JP2009223024A - Positive radiation-sensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive radiation-sensitive resin composition which contains a compound good also in compatibility with other components, can optimally control radiation transmittance particularly as a chemically amplified positive resist effectively sensitive to far-ultraviolet radiation, in particular, can effectively suppress a linewidth change of a resist pattern due to a thickness variation of a resist film on a highly reflecting substrate, and excels also in depth of focus latitude. <P>SOLUTION: The positive radiation-sensitive resin composition includes (A) a calix arene type compound of a specific structure, (B) a radiation-sensitive acid generator, and (C) an alkali-insoluble or slightly alkali-soluble resin having an acid-dissociable group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a positive radiation sensitive resin composition, and more particularly, as a chemically amplified positive resist useful for fine processing using actinic radiation, particularly far ultraviolet rays represented by KrF excimer laser or ArF excimer laser. The present invention relates to a positive-type radiation-sensitive resin composition that can be suitably used.

  In the field of microfabrication represented by the manufacture of integrated circuit elements, in order to obtain a higher degree of integration, recently, lithography technology capable of microfabrication at a level of 0.20 μm or less is required. In the conventional lithography technology, near ultraviolet rays such as i-line are generally used as radiation, and it is said that fine processing at the sub-quarter micron level is extremely difficult with this near ultraviolet rays.

  Therefore, in order to enable fine processing at a level of 0.20 μm or less, use of radiation having a shorter wavelength is being studied. Examples of such short-wavelength radiation include an emission line spectrum of a mercury lamp, deep ultraviolet rays typified by an excimer laser, X-rays, and electron beams. Among these, KrF excimer laser (wavelength 248 nm) and ArF excimer laser (wavelength 193 nm) are attracting attention.

  As a resist used for such short-wavelength radiation, a chemical amplification effect between a component having an acid-dissociable group and a radiation-sensitive acid generator that generates acid upon irradiation with radiation (hereinafter referred to as “exposure”). Many resists used (hereinafter referred to as “chemically amplified resist”) have been proposed (see, for example, Patent Document 1). Patent Document 1 proposes a resist composition containing a polymer having a t-butyl ester group of carboxylic acid or a t-butyl carbonate group of phenol, and a radiation-sensitive acid generator. In this resist composition, the t-butyl ester group or t-butyl carbonate group present in the polymer is dissociated by the action of an acid generated by exposure. The dissociated t-butyl ester group or t-butyl carbonate group becomes an acidic functional group composed of a carboxyl group or a phenolic hydroxyl group, and as a result, the exposed region of the resist film becomes readily soluble in an alkali developer.

  In recent years, chemically amplified resists are required to have high sensitivity to radiation, which can be a factor that determines productivity in a photolithography process, in addition to limit resolution and process margin. One way to increase the sensitivity of chemically amplified resists is to reduce the amount of basic substances that are constituents. However, in this method, the amount of acid generated from the radiation-sensitive acid generator is reduced as a result, the pattern surface becomes “unsteady”, and the holding time (PED) from exposure to heat treatment after exposure is increased. ) Environmental resistance such as line width stability (PED stability) with respect to fluctuations. On the other hand, a method of increasing the amount of the radiation-sensitive acid generator is also conceivable. However, this method has a drawback that the pattern shape tends to be a trapezoid rather than a preferred rectangle because the radiation transmittance of the resist film is lowered.

  Further, a chemically amplified radiation sensitive resin composition containing an anthracene-based additive, more specifically an anthracene derivative such as anthracene-9-methanol, anthracene-9-carboxyethyl, anthracene-9-carboxy-n-butyl, etc. It is disclosed that the product can improve the performance of the chemically amplified resist, particularly the antihalation effect (see, for example, Patent Document 2). Furthermore, a chemically amplified positive resist material having a tricyclic aromatic skeleton such as an anthracene skeleton and having a carboxylic acid derivative having a carboxyl group protected by an acid labile group is particularly suitable for standing waves and halation. It has been disclosed that expression can be suppressed (see, for example, Patent Document 3).

JP-B-2-27660 JP-A-8-217815 Japanese Patent Laid-Open No. 10-120628

  However, in the examples disclosed in these patent documents, in particular, suppression of line width variation of a resist pattern due to film thickness variation of a resist film on a highly reflective substrate such as a silicon (Si) substrate, improvement of a focal depth, etc. No consideration has been given to the process margin. Therefore, it cannot be said that the radiation-sensitive resin composition or the overall characteristics of the positive resist material as a chemically amplified resist are sufficient.

  The present invention has been made in view of such problems of the prior art, and the object of the present invention is to contain a compound having a predetermined structure with good compatibility with other components, and to be active. As a chemically amplified positive resist that effectively responds to radiation, especially deep ultraviolet radiation, the radiation transmittance can be optimally controlled, and the film of the resist coating on a highly reflective substrate can be used without sacrificing sensitivity, resolution, etc. An object of the present invention is to provide a positive-type radiation-sensitive resin composition capable of effectively suppressing a change in the line width of a resist pattern due to a thickness variation and having an excellent focal depth margin.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that a compound having a predetermined structure, a radiation-sensitive acid generator, and an alkali-insoluble or difficult-to-alkali compound having an acid-dissociable group that becomes alkali-soluble by the action of an acid. It has been found that the above-mentioned problems can be achieved by including a soluble resin as a constituent component, and the present invention has been completed.

  That is, according to the present invention, the following positive radiation sensitive resin composition is provided.

  [1] containing (A) a compound represented by the following general formula (1), (B) a radiation-sensitive acid generator, and (C) an alkali-insoluble or hardly-alkali-soluble resin having an acid-dissociable group. Positive type radiation sensitive resin composition.

  In said general formula (1), R shows a hydrogen atom or a monovalent | monohydric acid dissociable group mutually independently. X independently represents a substituted or unsubstituted alkylene group having 1 to 8 carbon atoms. Y is independently of each other a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, A substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group is shown. q represents 0 or 1 independently of each other.

  [2] The resin (C) has a repeating unit represented by the following general formula (2) and a repeating unit represented by at least one of the following general formula (3) and the following general formula (4). The positive radiation sensitive resin composition according to [1].

In the general formula (2), R ¹ represents a hydrogen atom or a methyl group, R ² independently represents a monovalent organic group, m represents an integer of 0 to 3, and n represents 1 to 1. An integer of 3 is shown. However, ^{R 2} except the group corresponding to -OR ⁵ in the general formula (3). In the general formula (3), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents a monovalent organic group independently of each other, and R ⁵ represents a monovalent independently of each other. An acid-dissociable group, p represents an integer of 0 to 3, and r represents an integer of 1 to 3; However, R ⁴ excludes a group corresponding to —OR ⁵ . Further, in the general formula (4), R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ represents a monovalent acid dissociable group.

  [3] In the general formula (1), the monovalent acid-dissociable group represented by R is a group represented by the following general formula (5-1) or (5-2) [1] Or the positive radiation sensitive resin composition as described in [2].

In the general formula (5-1), R ⁸ represents a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 40 carbon atoms, which may contain a hetero atom, and s is 0. An integer of ~ 3 is shown. In the general formula (5-2), R ⁹ represents a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 40 carbon atoms which may contain a hetero atom, and R ¹⁰ shows a hydrogen atom or a C1-C5 alkyl group.

  [4] The positive radiation sensitive resin composition according to any one of [1] to [3], wherein the compound represented by the general formula (1) is a compound represented by the following general formula (6): object.

  In the general formula (6), R independently represents a hydrogen atom or a monovalent acid dissociable group.

  [5] In the general formula (6), the monovalent acid dissociable group represented by R is the group represented by the following general formula (5-1) or (5-2) [4] The positive radiation sensitive resin composition described in 1.

In the general formula (5-1), R ⁸ represents a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 40 carbon atoms, which may contain a hetero atom, and s is 0. An integer of ~ 3 is shown. In the general formula (5-2), R ⁹ represents a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 40 carbon atoms which may contain a hetero atom, and R ¹⁰ shows a hydrogen atom or a C1-C5 alkyl group.

