, 4-tert-butylphenyldiphenylphosphonate, which is equivalent to radiation Sexual acid generator (B 1 ). Further, tris(4-t-butylphenyl)fluorene nonafluoro-n-butane according to tris(4-t-butylphenyl)phosphonium perfluorooctane sulfonate, tributylphenyl) hydrazine -2-(bicyclo[2.2.1]hept-2-yl)-1,1,2 ethanesulfonate, tris(4.th-butylphenyl) camphorsulfonate Acid agent (B2). In the formula (2-2), R4 means that a partial or full-window hydrocarbon group may also be used. The hydrocarbon group is a linear or branched group having 1 to 8 carbon atoms or an alicyclic hydroxyl group or an aromatic hydrocarbon group having 6 to 12 carbon atoms. An oxygen atom, a sulfur atom, an anthranylene group, a sulfonyl group, a hydroxysulfonyl group, a group or the like is shown. η is an integer representing 0 to 2. -Xinyuan expands 2,2-tetraubiquitin-radioalkanesulfonic acid-cyclohexyl, 2-tetrafluoro is equivalent to butane, 4, 1, 2, 3 sulfonate, (4- Tris- 1 2-tetrafluoro, the phase-fluorinated aliphatic hydrocarbon U is a specific example of episulfonyloxy-19-1333126 R4. The unfluorinated ones may include a hydrogen atom, a methyl group, an ethyl 'propyl group, and an isopropyl group. Base, butyl, isobutyl, cyclopentyl, cyclohexyl, bicyclo [2.2.1] heptyl, adamantyl, tricyclo [5.2.1.0''6] fluorenyl 'tetracyclic ring [6.2.1.13'6.02· 7] Dodecyl, camphoryl, etc., and those which have been fluorinated include trifluoromethyl, nonafluoro-n-butyl, perfluoro-n-octyl, 2-(bicyclo[2.2.1]hept-2-yl)- 1,1,2,2-tetrafluoroethyl, etc. Specific examples of the radiation-sensitive linear acid generator represented by the formula (2-2) include 4-n-butylsulfonylphenyldiphenylsulfonium hexafluoride. Butane sulfonate, 4-n-butylsulfonyl phenyl diphenyl fluorene perfluoro-n-octane sulfonate, 4-n-butylsulfonyl phenyl diphenyl fluorene 2-(bicyclo[2.2.1] Hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 4-n-butylsulfonylphenyldiphenyl camphole sulfonate, which is equivalent to a radiation-sensitive linear acid generator (B 1 ) Further, 4·cyclohexylsulfonylphenyldiphenylphosphonium nonafluoro-n-butanesulfonate, 4-cyclohexylsulfonylphenyldiphenylphosphonium perfluoro-n-octanesulfonate 4-cyclohexylsulfonylphenyldiphenylphosphonium 2-(bicyclo[2.2.1]hept-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexylsulfonate Phenylphenyl diphenyl sulfonate, which corresponds to a radiation sensitive linear acid generator (B1). Further, 4-nonafluoro-n-butylsulfonyloxyphenyldiphenylphosphonium hexafluoride-positive Butane sulfonate, 4·nonafluoro-n-butylsulfonyloxyphenyldiphenylphosphonium perfluoro-n-octanesulfonate, 4-nonafluoro-n-butylsulfonyloxyphenyl diphenyl锍2-(bicyclo[2.2.1]heptan-2-yl)-1,1,2,2-tetrafluoroethanesulfonate, 4-nonafluoro-n-butylsulfonyloxyphenyldiphenylphosphonium Camphorsulfonate, which corresponds to a radiation-sensitive linear acid generator (B2). Further, 4-camphorsulfonyloxyphenyldiphenylphosphonium hexafluoroanthr-butane-20- 1333126 sulfonate, 4 - camphorsulfonyloxyphenyldiphenylphosphonium perfluoro-n-octane acid vinegar, 4-camphorsulfonyloxyphenyldiphenylhydrazine 2-(bicyclo[2.2.1]heptan-2-yl)- 1, 1,2,2·tetrafluoroethane sulfonate 4-camphorsulfonyloxyphenyldiphenyl campholesulfonate, which corresponds to a radiation sensitive linear acid generator (B2). Further, 4-(bicyclo[2,2.1]hept-2-yl)- 1,1,2,2-tetrafluoroethyl oxyphenyl phenyl-phenyl sulphide sulphate sulphate vinegar, 4-(bicyclo[2.2.1]hept-2-yl)·1,1, 2,2-tetrafluoroethylsulfonyloxyphenyldiphenylphosphonium perfluorooctane sulfonate, 4·(bicyclo[2_2.1]hept-2-yl)-1,1,2,2- Tetrafluoroethylsulfonyloxyphenyldiphenylphosphonium 2-(bicyclo[2.2.1]hept-2-yl)-1,1,2,2-tetrafluoroethane sulfonate, 4-(bicyclo[ 2.2.1] Hept-2-yl)-1,1,2,2-tetrafluoroethylsulfonyloxyphenyldiphenyl campholesulfonate, which corresponds to a radiation sensitive linear acid generator (Β2). In the formula (2-3), R5 and R6 each independently represent a hydrogen atom or a hydrocarbon group. The hydrocarbon group is 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 is an integer representing 0 to 3, and η is an integer representing 0 to 2. Specific examples of R5 and R6 include 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, and an adamantyl group. , tricyclo [5.2.1.02·6] fluorenyl, tetracyclic [6.2.1.13, 6. 〇 2, 7] dodecyl and the like. Specific examples of the radiation-sensitive linear acid generator represented by the formula (2-3) include 1-(4-n-butoxynaphthalen-1-yl)tetrahydrophenylhydrazine nonafluoro-n-butanesulfonate. 1-(4-n-butoxynaphthalen-1-yl)tetrahydrophenylhydrazine perfluoro·n-octane sulfonate, 1·(4·n-butoxynaphthalen-1-yl)tetrahydrophenylhydrazine 2 -(bicyclo[2.2.1]hept-2-yl-21 - 1333126 )-1,1,2,2-tetrafluoroethane sulfonate, 1-(4-n-butoxynaphthalen-1-yl) Tetrahydrobenzene camphorsulfonate, which corresponds to a radiation-sensitive linear acid generator (Β1) ° Also, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrophenylhydrazine nonafluoro- n-Butane sulfonate, 1-(3,5-dimethyl-4.hydroxyphenyl)tetrahydrophenylhydrazine perfluoro-n-octane sulfonate, 1-(3,5·dimethyl 4-hydroxyphenyl)tetrahydrophenylhydrazine 2-(bicyclo[2.2.1]hept-2-yl)-1,1,2,2·tetrafluoroethanesulfonate, 1-(3,5- Dimethyl-4-hydroxyphenyl)tetrahydrobenzyl sulfonate, which corresponds to a radiation sensitive linear acid generator (Β 1 ). A suitable acid generator and an acid generator which can be used in the present invention represented by the formula (2-1), the formula (2-2), and the formula (2-3) are described as "other radiation-sensitive acidogenic acids. Specific examples thereof include diphenyl iodide nonafluoro-n-butane sulfonate, diphenyl iodine perfluoro-n-octane sulfonate, and diphenyl iodonium 2- (bicyclo[2.2.1] ]Hept-2-yl)-1,1,2,2-tetrafluoroethane sulfonic acid vinegar, diphenyl iodonium sulfonate, which corresponds to a radiation sensitive linear acid generator (Β 1 ). Further, bis(4-tert-butylphenyl)iodide nonafluoro-n-butanesulfonate and bis(4-t-butylphenyl)iron iodide perfluoro-n-octanesulfonate can be cited. Bis(4-tert-butylphenyl)iodonium 2·(bicyclo[2.2.1]hept-2-yl)-1 '1' 2,2-tetrafluoroethanesulfonate, double (4- Tributylphenyl) iodonium sulfonate 'is equivalent to a radiation sensitive linear acid generator (Β2). Further, Ν((nonafluoro-n-butanesulfonyloxy) succinimide, fluorene-(perfluoro-n-octanesulfonyloxy) amber quinone imine 'n-[2-(double ring) [2.2.1] Hept-2-yl)-1' 1,2' 2 -tetrafluoroethanesulfonyloxy] amber imine, N-(camphorsulfonyloxy) amber imine, which is equivalent Inductive radiation-22- 1333126 acidogenic agent (B 1 ).

