JP2010060693A - Pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pattern forming method that enables simple and efficient formation of a finer resist pattern. <P>SOLUTION: The pattern forming method includes the steps of: (1) forming a first pattern by forming a first resist layer comprising a positive radiation-sensitive resin composition containing an acid generator on a semiconductor substrate, selectively exposing the first resist layer and developing the layer; (2) forming a second resist layer comprising a negative radiation-sensitive resin composition containing an acid generator between adjacent first patterns; (3) forming a sidewall layer derived from the second resist layer on a sidewall of the first pattern by selectively exposing the first pattern and the second resist layer adjacent to the first pattern; and (4) removing the first pattern and the second resist layer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for forming a fine pattern.

  In the field of microfabrication represented by the manufacture of integrated circuit elements, a lithography technique capable of microfabrication is required in order to obtain a higher degree of integration. In such a lithography process, further fine pattern formation (for example, a resist pattern whose line width is finer than 45 nm) will be required in the future. In order to achieve such fine pattern formation of less than 45 nm, it is conceivable to shorten the light source wavelength of the exposure apparatus and increase the numerical aperture (NA) of the lens as described above. However, a new expensive exposure apparatus is required to shorten the light source wavelength. Further, when the lens has a high NA, the resolution and the depth of focus are in a trade-off relationship. Therefore, there is a problem that the depth of focus decreases even if the resolution is increased.

  Recently, as a lithography technique capable of solving such a problem, a method called an immersion exposure (liquid immersion lithography) method has been reported (for example, see Patent Document 1). In this method, at the time of exposure, a liquid high refractive index medium (immersion exposure liquid) such as pure water or a fluorine-based inert liquid having a predetermined thickness on at least the resist film between the lens and the resist film on the substrate. Is to intervene. In this method, a light source having the same exposure wavelength can be used by replacing the exposure optical path space, which has conventionally been an inert gas such as air or nitrogen, with a liquid having a higher refractive index (n), such as pure water. Similar to the case of using a light source with a shorter wavelength or the case of using a high NA lens, high resolution is achieved and there is no reduction in the depth of focus. If such immersion exposure is used, it is possible to realize the formation of a resist pattern that is low in cost, excellent in high resolution, and excellent in depth of focus, using a lens mounted on an existing apparatus. It has attracted a great deal of attention and is in practical use.

  However, it is said that the extension of the above-described exposure technique is limited to 45 nmhp, and technical development for the 32 nmhp generation that requires further fine processing is being carried out. In addition, since an apparatus (immersion exposure apparatus) used for immersion exposure is extremely expensive, there is a fact that it is not practical in an actual semiconductor manufacturing process.

On the other hand, as a technique for performing finer patterning, a predetermined film formed on the first resist pattern is processed to form a second resist pattern that leaves the film in the recesses of the first resist pattern. Method (for example, see Patent Document 2), resist pattern forming method for forming a predetermined film on a resist pattern formed by processing an upper resist film formed on a lower resist film (for example, see Patent Document 3) A pattern forming method for processing a processing layer using a second patterning layer embedded in a gap between the first patterning layers formed by processing a resist layer on the processing layer as a mask (for example, Patent Document 4) and the like. However, although there are proposals for several processes such as these, no proposal has yet been made for more specific and practical methods and materials.
JP-A-10-303114 JP 2001-343757 A JP 2002-110510 A JP 2004-335873 A

  The present invention has been made in view of such problems of the prior art, and the problem is that a finer pattern can be easily and efficiently formed and the semiconductor manufacturing process can be performed. An object of the present invention is to provide a highly practical pattern forming method that can be applied.

  As a result of intensive studies to achieve the above-described problems, the present inventors have found that the above-described problems can be achieved by adopting the following configuration, and have completed the present invention. That is, according to the present invention, the following pattern forming method is provided.

  In the present specification, “pattern” refers to, for example, an image (image) formed by a resin or the like remaining after exposure and development. May indicate the entire pattern. In addition, “near the interface” means within about 5 nm from the interface.

[1] (1) A first resist layer made of a positive radiation-sensitive resin composition containing an acid generator is formed on a semiconductor substrate, and the first resist layer is selectively exposed and developed. And forming a first pattern;
(2) forming a second resist layer comprising a negative radiation-sensitive resin composition containing an acid generator between the adjacent first patterns;
(3) selectively exposing portions of the first pattern and the second resist layer adjacent to the first pattern to form a sidewall layer derived from the second resist layer on the first pattern sidewall; ,
(4) A pattern forming method including a step of removing the first pattern and the second resist layer.

[2] The pattern forming method according to [1], wherein in the step (4), the first pattern and the second resist layer are removed by alkali development.

[3] The pattern forming method according to the above [1] or [2], wherein the negative radiation sensitive resin composition is a negative radiation sensitive resin composition containing silicon atoms.

[4] The pattern forming method according to [3], wherein the negative radiation sensitive resin composition containing the silicon atom contains the following (A) to (C).

(A) Hydrolytic condensation of at least one hydrolyzable silane compound selected from the hydrolyzable silane compound represented by the following general formula (1) and the hydrolyzable silane compound represented by the following general formula (2) A polymer obtained by
(B) a radiation sensitive acid generator;
(C) Solvent

^{_{R a Si (OR 1) 4}} -a (1)

[In general formula (1), R represents a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a cyano group, a cyanoalkyl group, an alkylcarbonyloxy group or an aryl group; ¹ represents a monovalent organic group, and a represents an integer of 1 to 3. ]

Si (OR ² ) ₄ (2)

[In General Formula (2), R ² represents a monovalent organic group. ]

[5] The pattern forming method according to [4], wherein the solvent is an alcohol or ether having 4 to 10 carbon atoms.

  According to the pattern forming method of the present invention, a finer resist pattern can be easily and efficiently formed. Therefore, the pattern forming method of the present invention is highly practical and can be applied to a semiconductor manufacturing process.

  BEST MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the present invention will be described below, but the present invention is not limited to the following embodiment, and is based on the ordinary knowledge of those skilled in the art without departing from the gist of the present invention. It should be understood that modifications and improvements as appropriate to the following embodiments also fall within the scope of the present invention.

Pattern formation method:
In the pattern forming method according to an embodiment of the present invention, (1) a first resist layer made of a positive radiation sensitive resin composition containing an acid generator is formed on a semiconductor substrate; A step of selectively exposing and developing the resist layer to form a first pattern; and (2) a negative radiation sensitive resin composition containing an acid generator between the adjacent first patterns. A step of forming a second resist layer made of a material, and (3) selectively exposing the first pattern and a portion of the second resist layer adjacent to the first pattern to form a first resist on the side wall of the first pattern. Forming a side wall layer derived from the second resist layer; and (4) removing the first pattern and the second resist layer.

((1) Process)
In the step (1), a positive radiation-sensitive resin composition (hereinafter referred to as “hereinafter referred to as“ positive radiation sensitive resin composition ”) is appropriately formed on a substrate such as a silicon wafer on which an organic underlayer film is arbitrarily formed by an appropriate application means such as spin coating, cast coating, roll coating or the like. (Also referred to as “positive resist agent” or “resist agent”). Thereby, the resist layer which consists of a resist agent can be formed. In addition, after apply | coating a resist agent, you may volatilize the solvent in a coating film by prebaking (PB) as needed. Although the prebaking heating conditions are appropriately selected depending on the composition of the resist agent, they are usually 30 to 200 ° C, preferably 50 to 150 ° C.

  When the negative radiation-sensitive resin composition used in the step (2) described below contains an inorganic component as a main component, as an organic underlayer film formed on a substrate, for example, trade name “CT08” (JSR Corporation) Manufactured). The organic underlayer film is preferably one that exhibits a sufficient antireflection function when resist patterning is performed. Furthermore, the pattern containing the predetermined resin composition formed on the organic underlayer film by the pattern forming method of the present invention is transferred to the organic underlayer film by etching and then transferred to the underlying oxide film or the like. The organic underlayer film is preferably a film having etching resistance against a fluorine-based etching gas. Specific examples of the more preferable organic underlayer film include the organic underlayer film disclosed in JP-A-2002-214777 and the like.

  When the negative radiation-sensitive resin composition used in the step (2) described below contains an organic component as a main component, a lower layer film is not used or a material that does not have etching resistance to oxygen (BARC) Is preferably used. As the BARC, a trade name “ARC29A” (manufactured by Brewer) can be mentioned.

  A desired region of the formed resist layer is exposed by irradiating with radiation through a mask having a predetermined pattern to form a pattern latent image portion (post-exposure alkali-insoluble portion). The radiation used is appropriately selected from visible rays, ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, etc., depending on the type of acid generator contained in the resist agent, but an ArF excimer laser (wavelength 193 nm). ) And KrF excimer laser (wavelength 248 nm) are preferred, and ArF excimer laser (wavelength 193 nm) is particularly preferred. The exposure conditions such as the exposure amount are appropriately selected according to the compounding composition of the resist agent and the type of additive. Furthermore, in this invention, it is preferable to perform heat processing (PEB) after exposure. By this PEB, the dissociation reaction of the acid dissociable group in the resin component can be smoothly advanced. The heating condition of PEB is appropriately selected depending on the composition of the resist agent, but is usually 30 to 200 ° C, preferably 50 to 170 ° C.

By developing the exposed resist layer, the pattern latent image portion is exposed, and the positive first pattern 1 having a predetermined line width L ₁ and having a predetermined space portion as shown in FIG. It is formed on the substrate 10 through the lower layer film 3. The line width L1 of the _first pattern 1 to be formed differs depending on the type of radiation to be irradiated. For example, when an ArF excimer laser (wavelength 193 nm) is used, L ₁ can be set to 95 to 155 nm.

  Examples of the developer that can be used for development include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, and di-n-propylamine. , Triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- An alkaline aqueous solution in which at least one of alkaline compounds such as [4.3.0] -5-nonene is dissolved is preferable. The concentration of the alkaline aqueous solution is usually 10% by mass or less. When the concentration of the alkaline aqueous solution is more than 10% by mass, the non-exposed portion tends to be easily dissolved in the developer. In addition, after developing using alkaline aqueous solution, generally it wash | cleans with water and dries.

  An organic solvent can also be added to the alkaline aqueous solution (developer). Examples of the organic solvent that can be added include ketones such as acetone, methyl ethyl ketone, methyl i-butyl ketone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, and 2,6-dimethylcyclohexanone; methyl alcohol, ethyl alcohol , N-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol, 1,4-hexanedimethylol, and the like; tetrahydrofuran, dioxane Ethers such as ethyl acetate, n-butyl acetate, i-amyl acetate, aromatic hydrocarbons such as toluene and xylene, phenol, acetonylacetone, dimethylformamide, etc. That. These organic solvents can be used individually by 1 type or in combination of 2 or more types.

  The addition amount of the organic solvent is preferably 100 parts by volume or less with respect to 100 parts by volume of the alkaline aqueous solution. When the addition amount of the organic solvent is more than 100 parts by volume with respect to 100 parts by volume of the alkaline aqueous solution, the developability may be deteriorated and the development residue in the exposed part may increase. An appropriate amount of a surfactant or the like can be added to the developer.