[6] In the general formula (5-1), R ⁸ is a t-butyl group, a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group, a 1-ethylcyclopentyl group, or 1-methylcyclopentyl. The positive radiation sensitive resin composition according to [3] or [5], which is a group and s is 0 or 1.

[7] In the general formula (5-2), R ⁹ is an adamantyl group and R ¹⁰ is a hydrogen atom or a methyl group, or R ⁹ is a 2-methyl-2-adamantyl group or 2-ethyl- The positive radiation sensitive resin composition according to the above [3] or [5], which is a 2-adamantyl group and R ¹⁰ is a methyl group.

  [8] Any of the above [1] to [7], wherein the (B) radiation sensitive acid generator is at least one compound selected from the group consisting of onium salts, diazomethane compounds, and sulfonimide compounds. The positive radiation sensitive resin composition described in 1.

  [9] The positive radiation sensitive resin composition according to any one of [1] to [8], further including (D) an acid diffusion controller.

  The positive radiation-sensitive resin composition of the present invention is a chemically amplified positive resist that is sensitive to actinic radiation, particularly far ultraviolet rays represented by KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), The radiation transmittance can be optimally controlled, and the line width variation of the resist pattern due to the film thickness fluctuation of the resist film on the highly reflective substrate can be effectively suppressed without losing sensitivity, resolution, etc. Further, the compound represented by the general formula (1) is excellent in the depth of focus margin, and has an effect that the compatibility with other components of the positive radiation sensitive resin composition is also good. Is.

  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.

1. Positive Type Radiation Sensitive Resin Composition The positive type radiation sensitive resin composition of the present invention comprises (A) a compound represented by the general formula (1) (hereinafter referred to as “(A) compound”), (B ) A radiation-sensitive acid generator and (C) an alkali-insoluble or alkali-insoluble resin having an acid-dissociable group (hereinafter referred to as “(C) resin”). The (C) resin becomes alkali-soluble when the acid-dissociable group is dissociated. The term “alkali-insoluble or alkali-insoluble” as used herein refers to a resist film (hereinafter referred to as “resist film”) formed using a positive radiation-sensitive resin composition containing (C) resin. When the film formed using only the resin (C) instead of the resist film is developed under the alkaline development conditions for forming the resist pattern, 50% or more of the initial film thickness remains after the development. Refers to nature. “Alkali-soluble” means that 50% or more of the initial film thickness does not remain after development under the same conditions.

  In the general formula (1), groups represented by R each independently represent a hydrogen atom or a monovalent acid dissociable group. The groups represented as X each independently represent a substituted or unsubstituted alkylene group having 1 to 8 carbon atoms. The groups represented by Y are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or non-substituted group having 2 to 10 carbon atoms. A substituted alkynyl group, a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group is shown. q represents 0 or 1 independently of each other.

  In the positive radiation sensitive resin composition of the present invention, the content of the compound (A) is preferably 0.1 to 80 parts by mass with respect to 100 parts by mass of the (C) resin, and 0.2 to More preferably, it is 70 mass parts, and it is especially preferable that it is 10-60 mass parts. When the content of the compound (A) is less than 0.1 parts by mass, the effect of suppressing the change in the line width of the resist pattern due to the change in the film thickness of the resist film and the effect of improving the depth of focus margin tend to decrease. On the other hand, if it exceeds 80 parts by mass, the top shape of the resist pattern tends to be rounded.

  Moreover, it is preferable that it is 0.1-20 mass parts with respect to 100 mass parts of (C) resin, and, as for content of (B) radiation sensitive acid generator, it is 0.5-15 mass parts. Is more preferable. (B) When content of a radiation sensitive acid generator is less than 0.1 mass part, a sensitivity and developability may fall. On the other hand, if it exceeds 20 parts by mass, transparency to radiation, pattern shape, heat resistance, and the like may decrease.

1.1 (A) Compound (A) The compound is a compound represented by the general formula (1).

  Among the groups represented by Y in the general formula (1), examples of the substituted or unsubstituted alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group. Among these, it is preferable that it is a methyl group from a viewpoint that the (A) compound of this embodiment can be synthesize | combined with a high yield.

  Of the groups represented by R in general formula (1), the monovalent acid-dissociable group is preferably a group represented by general formula (5-1) or (5-2).

In general formula (5-1), the group represented by R ⁸ represents a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 40 carbon atoms which may contain a hetero atom. S represents an integer of 0 to 3. In general formula (5-2), the group represented by R ⁹ is a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 40 carbon atoms which may contain a hetero atom. The group represented by R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

  Examples of the group represented by the general formula (5-1) include groups represented by the general formulas (7-1) to (7-9). Among these, it is preferable that it is group represented by general formula (7-1), (7-7), (7-8), (7-9) at the point that a raw material is industrially easy to obtain. .

In general formulas (7-1) to (7-9), examples of the group represented by R ¹¹ include an alkyl group having 1 to 5 carbon atoms, specifically, a methyl group, an ethyl group, and propyl. A linear or branched alkyl group such as a group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group and neopentyl group. Among these, a methyl group or an ethyl group is preferable, and a methyl group is more preferable. From these, specific examples of the group represented by R ⁸ in the general formula (5-1) include a t-butyl group, a 2-methyl-2-adamantyl group, and a 2-ethyl-2-adamantyl group. 1-ethylcyclopentyl group, 1-methylcyclopentyl group, group represented by formula (8), and the like.

  Therefore, as the group represented by the general formula (5-1), specifically, 2-methyl-2-adamantyloxycarbonylmethyl group, 2-ethyl-2-adamantyloxycarbonylmethyl group, 1-ethylcyclopentyloxy Examples thereof include a carbonylmethyl group, a 1-methylcyclopentyloxycarbonylmethyl group, a t-butoxycarbonylmethyl group, a t-butoxycarbonyl group, and a group represented by the formula (9).

In the group represented by the general formula (5-1), the group represented by R ⁸ is a t-butyl group, a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group, or a 1-ethylcyclopentyl group. Or a 1-methylcyclopentyl group and s is preferably 0 or 1. In addition, when there are a plurality of groups represented by the general formula (5-1), all the groups represented by R ⁸ in the general formula (5-1) may be the same group or different groups. There may be.

  Examples of the group represented by the general formula (5-2) include groups represented by the general formulas (10-1) to (10-10) and the general formulas (11-1) to (11-4). ) And the like. Among these, groups represented by general formula (10-5) or (10-7) are preferable. This is because a compound having a group represented by the general formula (10-5) or (10-7) is easily industrially available.

In general formulas (10-1) to (10-10), groups represented by R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and t is an integer of 0 to 2. Indicates.

In general formulas (11-1) to (11-4), the group represented by R ¹² represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

Of the groups represented by R ^{12 in the} general formulas (10-1) to (10-10), examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, There are linear or branched alkyl groups having 1 to 5 carbon atoms such as n-butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group and the like. In general formulas (10-1) to (10-10), t is preferably 0 or 1.

Of the groups represented by R ^{12 in} general formulas (11-1) to (11-4), examples of the alkyl group having 1 to 5 carbon atoms include general formulas (10-1) to (10-10). ) Are the same as the alkyl groups having 1 to 5 carbon atoms exemplified for the group represented by R ¹² .

  Further, the group represented by the general formula (5-2) is 2-adamantyloxymethyl among the groups represented by the general formula (10-7) because the etching resistance of the resist film to be formed is improved. Among groups represented by a group, a group represented by any of formulas (12-1) to (12-4), or a group represented by general formula (10-5), represented by formula (12-5) More preferably, it is a group.

Of the group represented by R in the compound represented by the general formula (1), the proportion of the monovalent acid dissociable group is preferably 10 to 100 mol%, and preferably 20 to 100 mol%. Further preferred. When the ratio of the monovalent acid dissociable group is less than 10 mol%, the resolution tends to be lowered. The ratio of monovalent acid dissociable groups can be calculated from the ratio of ¹ H by nuclear magnetic resonance spectrum analysis.