Further, N-(nonafluoro-n-butanesulfonyloxy)hept-5-ene-2,3-dicarboxyarsenine, N-(perfluoro-n-octyl)bicyclo[2.2.1] Gh-5-ene-2,3-dicarboxy quinone imine, I

[2.2.1] Hept-2-yl)-1 ' 1 ' 2,2-tetrafluoroethane sulfonate [2.2.1] Hept-5-ene-2,3-dicarboxy quinone imine, N-( Camphor bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyarmine, its linear linear acid generator (B 1 ). In the present invention, a radiation sensitive acid generator (2-1) Acidic acid generator (2-2), radiation sensitive linear acid generator (2-3) Radiation linear acid generator "generally known as radiation sensitive acid generator" is used alone or in combination of two or more. The amount of the acid generator (B) used is preferably from 1 to 15 parts by weight relative to the copolymer resin (A to '1 to 20 parts by weight of 'A parts) from the viewpoint of ensuring sensitivity and resolution. The amount of the acid agent (B) used is less than 0.1% by weight and the developing property tends to be lowered. On the other hand, if the transparency of the radiation is less than 20, the transparency of the radiation is reduced, and there is a tendency of the image (T-top phenomenon) only on the surface of the photoresist. Therefore, it is difficult to obtain the photoresist acid crosslinker (C): The acid crosslinker (C) in the present invention is, for example, in the presence of an acid generated by the radiation sensitive linear acid generator (B), bicyclo[2.2. 1] alkanesulfonyloxy L[2-(dicyclooxy)bicyclic sulfonate Oxy) to sense when the radiation, and other radiation-sensitive sense B) represents "as the photoresist) 100 wt. At this time, in the case of a feeling of weight, the weight portion is inferior, and the tendency to radiate the insoluble pattern is to be crosslinked by the copolymer resin (A) which is an alkaline soluble-23-1333126 resin and can be suppressed for the alkaline developing solution. The type of the solvent is not particularly limited, but in the present invention, it is represented by the N-(alkoxymethyl)glycol urea compound represented by the following formula (3-1). The acid crosslinking agent (C) is preferred.

In the above formula (3-1), R7 to R10 each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms. Specific examples thereof 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)ethylene glycol urea compound represented by the formula (3-1) include hydrazine, hydrazine, Ν'N-tetrakis(methoxymethyl)glycol urea, N, Ν. 'Ν' Ν,·tetrakis(ethoxymethyl)ethylene glycol urea, hydrazine, hydrazine, hydrazine, hydrazine - tetra (n-propoxymethyl) glycol urea, hydrazine, hydrazine, hydrazine, hydrazine - four (different Propoxymethyl)ethylene glycol urea, hydrazine, Ν' Ν' Ν -tetrakis (n-butoxymethyl) glycol urea, Ν' Ν, Ν' Ν - tetra (t-butoxymethyl) ethane Alcohol urea and the like. The negative-type radiation-sensitive resin composition of the present invention may further contain an acid crosslinking agent other than the acid crosslinking agent (3 -1 ) (so-called "other acid crosslinking agent"), and other acid crosslinking agents. The fluorene-(alkoxymethyl)urea compound represented by the following formula (3-2), the fluorene-(alkoxymethyl) melamine compound represented by the following formula (3-3), the following The indole-(alkoxymethyl-24- 1333126) represented by the formula (3-4) is an N-(alkoxymethyl)amino compound such as an ethyl urea compound.