((2) Process)
In the step (2), the resin composition for pattern formation is applied onto the formed first pattern by an appropriate application means such as spin coating, cast coating, roll coating or the like. At this time, the resin composition for pattern formation is applied so that the first pattern is covered. After applying the resin composition for pattern formation, it is usually composed of the resin composition 5 for pattern formation between the adjacent first patterns 1 as shown in FIG. 2 by heat treatment (baking). An uncrosslinked embedded portion 7 can be formed. In addition, you may perform this (2) process in multiple times as needed.

  The heating conditions for heat-treating the pattern-forming resin composition applied on the first pattern are appropriately selected depending on the blended composition of the applied pattern-forming resin composition, but are usually 50 to 200 ° C., preferably Is 80-180 ° C. In addition, when the resin composition for pattern formation containing the above-mentioned crosslinking agent is used, it is preferable to set the temperature of heat processing suitably according to the kind, content rate, etc. of a crosslinking agent.

In order to form the uncrosslinked buried portion 7, the upper surface 20 of the first pattern may be exposed by a technique such as etching as shown in FIG. Specifically, for example, using a normal etching apparatus, the pattern-forming resin composition 5 disposed on the upper surface 20 of the first pattern is removed (etch back) using CF ₄ gas, O ₂ gas, or the like. do it. Etching may be performed by a wet method in addition to a dry method using CF ₄ gas, O ₂ gas, or the like. Alternatively, the pattern-forming resin composition 5 mechanically disposed on the upper surface 20 of the first pattern may be removed.

((3) Process)
In step (3), the first pattern 1 and the uncrosslinked embedded portion 7 adjacent to the first pattern 1 are selectively exposed, and the uncrosslinked embedded portion 7 is in the vicinity of the interface with the first pattern 1. To form a sidewall layer (first crosslinked portion 11 and second crosslinked portion 12) derived from the second resist layer on the sidewall of the first pattern 1 (see FIG. 4). Thereby, as shown in FIG. 4, the first pattern 1, the first cross-linking portion 11, the non-cross-linking embedded portion 7, and the second cross-linking portion 12 are arranged in this order to repeat the arrangement structure 15. be able to. Here, since the 1st pattern 1 is also selectively exposed together with the part adjacent to the 1st pattern 1 of the unbridged embedding part 7, the solubility of the 1st pattern 1 improves and it mentions later ( 4) The first pattern 1 can be easily removed in the process.

((4) Process)
(4) In the step, the first pattern 1 and the uncrosslinked embedded portion 7 are removed. Thus, as shown in FIG. 5, to form a second pattern 2 having a first bridge portion 11 and the second bridge portion 12 of the predetermined line width _{L 2, L 3, L 4} , L 5 be able to.

  Although the first pattern 1 becomes soluble in the developer or the like by the above-mentioned step (3), the first crosslinked portion 11 and the second crosslinked portion 12 are hardly dissolved in the developer or the like. A stable state is maintained. Next, if development is performed using the developer described above, the first pattern 1 solubilized by exposure and the uncrosslinked embedded portion 7 soluble in the developer from the beginning can be removed at a time. It is possible to form the second pattern 2 including the first cross-linking portion 11 and the second cross-linking portion 12 shown in FIG.

The second pattern 2 formed in this way has line widths L _{2 to} L ₅ smaller than the line width L ₁ (see FIG. 1) of the first pattern 1. Specifically, for example, L _{2 to} L ₅ = 20 to 80 nm can be set with respect to L ₁ = 95 to 155 nm. Therefore, according to the pattern forming method of the present invention, a line width of 40 nm or less, which has been extremely difficult in the past, has been achieved even by an exposure method using a normal ArF excimer laser without using expensive equipment such as an immersion exposure apparatus. The fine pattern can be easily formed. For this reason, the pattern formation method of the present invention is a method that can be suitably incorporated into a semiconductor manufacturing process, and is extremely practical.

(Positive radiation sensitive resin composition)
The positive radiation sensitive resin composition used in the pattern forming method of the present invention (hereinafter sometimes referred to as a first resist agent or a positive resist agent) is an action of an acid generated from an acid generator upon exposure. As a result, the acid-dissociable group is dissociated, and the exposed portion of the resist whose solubility in the alkali developer is increased is dissolved and removed by the alkali developer, so that a positive pattern can be obtained.

(First Resin Resin)
As the resin for the first resist agent used in the present invention, both those not containing Si atoms and those containing Si atoms can be used. As what does not contain Si atom, what is described in Japanese Patent Application No. 2007-323349 can be used. Moreover, as what contains Si atom, the thing of Unexamined-Japanese-Patent No. 2003-020335 and Unexamined-Japanese-Patent No. 2007-182555 can be used.

  Specifically, the first resist agent resin described in Japanese Patent Application No. 2007-323349 is a resin having a repeating unit represented by the following general formula (3) (in this specification, the first resist agent) Resin and resin for positive resist agent.

In the general formula (3), R ³ represents hydrogen or a methyl group, and a plurality of R ^{4 s} are independently of each other a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, Or a C1-C4 linear or branched alkyl group is shown. In addition, at least one of R ⁴ is a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or any two R ⁴ are bonded to each other and bonded to each other. Forming a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof containing a carbon atom, and the remaining R ⁴ is a linear or branched alkyl having 1 to 4 carbon atoms Or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof.

  Specifically, the first resin for a resist agent containing Si atoms described in JP-A-2003-020335 is a structural unit (I) and / or a structural unit (II) represented by the following general formula (4). And a polysiloxane having a polystyrene-reduced weight average molecular weight of 500 to 1,000,000 as measured by gel permeation chromatography (GPC) having an acid dissociable group that is dissociated by an acid.

[In General Formula (4), R ⁵ is a monovalent aromatic group having 6 to 20 carbon atoms substituted with at least one group selected from the group consisting of a fluorine atom and a fluorinated alkyl group having 1 to 10 carbon atoms. Or a monovalent alicyclic group having 3 to 15 carbon atoms substituted with at least one group selected from the group consisting of a fluorine atom and a fluorinated alkyl group having 1 to 10 carbon atoms, and R ⁶ represents a fluorine atom. And a monovalent aromatic group having 6 to 20 carbon atoms, a fluorine atom and a fluorinated alkyl having 1 to 10 carbon atoms substituted with at least one group selected from the group of fluorinated alkyl groups having 1 to 10 carbon atoms C1-C15 monovalent alicyclic group substituted with at least one group selected from the group of groups, a hydrogen atom, a halogen atom, a C1-C20 monovalent hydrocarbon group, carbon number 1-20 halogenated alkyl groups, or 1 Shows a secondary or tertiary amino groups. ]

  Specifically, the first resin for a resist agent containing Si atoms described in JP-A-2007-182555 is specifically represented by the following general formula (IV):

(In the formula, R ⁷ represents an optionally substituted divalent hydrocarbon group having 1 to 20 carbon atoms, and R ⁸ represents a monovalent acid-dissociable group.), (V),

  And the following general formula (VI)

(In the formula, R ⁹ represents an optionally substituted divalent hydrocarbon group having 1 to 20 carbon atoms, and R ¹⁰ represents an alkoxyl group having 1 to 20 carbon atoms, a cyano group, or a hydroxyl group. .)
It is polysiloxane which has a structural unit represented by these.
(Acid generator)
The positive resist used in the present invention contains an acid generator. The acid generator is preferably a compound that has a structure represented by the following general formula (5) and is decomposed by exposure.

In the general formula (5), R ¹³ is a hydrogen atom, a fluorine atom, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, or a linear or branched group having 1 to 10 carbon atoms. Or a linear or branched alkoxycarbonyl group having 2 to 11 carbon atoms. R ¹¹ represents a linear or branched alkyl group or alkoxyl group having 1 to 10 carbon atoms, or a linear, branched or cyclic alkanesulfonyl group having 1 to 10 carbon atoms.

In the general formula (5), R ¹² are independently of each other a linear or branched alkyl group having 1 to 10 carbon atoms, an optionally substituted phenyl group, or an optionally substituted group. It may be a good naphthyl group, or two R ¹² may be bonded to each other to form a divalent group having 2 to 10 carbon atoms. In addition, the formed bivalent group may be substituted. k is an integer of 0 to 2, and Y ⁻ is a general formula: R ¹⁴ C _t F _2t SO ₃ ⁻ (wherein R ¹⁴ is a fluorine atom or an optionally substituted carbon atom having 1 to 12 carbon atoms. Represents an anion represented by a hydrocarbon group, t is an integer of 1 to 10, and q is an integer of 0 to 10.

In the general formula (5), examples of the linear or branched alkyl group having 1 to 10 carbon atoms represented by R ¹¹ , R ¹² , and R ¹³ include a methyl group, an ethyl group, and n-propyl. Group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl Group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like. Of these, a methyl group, an ethyl group, an n-butyl group, a t-butyl group, and the like are preferable.

In the general formula (5), examples of the linear or branched alkoxyl group having 1 to 10 carbon atoms represented by R ¹¹ and R ¹² include a methoxy group, an ethoxy group, an n-propoxy group, i- Propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-heptyloxy group, n- An octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, etc. can be mentioned. Of these, a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group and the like are preferable.

In the general formula (5), examples of the linear or branched alkoxycarbonyl group having 2 to 11 carbon atoms represented by R ¹³ include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, i -Propoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group, n-pentyloxycarbonyl group, neopentyloxycarbonyl group, n-hexyloxycarbonyl group N-heptyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxycarbonyl group and the like. Of these, a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, and the like are preferable.

Formula (5), of 1 to 10 carbon atoms represented by R ¹¹ linear, as the alkanesulfonyl group branched, or cyclic, for example, methanesulfonyl group, ethanesulfonyl group, n- propanesulfonyl Group, n-butanesulfonyl group, tert-butanesulfonyl group, n-pentanesulfonyl group, neopentanesulfonyl group, n-hexanesulfonyl group, n-heptanesulfonyl group, n-octanesulfonyl group, 2-ethylhexanesulfonyl group n -Nonanesulfonyl group, n-decanesulfonyl group, cyclopentanesulfonyl group, cyclohexanesulfonyl group, etc. can be mentioned. Of these, a methanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, an n-butanesulfonyl group, a cyclopentanesulfonyl group, a cyclohexanesulfonyl group, and the like are preferable. Moreover, q is preferably 0-2.

In the general formula (5), examples of the optionally substituted phenyl group represented by R ¹² include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, and 2,3-dimethylphenyl. Group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl Group, 4-ethylphenyl group, 4-t-butylphenyl group, 4-cyclohexylphenyl group, 4-fluorophenyl group and the like; linear, branched or cyclic alkyl having 1 to 10 carbon atoms A phenyl group substituted with a group; these phenyl group or alkyl-substituted phenyl group can be converted into a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxyl group, an alkoxy group; Examples thereof include a group substituted with at least one group such as a sialkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group. Examples of the alkoxyl group among the substituents for the phenyl group and the alkyl-substituted phenyl group include, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1 Examples thereof include linear, branched, or cyclic alkoxyl groups having 1 to 20 carbon atoms such as a methylpropoxy group, a t-butoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

  Examples of the alkoxyalkyl group include 2 to 21 carbon atoms such as a methoxymethyl group, an ethoxymethyl group, a 1-methoxyethyl group, a 2-methoxyethyl group, a 1-ethoxyethyl group, and a 2-ethoxyethyl group. The linear, branched, or cyclic alkoxyalkyl group can be exemplified. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, a 2-methylpropoxycarbonyl group, and a 1-methylpropoxycarbonyl group. , T-butoxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl, etc., having 2 to 21 carbon atoms, such as a linear, branched, or cyclic alkoxycarbonyl group.