  The compound (A) is a compound represented by the general formula (6), that is, the group represented by X in the general formula (1) is a propylene group, and q is 0. preferable. The compound represented by the general formula (6) can be synthesized in a good yield among the compounds represented by the general formula (1).

  In general formula (6), groups represented by R each independently represent a hydrogen atom or a monovalent acid dissociable group.

  Among the groups represented by R in the general formula (6), specific examples of the monovalent acid dissociable group include the same groups as those exemplified for the monovalent acid dissociable group. it can.

  The compound (A) includes, for example, a compound represented by the general formula (13-1) (hereinafter referred to as “compound (13-1)”) and a compound represented by the general formula (13-2) (hereinafter referred to as “compound (13-1)”). And a compound represented by “Compound (13-2)” can be synthesized as a compound represented by the general formula (13) (hereinafter referred to as “Compound (13)”). In addition, after isolating and purifying the compound (13), at least one monovalent acid dissociable group is introduced so that at least one of the groups represented by R in the general formula (1) is 1 A compound (A) having a divalent acid dissociable group can be synthesized.

  In general formula (13-1), the group represented by Y is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, or 2 to 10 carbon atoms. A substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group, q is 0 or 1 is shown.

  In general formula (13-2), the group represented by X represents a substituted or unsubstituted alkylene group having 1 to 8 carbon atoms.

  In general formula (13), the groups represented by X each independently represent a substituted or unsubstituted alkylene group having 1 to 8 carbon atoms, and the groups represented by Y are each independently carbon. A substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted group having 7 to 10 carbon atoms A substituted aralkyl group, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group; q represents 0 or 1 independently of each other;

  The method for the condensation reaction is not particularly limited, and a conventionally known method can be used. For example, there is a method of reacting compound (13-1) and compound (13-2) in a solvent at 60 to 90 ° C. for 12 to 50 hours in the presence of a catalyst such as an acid catalyst. Examples of the acid catalyst include hydrochloric acid. The solvent is not particularly limited as long as it can dissolve the compounds (13-1) and (13-2). More specifically, alcohol solvents such as methanol and ethanol can be mentioned.

  The molar ratio of compound (13-1) to compound (13-2) ((13-1) / (13-2)) is not particularly limited, but the yield of compound (13) obtained is high. From the viewpoint of increasing, it is preferably 1 to 8, more preferably 2 to 6, and particularly preferably 3 to 5. If the molar ratio is outside this range, the yield of compound (13) may be reduced.

  The substrate concentration in the reaction solution (the total concentration of the compound (13-1) and the compound (13-2)) is not particularly limited, but the viewpoint that the yield of the obtained compound (13) is increased. Therefore, it is preferably 2 mol / L or more, more preferably 4 mol / L or more, and particularly preferably 4 to 10 mol / L. When the substrate concentration is less than 2 mol / L, the yield of the compound (13) may decrease.

  The method for introducing at least one acid-dissociable group into compound (13) is not particularly limited, and a conventionally known method can be used. For example, there is a method in which a compound (13) and a compound having an acid dissociable group are reacted in a solvent in the presence of an acid or a base at −20 to 100 ° C. for 1 to 20 hours.

  The molar ratio of the compound (13) and the compound having an acid dissociable group (compound having an acid dissociable group / compound (13)) is not particularly limited, but the introduction rate of the acid dissociable group is high. From the viewpoint, it is preferably 1 or more, more preferably 5 to 40, and particularly preferably 5 to 20. When the molar ratio is 1 or more, there is an advantage that the introduction rate of the target acid dissociable group is good. On the other hand, when the molar ratio is less than 1, the introduction rate of the target acid dissociable group may decrease. In the compound represented by the general formula (1), the ratio of the acid dissociable group among the groups represented by R can be adjusted by adjusting the molar ratio.

  Here, as a suitable example of the compound having an acid dissociable group, there is a compound having a group represented by the general formula (5-1) or (5-2).

  More specifically, as a compound having a group represented by the general formula (5-1), chloroacetic acid-2-ethyl-2-adamantyl, bromoacetic acid-2-ethyl-2-adamantyl, chloroacetic acid-2- Examples thereof include methyl-2-adamantyl and bromoacetate-2-methyl-2-adamantyl.

  Examples of the compound having a group represented by the general formula (5-2) include 2-adamantyl-chloromethyl ether, 2-methyl-2-adamantyl vinyl ether, 2-ethyladamantyl vinyl ether, and 2-adamantyl vinyl ether. Can do.

  Here, it describes about the method of synthesize | combining the compound represented by General formula (6) among (A) compounds. First, a compound represented by formula (14-1) (hereinafter referred to as “compound (14-1)”) and a compound represented by formula (14-2) (hereinafter referred to as “compound (14-2)”). In a solvent such as an alcohol solvent in the presence of an acid catalyst such as hydrochloric acid for 12 to 50 hours under conditions of 60 to 90 ° C. to obtain a compound (in the general formula (13), q is A compound of 0 (hereinafter referred to as “compound (14)”) is obtained. Next, the compound (14) obtained and the compound having an acid-dissociable group can be synthesized by reacting them in a solvent in the presence of an acid or a base at −20 to 100 ° C. for 1 to 20 hours. it can.

  The molar ratio of compound (14-1) to compound (14-2) ((14-1) / (14-2)) is not particularly limited, but the yield of compound (14) is high. From the viewpoint of becoming, it is preferably 1 to 8, more preferably 2 to 6, and particularly preferably 3 to 5. If the molar ratio is outside this range, the yield of compound (14) may be reduced.

  The substrate concentration of the condensation reaction (the total concentration of compound (14-1) and compound (14-2)) is not particularly limited, but is 2 mol from the viewpoint of increasing the yield of compound (14). / L or more, preferably 4 mol / L or more, more preferably 4 to 10 mol / L. When the substrate concentration is less than 2 mol / L, the yield of the compound (14) may decrease.

  Specific examples of the compound having an acid-dissociable group include a compound having a group represented by the general formula (5-1) (hereinafter referred to as “compound (5-1)”) and a general formula (5- And a compound having a group represented by 2) (hereinafter referred to as “compound (5-2)”). Further, the compound having an acid dissociable group may be a single compound or a mixture of two or more compounds.

  The molar ratio of the compound (14) and the compound having an acid dissociable group (compound having an acid dissociable group / compound (14)) is not particularly limited, but is represented by the general formula (6). From the viewpoint that the yield of the compound is high, it is preferably 1 or more, more preferably 5 to 40, and particularly preferably 5 to 20. When the molar ratio is 1 or more, there is an advantage that the compound represented by the general formula (6) can be synthesized with high yield. On the other hand, when the molar ratio is less than 1, the yield of the compound represented by the general formula (6) may decrease.

1.2 (B) Radiation sensitive acid generator (B) As the radiation sensitive acid generator, from the viewpoint of good acid generation efficiency, heat resistance, etc., for example, onium salts, diazomethane compounds, sulfonimide compounds , Sulfone compounds, sulfonic acid ester compounds, disulfonylmethane compounds, oxime sulfonate compounds, hydrazine sulfonate compounds, and the like. In addition, these radiation sensitive acid generators may be used individually by 1 type, and may mix and use 2 or more types.