In the above formulas (3-2), (3-3) and (3-4), R11 to R12 each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms. Specific examples thereof 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)urea compound represented by the above formula (3-2) include N,N-bis(methoxymethyl)urea and N,N-bis(ethoxymethyl)urea. , N,N-di(n-propoxymethyl)urea, N,N-di(isopropoxymethyl)urea, N,N-di(n-butoxymethyl)urea, N,N-di (first Tributoxymethyl)urea and the like. Further, 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, :^,:^,1^,:^,:^,]^-hexa(ethoxymethyl)melamine, 1^,\ ,]^,1^,:^,:^6 (n-propoxylate) Melamine '1^,>1,1^,>}, ]^,>1-hexa(isopropoxymethyl)melamine, >4,:^,:^,1\1 , 1 \ [, 1 ^ - hexa(n-butoxymethyl) melamine, N, N, N, N, N, N-hexa(t-butoxymethyl) melamine, and the like. Further, specific examples of the N-(alkoxymethyl)-extended ethyl urea compound represented by the above formula (3-4) include N,N-di(methoxymethyl)-4,5- Di(methoxymethyl)exylethylurea, Ν'N-bis(ethoxymethyl)-4,5-di(ethoxymethyl)exylethylurea, anthracene, fluorene-di(n-propoxylate) Base)·4,5·di(n-propoxymethyl)-extension ethyl urea, hydrazine, hydrazine-bis(isopropoxymethyl)_4,5-di(isopropoxymethylethyl)ethyl Urea' Ν, Ν-bis(n-butoxymethyl)-4,5·di(n-butoxymethyl)-extended ethylurea ν, Ν-bis(t-butoxymethyl)-4' 5 - Di(t-butoxymethylmethyl)-extended ethylurea or the like is used in the present invention. The acid crosslinking agent (C) may be used alone or in combination of two or more, but particularly preferably contains at least one acid crosslinking. The agent (3 -1 ), preferably with other acid crosslinking agents, is preferred. In the present invention, the content of the acid crosslinking agent (C) is preferably from 0.5 to 50 parts by weight, preferably from 1 to 30 parts by weight, based on 1 part by weight of the copolymer resin (A) of the alkali-soluble resin. More preferably, it is 2 to 20 parts by weight. When the amount of the acid crosslinking agent (C) is less than 0.05 parts by weight, the solubility of the copolymer resin (a) for the alkaline developing solution is lowered and the insolubilization effect is insufficient, the pattern is easily swollen, and the pattern is felt and the sensitivity is observed. There is a tendency to decrease significantly. On the other hand, when it exceeds 50 parts by weight, the heat resistance and transparency of the photoresist are lowered, and it is observed that only the surface of the photoresist is insolubilized. Acid diffusion inhibitor (D): Negative in the present invention In the radiation-sensitive linear resin composition, the diffusion of the acid-26-I333126 produced by the radiation-sensitive linear acid generator (Β) in the photoresist film by irradiation with radiation can be suppressed, and the non-radioactive irradiation region is suppressed. An acid diffusion inhibitor which is an unwanted chemical reaction is preferred. The acid diffusion inhibitor (D) is not particularly limited as long as it has high acidity and affinity. However, in the present invention, it is preferred to contain at least one acid diffusion inhibitor represented by the following formula (4).

In the above formula (4), R 2 3 and R 24 each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or R 23 and R 24 are bonded to each other to form a carbon number of 4 to 4 12 alicyclic or aromatic hydrocarbon groups. R25 is a linear or branched or cyclic alkyl group having a hydrogen atom or a carbon number of 1 to 6, or a -C(0)OR27 group. R26 represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms or an alicyclic hydrocarbon group or an aromatic hydrocarbon group having 6 to 12 carbon atoms. R27 is a linear, branched or cyclic alkyl group representing a hydrogen atom or a carbon number of 1 to 6. Examples of the straight-chain, branched or cyclic alkyl group having 1 to 6 carbon atoms in R23 and R24 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a cyclopentyl group. Examples of the alicyclic hydrocarbon group or the aromatic hydroxy group having 4 to 12 carbon atoms formed by bonding with a cyclohexyl group may be a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a phenyl group, a naphthyl group or the like and may also have Substituent. -27- 1333126 A hydrogen atom or a linear one, a branched or a cyclic alkyl group in R25 may be a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or an isobutyl group. The group 'cyclopentyl group, cyclohexyl group, and further, -c(o) OR27 group can be mentioned. The linear, branched or cyclic alkyl group having 1 to 6 carbon atoms in R26 may, for example, be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, cyclopentyl or cyclohexyl. Examples of the 6 to 12 carbon atoms of the alicyclic hydrocarbon group or the aromatic hydrocarbon group include a cyclohexyl group, a cyclopentyl group, a phenyl group, and a naphthyl group, and they may have a substituent. The hydrogen atom in R27 or the linear, branched or cyclic alkyl group having 1 to 6 carbon atoms may, for example, be a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or an isobutyl group. Cyclopentyl, cyclohexyl. Specific examples of the acid diffusion inhibitor represented by the above formula (4) include imidazole, 4-methylimidazole, 1-benzyl-2-methylimidazole, 4-methyl-2-phenylimidazole, and benzimidazole. , 2-phenylbenzimidazole, N-tertoxybutyrylbenzimidazole, N-tert-butylcarbonyl-2-methylbenzimidazole, N-tert-butoxy-2-phenylbenzene Imidazole, 1-benzylimidazole, 1-methyl-2-phenylbenzimidazole, 1-benzyl-2-phenylbenzimidazole, and the like. By blending such an acid diffusion inhibitor, the storage stability of the resulting negative-type radiation-sensitive resin composition can be further improved, the resolution of the photoresist can be further improved, and the radiation can be suppressed until the development process is performed. The change in the line width of the pattern caused by the change in the time (PED) can not only obtain a composition excellent in step stability, but also suppress the solubility deviation from above to below the pattern, and particularly suppress the bridge above the pattern and under the pattern - 28- 1333126 Dissolved residue. Further, the negative-type radiation-sensitive resin composition of the present invention may contain an acid diffusion inhibitor (hereinafter referred to as "another acid diffusion inhibitor") having a skeleton other than the acid diffusion inhibitor represented by the above formula (4). Other acid diffusion inhibitors include "tribasic amine compounds", "amine-containing compounds", "quaternary ammonium hydroxides", and "nitrogen-containing heterocyclic