Examples of the alkoxycarbonyloxy group include methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i-propoxycarbonyloxy group, n-butoxycarbonyloxy group, t-butoxycarbonyloxy group, Examples thereof include linear, branched, or cyclic alkoxycarbonyloxy groups having 2 to 21 carbon atoms such as cyclopentyloxycarbonyl group and cyclohexyloxycarbonyl. In the general formula (5), the optionally substituted phenyl group represented by R ¹² includes a phenyl group, a 4-cyclohexylphenyl group, a 4-t-butylphenyl group, a 4-methoxyphenyl group, a 4-t -A butoxyphenyl group and the like are preferable.

In the general formula (5), examples of the optionally substituted naphthyl group represented by R ¹² include 1-naphthyl group, 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, 4 -Methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 5-methyl-1-naphthyl group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1- Naphthyl group, 2,3-dimethyl-1-naphthyl group, 2,4-dimethyl-1-naphthyl group, 2,5-dimethyl-1-naphthyl group, 2,6-dimethyl-1-naphthyl group, 2,7 -Dimethyl-1-naphthyl group, 2,8-dimethyl-1-naphthyl group, 3,4-dimethyl-1-naphthyl group, 3,5-dimethyl-1-naphthyl group, 3,6-dimethyl-1-naphthyl Group, 3,7-dimethyl-1-naphthyl group, 3 , 8-dimethyl-1-naphthyl group, 4,5-dimethyl-1-naphthyl group, 5,8-dimethyl-1-naphthyl group, 4-ethyl-1-naphthyl group, 2-naphthyl group, 1-methyl- A naphthyl group such as a 2-naphthyl group, a 3-methyl-2-naphthyl group, and a 4-methyl-2-naphthyl group; substituted with a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms One or more of these naphthyl groups or alkyl-substituted naphthyl groups as at least one group such as hydroxyl group, carboxyl group, cyano group, nitro group, alkoxyl group, alkoxyalkyl group, alkoxycarbonyl group, alkoxycarbonyloxy group, etc. Examples include substituted groups. Specific examples of the alkoxyl group, alkoxyalkyl group, alkoxycarbonyl group, and alkoxycarbonyloxy group among these substituents include the groups exemplified for the aforementioned phenyl group and alkyl-substituted phenyl group.

In the general formula (5), the divalent group having 2 to 10 carbon atoms formed by bonding two R ¹² to each other is a 5-membered or 6-membered group together with the sulfur atom in the general formula (5). Groups that form a ring, preferably a 5-membered ring (ie, a tetrahydrothiophene ring) are desirable. Examples of the substituent for the divalent group include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxyl group, an alkoxyalkyl group, an alkoxy group exemplified as the substituent for the phenyl group and the alkyl-substituted phenyl group. Examples thereof include a carbonyl group and an alkoxycarbonyloxy group. Incidentally, Examples R ¹² in the general formula (5), a methyl group, an ethyl group, a phenyl group, a 4-methoxyphenyl group, 1-naphthyl group, tetrahydrothiophene two R ¹² are taken together with the attached to a sulfur atom each other to form a ring structure A divalent group or the like that forms is preferable.

  As the cation moiety in the general formula (5), triphenylsulfonium cation, tri-1-naphthylsulfonium cation, tri-tert-butylphenylsulfonium cation, 4-fluorophenyl-diphenylsulfonium cation, di-4-fluorophenyl- Phenylsulfonium cation, tri-4-fluorophenylsulfonium cation, 4-cyclohexylphenyl-diphenylsulfonium cation, 4-methanesulfonylphenyl-diphenylsulfonium cation, 4-cyclohexanesulfonyl-diphenylsulfonium cation, 1-naphthyldimethylsulfonium cation, 1- Naphthyldiethylsulfonium cation, 1- (4-hydroxynaphthyl) dimethylsulfonium cation, 1- (4 Methylnaphthyl) dimethylsulfonium cation, 1- (4-methylnaphthyl) diethylsulfonium cation, 1- (4-cyanonaphthyl) dimethylsulfonium cation, 1- (4-cyanonaphthyl) diethylsulfonium cation, 1- (3,5- Dimethyl-4-hydroxyphenyl) tetrahydrothiophenium cation, 1- (4-methoxynaphthyl) tetrahydrothiophenium cation, 1- (4-ethoxynaphthyl) tetrahydrothiophenium cation, 1- (4-n-propoxynaphthyl) ) Tetrahydrothiophenium cation, 1- (4-n-butoxynaphthyl) tetrahydrothiophenium cation, 2- (7-methoxynaphthyl) tetrahydrothiophenium cation, 2- (7-ethoxynaphthyl) tetrahi B thiophenium cation, 2- (7-n- propoxy-naphthyl) tetrahydrothiophenium cation, 2- (7-n- butoxynaphthyl) can be exemplified tetrahydrothiophenium cation, or the like.

In the general formula (5), the “C _t F _2t —” group in the anion represented by Y ⁻ (general formula: R ¹⁴ C _t F _2t SO ³⁻ ) is a perfluoroalkylene group having n carbon atoms. However, the perfluoroalkylene group may be linear or branched. T is preferably 1, 2, 4, or 8. The optionally substituted hydrocarbon group having 1 to 12 carbon atoms represented by R ¹⁴ is preferably an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, or a bridged alicyclic hydrocarbon group. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, neopentyl group N-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, norbornyl group, norbornylmethyl group, hydroxynorbornyl group, adamantyl group Etc.

  Preferred anion sites in the general formula (5) include trifluoromethanesulfonate anion, perfluoro-n-butanesulfonate anion, perfluoro-n-octanesulfonate anion, 2-bicyclo [2.2.1] hept-2- Yl-1,1,2,2-tetrafluoroethanesulfonate anion, 2-bicyclo [2.2.1] hept-2-yl-1,1-difluoroethanesulfonate anion, and the like.

  Said acid generator can be used individually by 1 type or in combination of 2 or more types. It is also possible to use “other acid generators” other than the above acid generators. Specific examples of “other acid generators” include onium salt compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, and sulfonic acid compounds.

  Examples of the onium salt compounds include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like. Specific examples of the onium salt compound include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hepta-2. -Yl-1,1,2,2-tetrafluoroethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis ( 4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2- Te La tetrafluoroethane sulfonate, cyclohexyl 2-oxo-cyclohexyl methyl trifluoromethanesulfonate, dicyclohexyl-2-oxo-cyclohexyl trifluoromethane sulfonate, and 2-oxo-cyclohexyl dimethyl sulfonium trifluoromethanesulfonate, and the like.

  Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Specific examples of halogen-containing compounds include (trichloromethyl such as phenylbis (trichloromethyl) -s-triazine, 4-methoxyphenylbis (trichloromethyl) -s-triazine, 1-naphthylbis (trichloromethyl) -s-triazine. ) -S-triazine derivatives and 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane.

  Examples of the diazoketone compound include a 1,3-diketo-2-diazo compound, a diazobenzoquinone compound, a diazonaphthoquinone compound, and the like. Specific examples of the diazo ketone include 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2, naphthoquinonediazide of 2,3,4,4′-tetrahydroxybenzophenone. -4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester; 1,2-naphthoquinonediazide-4-sulfonic acid ester of 1,1,1-tris (4-hydroxyphenyl) ethane Examples include 2-naphthoquinonediazide-5-sulfonic acid ester.

  Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, α-diazo compounds of these compounds, and the like. Specific examples of the sulfone compound include 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, and the like.

  Examples of the sulfonic acid compounds include alkyl sulfonic acid esters, alkyl sulfonic acid imides, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Specific examples of the sulfonic acid compounds include benzoin tosylate, pyrogallol tris (trifluoromethanesulfonate), nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, trifluoromethanesulfonylbicyclo [2.2.1] hept- 5-ene-2,3-dicarbodiimide, nonafluoro-n-butanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide, perfluoro-n-octanesulfonylbicyclo [2.2 .1] Hept-5-ene-2,3-dicarbodiimide, 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarbodiimide, N- (trifluoromethanesulfonyl Xyl) succinimide, N- (nonafluoro-n-butanesulfonyloxy) succinimide, N- (perfluoro-n-octanesulfonyloxy) succinimide, N- (2-bicyclo [2.2.1] hept-2-yl- 1,1,2,2-tetrafluoroethanesulfonyloxy) succinimide, 1,8-naphthalenedicarboxylic imide trifluoromethanesulfonate, 1,8-naphthalenedicarboxylic imidononafluoro-n-butanesulfonate, 1,8-naphthalenedicarboxylic Examples include acid imido perfluoro-n-octane sulfonate.

  Among these “other acid generators”, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hepta. 2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, Bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2, 2-te Lafluoroethanesulfonate, cyclohexyl, 2-oxocyclohexyl, methylsulfonium trifluoromethanesulfonate, dicyclohexyl, 2-oxocyclohexylsulfonium trifluoromethanesulfonate, 2-oxocyclohexyldimethylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonylbicyclo [2.2.1] Hept-5-ene-2,3-dicarbodiimide, nonafluoro-n-butanesulfonylbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide, perfluoro-n-octanesulfonylbicyclo [2 2.1] hept-5-ene-2,3-dicarbodiimide, 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfur Nilbicyclo [2.2.1] hept-5-ene-2,3-dicarbodiimide, N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoro-n-butanesulfonyloxy) succinimide, N- (perfluoro- n-octanesulfonyloxy) succinimide, N- (2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) succinimide, 1,8-naphthalenedicarboxylic acid Imidotrifluoromethanesulfonate and the like are preferable. These “other acid generators” can be used alone or in combination of two or more.

  It is also preferable to use an acid generator having the structure represented by the general formula (5) in combination with “other acid generator”. When “other acid generator” is used in combination, the ratio of “other acid generator” used is the sum of the acid generator having the structure represented by the general formula (5) and “other acid generator”. Is usually 80% by mass or less, preferably 60% by mass or less.

  The total content of the acid generator contained in the positive resist agent is 0.1 to 20 parts by mass with respect to 100 parts by mass of the resist resin from the viewpoint of ensuring the sensitivity and developability as the resist agent. It is preferable that it is 0.5 to 10 parts by mass. When the total content of the acid generator is less than 0.1 parts by mass, the sensitivity and developability of the positive resist agent tend to be lowered. On the other hand, if it exceeds 20 parts by mass, the transparency to radiation is lowered, and it tends to be difficult to form a rectangular pattern.

(Acid diffusion control agent)
The positive resist agent used in the present invention preferably contains an acid diffusion controller. The acid diffusion control agent is a component having an action of controlling a diffusion phenomenon of an acid generated from an acid generator by exposure in a resist layer and suppressing an undesirable chemical reaction in a non-exposed region. By blending such an acid diffusion control agent, the storage stability of the resist agent is improved, the resolution of the resist is further improved, and due to fluctuations in the holding time (PED) from exposure to heat treatment after exposure. A change in the line width of the pattern can be suppressed, and a composition having extremely excellent process stability can be obtained. As the acid diffusion controller, it is preferable to use a nitrogen-containing organic compound or a photodisintegratable base. This photodegradable base is an onium salt compound that is decomposed by exposure and exhibits acid diffusion controllability.