  Examples of onium salts include sulfonium salts, iodonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like. In addition, onium salt may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  More specifically, examples of the onium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium benzenesulfonate, triphenylsulfonium 10-camphorsulfonate, and triphenyl. Sulfonium n-octanesulfonate, triphenylsulfonium 4-trifluoromethylbenzenesulfonate, triphenylsulfonium naphthalenesulfonate, triphenylsulfonium perfluorobenzenesulfonate;

  (4-t-butoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (4-t-butoxyphenyl) diphenylsulfonium nonafluoro-n-butanesulfonate, (4-t-butoxyphenyl) diphenylsulfonium perfluoro-n-octanesulfonate, (4-t-butoxyphenyl) diphenylsulfonium 10-camphorsulfonate, (4-hydroxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (4-hydroxyphenyl) diphenylsulfonium nonafluoro-n-butanesulfonate, (4-hydroxyphenyl) diphenyl Sulfonium perfluoro-n-octanesulfonate, (4-hydroxyphenyl) diphenylsulfonium 10-camphorsulfonate DOO, (4-hydroxyphenyl) diphenyl sulfonium n- octane sulfonate;

  Tris (4-methoxyphenyl) sulfonium trifluoromethanesulfonate, tris (4-methoxyphenyl) sulfonium nonafluoro-n-butanesulfonate, tris (4-methoxyphenyl) sulfonium perfluoro-n-octanesulfonate, tris (4-methoxyphenyl) ) Sulfonium 10-camphorsulfonate; (4-fluorophenyl) diphenylsulfonium trifluoromethanesulfonate, (4-fluorophenyl) diphenylsulfonium nonafluoro-n-butanesulfonate, (4-fluorophenyl) diphenylsulfonium 10-camphorsulfonate;

  Tris (4-fluorophenyl) sulfonium trifluoromethanesulfonate, tris (4-fluorophenyl) sulfonium nonafluoro-n-butanesulfonate, tris (4-fluorophenyl) sulfonium 10-camphor sulfonate, tris (4-fluorophenyl) sulfonium p -Toluenesulfonate, tris (4-trifluoromethylphenyl) sulfonium trifluoromethanesulfonate;

  2,4,6-trimethylphenyldiphenylsulfonium trifluoromethanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium 2,4-difluorobenzenesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium 4-trifluoromethylbenzenesulfonate, etc. Can be mentioned.

  Among these, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium 10-camphorsulfonate, (4-hydroxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (4-hydroxyphenyl) diphenylsulfonium Nonafluoro-n-butanesulfonate, tris (4-methoxyphenyl) sulfonium trifluoromethanesulfonate, tris (4-methoxyphenyl) sulfonium nonafluoro-n-butanesulfonate, (4-fluorophenyl) diphenylsulfonium trifluoromethanesulfonate, (4 -Fluorophenyl) diphenylsulfonium nonafluoro-n-butanesulfonate 2,4,6-trimethylphenyldiphenylsulfonium trifluoromethanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium 2,4-difluorobenzenesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium 4-trifluoromethylbenzenesulfonate Can be suitably used.

  Further, as iodonium salts in the examples of onium salts, more specifically, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 10-camphorsulfonate Diphenyliodonium n-octanesulfonate;

  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 10-camphorsulfonate, bis (4-t-butylphenyl) iodonium n-octanesulfonate, (4-methoxyphenyl) phenyliodonium trifluoromethanesulfonate, (4-methoxyphenyl) phenyliodonium Nonafluoro-n-butanesulfonate, (4-methoxyphenyl) phenyliodonium perfluoro-n-octanesulfonate;

  (4-fluorophenyl) phenyliodonium trifluoromethanesulfonate, (4-fluorophenyl) phenyliodonium nonafluoro-n-butanesulfonate, (4-fluorophenyl) phenyliodonium 10-camphorsulfonate; bis (4-fluorophenyl) iodonium trifluoro Lomethanesulfonate, bis (4-fluorophenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-fluorophenyl) iodonium 10-camphorsulfonate;

  Bis (4-chlorophenyl) iodonium trifluoromethanesulfonate, bis (4-chlorophenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-chlorophenyl) iodonium perfluoro-n-octanesulfonate, bis (4-chlorophenyl) iodonium n- Dodecylbenzenesulfonate, bis (4-chlorophenyl) iodonium 10-camphorsulfonate, bis (4-chlorophenyl) iodonium n-octanesulfonate, bis (4-chlorophenyl) iodonium 4-trifluoromethylbenzenesulfonate, bis (4-chlorophenyl) iodonium Perfluorobenzenesulfonate;

  Bis (4-trifluoromethylphenyl) iodonium trifluoromethanesulfonate, bis (4-trifluoromethylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-trifluoromethylphenyl) iodonium perfluoro-n-octanesulfonate, Bis (4-trifluoromethylphenyl) iodonium n-dodecylbenzenesulfonate, bis (4-trifluoromethylphenyl) iodonium p-toluenesulfonate, bis (4-trifluoromethylphenyl) iodoniumbenzenesulfonate, bis (4-trifluoro Methylphenyl) iodonium 10-camphorsulfonate, bis (4-trifluoromethylphenyl) iodonium n-octanesulfonate, bis (4-trifluoro) B methylphenyl) iodonium 4-trifluoromethyl benzenesulfonate, bis (4-trifluoromethylphenyl) iodonium perfluoro benzene sulfonate, and the like.

  Among these, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium 10-camphorsulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) Iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium 10-camphorsulfonate, (4-fluorophenyl) phenyliodonium trifluoromethanesulfonate, (4-fluorophenyl) phenyliodonium nonafluoro-n-butane Sulfonate, (4-fluorophenyl) phenyliodonium 10-camphorsulfonate, bis (4-fluorophenyl) Preferred are iodonium trifluoromethanesulfonate, bis (4-fluorophenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-fluorophenyl) iodonium 10-camphorsulfonate, tris (4-trifluoromethylphenyl) sulfonium trifluoromethanesulfonate. Can be used.

  Specific examples of the diazomethane compound include bis (trifluoromethanesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, and bis (3,3-dimethyl-1,5-dioxaspiro [5.5] dodecane-8-sulfonyl). Examples thereof include diazomethane, bis (1,4-dioxaspiro [4.5] decan-7-sulfonyl) diazomethane, and bis (t-butylsulfonyl) diazomethane.

  Among these, bis (cyclohexylsulfonyl) diazomethane, bis (3,3-dimethyl-1,5-dioxaspiro [5.5] dodecane-8-sulfonyl) diazomethane, bis (1,4-dioxaspiro [4.5] decane -7-sulfonyl) diazomethane can be preferably used. In addition, these diazomethane compounds may be used individually by 1 type, and may mix and use 2 or more types.

  Further, as the sulfonimide compound, specifically, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyl) Oxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5,6 -Oxy-2,3-dicarboximide;

  N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2 , 3-dicarboximide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (10-camphorsulfonyloxy) naphthyl Imido, N-[(5-methyl-5-carboxymethylbicyclo [2.2.1] heptan-2-yl) sulfonyloxy] succinimide;

  N- (n-octylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (n-octylsulfonyloxy) bicyclo [2.2.1] heptane- 5,6-oxy-2,3-dicarboximide, N- (perfluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluoro Phenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5 , 6-oxy-2,3-dicarboximide, N- (nonafluoro-n-butylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3 Dicarboximide, N- (nonafluoro-n-butylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butylsulfonyl) Oxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide;

  N- (perfluoro-n-octylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octylsulfonyloxy) -7-oxa Bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy- 2,3-dicarboximide and the like can be mentioned.

  Among these, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) succinimide, N-[( 5-Methyl-5-carboxymethylbicyclo [2.2.1] heptan-2-yl) sulfonyloxy] succinimide can be preferably used. In addition, these sulfonimide compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds thereof. More specifically, phenacylphenylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, 4-trisphenacylsulfone and the like can be mentioned.

  Furthermore, examples of the sulfonate compound include alkyl sulfonate, haloalkyl sulfonate, aryl sulfonate, and imino sulfonate. More specifically, benzoin tosylate, pyrogallol tris (trifluoromethanesulfonate), pyrogallol tris (nonafluorobutane sulfonate), pyrogallol tris (methanesulfonate), nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, α Examples include -methylol benzoin tosylate, α-methylol benzoin trifluoromethanesulfonate, α-methylol benzoin n-octane sulfonate, α-methylol benzoin n-dodecane sulfonate, and the like.

  Moreover, as a disulfonylmethane compound, there exists a compound represented by General formula (15), for example.

In general formula (15), groups represented by R ¹³ are each independently a linear or branched monovalent aliphatic hydrocarbon group, cycloalkyl group, aryl group, aralkyl group, or heteroatom. The other monovalent organic group which has is shown. The groups represented as V each independently represent a hydrogen atom, an aryl group, a linear or branched monovalent aliphatic hydrocarbon group, or another monovalent organic group having a hetero atom ( Provided that at least one is an aryl group), a group having a carbon monocyclic structure or a carbon polycyclic structure having at least one unsaturated bond formed by mutual connection, or a group represented by the general formula (16) The group represented is shown.