compounds". Examples of the "tribasic amine compound" include triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, cyclohexyldimethylamine, and dicyclohexyl. Tris(cyclo)alkylamines such as methylamine, tricyclohexylamine, etc.; aniline, N-methylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, 4-methyl An aromatic amine such as aniline, 4-nitroaniline, 2,6-dimethylaniline or 2,6-diisopropylaniline; an alkane such as triethanolamine or N,N-bis(hydroxyethyl)aniline Alcoholamines; hydrazine, hydrazine, hydrazine 1, Ν'-tetramethylmethylenediamine, hydrazine, hydrazine, hydrazine, Ν'-tetrakis(2-hydroxypropyl)ethylenediamine, 1,3-double [ 1-(4-Aminophenyl)-1-methylethyl]benzenetetramethylenediamine, bis(2-dimethylaminoethyl)ether bis(2-diethylamineethyl)ether, and the like. The "melamine-containing compound" may, for example, be N-tertoxycarbonyldi-n-octylamine, N-tert-butoxycarbonyldicyclohexylamine, N-tert-butoxycarbonyl-1-adamantanamine, or the like. N-tert-butoxycarbonyl-N-methyl-1. amantadine, N,N-di-t-butoxycarbonyl-1-adamantanamine, Ν'N-di-t-butoxycarbonyl-N -methyl-1-adamantanamine, N-tert-butoxycarbonyl-4,4·-diaminodiphenylmethane, N,N,-di-t-butoxycarbonylhexamethylenediamine N,N,N·' N, tetra-t-butoxycarbonylhexamethylenediamine' 丨 (third butoxycarbonyl-29- 1333126 base)-2·pyrrolidine methanol, tert-butyl (tetrahydrogen) - 2-Pf-3-furyl)carbamate, Ν' Ν'-di-t-butoxycarbonyl-4,4'-diaminodiphenylmethane, hydrazine-tert-butoxycarbonylbenzene An amidino-tertiary oxycarbonyl-containing amino group compound such as imidazole, hydrazine-t-butoxycarbonyl-2-methylbenzimidazole, anthracene-t-butoxycarbonyl-2-phenylbenzimidazole or the like. Examples of the "quaternary ammonium hydroxide" include tetra-n-propylammonium hydroxide and tetra-n-butylammonium hydroxide. Examples of the "nitrogen-containing heterocyclic compound" include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, and 2- Pyridines such as methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-hydroxyquinoline, acridine, etc.; piperidine, 1 - ( 2 - Hydroxyethyl) piperidine and other piperidines, pyridin, pyrazole, sorghum, quetialine, porphyrin, pyrrolidine, piperidine, 3-piperidinyl-1,2-propanediol, morpholine , 4-methylmorpholine, 1,4 -dimethylpiperidane D, 1,4 -diindenylbicyclo[2.2.2]octane, and the like. Among these other acid diffusion inhibitors, a tertiary amine compound and an amine compound containing a ruthenium-tertiary butoxycarbonyl group are preferred. In the present invention, the acid diffusion inhibitor (D) may be used alone or in combination of two or more, particularly preferably at least one acid diffusion inhibitor represented by the formula (4), and suitably contains other acid diffusion inhibitors. good. The amount of the acid diffusion inhibitor (D) to be added is usually 15 parts by weight or less, preferably 1 part by weight or less, more preferably 5 parts by weight or less based on 1 part by weight of the copolymer resin (a). At this time, if the amount of the acid diffusion inhibitor (d) is more than 15 parts by weight, the sensitivity as a photoresist tends to be significantly lowered by -30 to 1333126. In addition, if the amount of the acid diffusion inhibitor is less than 0.001 part by weight, the pattern shape and the dimensional fidelity of the photoresist are lowered depending on the step conditions. In the negative-type radiation-sensitive resin composition of the present invention. It can be combined with various additives such as a dissolution inhibitor, a dissolution promoter, a surfactant, and a sensitizer. Dissolution inhibitor: The dissolution inhibitor is such that when the solubility of the copolymer resin (A) of the alkali-soluble resin is too high for the alkaline imaging solution, the solubility thereof is controlled, and the dissolution of the resin is moderately reduced in the case of alkaline development. The component of speed effect. Such a dissolution controlling agent is preferably one in which no chemical change occurs in the steps of calcination, radiation irradiation, development, or the like of the photoresist film. The dissolution inhibitor is a saturated hydrocarbon, particularly preferably a hydrocarbon having an alicyclic skeleton, and a compound which does not exhibit alkaline solubility alone is preferred. These dissolution inhibitors may be used alone or in combination of two or more. Dissolution promoter: The dissolution promoter is such that when the solubility of the copolymer resin (A) of the alkali-soluble resin to the alkaline developing solution is too low, the solubility is improved, and the solubility is moderately increased in the case of alkaline development. The component of the resin dissolution rate. Such a dissolution promoter is preferably one which does not have a chemical change in the step of calcination, radiation irradiation, development or the like of the photoresist film. The dissolution promoter is a saturated hydrocarbon, particularly preferably a hydrocarbon having an alicyclic skeleton -31 - 1333126, and a compound which exhibits alkali solubility alone is preferred. These kinds of dissolution accelerators may be used alone or in combination of two or more. The compounding amount of the above-mentioned dissolution inhibitor or dissolution promoter is usually 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, when the amount of the dissolution inhibitor or the dissolution promoter is more than 50 parts by weight, the heat resistance of the photoresist tends to be lowered. Surfactant: In the negative-type radiation-sensitive resin composition of the present invention, A surfactant exhibiting an effect of improving coating properties and developing properties is blended. The surfactant may, for example, be polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octyl phenyl ether, polyoxyethylene n-decyl phenyl ether, polyethylene glycol lauric Other than the nonionic surfactant such as an acid ester or polyethylene glycol distearate, the following trade names KP34 1 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, and No. 95 (Kyoeisha) can be used. Chemical (share) system, Efutop EP301, EF303, EF352 (made by Tokem Products), Megafax F 1 7 1, same as F173 (made by Dainippon Ink Chemical Industry Co., Ltd.), Fuloride FC430, and FC431 ( Sumitomo 3M (share) system, Asahi guard AG710, Surfuron S-3 82, with SC-101, with SC.102, with SC-103, with SC-104, with SC-105, with SC-106C Asahi Glass (shares) )), etc. These surfactants may be used alone or in combination of two or more. The blending amount of the surfactant is 1 part by weight or less based on the copolymer resin (A), and