(Nitrogen-containing organic compounds)
Examples of the nitrogen-containing organic compound include a compound represented by the following general formula (6) (hereinafter, also referred to as “nitrogen-containing compound (6I)”), a compound having two nitrogen atoms in the same molecule (hereinafter, “ A nitrogen-containing compound (6II) ”, a polyamino compound having three or more nitrogen atoms in the same molecule and a polymer thereof (hereinafter collectively referred to as“ nitrogen-containing compound (6III) ”), an amide group-containing compound , Urea compounds, nitrogen-containing heterocyclic compounds, and the like.

In the general formula (6), R ¹⁵ are independently of each other a hydrogen atom, a substituted or unsubstituted linear, branched or cyclic alkyl group, a substituted or unsubstituted aryl group, or a substituted or non-substituted group. A substituted aralkyl group is shown.

  Examples of the nitrogen-containing compound (6I) include mono (cyclo) alkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, cyclohexylamine; di-n- Butylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, cyclohexylmethylamine, dicyclohexylamine, etc. Di (cyclo) alkylamines; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine , Tri-n-nonylamine, tri-n-decylamine, cyclohexyl Tri (cyclo) alkylamines such as dimethylamine, methyldicyclohexylamine, tricyclohexylamine; substituted alkylamines such as 2,2 ′, 2 ″ -nitrotriethanol; aniline, N-methylaniline, N, N-dimethyl Aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, naphthylamine, 2,4,6-tri-tert-butyl-N-methylaniline, N-phenyl Aromatic amines such as diethanolamine and 2,6-diisopropylaniline are preferred.

  Examples of the nitrogen-containing compound (6II) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, and 4,4′-diaminodiphenylether. 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2, -(4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) ) -1-Methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methyl Til] benzene, bis (2-dimethylaminoethyl) ether, bis (2-diethylaminoethyl) ether, 1- (2-hydroxyethyl) -2-imidazolidinone, 2-quinoxalinol, N, N, N ′ , N′-tetrakis (2-hydroxypropyl) ethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine and the like are preferable.

  As the nitrogen-containing compound (6III), for example, polyethyleneimine, polyallylamine, 2-dimethylaminoethylacrylamide polymer and the like are preferable.

  Examples of the amide group-containing compound include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, Nt- Butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-2-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, (S)-( -)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, (R)-(+)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, Nt-butoxycarbonyl-4-hydroxypiperidine Nt-butoxycarbonylpyrrolidine, Nt-butoxycarbonyl Perazine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4′- Diaminodiphenylmethane, N, N′-di-t-butoxycarbonylhexamethylenediamine, N, N, N′N′-tetra-t-butoxycarbonylhexamethylenediamine, N, N′-di-t-butoxycarbonyl-1 , 7-diaminoheptane, N, N′-di-t-butoxycarbonyl-1,8-diaminooctane, N, N′-di-t-butoxycarbonyl-1,9-diaminononane, N, N′-di- t-butoxycarbonyl-1,10-diaminodecane, N, N′-di-t-butoxycarbonyl-1,12-diaminododecane, N, N -Di-t-butoxycarbonyl-4,4'-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2-phenylbenzimidazole Nt-butoxycarbonyl group-containing amino compounds such as Nt-butoxycarbonylpyrrolidine, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide Propionamide, benzamide, pyrrolidone, N-methylpyrrolidone, N-acetyl-1-adamantylamine, isocyanuric acid tris (2-hydroxyethyl) and the like are preferable.

  Examples of urea compounds include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butylthiourea. Etc. are preferred. Examples of the nitrogen-containing heterocyclic compound include imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2- Imidazoles such as methyl-1H-imidazole; pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine , Nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline, acridine, pyridines such as 2,2 ′: 6 ′, 2 ″ -terpyridine; piperazine, 1- (2-hydroxyethyl ) In addition to piperazines such as piperazine, Gin, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, piperidine ethanol, 3-piperidino-1,2-propanediol, morpholine, 4-methylmorpholine, 1- (4-morpholinyl) ethanol, 4-acetylmorpholine, 3 -(N-morpholino) -1,2-propanediol, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane and the like are preferable.

(Photodegradable base)
A photodegradable base is an onium salt compound that generates a base that decomposes upon exposure and exhibits acid diffusion controllability. Specific examples of such an onium salt compound include a sulfonium salt compound represented by the following general formula (7) and an iodonium salt compound represented by the following general formula (8).

In the general formulas (7) and (8), R ^{16 to} R ²⁰ each independently represent a hydrogen atom, an alkyl group, an alkoxyl group, a hydroxyl group, or a halogen atom. Z ⁻ represents OH ⁻ , R—COO ⁻ , R—SO ₃ ^— (wherein R represents an alkyl group, an aryl group, or an alkaryl group), or an anion represented by the following formula (9). Show.

  Specific examples of the sulfonium salt compound and the iodonium salt compound include triphenylsulfonium hydroxide, triphenylsulfonium acetate, triphenylsulfonium salicylate, diphenyl-4-hydroxyphenylsulfonium hydroxide, diphenyl-4-hydroxyphenylsulfonium acetate, Diphenyl-4-hydroxyphenylsulfonium salicylate, bis (4-t-butylphenyl) iodonium hydroxide, bis (4-t-butylphenyl) iodonium acetate, bis (4-t-butylphenyl) iodonium hydroxide, bis (4-t-butylphenyl) iodonium acetate, bis (4-t-butylphenyl) iodonium salicylate, 4-t-butyl Phenyl-4-hydroxyphenyliodonium hydroxide, 4-t-butylphenyl-4-hydroxyphenyliodonium acetate, 4-t-butylphenyl-4-hydroxyphenyliodonium salicylate, bis (4-t-butylphenyl) iodonium Examples thereof include 10-camphor sulfonate, diphenyliodonium 10-camphor sulfonate, triphenylsulfonium 10-camphor sulfonate, and 4-t-butoxyphenyl diphenylsulfonium 10-camphor sulfonate.

  The above acid diffusion control agents can be used singly or in combination of two or more. The compounding amount of the acid diffusion controller is usually 15 parts by mass or less, preferably 10 parts by mass or less, and more preferably 5 parts by mass or less with respect to 100 parts by mass of the first resist resin. When the blending amount of the acid diffusion controller is more than 15 parts by mass, the sensitivity of the first resist agent tends to decrease. If the amount of the acid diffusion controller is less than 0.001 part by mass, the pattern shape and dimensional fidelity may be lowered depending on the process conditions.

(solvent)
The positive resist agent used in the present invention is preferably obtained by dissolving the first resin for resist agent, acid generator, acid diffusion controller and the like in a solvent. The solvent is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate, 2-heptanone, and cyclohexanone (hereinafter also referred to as “solvent (S)”). In addition, a solvent other than the solvent (S) (hereinafter, also referred to as “other solvent”) can be used. Furthermore, the solvent (S) and other solvents can be used in combination.

  Examples of other solvents include propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-i-propyl ether acetate, propylene glycol mono-n-butyl ether acetate, propylene glycol mono-i- Propylene glycol monoalkyl ether acetates such as butyl ether acetate, propylene glycol mono-sec-butyl ether acetate, propylene glycol mono-t-butyl ether acetate; 2-butanone, 2-pentanone, 3-methyl-2-butanone, 2-hexanone, 4-methyl-2-pentanone, 3-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2-octanone, etc. Branched ketones;

  Cyclic ketones such as cyclopentanone, 3-methylcyclopentanone, 2-methylcyclohexanone, 2,6-dimethylcyclohexanone, isophorone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-hydroxypropionic acid n-propyl, i-propyl 2-hydroxypropionate, n-butyl 2-hydroxypropionate, i-butyl 2-hydroxypropionate, sec-butyl 2-hydroxypropionate, t-butyl 2-hydroxypropionate, etc. Alkyl 2-hydroxypropionates; in addition to alkyl 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate,

  Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, toluene, xylene, 2-hydroxy Ethyl-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl Propionate, 3-methyl-3-methoxybutyl butyrate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl acetoacetate, ethyl acetoacetate Methyl pyruvate, ethyl pyruvate, N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, carbonic acid Examples include propylene.

  Of these solvents, linear or branched ketones, cyclic ketones, propylene glycol monoalkyl ether acetates, alkyl 2-hydroxypropionate, alkyl 3-alkoxypropionate, γ-butyrolactone and the like are preferable. . These solvents can be used alone or in combination of two or more.

  When the solvent (S) and another solvent are used in combination as the solvent, the proportion of the other solvent is usually 50% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less, based on the total amount of the solvent. It is. The amount of the solvent contained in the positive resist agent is such that the concentration of the total solid content contained in the positive resist agent is usually 2 to 70% by mass, preferably 4 to 25% by mass, and more preferably 4 to 4%. The amount is 10% by mass.

  The positive resist agent is prepared by dissolving each component in a solvent so that the total solid content concentration is in the above-described numerical range to obtain a uniform solution, and then filtering with a filter having a pore size of about 0.02 μm, for example. Can be prepared.

  Various additives such as a surfactant, a sensitizer, and an aliphatic additive can be blended with the positive resist agent as necessary.

  A surfactant is a component that exhibits an effect of improving coating properties, striation, developability, and the like. Examples of such surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, and polyethylene glycol dilaurate. Nonionic surfactants such as polyethylene glycol distearate; hereinafter referred to as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (above, manufactured by Kyoeisha Chemical Co., Ltd.), Ftop EF301, EF303, EF352 (above, manufactured by Tochem Products), Megafax F171, F173 (above, manufactured by Dainippon Ink and Chemicals), Florad FC430, FC431 (above, manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 ( As mentioned above, Asahi Glass Co., Ltd.) can be mentioned. These surfactants can be used singly or in combination of two or more. The compounding quantity of surfactant is 2 mass parts or less normally with respect to 100 mass parts of 1st resin for resist agents.

  The sensitizer absorbs radiation energy and transmits the energy to the acid generator, thereby increasing the amount of acid generated, improving the apparent sensitivity of the first resist agent. Has the effect of Examples of such sensitizers include carbazoles, acetophenones, benzophenones, naphthalenes, phenols, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines, and the like. These sensitizers can be used alone or in combination of two or more. Further, by blending a dye or a pigment, the latent image in the exposed portion can be visualized, and the influence of halation during exposure can be reduced. Furthermore, adhesiveness with a board | substrate can be improved by mix | blending an adhesion aid. The compounding amount of the sensitizer is usually 50 parts by mass or less with respect to 100 parts by mass of the positive resist resin.