  In general formula (16), the groups represented by W each independently represent a hydrogen atom, a halogen atom, a linear or branched alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, Or the group which has a carbon monocyclic structure formed by mutually connecting is shown. u represents an integer of 2 to 10. In addition, when the group represented as W is a group having a carbon monocyclic structure formed by being connected to each other, a carbon monocyclic structure may be formed by W bonded to the same carbon atom, A carbon monocyclic structure may be formed by W bonded to different carbon atoms.

  Further, examples of the oxime sulfonate compound include compounds represented by general formula (17-1) and general formula (17-2).

In general formulas (17-1) and (17-2), groups represented by R ¹⁴ each independently represent a monovalent organic group, and groups represented by R ¹⁵ independently represent each other. A monovalent organic group is shown.

Of the groups represented by R ^{14 in the} general formulas (17-1) and (17-2), as the monovalent organic group, specifically, methyl group, ethyl group, n-propyl group, phenyl group , Tosyl group, trifluoromethyl group, pentafluoroethyl group and the like. In the general formulas (17-1) and (17-2), among the groups represented by R ¹⁵ , preferred specific examples of the monovalent organic group include a phenyl group, a tosyl group, and a 1-naphthyl group. Etc.

  Specific examples of hydrazine sulfonate compounds include bis (benzenesulfonyl) hydrazine, bis (p-toluenesulfonyl) hydrazine, bis (trifluoromethanesulfonyl) hydrazine, bis (pentafluoroethanesulfonyl) hydrazine, and bis (n-propane). And sulfonyl) hydrazine, benzenesulfonylhydrazine, p-toluenesulfonylhydrazine, trifluoromethanesulfonylhydrazine, pentafluoroethanesulfonylhydrazine, n-propanesulfonylhydrazine, trifluoromethanesulfonyl and p-toluenesulfonylhydrazine.

1.3 (C) Resin (C) The resin is an alkali-insoluble or hardly-alkali-soluble one having an acid-dissociable group and becomes alkali-soluble when the acid-dissociable group is dissociated.

  (C) As the resin, for example, a hydrogen atom of an acidic functional group in an alkali-soluble resin having one or more acidic functional groups such as a phenolic hydroxyl group and a carboxyl group can be dissociated in the presence of an acid. Examples of the resin substituted with an acid dissociable group of more than one species include alkali-insoluble or alkali-insoluble resins.

  (C) In the resin, the introduction rate of the acid dissociable group (number of acid dissociable groups / (C) the total number of unprotected acidic functional groups and acid dissociable groups in the resin) is the acid dissociable group. However, it is preferably 10 to 100%, more preferably 15 to 100%, although it cannot be generally defined by the type of alkali-soluble resin into which an acid-dissociable group is introduced.

  (C) The weight average molecular weight (hereinafter referred to as “Mw”) in terms of polystyrene measured by gel permeation chromatography (GPC) of the resin is preferably 1,000 to 150,000, more preferably 3 , 100,000 to 100,000. The ratio (Mw / Mn) of (C) resin Mw and polystyrene-reduced number average molecular weight (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC) is usually 1 to 1. 10, preferably 1-5.

  (C) The resin includes a repeating unit represented by the general formula (2) (hereinafter referred to as “repeating unit (2)”) and a repeating unit represented by the general formula (3) (hereinafter referred to as “repeating unit”). (3) ”and a resin having at least one of repeating units represented by the general formula (4) (hereinafter referred to as“ repeating unit (4) ”). The (C) resin may be a single resin or a resin in which two or more resins are mixed.

In general formula (2), the group represented as R ¹ represents a hydrogen atom or a methyl group, the groups represented as R ² independently represent a monovalent organic group, and m represents 0 to 0. 3 represents an integer, and n represents an integer of 1 to 3. However, the group represented as R ² excludes a group corresponding to —OR ⁵ in the general formula (3). In general formula (3), the group represented by R ³ represents a hydrogen atom or a methyl group, the groups represented by R ⁴ represent each independently a monovalent organic group, and R ⁵ The groups represented as are independently of each other a monovalent acid dissociable group, p is an integer of 0 to 3, and r is an integer of 1 to 3. However, the group represented as R ⁴ excludes a group corresponding to —OR ⁵ . Furthermore, in General Formula (4), the group represented as R ⁶ represents a hydrogen atom or a methyl group, and the group represented as R ⁷ represents a monovalent acid-dissociable group.

Of the group represented by R ² in the general formula (2) and the group represented by R ⁴ in the general formula (3), examples of the monovalent organic group include a straight chain having 1 to 12 carbon atoms. Examples thereof include a chain, branched or cyclic alkyl group, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent oxygen atom-containing organic group, and a monovalent nitrogen atom-containing organic group. More specifically, examples of the linear, branched or cyclic alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group and 2-methylpropyl group. Group, 1-methylpropyl group, t-butyl group, cyclopentyl group, cyclohexyl group and the like.

  Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,4-xylyl group, and 2,6-xylyl group. 3,5-xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, benzyl group, phenethyl group, 1-naphthyl group, 2-naphthyl group and the like.

  Furthermore, as the monovalent oxygen atom-containing organic group, a carboxyl group; a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, 3-hydroxycyclopentyl group, 4-hydroxycyclohexyl group, etc. Cyclic hydroxyalkyl group; methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, cyclopentyloxy group, cyclohexyloxy C1-C8 linear, branched or cyclic alkoxyl groups such as groups

  A linear alkoxycarbonyloxy group having 2 to 9 carbon atoms such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propoxycarbonyloxy group, and an n-butoxycarbonyloxy group; a (1-methoxyethoxy) methyl group, ( 1-ethoxyethoxy) methyl group, (1-n-propoxyethoxy) methyl group, (1-n-butoxyethoxy) methyl group, (1-cyclopentyloxyethoxy) methyl group, (1-cyclohexyloxyethoxy) methyl group, A linear, branched or cyclic (1-alkoxyalkoxy) alkyl group having 3 to 11 carbon atoms such as (1-methoxypropoxy) methyl group, (1-ethoxypropoxy) methyl group;

  Methoxycarbonyloxymethyl group, ethoxycarbonyloxymethyl group, n-propoxycarbonyloxymethyl group, i-propoxycarbonyloxymethyl group, n-butoxycarbonyloxymethyl group, t-butoxycarbonyloxymethyl group, cyclopentyloxycarbonyloxymethyl group And a straight-chain, branched or cyclic alkoxycarbonyloxyalkyl group having 3 to 10 carbon atoms such as a cyclohexyloxycarbonyloxymethyl group.

  Examples of the monovalent nitrogen atom-containing organic group include cyano group; cyanomethyl group, 1-cyanoethyl group, 2-cyanoethyl group, 1-cyanopropyl group, 2-cyanopropyl group, 3-cyanopropyl group, 1-cyanobutyl. A linear, branched or cyclic cyanoalkyl group having 2 to 9 carbon atoms such as a group, 2-cyanobutyl group, 3-cyanobutyl group, 4-cyanobutyl group, 3-cyanocyclopentyl group, 4-cyanocyclohexyl group, etc. Can be mentioned.

Among the groups represented by R ⁵ in the general formula (3), examples of the monovalent acid dissociable group include a substituted methyl group, a 1-substituted ethyl group, a 1-branched alkyl group, a triorganosilyl group, Examples include a triorganogermyl group, an alkoxycarbonyl group, an acyl group, and a monovalent cyclic acid dissociable group. More specifically, examples of the substituted methyl group include methoxymethyl group, methylthiomethyl group, ethoxymethyl group, ethylthiomethyl group, methoxyethoxymethyl group, benzyloxymethyl group, benzylthiomethyl group, phenacyl group, bromophenacyl group, methoxy Phenacyl group, methylthiophenacyl group, α-methylphenacyl group, cyclopropylmethyl group, benzyl group, diphenylmethyl group, triphenylmethyl group, bromobenzyl group, nitrobenzyl group, methoxybenzyl group, methylthiobenzyl group, ethoxy Benzyl group, ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, i-propoxycarbonylmethyl group, n-butoxycarbonylmethyl group, t-butoxy It can be exemplified carbonyl methyl group.