usually 2 parts by weight or less. -32- 1333126 Sensitizer: In the negative-type radiation-sensitive resin composition of the present invention, a sensitizer which improves the sensitivity and the like can be provided. Preferred examples of the sensitizer include oxazoles, benzophenones, bengals, anthraquinones, phenols and the like. These sensitizers may be used alone or in combination of two or more. The compounding amount of the sensitizer is 100 parts by weight, preferably 50 parts by weight or less, based on the copolymer resin (A). Further, examples of the additives other than the above may be an antihalation agent, an adhesion promoting stabilizer, an antifoaming agent, or the like. When the negative-type radiation-sensitive resin composition of the present invention is used, the composition has a total solid content concentration of usually 3 to 50% by weight, preferably % by weight, and is, for example, filtered by a filter paper having a pore diameter of about 200 nm. Solution. The solvent used for preparing the composition solution may, for example, be 2-, 2-heptanone, 2-octanone, cyclopentanone, cyclohexanone' propylene glycol monomethyl ether ester, propylene glycol monoethyl ether acetate, or 2-hydroxypropionic acid. Methyl ester '2-hydroxyethyl ester, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl dimethyl ether, ethylene glycol monoethyl ether, diglyme, diethylene glycol Diethyl ether glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate 'propylene glycol mono, propylene glycol monoethyl ether, n-butyl acetate, methyl pyruvate, pyruvic acid, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , butyrolactone and the like. These solvents may be used singly or in combination of two or more kinds, and the above-mentioned examples show that Rose is used in a portion of the solution of 5~25, adjusted to be an acetic acid propionate mono- and ethyl ether ethyl ester, -33- 1333126 to 2 · heptanone, cyclohexanone, propylene glycol monomethyl ether acetate, ethyl 2-hydroxypropionate, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether, r-butyrolactone is preferred, especially in the present invention Among them, at least propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether or the like is preferred. The negative-type radiation-sensitive resin composition of the present invention is particularly useful as an enhanced chemical type photoresist. In the enhanced chemical type negative photoresist, an electron portion is formed from the acid crosslinking agent (C) by the action of an acid generated by the radiation-sensitive linear acid generator (B) by irradiation with radiation, which is a copolymer resin. The acidic group in (A), for example, attacks the spherical electrons on the hydroxyl group and causes a crosslinking reaction. As a result, the solubility of the radiation irradiation portion of the photoresist is lowered in the alkaline developing solution, and the radiation non-irradiated portion is dissolved and removed by the alkaline developing solution, and a negative resist pattern is obtained. When a photoresist pattern is formed from the negative-type radiation-sensitive resin composition of the present invention, a suitable coating means such as spin coating, cast coating, roll coating, spray coating, or the like is used, for example, in a crucible. When a substrate such as a wafer is coated, a photoresist film can be formed, and if necessary, heat treatment (hereinafter referred to as "PB") is performed, and then the photoresist film is irradiated with radiation to form a predetermined photoresist pattern. For the radiation to be used at this time, for example, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength I57 nm), EUV (extreme ultraviolet ray, wavelength 13 nm, etc.), etc. can be appropriately selected. X-rays such as charged particle lines such as ultraviolet rays and electron beams, and synchrotron radiation, etc., among which far ultraviolet rays and electron rays are preferred. Further, the radiation irradiation conditions of the radiation exposure amount -34 - 1333126 are appropriately selected depending on 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 form a fine pattern having a high definition, it is preferable to perform heat treatment (hereinafter referred to as "PEB") after radiation irradiation. By this PEB, the crosslinking reaction can be smoothly performed in the radiation irradiation section. The heating condition of the PEB is changed according to the composition of the negative-type radiation-sensitive resin composition, and is usually 30 to 200 ° C, preferably 50 to 17 (TC » in the present invention, in order to draw the negative type at the maximum limit The potential ability of the radiation-sensitive resin composition is such that an organic or inorganic anti-reflection film can be formed on the substrate to be used, as disclosed in Japanese Patent Publication No. Hei 6 - 1 2 4 5 2, and the like. For example, it is possible to provide a protective film on the photoresist film, or to use such a technique, as disclosed in Japanese Laid-Open Patent Publication No. Hei 5-188598, and the like. A predetermined resist pattern can be formed by developing a photoresist film that irradiates radiation. The developing solution used for development is preferably an alkaline aqueous solution in which tetramethylammonium hydroxide is dissolved. The concentration is usually from 1 to 10% by weight, preferably 5% by weight. Further, a surfactant or the like may be appropriately added to the developing solution composed of an aqueous alkaline solution. After the imaging solution is developed, one The embodiment of the present invention will be described in more detail below. In the following, "part j" is based on the weight unless otherwise specified. -35 - 1333126 Examples and Each measurement and evaluation in the comparative example was carried out in the following manner: (1) Mw and Mw/Mn: A GPC column (G2000HXL, G3 000 HXL-root, G4 000 HXL-root) made of H.S. It was determined by gel permeation chromatography (GPC) using monodisperse polystyrene as the standard at a flow rate of 1.0 ml/min, solvent tetrahydrofuran, and column temperature of 40 ° C. (2) Sensitivity: Using twin crystal A substrate of ARC29A (manufactured by Nissan Chemical Co., Ltd.) having a thickness of 78 nm was formed on the surface of the round surface, and each composition solution was spin-coated on the substrate, and on a hot plate at a temperature of 105 ° C for 90 seconds. A photoresist film having a film thickness of 265 nm formed by PB was used, and an ArF excimer laser exposure