  Examples of the alicyclic additive that can be added to the positive resist agent include an alicyclic additive having an acid dissociable group and an alicyclic additive having no acid dissociable group. Such an alicyclic additive is a component having an effect of further improving dry etching resistance, pattern shape, adhesion to a substrate, and the like. Specific examples of the alicyclic additive include 1-adamantanecarboxylic acid, 2-adamantanone, 1-adamantanecarboxylic acid t-butyl, 1-adamantanecarboxylic acid t-butoxycarbonylmethyl, 1-adamantanecarboxylic acid α-butyrolactone Ester, 1,3-adamantane dicarboxylate di-t-butyl, 1-adamantane acetate t-butyl, 1-adamantane acetate t-butoxycarbonylmethyl, 1,3-adamantane diacetate di-t-butyl, 2,5- Adamantane derivatives such as dimethyl-2,5-di (adamantylcarbonyloxy) hexane; deoxycholic acid t-butyl, deoxycholic acid t-butoxycarbonylmethyl, deoxycholic acid 2-ethoxyethyl, deoxycholic acid 2-cyclohexyloxy Ethyl, deoxycholic acid -Deoxycholic acid esters such as oxocyclohexyl, deoxycholic acid tetrahydropyranyl, deoxycholic acid mevalonolactone ester; lithocholic acid t-butyl, lithocholic acid t-butoxycarbonylmethyl, lithocholic acid 2-ethoxyethyl, lithocholic acid 2 -Lithocholic acid esters such as cyclohexyloxyethyl, lithocholic acid 3-oxocyclohexyl, lithocholic acid tetrahydropyranyl, lithocholic acid mevalonolactone ester; dimethyl adipate, diethyl adipate, dipropyl adipate, di-n-butyl adipate, Alkyl carboxylic acid esters such as di-t-butyl adipate; 3- [2-hydroxy-2,2-bis (trifluoromethyl) ethyl] tetracyclo [4.4.0.12,5.17,10] A dodecane etc. can be mentioned.

  These alicyclic additives can be used singly or in combination of two or more. The compounding quantity of an alicyclic additive is 50 mass parts or less normally with respect to 100 mass parts of resin for resist agents, Preferably it is 30 mass parts or less. When the compounding amount of the alicyclic additive is more than 50 parts by mass with respect to 100 parts by mass of the resist resin, the heat resistance as a resist tends to be lowered. Furthermore, examples of additives other than the above include alkali-soluble resins, low-molecular alkali solubility control agents having an acid-dissociable protecting group, antihalation agents, storage stabilizers, antifoaming agents, and the like.

(Negative type radiation sensitive composition)
As the negative radiation-sensitive composition that can be used in the present invention, any of those in which the polymer component in the composition contains Si atoms and those that do not contain Si atoms can be used. As the polymer component in the composition containing Si atoms, those described in Japanese Patent Application No. 2008-191424 can be used. Moreover, as what does not contain Si atom in the polymer component in a composition, the thing as described in Unexamined-Japanese-Patent No. 2003-215802 and Unexamined-Japanese-Patent No. 2000-039709 can be used.

  The negative radiation-sensitive composition in which the polymer component described in Japanese Patent Application No. 2008-191424 contains Si atoms includes (A) a hydrolyzable silane compound represented by the following general formula (1), and the following general formula ( A polymer obtained by hydrolytic condensation of at least one hydrolyzable silane compound selected from the hydrolyzable silane compounds represented by 2), (B) a radiation-sensitive acid generator, (C) a solvent, , Containing.

R _a Si (OR ¹ ) _4-a (1)

[In General Formula (1), R represents a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a cyano group, a cyanoalkyl group, or an alkylcarbonyloxy group, and R ¹ represents Represents a monovalent organic group, and a represents an integer of 1 to 3; ]

Si (OR ² ) ₄ (2)

[In General Formula (2), R ² represents a monovalent organic group. ]

(Polymer (A))
The polymer (A) is a hydrolyzable silane compound represented by the following general formula (1) (hereinafter also referred to as “compound (1)”), and a hydrolysis represented by the following general formula (2). It is obtained by hydrolytic condensation of at least one hydrolyzable silane compound selected from a functional silane compound (hereinafter also referred to as “compound (2)”).

R _a Si (OR ¹ ) _4-a (1)

[In General Formula (1), R represents a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a cyano group, a cyanoalkyl group, or an alkylcarbonyloxy group, and R ¹ represents Represents a monovalent organic group, and a represents an integer of 1 to 3; ]

Si (OR ² ) ₄ (2)

[In General Formula (2), R ² represents a monovalent organic group. ]

(Compound (1))
Examples of the linear or branched alkyl group having 1 to 5 carbon atoms in R of the general formula (1) include a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group, a propenyl group, and 3-butenyl. Group, 3-pentenyl group, 3-hexenyl group and the like. In addition, one or two or more hydrogen atoms in these alkyl groups may be substituted with a fluorine atom or the like.
Examples of the cyanoalkyl group in R include a cyanoethyl group and a cyanopropyl group.

  Furthermore, examples of the alkylcarbonyloxy group in R include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, a butylcarbonyloxy group, a vinylcarbonyloxy group, and an allylcarbonyloxy group.

  When a plurality of Rs are present (that is, when a is 2 or 3), all Rs may be the same, or all or some of them may be different.

The monovalent organic group represented by R ^1, for example, an alkyl group, an alkenyl group, an aryl group, an allyl group, etc. glycidyl group. Among these, an alkyl group and an aryl group are preferable.

As said alkyl group, a C1-C5 linear or branched alkyl group is mentioned, for example. Specific examples include a methyl group, an ethyl group, a propyl group, and a butyl group. In addition, one or two or more hydrogen atoms in these alkyl groups are fluorine atoms, etc. Examples of the aryl group include phenyl, naphthyl, methylphenyl, ethylphenyl, chlorophenyl, bromophenyl, fluoro A phenyl group etc. are mentioned. Among these, a phenyl group is preferable.

  Examples of the alkenyl group include a vinyl group, a propenyl group, a 3-butenyl group, a 3-pentenyl group, and a 3-hexenyl group.

  Specific examples of the compound (1) represented by the general formula (1) include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, methyltri-n-butoxy. Silane, methyltri-sec-butoxysilane, methyltri-tert-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane , Ethyltri-sec-butoxysilane, ethyltri-tert-butoxysilane, ethyltriphenoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxy N-propyltriisopropoxysilane, n-propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane, n-propyltri-tert-butoxysilane, n-propyltriphenoxysilane, isopropyltrimethoxy Silane, isopropyltriethoxysilane, isopropyltri-n-propoxysilane, isopropyltriisopropoxysilane, isopropyltri-n-butoxysilane, isopropyltri-sec-butoxysilane, isopropyltri-tert-butoxysilane, isopropyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltriisopropoxysilane, n-butyltri-n-butoxy Emissions, n- butyltri -sec- butoxysilane, n- butyltri -tert- butoxysilane, n- butyl triphenoxy silane,

  sec-butyltrimethoxysilane, sec-butylisotriethoxysilane, sec-butyltri-n-propoxysilane, sec-butyltriisopropoxysilane, sec-butyltri-n-butoxysilane, sec-butyltri-sec-butoxysilane, sec-butyltri-tert-butoxysilane, sec-butyltriphenoxysilane, tert-butyltrimethoxysilane, tert-butyltriethoxysilane, tert-butylto-n-propoxysilane, tert-butyltriisopropoxysilane, tert-butyltri -N-butoxysilane, tert-butyltri-sec-butoxysilane, tert-butyltri-tert-butoxysilane, tert-butyltriphenoxysilane, dimethyldimethoxy Silane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldiisopropoxysilane, dimethyldi-n-butoxysilane, dimethyldi-sec-butoxysilane, dimethyldi-tert-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, Diethyldiethoxysilane, diethyldi-n-propoxysilane, diethyldiisopropoxysilane, diethyldi-n-butoxysilane, diethyldi-sec-butoxysilane, diethyldi-tert-butoxysilane, diethyldiphenoxysilane, di-n-propyldimethoxy Silane, di-n-propyldiethoxysilane, di-n-propyldi-n-propoxysilane, di-n-propyldiisopropoxysilane, di-n-propyldi-n-but Shishiran, di -n- propyl di -sec- butoxysilane, di -n- propyl di -tert- butoxysilane, di -n- propyl di - phenoxy silane,

  Diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyldi-n-propoxysilane, diisopropyldiisopropoxysilane, diisopropyldi-n-butoxysilane, diisopropyldi-sec-butoxysilane, diisopropyldi-tert-butoxysilane, diisopropyldiphenoxy Silane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-butyldi-n-propoxysilane, di-n-butyldiisopropoxysilane, di-n-butyldi-n-butoxysilane , Di-n-butyldi-sec-butoxysilane, di-n-butyldi-tert-butoxysilane, di-n-butyldi-phenoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxy Run, Di-sec-butyldi-n-propoxysilane, di-sec-butyldiisopropoxysilane, di-sec-butyldi-n-butoxysilane, di-sec-butyldi-sec-butoxysilane, di-sec-butyldi -Tert-butoxysilane, di-sec-butyldi-phenoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyldi-n-propoxysilane, di-tert-butyldiiso Examples include propoxysilane, di-tert-butyldi-n-butoxysilane, di-tert-butyldi-sec-butoxysilane, di-tert-butyldi-tert-butoxysilane, and di-tert-butyldi-phenoxysilane.

  Among these compounds (1), methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane, dimethyldi Ethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane and the like are preferable.

  In addition, these compounds (1) may be used individually by 1 type, and may be used in combination of 2 or more type.

(Compound (2))
As the monovalent organic group in R ² of the general formula (2), the description of the monovalent organic group in R ¹ of the general formula (1) can be applied as it is.

  Specific examples of the compound (2) represented by the general formula (2) include, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, Examples include tetra-sec-butoxysilane, tetra-tert-butoxysilane, and tetraphenoxysilane.

  Among these, tetramethoxysilane and tetraethoxysilane are preferable.

  In addition, these compounds (2) may be used individually by 1 type, and may be used in combination of 2 or more type.

(Acid generator (B))
The acid generator (B) generates an acid upon exposure, and the resin component is cross-linked by the action of the acid generated by the exposure. As a result, the exposed portion of the resist film becomes hardly soluble in an alkali developer. It has the function of forming a negative resist pattern.
Examples of the acid generator (B) include onium salts such as sulfonium salts and iodonium salts, organic halogen compounds, sulfone compounds such as disulfones and diazomethane sulfones, and the like.