  Examples of the 1-substituted ethyl group include 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1-diethoxyethyl. Group, 1-propoxyethyl group, 1-cyclohexyloxyethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1,1-diphenoxyethyl group, 1-benzyloxyethyl group, 1-benzylthioethyl group 1-cyclopropylethyl group, 1-phenylethyl group, 1,1-diphenylethyl group, 1-methoxycarbonylethyl group, 1-ethoxycarbonylethyl group, 1-n-propoxycarbonylethyl group, 1-isopropoxycarbonyl Examples include an ethyl group, 1-n-butoxycarbonylethyl group, 1-t-butoxycarbonylethyl group, etc. Rukoto can.

  Further, examples of the 1-branched alkyl group include i-propyl group, sec-butyl group, t-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group and the like. it can.

  Examples of the triorganosilyl group include trimethylsilyl group, ethyldimethylsilyl group, diethylmethylsilyl group, triethylsilyl group, dimethyl i-propylsilyl group, methyldi-i-propylsilyl group, tri-i-propylsilyl group, t -Butyldimethylsilyl group, di-t-butylmethylsilyl group, tri-t-butylsilyl group, dimethylphenylsilyl group, methyldiphenylsilyl group, triphenylsilyl group and the like can be mentioned.

  Further, as the triorganogermyl group, trimethylgermyl group, ethyldimethylgermyl group, diethylmethylgermyl group, triethylgermyl group, dimethyl i-propylgermyl group, methyldi-i-propylgermyl group, tri- i-propylgermyl group, t-butyldimethylgermyl group, di-t-butylmethylgermyl group, tri-t-butylgermyl group, dimethylphenylgermyl group, methyldiphenylgermyl group, triphenylgermyl group, etc. Can be mentioned.

  Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an i-propoxycarbonyl group, and a t-butoxycarbonyl group.

  Furthermore, as the acyl group, acetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, oxalyl group, malonyl group, succinyl group Group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacoyl group, acryloyl group, propioyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, canphoroyl group, benzoyl group , Phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, thenoyl group, nicotinoyl group, isonicotino It can be exemplified Le group.

  Monovalent cyclic acid dissociable groups include cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, 4-methoxycyclohexyl group, tetrahydrofuranyl group, tetrahydropyranyl group, tetrahydrothiofuranyl group, tetrahydro group. A thiopyranyl group, a 3-bromotetrahydropyranyl group, a 4-methoxytetrahydropyranyl group, a 4-methoxytetrahydrothiopyranyl group, a 3-tetrahydrothiophene-1,1-dioxide group, and the like can be given.

  Among these examples, monovalent acid dissociable groups are t-butyl group, benzyl group, 1-methoxyethyl group, 1-ethoxyethyl group, trimethylsilyl group, t-butoxycarbonyl group, t-butoxycarbonylmethyl group. , A tetrahydrofuranyl group, a tetrahydropyranyl group, a tetrahydrothiofuranyl group, and a tetrahydrothiopyranyl group are preferable.

Among the groups represented by R ⁷ in the general formula (4), as the monovalent acid dissociable group, specifically, t-butyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 2- Examples thereof include a methyladamantyl group and 2-ethyladamantyl group.

  (C) Examples of the repeating unit (2) contained in the resin include 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 2-hydroxy-α-methylstyrene, 3-hydroxy-α-methylstyrene, 4-hydroxy-α-methylstyrene, 2-methyl-3-hydroxystyrene, 4-methyl-3-hydroxystyrene, 5-methyl-3-hydroxystyrene, 2-methyl-4-hydroxystyrene, 3-methyl-4 There are repeating units in which a polymerizable unsaturated bond is cleaved, such as -hydroxystyrene, 3,4-dihydroxystyrene, 2,4,6-trihydroxystyrene. The repeating unit (2) contained in the resin (C) may be composed of one type of repeating unit (2), or a mixture of two or more types of repeating units (2). Also good.

  The content of the repeating unit (2) is preferably 60 to 80 mol%, more preferably 65 to 75 mol%, based on all repeating units contained in the (C) resin. If the content is less than 60 mol%, the adhesion of the resist pattern to the substrate tends to be reduced. On the other hand, if it exceeds 80 mol%, the contrast after development tends to decrease.

  Examples of the repeating unit (3) contained in the (C) resin include 4-t-butoxystyrene, 4-t-butoxy-α-methylstyrene, 4- (2-ethyl-2-propoxy) styrene, Polymeric unsaturated bonds such as 4- (2-ethyl-2-propoxy) -α-methylstyrene, 4- (1-ethoxyethoxy) styrene, 4- (1-ethoxyethoxy) -α-methylstyrene are cleaved. There are repeating units. The repeating unit (3) contained in the resin (C) may be composed of one type of repeating unit (3) or a mixture of two or more types of repeating units (3). Also good.

  The content of the repeating unit (3) is preferably 15 to 40 mol%, more preferably 20 to 35 mol%, based on all repeating units contained in the (C) resin. If the content is less than 15 mol%, the resolution tends to decrease. On the other hand, if it exceeds 40 mol%, the adhesion of the resist pattern to the substrate tends to be lowered.

  Furthermore, preferred specific examples of the repeating unit (4) contained in the (C) resin include t-butyl (meth) acrylate, 1-methylcyclopentyl (meth) acrylate, 1-ethylcyclopentyl (meth) acrylate, Mention may be made of repeating units in which a polymerizable unsaturated bond is cleaved, such as (meth) acrylic acid 2-methyladamantyl and (meth) acrylic acid 2-ethyladamantyl. The repeating unit (4) contained in the resin (C) may be composed of one type of repeating unit (4), or a mixture of two or more types of repeating units (4). Also good.

  The content of the repeating unit (4) is preferably 10 to 40 mol%, more preferably 10 to 30 mol%, based on all repeating units contained in the (C) resin. If the content is less than 10 mol%, the resolution tends to decrease. On the other hand, if it exceeds 40 mol%, dry etching resistance may be insufficient.

  (C) The resin is more preferably a resin having a repeating unit other than the repeating units (2) to (4) (hereinafter referred to as “other repeating unit”). Examples of other repeating units include vinyl aroma such as styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, and the like. Group compounds;

  Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-methylpropyl (meth) acrylate 1-methylpropyl (meth) acrylate, n-pentyl (meth) acrylate, neopentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid 2-hydroxyethyl, 2-hydroxy-n-propyl (meth) acrylate, 3-hydroxy-n-propyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid 1-methyladamantyl, 1-ethyladamantyl (meth) acrylate, 8-methyl-8- (meth) acrylate Licyclodecyl, 8-ethyl-8-tricyclodecyl (meth) acrylate, 3-methyl-3-tetracyclododecenyl (meth) acrylate, 3-ethyl-3-tetracyclodode (meth) acrylate (Meth) acrylic acid esters such as senyl and 2,5-dimethylhexane-2,5-di (meth) acrylate;

  Unsaturated carboxylic acids (anhydrides) such as (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, cinnamic acid; 2-carboxyethyl (meth) acrylate, (meth) acrylic acid 2 -Carboxyalkyl esters of unsaturated carboxylic acids such as carboxy-n-propyl and (meth) acrylic acid 3-carboxy-n-propyl; (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinonitrile, fumaronitrile, etc. Unsaturated nitrile compounds;

  Unsaturated amide compounds such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, crotonamide, maleinamide, and fumaramide; unsaturated imide compounds such as maleimide, N-phenylmaleimide, and N-cyclohexylmaleimide; N-vinyl Polymerizable unsaturated bonds such as nitrogen-containing vinyl compounds such as -ε-caprolactam, N-vinyl pyrrolidone, 2-vinyl pyridine, 3-vinyl pyridine, 4-vinyl pyridine, 2-vinyl imidazole, and 4-vinyl imidazole are cleaved. There are units. In addition, the other repeating unit contained in (C) resin may consist of one type of repeating unit, or may be a mixture of two or more types of repeating units.