apparatus (optical conditions: NA = 0.5 5, 2/3 Annular) manufactured by Nikkon was used, and the portion covered by Cr was 6% penetrated. ArF laser and phase-shifted reticle with phase reversal of 180 degrees (PSM mask) Radiation was irradiated. Thereafter, PEB was carried out at a temperature of 105 ° C for 90 seconds, and then developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide at 25 ° C for 60 seconds, and washed with water. And drying to form a negative resist pattern. At this time, the radiation dose of the line/space pattern (1L1S) having a line width of 140 nm with a line width of 1 to 1 is regarded as the optimum radiation exposure amount, and this is The optimum radiation exposure is regarded as sensitivity. -36- 1333126 (3) Resolution: The size of the smallest line/space pattern that is resolved by the optimum radiation exposure is regarded as the resolution, and is defined by three levels of 140 nm, 130 nm, and 120 nm. (4) HPLC measurement conditions of an acid generator: An ODS column manufactured by GL Science Co., Ltd. was used, and 0.1% by weight of phosphoric acid was added to water as an elution solution using acetonitrile/water = 60/40 (weight ratio) as a solution. Determined at 1.0 ml/min. In the detection, the maximum enthalpy was measured based on the absorption area of 220 nm. The radiation-sensitive acid generator having a dissolution time of less than 7 minutes is regarded as (B1), and a radiation-sensitive acid generator having a dissolution time of 7 minutes or longer is regarded as (B2). (5) Radiation transmittance: A resin solution in which a resin is dissolved in propylene glycol monomethyl ether acetate (PGMEA) is applied by spin coating on quartz glass and placed on a hot plate at a temperature of 10 ° C. The photoresist film formed of PB was subjected to a film thickness of 265 nm from the absorbance measured at a wavelength of 193 nm under the conditions of 90 seconds. (6) Residual film rate: The surface of the crucible wafer is coated by spin coating, and the film thickness of PB formed on the hot plate at a temperature of 105 ° C for 90 seconds is regarded as A. And the photoresist film was observed at 25 ° C for 60 seconds with respect to the photoresist film in a 2.38 wt% aqueous solution of tetramethyl-37- 1333126 ammonium hydroxide, and the film thickness of the photoresist film measured after washing with water was regarded as B. In the case of the residual film ratio = (B/A) xlOO. (7) Dissolution residue under the pattern: Under the balance of the solubility of the resin and the solubility after crosslinking, the extreme saw shape may be displayed below the pattern. According to the visual observation of the cross-sectional SEM observation, the person who does not see the edge is indicated by "〇", and the person who sees the pull but the image reaches the substrate is indicated by "△", and the substrate is observed and the image is not imaged. It is indicated by "X". (8) Bridging above the pattern: Under the balance of the solubility of the resin and the solubility after crosslinking, the bridge may be confirmed above the pattern. Under the visual observation of the cross-sectional SEM observation, the undetected bridge is followed by " 〇" indicates that the linker who has visited the ruins of the bridge but has not reached the pattern is indicated by "△", and the apparent connection between the patterns is indicated by ^X". Synthesis Example 1 -38- 1333126

Ch2=c

c=o o CH—CH3 h2c \ /c—cf3

FjC 〇H (SI-1) in a 100 ml three-necked flask containing (1,1,^trifluoro-2-trifluoromethyl-2-hydroxy-4-pentyl) methacrylate (S1-1 5.42 g (70 mol%), (3-hydroxyadamantan-1-yl)methacrylate (S1-2) 1.24 g (20 mol%), (1-hydroxyethyl) methacrylate (S1-3) 0.34 g (10 mol%) and 2-propanol 17.86 g, after stirring and dissolving, were replaced with nitrogen at an internal temperature of 80 ° C for 30 minutes. 0.09 g of 2,2-azobis(isobutyronitrile) was added thereto, and polymerization was carried out for 16 hours under reflux under a nitrogen atmosphere. After the completion of the polymerization, the polymerization solution was cooled to 30 ° C or lower with water cooling, and 2200 g of n-hexane was charged, and the precipitated white powder was collected by filtration. The white powder which was collected by filtration was washed three times with 55 g of n-hexane, and then filtered, and dried at 60 ° C for 17 hours to obtain a white powder of a copolymer resin (5.67 g, yield 81%). This copolymer resin had a Mw of 39,400 and an Mn/Mn of 3.17. According to the measurement by l3C-NMR, the copolymers of (S1-1), (Sl-2), and (S1-3) each having a repeating unit content of 69.0 : 20.1 : 10.9 (mole %). Treat this copolymer resin as a resin ( -39- 1333126

). Radiation transmittance of this resin (Al) I Synthesis Example 2 Preparation of 11.60 g of methacrylic acid (1,1,1-triyl-4·pentyl) ester (S1-1) (70 acid (3-hydroxy Donkey Kong) Alkyl-1-yl)ester (S1-2)), (1-hydroxyethyl) methacrylate (S: ear %) is dissolved in 30 grams of 2-butanone, and then 7 eyes are added) 0.19 grams of single The solution was applied and a 1 liter three-necked flask was placed and purged with nitrogen for 30 minutes. The nitrogen reaction vessel was heated at an internal temperature of 80 ° C, and the body solution was dropped using a dropping funnel for 3 hours. The start time was carried out and a polymerization reaction was carried out for 6 hours. The liquid was cooled to 30 ° C or lower by water cooling, and J was added, and the precipitated white powder was collected by filtration. The white n-hexane thus filtered was washed in a slurry form, and then filtered, and a copolymer resin obtained as a white powder (12.12 g of a copolymer resin as Mw was measured by 1, 4,600, Mw/Mn NMR, (Sl-1), ( S1-2), (content ratio 67, 2: 21.8: 11.0 (mol%% poly resin is regarded as resin (A-2). This resin (/ is 8 1.6%. Synthesis Example 3 82.5%.: Fluorine-2) -trifluoromethyl-2-hydroxymol%), 2.66 g of methacryl (20 mol% 1-3) 0.73 g (10 mol, 2,2-azobis (isobutyl 5 g 2-butanone) After 100 milliliters of air purge, the above-mentioned single prepared before starting to be dropped is regarded as the end of polymerization polymerization, and the polymer powder of 600 g of n-hexane is melted at a temperature of 60 g at 60 ° C for 17 hours. The rate is 80.8%). This is 2.05. According to the respective repeating units of 13C-S1-3), the total transmittance of /2 - 3,333,126 is prepared to prepare methacrylic acid (1,1, 1-trisyl-4-pentyl)ester (S1-1) 11.60 g (70 acid (3-hydroxyadamantan-1-yl) ester (S1-2)), methacrylic acid (1-hydroxyethyl) The ester (S1 ear %) is