Preferable specific examples of the acid generator (B) include, for example, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2- Bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2- (3-tetracyclo [4.4.0.1 ^2,5 .1 ^{7 , 10} ] dodecanyl) -1,1-difluoroethanesulfonate, triphenylsulfonium salt compounds such as triphenylsulfonium N, N′-bis (nonafluoro-n-butanesulfonyl) imidate, triphenylsulfonium camphorsulfonate;

4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-cyclohexylphenyldiphenylsulfonium 2-bicyclo [2. 2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexyl-phenyl diphenyl sulfonium 2- (3-tetracyclo ^[4.4.0.1 2,5 ^{.1 7, 10]} dodecanyl) -1,1-difluoroethanesulfonate, 4-cyclohexyl-phenyl diphenyl sulfonium N, N'-bis (nonafluoro -n- butanesulfonyl) imidate 4-cyclohexyl-phenyl diphenyl sulfonium salt compounds such as 4-cyclohexyl-phenyl camphorsulfonate;

4-t-butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-t-butylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-t-butylphenyl Diphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-t-butylphenyldiphenylsulfonium 2- (3-tetracyclo [4.4. 0.1 ^2,5 .1 ^7,10] dodecanyl) -1,1-difluoroethanesulfonate, 4-t-butylphenyl diphenyl sulfonium N, N'-bis (nonafluoro -n- butanesulfonyl) imidate, 4-t- Butylphenyl 4-t-butylphenyl diphenyl sulfonium salt compounds such as triphenylsulfonium camphorsulfonate;

Tri (4-t-butylphenyl) sulfonium trifluoromethanesulfonate, tri (4-t-butylphenyl) sulfonium nonafluoro-n-butanesulfonate, tri (4-t-butylphenyl) sulfonium perfluoro-n-octanesulfonate, Tri (4-t-butylphenyl) sulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, tri (4-t-butylphenyl) sulfonium 2 - (3-tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) -1,1-difluoroethanesulfonate, tri (4-t- butylphenyl) sulfonium N, N'-bis (nonafluoro -N-butanesulfonyl) imidate, tri (4-t-butylphenyl) sulfur Bromide tri (4-t- butylphenyl) such as camphorsulfonate sulfonium salt compound;

Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2, 2-tetrafluoroethane sulfonate, diphenyliodonium 2- (3-tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) -1,1-difluoroethanesulfonate, diphenyliodonium N, N'-bis Diphenyliodonium salt compounds such as (nonafluoro-n-butanesulfonyl) imidate, diphenyliodonium camphorsulfonate;

Bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, Bis (4-t-butylphenyl) iodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis (4-t-butylphenyl) iodonium 2 - (3-tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) -1,1-difluoroethanesulfonate, bis (4-t- butylphenyl) iodonium N, N'-bis (nonafluoro -N-butanesulfonyl) imidate, bis (4-t-butylphenyl) io Bis (4-t- butylphenyl) such as camphorsulfonate iodonium salt compounds;

1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, (4-n-Butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 2-bicyclo [2.2. 1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 2- (3-tetracyclo [4.4. 0.1 ^2,5 .1 ^7,10] dodecanyl) -1,1-difluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium N, N′-bis (nonafluoro-n-butanesulfonyl) imidate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothio 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium salt compounds such as phenium camphorsulfonate;

1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, (3,5-Dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2-bicyclo [2.2. 1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2- (3-tetracyclo [4.4. 0.1 ^2,5 .1 ^7,10 ] dodecanyl) -1,1-difluoro Ethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium N, N′-bis (nonafluoro-n-butanesulfonyl) imidate, 1- (3,5-dimethyl-4-hydroxyphenyl) ) 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium salt compounds such as tetrahydrothiophenium camphorsulfonate;

N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoro-n-butanesulfonyloxy) succinimide, N- (perfluoro-n-octanesulfonyloxy) succinimide, N- (2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethane sulfonyloxy) succinimide, N- (2- (3- tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) Succinimide compounds such as -1,1-difluoroethanesulfonyloxy) succinimide and N- (camphorsulfonyloxy) succinimide;

N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- ( 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy imide, N- (2- (3- tetracyclo ^[4.4.0.1 2,5 ^{.1 7,10]} dodecanyl) -1,1-difluoroethane-sulfonyloxy) bicyclo [2.2.1] hept Bicyclo [2.2.1] such as -5-ene-2,3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide. And hept-5-ene-2,3-dicarboximide compounds.

  In addition, these acid generators (B) may be used individually by 1 type, and may be used in combination of 2 or more type.

  The amount of the acid generator (B) used is usually 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymer (A) from the viewpoint of ensuring sensitivity and resolution as a resist. The amount is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 15 parts by mass. When the amount of the acid generator used is less than 0.1 parts by mass, the sensitivity and resolution tend to decrease. On the other hand, when it exceeds 30 parts by mass, the transparency to radiation is lowered, and it tends to be difficult to obtain a rectangular resist pattern.

(Solvent (C))
As the solvent (C), it is preferable to use an organic solvent, and usually the respective components are dissolved or dispersed in the organic solvent.

  The organic solvent is at least one selected from the group consisting of alcohol solvents, ketone solvents, amide solvents, ether solvents, ester solvents, aliphatic hydrocarbon solvents, aromatic solvents, and halogen-containing solvents. Is mentioned.

Examples of the alcohol solvent include methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, and 2-methyl. Butanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2- Ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl al Lumpur, furfuryl alcohol, phenol, cyclohexanol, methyl cyclohexanol, 3,3,5-trimethyl cyclohexanol, benzyl alcohol, mono-alcohol solvents such as diacetone alcohol;
Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2 Polyhydric alcohol solvents such as ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol;

  Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol It may be mentioned monomethyl ether, dipropylene glycol monoethyl ether, polyhydric alcohol partial ether solvents such as dipropylene glycol monopropyl ether. These alcohol solvents may be used alone or in combination of two or more.

  Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl- n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, 2-hexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol , Acetophenone, fenchon and the like. These ketone solvents may be used alone or in combination of two or more.

  Examples of the amide solvent include N, N-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide. And nitrogen-containing solvents such as N-methylpropionamide and N-methylpyrrolidone. These amide solvents may be used alone or in combination of two or more.

  Examples of the ether solvent include ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, and dimethyl. Dioxane, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2 -Ethyl butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, di Tylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, di Phenyl ether, anisole, and the like. These ether solvents may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the ester solvent include diethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, Sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, Methyl acetoacetate, ethyl acetoacetate, ethylene acetate monomethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol acetate Mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate Methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, Examples include diethyl malonate, dimethyl phthalate, and diethyl phthalate. These ester solvents may be used alone or in combination of two or more.

  Examples of the aliphatic hydrocarbon solvent include n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i -Octane, cyclohexane, methylcyclohexane and the like. These aliphatic hydrocarbon solvents may be used alone or in combination of two or more.

  Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propyl benzene, i-propyl benzene, diethyl benzene, i-butyl benzene, triethyl benzene, di-i-. Examples include propyl benzene, n-amyl naphthalene, and trimethyl benzene. These aromatic hydrocarbon solvents may be used alone or in combination of two or more.

  Examples of the halogen-containing solvent include dichloromethane, chloroform, chlorofluorocarbon, chlorobenzene, dichlorobenzene, and the like. These halogen-containing solvents may be used alone or in combination of two or more.

  Among these solvents (C), it is preferable to use an organic solvent having a boiling point of less than 150 ° C. In particular, it is preferable to use one or more of alcohol solvents, ketone solvents and ester solvents. Furthermore, C4-C10 alcohol or ether is more preferable.

  These solvents may be the same as those used for the synthesis of the polymer (A), or after the synthesis of the polymer (A) is completed, the solvent is replaced with a desired organic solvent. You can also.

(Additive)
In the negative radiation sensitive composition, additive components such as an organic polymer, an acid diffusion controller, and a surfactant may be blended.

(Organic polymer)
Examples of the organic polymer include a polymer having a sugar chain structure, a vinylamide polymer, a (meth) acrylic polymer, an aromatic vinyl compound polymer, a dendrimer, polyimide, polyamic acid, polyarylene, polyamide, poly Examples include quinoxaline, polyoxadiazole, fluorine-based polymers, and polymers having a polyalkylene oxide structure.

  Examples of the polymer having a polyalkylene oxide structure include a polymethylene oxide structure, a polyethylene oxide structure, a polypropylene oxide structure, a polytetramethylene oxide structure, and a polybutylene oxide structure. Specifically, polyoxymethylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, ethylene oxide derivative of alkylphenol formalin condensate, polyoxyethylene poly Oxypropylene block copolymer, ether type compounds such as polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid alkanolamide sulfate, etc. Ether ester type compound, polyethylene glycol fatty acid ester, ethylene glycol fatty acid Ester, fatty acid monoglycerides, polyglycerol fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, ether-ester type compounds such as sucrose fatty acid esters.

  Examples of the polyoxyethylene polyoxypropylene block copolymer include compounds having the following block structure.

− (X ′) ₁ − (Y ′) _m −
− (X ′) ₁ − (Y ′) _m − (X ′) _n −

(In the formula, X ′ represents a group represented by —CH ₂ CH ₂ O—, Y ′ represents a group represented by —CH ₂ CH (CH ₃ ) O—, l is 1 to 90, and m is 10 to 99, n represents a number from 0 to 90)

  Among these organic polymers, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol Ether type compounds such as fatty acid esters are preferred.

  In addition, these organic polymers may be used individually by 1 type, and may be used in combination of 2 or more type.

(Acid diffusion control agent)
The acid diffusion control agent is a component having an action of controlling an undesired chemical reaction in a non-irradiated region by controlling a diffusion phenomenon of an acid generated from an acid generator upon irradiation in a resist film.

By blending such an acid diffusion control agent, the resolution as a resist is further improved, and the change in the line width of the resist pattern due to fluctuations in the holding time (PED) from irradiation to development processing can be suppressed. A composition having excellent process stability can be obtained.
The acid diffusion controller is preferably a nitrogen-containing organic compound whose basicity does not change by irradiation or heat treatment during the resist pattern formation process.

  Examples of the nitrogen-containing organic compound include a tertiary amine compound, an amide group-containing compound, a quaternary ammonium hydroxide compound, and a nitrogen-containing heterocyclic compound.

  Examples of the tertiary amine compound include triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n- Tri (cyclo) alkylamines such as octylamine, tri-n-nonylamine, tri-n-decylamine, cyclohexyldimethylamine, dicyclohexylmethylamine, tricyclohexylamine; aniline, N-methylaniline, N, N-dimethylaniline, Aromatic amines such as 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, 2,6-dimethylaniline, 2,6-diisopropylaniline, diphenylamine, triphenylamine, naphthylamine; triethanol Amines, Alkanolamines such as ethanolaniline; N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, 1,3-bis [1- ( 4-aminophenyl) -1-methylethyl] benzenetetramethylenediamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, bis (2-dimethyla Aminoethyl) ether, bis (2-diethylaminoethyl) ether.

  Examples of the amide group-containing compound include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, Nt -Butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4′-diaminodiphenylmethane, N, N′-di-t-butoxycarbonylhexamethylenediamine, N, N, N ′, N′-tetra-t-butoxycarbonylhexame Range amine, N, N-di-t-butoxycarbonyl-1,7-diaminoheptane, N, N′-di-t-butoxycarbonyl-1,8-diaminooctane, N, N′-di-t-butoxy Carbonyl-1,9-diaminononane, N, N′-di-t-butoxycarbonyl-1,10-diaminodecane, N, N′-di-t-butoxycarbonyl-1,12-diaminododecane, N, N ′ -Di-t-butoxycarbonyl-4,4'-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2-phenylbenzimidazole Nt-butoxycarbonyl-pyrrolidine, Nt-butoxycarbonyl-piperidine, Nt-butoxy In addition to Nt-butoxycarbonyl group-containing amino compounds such as carbonyl-4-hydroxy-piperidine, Nt-butoxycarbonyl-morpholine, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N- Examples thereof include methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone and the like.

Examples of the quaternary ammonium hydroxide compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetra-n-butylammonium hydroxide, and the like.
Examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, 4-methylimidazole, 1-benzyl-2-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, and 2-phenylbenzimidazole; 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline Pyridines such as 4-hydroxyquinoline, 8-oxyquinoline, acridine; piperazines such as piperazine and 1- (2-hydroxyethyl) piperazine, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, 3 Piperidino-1,2-propanediol, morpholine, 4-methylmorpholine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane.