dissolved in 30 grams of 2-butanone, and then put into the nitrile) 0.37 Grams of monomer solution. A 1:3 liter three-necked flask was purged with nitrogen for 30 minutes. The nitrogen reaction vessel was heated at an internal temperature of 80 ° C, and the H solution was dropped using a dropping funnel for 3 hours. The start time was carried out and a polymerization reaction was carried out for 6 hours. The liquid was cooled to 30 ° C or lower by water cooling, and A was poured, and the precipitated white powder was collected by filtration. The white n-hexane thus filtered was washed in a slurry form, and then filtered, and a copolymer resin obtained as a white powder (12.24 g of a copolymer resin was measured for Mw of 10,500, Mw/Mn NMR, (SI -1 ) , ( S 1-2 ), (content ratio: 68.3 : 21.0 : 10.7 (mol %: poly resin is regarded as resin (A - 3 ). This resin (A is 8 0.6%. Synthesis Example 4 Preparation of methacrylic acid (1) ,1,1-triyl-4-pentyl)ester (S1-1) 15.47 g (70 acid (3-hydroxyadamantane-indoleyl) ester (si_2) fluoro-2-trifluoromethyl-2- Hydroxymol%), 2.66 g of methacryl (20 mol% -3 ) 0.73 g (10 mol 2,2-azobis (isobutyl; g 2-butanone after 100 m purge, while stirring The above-mentioned single sheet prepared before the event is started to be dropped as the end of the polymerization polymerization, and the 600 g of the n-hexane medium color powder is dried at a temperature of 60 g 6 〇 ° C for 17 hours, and the yield is 81.6%. 2.00. According to the copolymer of each repeat unit of "c· S1-3), the radiation transmittance of this total -3) is fluorine-2-trifluoromethyl-2_hydroxymol%, A 3.55 g of propylene (20 mol% -41 - I333126), methacryl (1-Hydroxyethyl) ester (Sl-3) 〇_98 g (l〇 mol%) was dissolved in 40 g of 2-butanone, and then 2,2-azobis(isobutyronitrile) 0.99 g was added. a monomer solution, and a 20-mL three-necked flask containing 20 g of 2-butanone was purged with nitrogen for 30 minutes. After purging with nitrogen, the reaction vessel was stirred while heating at an internal temperature of 80 ° C, and prepared in advance. The above monomer solution was dropped using a dropping funnel for 3 hours, and the start of dropping was regarded as the polymerization start time, and the polymerization reaction was carried out for 6 hours. After the completion of the polymerization, the polymerization solution was cooled to 30 ° C or less by water cooling, and 800 g of the positive solution was poured. In the alkane, the precipitated white powder was collected by filtration, and the white powder obtained by filtration was washed with a slurry of 80 g of n-hexane twice, filtered, and dried at 60 ° C for 1 hour to obtain a white powder copolymer resin. (I4.92 g, yield 74.6%). The copolymer resin had a Mw of 6,600 and a Mw/Mn of 1.88. (According to "C-NMR measurement, (Sl-1), (Sl-2), (S1) -3) a copolymer having a repeating unit content of 66.6: 23.1: 10.4 (mole %). This copolymer resin is regarded as a resin (A-4). This resin (A-4) The ray transmittance was 7 6.4%. Synthesis Example 5 Preparation of (1,1,1-trifluoro-2·trifluoromethyl-2-hydroxy-4-pentyl) methacrylate (S1-1) 15.47 Gram (70 m. /. ), (3-hydroxyadamantyl) methacrylate (S1-2) 3.55 g (20 mol/°) '1-hydroxyethyl) methacrylate (S1-3) 0.98 g (10) Mol %) was dissolved in 40 g of 2-butanone, and then a monomer solution of 2.8 g of 2,2-azobis(isobutyronitrile) was added, and 20 g of 2-butanone was added to 100 g-42- A 1333126 liter three-necked flask was purged with nitrogen for 30 minutes. After purging with nitrogen, the reaction vessel was stirred while being heated at an internal temperature of 80 ° C, and the above-mentioned monomer solution prepared beforehand was dropped using a dropping funnel for 3 hours. The start of dripping was regarded as the polymerization start time, and the polymerization reaction was carried out for 6 hours. After the completion of the polymerization, the polymerization solution was cooled to 30 ° C or lower by water, and poured into 800 g of n-hexane to remove the white powder which was precipitated. The white powder thus filtered was washed with a slurry of 80 g of n-hexane twice, and then filtered, and taken to 60. (: After drying for 7 hours, a white powder copolymer resin (15.92 g, yield 79.6%) was obtained. The copolymer resin had a Mw of 4,300 and a Mw/Mn of 1.60. According to l3C-NMR measurement, (Sl-1), ( Sl-2) '(S1-3) a copolymer having a repeating unit content of 67.5: 22_2: 10.3 (mole %). This copolymer resin was regarded as a resin (A-5). This resin (A-5) The radiation transmittance was 7 6.2%. Synthesis Example 6 Preparation of (1,1,1-trifluoro-2-trifluoromethyl-2.hydroxy-4-pentyl)methacrylate (S1-1) 13.56 g (60 mol%), (3-hydroxyadamantan-1-yl)methacrylate (S1-2) 5.44 g (30 mol%) '1-hydroxyethyl methacrylate (S1-3) 1.00 g (10 mol%) was dissolved in 40 g of 2-butanone, and then 2.3 g of 2,2-azobis(isobutylene) and 0.31 g of n-dodecyl mercaptan were added. A monomer solution, and a 100 ml three-necked flask containing 2 g of 2-butanone was purged with nitrogen for 30 minutes. After purging with nitrogen, the reaction vessel was stirred while heating at an internal temperature of 80 ° C and prepared in advance. The above monomer solution was dropped using a dropping funnel for 3 hours at -43 to 1333126. The start of the dropwise addition was regarded as the polymerization start time, and the polymerization reaction was carried out for 6 hours. After the completion of the polymerization, the polymerization solution was cooled to 3 〇C or less by water cooling, and charged into 800 g of n-hexane, and the precipitated white powder was collected by filtration. The white powder was washed in a stream of 80 g of a positive sensation, filtered, and dried at 60 ° C for 17 hours to obtain a white powder copolymer resin (15 92 g, yield 79.6%). The copolymer resin was 1^. It is 1.69 from 5,600, 1^^/1^11. According to the "C-NMR measurement, the repeating unit content of (Sl-1), (S1-2), (S1-3) is 67.0: 22.4: 10.6 (mol%) copolymer. The copolymer resin was regarded as the resin (A-6). The radiation transmittance of this resin (A-6) was 75.6%. Examples 1 to 17 Each of the composition solutions composed of the components shown in Fig. 1 was subjected to various evaluations. The evaluation results are shown in Table 2. The components other than the polymers (Al) to (A to 6) in Table 1 are as follows. (B) B-1 : 4-t-butylphenyl dibenzoquinone • nonafluoro-n-butanesulfonate (HPLC dissolution time: 7.21 minutes) B-2 : triphenylsulfonium • nonafluoro - n-butane sulfonate (HPLC dissolution time: 4.71 min) B-3: cyclohexylsulfonyl phenyl diphenyl sulfonium n-butane sulfonate (HPLC dissolution time: 6.60 min) B- 4: 4 - Camphor expanded oxyphenyl. Diphenyl quinone non-fluorine-positive-butyl compound acid-44- 1333126 ester (HPLC dissolution time: 8.30 minutes) 3 hydrogen benzoquinone hexafluoro-n-butyl)) Alcohol urea B5: Bu (4-n-butoxynaphthalen-1-yl) E alkane sulfonate (HP LC dissolution time: 7.32 minutes acid crosslinker (C) Cl: N, N, N, N-four (Methoxymethyl acid diffusion inhibitor (D) D-1: tetra(n-butyl)ammonium hydroxide D-2 : 2-phenylbenzimidazole solvent (E) E-1: propylene glycol monomethyl ether acetate -45 - 1333126 Table 1 Resin (A) Acid generator (B) Acid crosslinker (C) Acid diffusion inhibitor (D) Solvent (E) 1 A-2 (100) Bl (3.32) C-1 (6.61 ) Dl(0.557) E- 1 (900) 2 A-3(100) B-K3.32) C-1 (6.61) Dl (0.5 5 7) E- 1 (900) 3 Al(lOO) B-3 (3.80) Cl(6.61) Dl(0.5 5 7) E- 1 (900) 4 A-1 (100) B-4(4.25) C-1(6.61) Dl(0.5 5 7) E- 1 (900) 5 A-1 (100) B-1 (3.32) Cl(6.61) D-2(0.417) E- 1 (900) 6 Al(lOO) B-1 (2.2), B-2 (1.0 Cl(6.61) D-2(0.414) E- 1 (900) Real 7 A-1 (100) Bl(ll), B-2(2.0) C-1 (6.6 1) D-2(0.414) E - 1 (900) Shi 8 A-1 (100) B-2(3.0 ) C-1 (6.61 ) D-2(0.414) E- 1 (900) Example 9 A-1 (100) B-5 (5.00 ) Cl (6.61) D-2(0_497) E- 1 (900) 10 A-2(100) Bl(3.32) Cl(6.61) D-2(0.313) E- 1 (900) 11 A-3(l00 B-K3.32) C-1(6.61) D-2(0_313) E- 1 (900) 12 A-4(l00) B-1 (3.32) C-1 (6.6 1) D-2 (0.313 E- 1 (900) 13 A-5(l00) B-1 (3.32) C-1(6.61) D-2(0.313) E- 1 (900) 14 A-2(100) B-5(5.00 C-1 (6.6 1 ) D-2(0.414) E- 1 (900) 15 A-3(l00) B-5(5.00) Cl(6.61) D-2(0.414) E- 1 (900) 16 A-6(100) B-5(5.00) C- 1 (6.61 ) D-2(0_414) E- 1 (900) 17 A-6(100) B-5(3.00) Cl (6.40) D-2 (0.256) E- 1 (900) -46 - 1333126 Table 2 Sensitivity (J/m2) Resolution (nm) Residual film rate (%) Bridge above the dissolved residual pattern below the pattern 1 550 130 0 〇Ο -Δ 2 640 130 0 〇Ο -Δ 3 480 130 0 〇Ο -Δ 4 490 130 0 〇Δ 5 470 120-130 22.1 △ ~x 〇6 460 130 0 Ο ~Δ Ο -Δ 7 4 10 1 20~130 0 〇Ο -Δ Real 8 440 14 0 0 〇Δ Shi 9 520 120-130 0 〇〇~△ Example 10 420 130 0 〇〇~△ 11 480 130 0 〇Ο -Δ 12 530 130 0 〇〇13 620 130 0 〇〇14 560 120 0 〇〇 15 630 120~130 0 〇〇16 420 120 0 〇〇17 380 120 0 〇〇Industrial Applicability The negative-type radiation-sensitive linear resin composition of the present invention is an inductively active radiation, particularly an ArF excimer laser ( The enhanced chemical type negative resist type of the outer line represented by the wavelength of 193 nm) is extremely suitable for use in manufacturing a semi-conductor device which is expected to be more refined in the future.

Claims (1)

1333126 Pickup, Patent Application No. 1. A negative-type radiation-sensitive resin composition characterized by containing a repeating unit (1-1) represented by the following formula (1-1) and the following formula (1-2) The copolymer (A) of the repeating unit (1-2) shown, and the radiation-sensitive linear acid generator (B), and the acid crosslinking agent (C) R1 R* (1-1) (1-2) (In the above formula (1-1) and formula (1_2), R1 represents a hydrogen atom or a methyl group 'in the formula (1-1), 'χΐ and X2 are independent of each other Representing a hydrogen atom or a fluorine-based group 'and at least X1 and X2 means a fluorine-based group, Υ means a divalent organic group' Ζ means a di-tetravalent organic group, and τ means a single bond or a carbon number of 1~ 3 bis-valent organic groups, η is an integer representing ^) ^ 2 · A negative-type radiation-sensitive resin composition as in the first application of the patent scope ' wherein the copolymer resin (Α) is subjected to gel permeation chromatography (GPC) The weight average molecular weight measured in terms of polystyrene is i, 〇〇〇~5〇, 〇〇〇. 3. The negative-type radiation-sensitive resin composition of claim 1, wherein the copolymerized resin (A), the radiation-sensitive linear acid generator (B), and the acid crosslinking agent (C) are contained, Acid diffusion inhibitor (D). 4. The negative-type radiation-sensitive resin group of the first aspect of the patent application-49- 1333126, wherein the amount of the radiation-sensitive linear acid generator (B) is 100 parts by weight relative to the copolymer resin (A) 0·b 20 parts by weight. 5. The negative-type radiation-sensitive resin composition of claim 1, wherein the radiation-sensitive linear acid generator (B) contains at least one of the following formula (2-1) and formula (2-2); And the acid generator selected by formula (2-3) (In the above formula (2-1), formula (2-2) and formula (2-3), X - represents R3-S〇3-, and R3 represents a hydrocarbon group which may be partially or wholly fluorinated, R2 represents a hydrogen atom or a hydrocarbon group, R4 represents a hydrocarbon group which may also be partially or fully fluorinated, U represents a divalent organic group, R5 and R6 represent a hydrogen atom or a hydrocarbon group independently of each other, and m represents an integer of 〇~3 , η is an integer that is not 0~2). 6. The negative-type radiation-sensitive resin composition according to claim 5, wherein the radiation-sensitive linear acid generator (?) is a formula (2-3). 7. The negative-type radiation-sensitive resin group of the first application of claim 1-50-^33126' wherein the amount of the acid crosslinking agent (c) is 100 parts by weight relative to the copolymerized tree (A) 0.5 to 50 parts by weight. 8. The negative-type radiation-sensitive resin group 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-type radiation-sensitive resin group of the invention of claim 8 wherein the solvent is a solvent selected from at least one of the group consisting of 2-hexanone, 2-heptanone, 2- Octanone, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 2-hydroxypropyl propionate methyl acetate, ethyl 2-hydroxypropionate, methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate 'ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diglyme, diethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, n-butyl acetate, methyl pyruvate, ethyl pyruvate, diethylene glycol monomethyl ether 'diethylene glycol monoethyl ether, r-butyrolactone. 10. The negative-type radiation-sensitive resin composition of claim 3, wherein the acid diffusion inhibitor (D) is represented by the following formula (4) (In the above formula (4), R23 and R24 are an alicyclic hydrocarbon group or an aromatic hydrocarbon group which are independently represented by a hydrogen atom or an alkyl group, or are bonded to each other, and -51 - 1333126 R25 represents a hydrogen atom or an alkyl group. Or -C(0) OR27 group, R27 represents an alkyl group, and R26 represents a hydrogen atom 'alkyl group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group). -52-