  Among these acid diffusion control agents, tertiary amine compounds, amide group-containing compounds, and nitrogen-containing heterocyclic compounds are preferable. Further, among the amide group-containing compounds, Nt-butoxycarbonyl group-containing amino compounds are preferable, and among the nitrogen-containing heterocyclic compounds, imidazoles are preferable. These acid diffusion controlling agents may be used alone or in combination of two or more.

  Moreover, the compounding quantity of an acid diffusion control agent is 15 mass parts or less normally with respect to 100 mass parts of polymers (A), Preferably it is 10 mass parts or less, More preferably, it is 5 mass parts or less. When this compounding quantity exceeds 15 mass parts, there exists a tendency for the sensitivity as a resist and the developability of a radiation irradiation part to fall. In addition, when this compounding quantity is less than 0.001 mass part, there exists a possibility that the pattern shape and dimension fidelity as a resist may fall depending on process conditions.

(Surfactant)
The surfactant is a component having an effect of improving coating properties, striation, developability, etc., for example, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, Examples include silicone surfactants, polyalkylene oxide surfactants, fluorine surfactants, poly (meth) acrylate surfactants, and the like. Specifically, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate In addition to nonionic surfactants such as SH8400 FLUID (Toray Dow Corning Silicone Co.), KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (above, manufactured by Kyoeisha Chemical Co., Ltd.), F-top EF301, EF303, EF352 (above, manufactured by Tochem Products Co., Ltd.), Megafax F171, F173 (above, Dainippon Ink & Chemicals, Inc.) Manufactured), FLORARD FC430, FC431 (above, manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC -105, SC-106 (above, manufactured by Asahi Glass Co., Ltd.) and the like. Of these, fluorine-based surfactants and silicone-based surfactants are preferable. In addition, these may be used individually by 1 type and may be used in combination of 2 or more type.

  Moreover, the said surfactant is normally used in 0.00001-1 mass part with respect to 100 mass parts of said polymers (A).

  A negative radiation-sensitive composition in which the polymer component in the composition described in JP-A-2003-215802 does not contain an Si atom is an alkali-soluble resin having a phenolic hydroxyl group, at least two alkyls in the molecule It contains an etherified amino group-containing compound, crosslinked fine particles, an oxirane ring-containing compound, a photosensitive acid generator, and a solvent.

(Alkali-soluble resin having phenolic hydroxyl group)
The alkali-soluble resin having a phenolic hydroxyl group (hereinafter referred to as “phenol resin”) is not particularly limited, but a novolak resin is preferable. Such a novolak resin can be obtained by condensing phenols and aldehydes in the presence of a catalyst.

  Examples of phenols used in this case include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p- Butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4 , 5-trimethylphenol, catechol, resorcinol, pyrogallol, α-naphthol, β-naphthol and the like.

  Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde. Specific examples of such novolak resins include phenol / formaldehyde condensed novolak resins, cresol / formaldehyde condensed novolak resins, phenol-naphthol / formaldehyde condensed novolak resins, and the like.

  Examples of alkali-soluble resins having phenolic hydroxyl groups other than novolak resins include polyhydroxystyrene and copolymers thereof, phenol-xylylene glycol condensed resins, cresol-xylylene glycol condensed resins, phenol-dicyclopentadiene condensed resins, etc. Can be mentioned.

(Compound having at least two alkyl etherified amino groups in the molecule)
A compound having at least two alkyl etherified amino groups in the molecule (hereinafter referred to as “crosslinking agent”) acts as a crosslinking component (curing component) that reacts with the phenol resin. Nitrogen-containing compounds obtained by alkyl etherifying all or part of active methylol groups such as (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, (poly) methylolated urea as crosslinking agents Can be mentioned. Here, examples of the alkyl group include a methyl group, an ethyl group, a butyl group, or a mixture thereof, and may contain an oligomer component that is partially self-condensed. Specifically, hexamethoxymethylated melamine, hexabutoxymethylated melamine, tetramethoxymethylated glycoluril, tetrabutoxymethylated glycoluril and the like can be used.

(Crosslinked fine particles)
This is referred to as a crosslinked fine particle (hereinafter referred to as “crosslinked fine particle”). ) Is not particularly limited as long as the Tg of the polymer constituting the crosslinked fine particles is 0 ° C. or lower. However, the crosslinkable monomer having two or more unsaturated polymerizable groups (hereinafter referred to as “crosslinkable monomer”) And other one or more other monomers (hereinafter referred to as “other monomers”) selected so that the Tg of the crosslinked fine particles is 0 ° C. or lower. Monomers containing a crosslinked fine particle having a Tg of 0 ° C. or lower and having a functional group other than a polymerizable group, for example, a functional group such as a carboxyl group, an epoxy group, an amino group, an isocyanate group, or a hydroxyl group A copolymer obtained by copolymerizing is used.

  Examples of crosslinkable monomers include divinylbenzene, diallyl phthalate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, polyethylene glycol di Examples thereof include compounds having a plurality of polymerizable unsaturated groups such as (meth) acrylate and polypropylene glycol di (meth) acrylate.

(Oxirane ring-containing compound)
The oxirane ring-containing compound (hereinafter referred to as “epoxy resin”) is not particularly limited as long as it contains an oxirane ring in the molecule, and specifically, phenol novolac type epoxy resins and cresol novolac type epoxy resins. Bisphenol type epoxy resin, trisphenol type epoxy resin, tetraphenol type epoxy resin, phenol-xylylene type epoxy resin, naphthol-xylylene type epoxy resin, phenol-naphthol type epoxy resin, phenol-dicyclopentadiene type epoxy resin, alicyclic Formula epoxy resin, aliphatic epoxy resin and the like.

(Photosensitive acid generator)
A photosensitive acid generator (hereinafter referred to as “acid generator”) is a compound that generates an acid upon irradiation with radiation or the like, and the catalytic action of this acid causes the alkyl ether group and the phenol resin in the cross-linking agent to form. By reacting with dealcoholization, a negative pattern can be formed. The acid generator is not particularly limited as long as it is a compound that generates an acid upon irradiation with radiation and the like. Can be mentioned.

(solvent)
A solvent is added in order to improve the handleability of a resin composition, or to adjust a viscosity or storage stability. The type of the organic solvent is not particularly limited, but examples thereof include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether, propylene glycol mono Propylene glycol monoalkyl ethers such as ethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether; Propylene Glycol monomethyl ether ace Propylene glycol monoalkyl ether acetates such as propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate; cellosolves such as ethyl cellosolve and butyl cellosolve; carbitols such as butyl carbitol; Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, Aliphatic carboxylic acid esters such as n-butyl propionate and isobutyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3 Other esters such as methyl ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate; aromatic hydrocarbons such as toluene, xylene; 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone Ketones such as N; dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, amides such as N-methylpyrrolidone, and lactones such as γ-butyrolacun. These organic solvents can be used alone or in combination of two or more.

  The negative radiation-sensitive composition in which the polymer component in the composition described in JP-A No. 2000-039709 contains no Si atom is (a) a structural unit derived from a radically polymerizable compound having a carboxyl group, ( b) a structural unit derived from a radically polymerizable compound having a phenolic hydroxyl group, (c) an alkali-soluble copolymer composed of a structural unit derived from another radically polymerizable compound, and at least one ethylenically unsaturated disilane. A compound having a heavy bond and a radiation radical polymerization initiator are contained.

(Alkali-soluble copolymer)
(A) A radically polymerizable compound having a carboxyl group (hereinafter referred to as “carboxyl group compound (a)”) adjusts the alkali solubility of the alkali-soluble copolymer. For example, acrylic acid, methacrylic acid, crotonic acid, 2-succin Noroylethyl (meth) acrylate, 2-malenoroylethyl (meth) acrylate, 2-hexahydrophthaloylethyl (meth) acrylate, ω-carboxy-polycaprolactone monoacrylate (commercially available products include, for example, Toagosei Co., Ltd.) ) Aronix M-5300), monohydroxyethyl acrylate phthalate (commercially available products, for example, Aronix M-5400 manufactured by the company), acrylic acid dimer (commercially available products, for example, Aronix M-5600 manufactured by the company), 2-hydroxy -3-phenoxypropyla (Meth) acrylic acid having a carboxyl group such as monocarboxylic acid such as relate (commercially available, for example, Aronix M-5700 manufactured by the company); dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid Derivatives can be used. These compounds can be used alone or in combination of two or more. Among these, acrylic acid, methacrylic acid, and 2-hexahydrophthaloylethyl methacrylate are preferable.

  (B) As a radically polymerizable compound having a phenolic hydroxyl group (hereinafter referred to as “phenolic hydroxyl compound (b)”), for example, p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, α-methyl-p -Hydroxystyrene, α-methyl-m-hydroxystyrene, α-methyl-o-hydroxystyrene, 2-allylphenol, 4-allylphenol, 2-allyl-6-methylphenol, 2-allyl-6-methoxyphenol, Examples include 4-allyl-2-methoxyphenol, 4-allyl-2,6-dimethoxyphenol, 4-allyloxy-2-hydroxybenzophenone, and the like.

  (C) Other radical polymerizable compounds (hereinafter referred to as “other radical compounds (c)”) are mainly used for the purpose of appropriately controlling the mechanical properties of the alkali-soluble copolymer. Here, “other” means a radical polymerizable compound other than the above-mentioned radical polymerizable compounds. Such other radical polymerizable compounds (c) include (meth) acrylic acid alkyl esters, (meth) acrylic acid aryl esters, dicarboxylic acid diesters, nitrile group-containing polymerizable compounds, amide bond-containing polymerizable compounds. Examples thereof include compounds, fatty acid vinyls, chlorine-containing polymerizable compounds, and conjugated diolefins. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isopropyl (meth) acrylate, n-hexyl (Meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, methoxydipropylene glycol (Meth) acrylate, butoxy-dipropylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, etc. Alkyl acrylates; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate; aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; styrene, α-methylstyrene, M-methylstyrene, p-methylstyrene, vinyl toluene, aromatic vinyls such as p-methoxystyrene, nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide Compounds; Fatty acid vinyls such as vinyl acetate; Chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; Conjugated diolefins such as 1,3-butadiene, isoprene and 1,4-dimethylbutadiene can be used.

(Compound having at least one ethylenically unsaturated double bond)
The compound having at least one ethylenically unsaturated double bond (hereinafter referred to as “ethylenically unsaturated compound”) is a liquid or solid compound at room temperature having at least one ethylenically unsaturated group in the molecule, In general, a (meth) acrylate compound having a (meth) acryloyl group as an ethylenically unsaturated group or a compound having a vinyl group is preferably used, and the (meth) acrylate compound is classified into a monofunctional compound and a polyfunctional compound. However, any compound can be used.

(Radiation radical polymerization initiator)
Examples of the radiation radical polymerization initiator (hereinafter referred to as “radiation radical polymerization initiator”) include α-diketones such as benzyl and diacetyl; acyloins such as benzoin; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and the like. Acyloin ethers; benzophenones such as thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone; Acetophenone, p-dimethylaminoacetophenone, α, α-dimethoxy-α-acetoxybenzophenone, α, α-dimethoxy-α-phenylacetophenone, p-methoxyacetophenone, 1- [2-methyl- 4-methylthiophenyl] -2-morpholino-1-propanone, α, α-dimethoxy-α-morpholino-methylthiophenylacetophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1 -Acetophenones such as ON; quinones such as anthraquinone and 1,4-naphthoquinone; halogen compounds such as phenacyl chloride, tribromomethylphenyl sulfone, tris (trichloromethyl) -s-triazine; [1,2'-bis Bisimidazoles such as [imidazole] -3,3 ′, 4,4′-tetraphenyl and [1,2′-bisimidazole] -1,2′-dichlorophenyl-3,3 ′, 4,4′-tetraphenyl , Peroxides such as di-tert-butyl peroxide; 2,4,6-trimethylbenzoyldiphenyl Examples include acyl phosphine oxides such as phosphine oxide.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Here, “part” and “%” are based on mass unless otherwise specified.

[Synthesis Example 1] Production of Polymer 1 Into a nitrogen-substituted quartz three-necked flask, 2.14 g of a 20% maleic acid aqueous solution and 139.6 g of ultrapure water were added and heated to 65 ° C. Next, a solution in which 25.7 g (0.169 mol) of tetramethoxysilane, 206.7 g (1.52 mol) of methyltrimethoxysilane, and 25.9 g of 4-methyl-2-pentanol were mixed for 1 hour. The solution was added dropwise to the reaction vessel and stirred at 65 ° C. for 4 hours. The reaction solution was returned to room temperature and concentrated under reduced pressure until the solid concentration was 25% to obtain 440 g of a silicon-containing resin solution. The resin in the resin solution is a silicon-containing resin (refer to the following formula for the structural unit). The constituent monomer ratio a: b of the silicon-containing resin was 10:90 (mol%), and Mw was 8600.

  In addition, the measurement of the weight average molecular weight (Mw) of the silicon-containing resin obtained by a synthesis example was performed by the following method.

<Measurement of weight average molecular weight (Mw)>
Measured by size exclusion chromatography (SEC) method.
Sample: A 2-methoxyethanol solution of LiBr—H ₃ PO _{4 at} a concentration of 10 mmol / L was used as a solvent, and 0.1 g of a hydrolysis condensate was added to 100 cc of 10 mmol / L LiBr—H ₃ PO _{4 in} a 2-methoxyethanol solution. And dissolved.
Standard sample: Polyethylene oxide manufactured by WAKO was used.
Apparatus: A high-speed GPC apparatus (model HLC-8120GPC) manufactured by Tosoh Corporation was used.
Column: Tosoh Co., Ltd. product, TSK-GEL SUPER AWM-H (15 cm in length) was installed in series and used.
Measurement temperature: 40 ° C
Flow rate: 0.6 ml / min.
Detector: Detected by RI of a built-in high-speed GPC device (model HLC-8120GPC) manufactured by Tosoh Corporation.

[Synthesis Example 2] Production of Polymer 2 In a three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 0.87 g of a compound represented by the following formula (10), 1.79 g of trifluoromethanesulfonic acid, 1.35 g of pentafluorophenyltriethoxysilane, 2 g of 4-methyl-2-pentanone, and 0.75 g of an aqueous 1.75% by weight oxalic acid solution were added and reacted at 80 ° C. for 6 hours while stirring. Then, after cooling the reaction vessel with ice and stopping the reaction, transfer to a separatory funnel, discard the aqueous layer, add ion-exchanged water, and wash with water until the reaction solution becomes neutral. Was repeated. Thereafter, the organic layer was distilled off under reduced pressure to obtain 2.6 g of the polymer 2. With respect to this polymer, the nuclear magnetic resonance spectrum (chemical shift σ), infrared absorption spectrum (IR) and Mw were measured. _{σ: 2.3ppm (CH 2 C (} CF 3) 2 group), 1.4 ppm (t-butyl group). IR: 1703 cm ⁻¹ (ester group), 1641 cm ⁻¹ (phenyl group), 1473 cm ⁻¹ (C—F bond), 1296 cm ⁻¹ (C—F bond), 1215 cm ⁻¹ (C—F bond), 1095 cm ^{− 1} (siloxane group). Mw: 2,300.

[Preparation Example 1] Preparation of negative-type radiation-sensitive resin composition containing silicon atom (A) 100 parts by weight of polymer 1 and (B) triphenylsulfonium nonafluoro-n-butanesulfonate as an acid generator 12 parts by weight, (C) 2.8 parts by weight of Nt-butoxycarbonyl-2-phenylbenzimidazole as the acid diffusion controller, and (D) 2260 parts by weight of 4-methyl-2-pentanol as the solvent Then, a negative radiation sensitive resin composition containing silicon atoms was prepared.

[Preparation Example 2] Preparation of positive-type radiation-sensitive resin composition containing silicon atom (A) 100 parts by weight of polymer 2 and (B) triphenylsulfonium nonafluoro-n-butanesulfonate as an acid generator. 1 part by weight, (C) 0.04 part by weight of tri-n-octylamine as an acid diffusion control agent, (D) 900 parts by weight of 2-heptanone as a solvent, and a positive radiation sensitive material containing silicon atoms A resin composition was prepared.

[Example 1]
(Preparation of evaluation substrate A)
An 8-inch silicon wafer was spin-coated with an underlayer antireflection film (“ARC29A”, manufactured by Brewer Science) using a trade name “CLEAN TRACK ACT8” (manufactured by Tokyo Electron), and then baked at 205 ° C. A film having a thickness of 77 nm was formed. On the formed coating film, a positive resist agent (trade name “JSR ArF AIM5056JN”, manufactured by JSR) was spin-coated, and then a resist layer having a thickness of 120 nm was formed by PB (110 ° C., 90 seconds). . Using an ArF exposure apparatus (trade name “NSR-S306C”, manufactured by Nikon Corporation) and using a mask for 60 nm line / 180 nm space under optical conditions of NA: 0.78, σ: 0.85, 2/3 Ann And exposed. After performing paddle development (60 seconds) using an LD nozzle with the product name “CLEAN TRACK ACT8”, rinsing with ultrapure water and spin-drying at 4000 rpm for 15 seconds to spin out the first pattern An evaluation substrate A on which was formed was obtained. The obtained evaluation substrate A was observed with a scanning electron microscope (trade name “S9380”, manufactured by Hitachi Keiki Co., Ltd.), and it was confirmed that the first pattern of 60 nm line / 240 nm pitch was formed.

(First pattern persistence)
A negative radiation-sensitive resin composition containing silicon atoms is applied onto the evaluation substrate A by spin coating using a trade name “CLEAN TRACK ACT8” and baked (90 ° C., 60 seconds). Developed. The amount of change in the measured value (nm) of the first pattern was measured, and the survivability of the first pattern was evaluated according to the following criteria. The evaluation results are shown in Table 1. A scanning electron microscope (“S-9380”, manufactured by Hitachi Keiki Co., Ltd.) was used for measuring the line width.
○: Change in measured value is less than 5 nm ×: Change in measured value is 5 nm or more

(Preparation of evaluation substrate B)
A negative radiation sensitive resin composition containing silicon atoms is applied onto the evaluation substrate A by spin coating using a trade name “CLEAN TRACK ACT8”, and then baked at 90 ° C. for 60 seconds to be adjacent. The resin composition was embedded between the first patterns (space portions) to form a second resist layer. Using an ArF exposure apparatus (trade name “NSR-S306C”, manufactured by Nikon Corp.) and using a mask for 180 nm line / 240 nm pitch under optical conditions of NA: 0.78, σ: 0.85, 2/3 Ann The first pattern was exposed at a time with a light intensity of 25 mJ / cm ² . After performing paddle development (60 seconds) using an LD nozzle with a trade name of “CLEAN TRACK ACT8”, rinsing with ultrapure water, and spin-drying at 4000 rpm for 15 seconds, spin-drying is performed. Got. The cross section of the obtained evaluation substrate C was observed, and the curability and peelability were evaluated according to the following criteria. The evaluation results are shown in Table 2.
○: The line width of the first pattern is thick ×: The line width of the first pattern is not thick

  In addition, 3σ of the dispersion | variation (LWR) of the line | wire width was calculated | required about what the line width of the pattern became thick. The evaluation results are shown in Table 1. A scanning electron microscope (“S-9380”, manufactured by Hitachi Keiki Co., Ltd.) was used for measuring the line width.

[Example 2]
In Example 1, in place of the positive resist agent (trade name “JSR ArF AIM5056JN”, manufactured by JSR Corporation), the positive radiation sensitive resin composition containing silicon atoms obtained in Preparation Example 2 was used. Evaluated and produced the evaluation board | substrate A and the evaluation board | substrate B by the method similar to Example 1. FIG. The evaluation results are shown in Table 1.

  According to the pattern forming method of the present invention, the pattern can be miniaturized with high accuracy, and a pattern exceeding the wavelength limit can be formed favorably and economically. For this reason, the resist pattern forming method of the present invention is a technique that can be very suitably employed in the field of microfabrication represented by the manufacture of integrated circuit elements, which are expected to become increasingly finer in the future.

It is sectional drawing which shows an example of a 1st pattern typically. It is sectional drawing which shows typically an example of the state in which the unbridged embedding part was formed. It is sectional drawing which shows typically an example of the state which exposed the upper surface of the 1st pattern. It is sectional drawing which shows an example of an arrangement | sequence structure typically. It is sectional drawing which shows an example of a 2nd pattern typically.

Explanation of symbols

1: first pattern, 2: second pattern, 3: organic underlayer film, 5: resin composition for pattern formation, 7: uncrosslinked embedded portion, 10: substrate, 11: first crosslinked portion, 12: second bridge portion, 13: cross section, 15: array structure, 20: upper surface of the first _pattern, L 1 ~L _5: line width.

Claims (5)

(1) A first resist layer made of a positive radiation sensitive resin composition containing an acid generator is formed on a semiconductor substrate, the first resist layer is selectively exposed, developed, and developed. Forming a pattern,
(2) forming a second resist layer comprising a negative radiation-sensitive resin composition containing an acid generator between the adjacent first patterns;
(3) selectively exposing portions of the first pattern and the second resist layer adjacent to the first pattern to form a sidewall layer derived from the second resist layer on the first pattern sidewall; ,
(4) A pattern forming method including a step of removing the first pattern and the second resist layer.   The pattern forming method according to claim 1, wherein in the step (4), the first pattern and the second resist layer are removed by alkali development.   The pattern forming method according to claim 1, wherein the negative radiation-sensitive resin composition is a negative radiation-sensitive resin composition containing silicon atoms. The pattern formation method of Claim 3 in which the negative radiation sensitive resin composition containing the said silicon atom contains the following (A)-(C).
(A) Hydrolytic condensation of at least one hydrolyzable silane compound selected from the hydrolyzable silane compound represented by the following general formula (1) and the hydrolyzable silane compound represented by the following general formula (2) A polymer obtained by
(B) a radiation sensitive acid generator;
(C) Solvent R _a Si (OR ¹ ) _4-a (1)
[In general formula (1), R represents a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a cyano group, a cyanoalkyl group, an alkylcarbonyloxy group or an aryl group; ¹ represents a monovalent organic group, and a represents an integer of 1 to 3. ]
Si (OR ² ) ₄ (2)
[In General Formula (2), R ² represents a monovalent organic group. ]   The pattern forming method according to claim 4, wherein the solvent is an alcohol or ether having 4 to 10 carbon atoms.

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