  The content of other repeating units is usually 25 mol% or less, preferably 10 mol% or less, based on all repeating units contained in the resin (C). If the content is more than 25 mol%, the resolution tends to decrease.

  (C) As preferred examples of the resin, 4-hydroxystyrene / 4-t-butoxystyrene copolymer, 4-hydroxystyrene / 4-t-butoxystyrene / 1-methylcyclopentyl acrylate copolymer, 4-hydroxystyrene / 4-t-butoxystyrene / acrylic acid 1-ethylcyclopentyl copolymer, 4-hydroxystyrene / 4-t-butoxystyrene / styrene copolymer, 4-hydroxystyrene / t-butyl acrylate / styrene copolymer 4-hydroxystyrene / 1-methylcyclopentyl acrylate / styrene copolymer, 4-hydroxystyrene / 1-ethylcyclopentyl acrylate / styrene copolymer, 4-hydroxystyrene / 4-t-butoxystyrene / 2,5 -For dimethylhexane-2,5-diacrylate 4-hydroxystyrene / acrylic acid 2-ethyladamantyl / styrene copolymer, 4-hydroxystyrene / acrylic acid 2-ethyladamantyl copolymer, 4-hydroxystyrene / 4- (1-ethoxyethoxy) styrene / 4 -Tert-butoxystyrene, 4-hydroxystyrene / 4- (1-ethoxyethoxy) styrene, 4-hydroxystyrene / 4- (1-ethoxyethoxy) styrene / styrene, and the like.

1.4 (D) Acid Diffusion Control Agent It is preferable that the positive radiation sensitive resin composition of the present invention further contains (D) an acid diffusion control agent. (D) The acid diffusion control agent controls the diffusion phenomenon in the resist film of the acid generated from the (B) radiation-sensitive acid generator by exposure, and has an action of suppressing an undesirable chemical reaction in a non-exposed region. .

  (D) The content of the acid diffusion controller is preferably 15 parts by mass or less, more preferably 0.001 to 10 parts by mass, with respect to 100 parts by mass of (C) resin, and 0.005. It is especially preferable that it is -5 mass parts. When the content is more than 15 parts by mass, the sensitivity as a resist and the developability of the exposed part may be deteriorated. On the other hand, if the content is less than 0.001 part by mass, the pattern shape and dimensional fidelity as a resist may be lowered depending on the process conditions.

  (D) Preferable examples of the acid diffusion controller include nitrogen-containing organic compounds or photosensitive basic compounds. Examples of the nitrogen-containing organic compound include a compound represented by the general formula (18) (hereinafter referred to as “nitrogen-containing compound (i)”), a compound having two nitrogen atoms in the same molecule (hereinafter referred to as “ A nitrogen-containing compound (ii) ”, a polyamino compound or polymer having 3 or more nitrogen atoms (hereinafter collectively referred to as“ nitrogen-containing compound (iii) ”), an amide group-containing compound, urea Compounds and nitrogen-containing heterocyclic compounds. The (D) acid diffusion controller may be a single compound or a mixture of two or more.

In general formula (18), groups represented by R ¹⁶ are each independently a hydrogen atom, an optionally substituted linear, branched or cyclic alkyl group, or an optionally substituted aryl group. Or an aralkyl group which may be substituted.

  Preferred examples of the nitrogen-containing compound (i) 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. Of di (cyclo) alkylamines; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octyl Amine, tri-n-nonylamine, tri-n-decylamine, cyclo Tri (cyclo) alkylamines such as xyldimethylamine, methyldicyclohexylamine, tricyclohexylamine; substituted alkylamines such as triethanolamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3 -Methylaniline, 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, naphthylamine, 2,4,6-tri-tert-butyl-N-methylaniline, N-phenyldiethanolamine, 2,6-diisopropylaniline And aromatic amines.

  Preferred examples of the nitrogen-containing compound (ii) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, and 4,4′-diamino. Diphenyl ether, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-amino Phenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-me Ruethyl] 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.

  Preferable examples of the nitrogen-containing compound (iii) include polyethyleneimine, polyallylamine, 2-dimethylaminoethylacrylamide polymer, and the like.

  Preferred 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-hydroxy Piperidine, Nt-butoxycarbonylpyrrolidine, Nt-butoxycal Nilpiperazine, 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′-di-t-butoxycarbonyl-4,4′-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2- In addition to Nt-butoxycarbonyl group-containing amino compounds such as phenylbenzimidazole, 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.

  Preferred examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butyl. There is thiourea.

  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-phenyl Pyridines such as pyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 4-hydroxyquinoline, 8-oxyquinoline, acridine, 2,2 ′: 6 ′, 2 ″ -terpyridine; piperazine, 1- (2-hydroxy In addition to piperazines such as ethyl) piperazine Pyrazine, 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.

  The photosensitive basic compound is a component that efficiently decomposes into the corresponding neutral fragment in the exposed region and remains as it is without being decomposed in the unexposed portion. Such a photosensitive basic compound can improve the sensitivity because it can effectively use the acid generated in the exposed portion (exposed region) as compared with the non-photosensitive basic compound.

  The photosensitive basic compound is not particularly limited, and for example, a compound represented by General Formula (19-1) or General Formula (19-2) can be preferably used.

In general formula (19-1), groups represented by R ^{17 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, or The alicyclic hydrocarbon group which may have a substituent is shown. In general formula (19-2), the groups represented by R ²⁰ or R ²¹ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms that may have a substituent. Or an alicyclic hydrocarbon group which may have a substituent. Furthermore, in the general formula (19-1) and the formula (19-2), Z ^- anion represented as ^{the, OH -, R 22 O -} , or ^R 22 COO ^- an anion expressed as. However, the group represented as R ²² represents a monovalent organic group.

Of the groups represented by R ^{17 to} R ¹⁹ in general formula (19-1), or the groups represented by R ²⁰ or R ^{21 in} general formula (19-2), they may have a substituent. Specific examples of preferable alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, n-butyl group, t-butyl group, trifluoromethyl group, methoxy group, t-butoxy group, and t-butoxycarbonylmethyl. An oxy group etc. can be mentioned. In general formula (19-1), the group represented by R ^{17 to} R ¹⁹ , or the group represented by R ²⁰ or R ^{21 in} general formula (19-2) is a hydrogen atom or a t-butyl group. Preferably there is.

Furthermore, Z ^- anion in which is represented ^{as, R 22} O ^-, or ^R 22 COO ^- contained in the anion expressed ^as, as the monovalent organic group represented by ^{R 22,} for example, have a substituent There may be an alkyl group which may be substituted and an aryl group which may have a substituent.

In general formula (19-1) and general formula (19-2), the anion represented as Z ⁻ is an anion selected from OH ⁻ , CH ₃ COO ⁻ , and the anion group represented by formula (20). It is preferable that

Specifically, the photosensitive basic compound is a triphenylsulfonium compound (a compound represented by the general formula (19-1)), and an anion portion (Z ⁻ ) thereof is OH ⁻ , CH ₃ COO ⁻ , And a compound that is an anion selected from the group of anions represented by formula (21) can be given as a preferred example.

1.5 (E) Other Additives The positive radiation sensitive resin composition of the present invention includes surfactants, sensitizers such as rose bengals, dyes, pigments, adhesion aids, 4-hydroxy-4 An antihalation agent such as' -methylchalcone, a shape improver, a storage stabilizer, an antifoaming agent, and the like can be blended.

  The surfactant has an effect of improving the coating property and striation of the composition, the developing property as a resist, and the like. When the surfactant is blended, the blending amount is usually 2 parts by mass or less per 100 parts by mass of the (C) resin.

  Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenol ether, polyoxyethylene n-nonylphenol ether, polyethylene glycol dilaurate, polyethylene glycol distearate. There are rates. As commercial products, for example, “F-top EF301”, EF303, EF352 (above, manufactured by Tochem Products), “Megafax F171”, F173 (above, manufactured by Dainippon Ink and Chemicals, Inc.). ), "Florard FC430", FC431 (above, manufactured by Sumitomo 3M), "Asahi Guard AG710", "Surflon S-382", SC101, SC102, SC103, SC104, SC105, SC106 (and above) Manufactured by Asahi Glass Co., Ltd.), “KP341” (manufactured by Shin-Etsu Chemical Co., Ltd.), “Polyflow No. 75”, 95 (above, manufactured by Kyoeisha Chemical Co., Ltd.). In addition, surfactant may be mix | blended individually by 1 type and may mix and mix 2 or more types.

  When mix | blending a sensitizer, the compounding quantity is 50 mass parts or less normally per 100 mass parts of (C) resin.

  Dyes and pigments can visualize the latent image in the exposed area and reduce the influence of halation during exposure. The adhesion assistant can further improve the adhesion to the substrate.

  As the dye, a dye component other than the above dye (hereinafter referred to as “other dye”) may be added. Examples of other dyes include anthracene carboxylic acid, anthracene-9-carboxylic acid methoxycarbonylmethyl, anthracene-9-carboxylic acid t-butoxycarbonylmethyl, 9-methoxycarbonylmethylanthracene, 9-t-butoxycarbonylmethylanthracene, and the like. Anthracene derivatives of: carbazole derivatives such as N- (methoxycarbonylmethyl) carbazole, N- (t-butoxycarbonylmethyl) carbazole, 9-carbazoylacetic acid; benzophenone-2-carboxylic acid t-butoxycarbonylmethyl, benzophenone-4 -Benzophenone derivatives such as t-butoxycarbonylmethyl carboxylate. In addition, these other dyes may be added individually by 1 type, and may mix and add 2 or more types.

  When another dye is added, the ratio of the other dye to the total amount of the compound (A) and the other dye (the other dye / the total amount of the (A) compound and the other dye) is usually 40 masses. % Or less, preferably 30% by mass or less. If the proportion of the other dye is more than 40% by mass, the intended effect of the present invention may be impaired.

1.6 (F) Solvent The positive radiation-sensitive resin composition of the present invention is usually uniform in the solvent so that the concentration of the total solid content is 0.1 to 50% by mass, preferably 1 to 40% by mass. For example, it is used as a composition solution prepared by filtering with a filter having a pore size of about 0.2 μm.

  Examples of the solvent include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate; propylene glycol monomethyl Propylene glycol monoalkyl ethers such as ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-n-propyl ether , Propylene glycol di-n-butyl ether Propylene glycol dialkyl ethers; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono -n- propyl ether acetate, propylene glycol monoalkyl ether acetates such as propylene glycol monobutyl -n- butyl ether acetate;

  Lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate, i-propyl lactate; n-amyl formate, i-amyl formate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate , Aliphatic carboxylic acid esters such as i-butyl acetate, n-amyl acetate, i-amyl acetate, i-propyl propionate, n-butyl propionate and i-butyl propionate; ethyl hydroxyacetate, 2-hydroxy- Ethyl 2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropion Ethyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate , Esters such as 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate, ethyl pyruvate; toluene, xylene, etc. Aromatic hydrocarbons; ketones such as methyl ethyl ketone, 2-pentanone, 2-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone; N-methylformamide, N, N-dimethylformamide, N-methylacetamide Amides such as N, N-dimethylacetamide and N-methylpyrrolidone; and lactones such as γ-butyrolacun. In addition, these solvents may be used individually by 1 type, and 2 or more types may be mixed and used for them.

2. Method of forming resist pattern When forming a resist pattern using the positive radiation sensitive resin composition of the present invention, first, a composition solution prepared by the method described in "1.6 (F) solvent" Is applied onto a substrate such as a silicon wafer, a wafer coated with aluminum, or the like by an appropriate coating means such as spin coating, cast coating, roll coating, or the like to form a resist film. Next, if necessary, a heat treatment (hereinafter referred to as “PB”) is performed in advance at a temperature of about 70 to 160 ° C., and exposure is performed through a predetermined mask pattern. Thereafter, using an alkali developer, development is usually performed at 10 to 50 ° C. for 10 to 200 seconds, preferably at 15 to 30 ° C. for 15 to 100 seconds, particularly preferably at 20 to 25 ° C. for 15 to 90 seconds. Thus, a predetermined resist pattern can be formed. In order to stably form a fine resist pattern with high accuracy, it is preferable to perform a heat treatment (hereinafter referred to as “PEB”) for 30 seconds or more at a temperature of 70 to 160 ° C. after exposure. Here, when the temperature of the PEB is less than 70 ° C., there is a possibility that the variation in sensitivity depending on the type of the substrate is widened.

  As radiation used for exposure, for example, far ultraviolet rays such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) are preferable. The exposure conditions such as the exposure amount are appropriately selected according to the composition of the positive radiation sensitive resin composition, the type of additive, and the like.

  Preferable examples of the alkali developer include, for example, alkali metal hydroxide, ammonia, mono-, di- or tri-alkylamines, mono-, di- or tri-alkanolamines, heterocyclic amines, tetra Alkaline compounds such as alkyl ammonium hydroxides, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene are usually used. There is an alkaline aqueous solution dissolved to a concentration of 1 to 10% by mass, preferably 1 to 5% by mass, particularly preferably 1 to 3% by mass. In addition, for example, a water-soluble organic solvent such as methanol or ethanol or a surfactant can be appropriately added to the alkaline developer.

  In forming the resist pattern, a protective film can be provided on the resist film in order to prevent the influence of basic impurities contained in the environmental atmosphere.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified. Moreover, the measuring method of various physical-property values and the evaluation method of various characteristics are shown below.

[Sensitivity (mJ / cm ² )]: A resist film formed on a silicon wafer was exposed, immediately subjected to PEB, developed, washed with water, and dried to form a resist pattern. The exposure amount (optimum exposure amount) for forming an AND space pattern (1L1S) with a line width of 1: 1 was measured as sensitivity.

  [Resolution (μm)]: For the line and space pattern (1L1S), the minimum line width of the line pattern resolved by the optimum exposure dose was measured as the resolution.

  [Depth of focus (μm)]: A line formed when a resist pattern is formed by changing the depth of focus to a range of −1.0 to +1.0 μm in increments of 0.1 μm and exposing at an optimum exposure amount. The depth of focus range where the line width of the pattern falls within the range of 153 to 187 nm was measured as the depth of focus.

  [Line width variation value (nm)]: Each of the resist film having a film thickness of 250 nm and the film thicknesses changed from 250 nm to −40 nm, −30 nm, −20 nm, −10 nm, +10 nm, +20 nm, +30 nm, and +40 nm. A line-and-space pattern (1L1S) is formed with an optimum exposure amount for the resist film, and the line width of the formed line pattern is measured using a scanning electron microscope for semiconductors (trade name “S-9220 Hitachi High-Resolution FEB Length Measuring System”). And the difference between the maximum value and the minimum value of the line width was defined as the line width variation value.

  [Mass Spectrometry]: Measured using a trade name “MALDI-TOF-MS”, model number SHIMAZU / KRATOS matrix-assisted laser ionization time-of-flight mass spectrometer KOMPACT MALDI IV tDE, manufactured by Shimadzu Corporation.

[Infrared absorption spectrum (cm ⁻¹ )]: Measured using model number FT-IR 420 type, manufactured by JASCO Corporation.

  [Nuclear magnetic resonance spectrum]: Measured using model number JNM-ECA-500, manufactured by JEOL Ltd.

[Weight average molecular weight (Mw) and number average molecular weight (Mn)]: Using GPC columns manufactured by Tosoh Corporation (trade names “G2000H _XL ”, G3000H _XL , G4000H _XL, 1) and flow rate 1. Measurement was performed by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard under the analysis conditions of 0 ml / min, elution solvent tetrahydrofuran, and column temperature of 40 ° C.

  [Mw / Mn]: Calculated from the measured values of Mw and Mn.

(Synthesis Example 1)
Resorcinol (22.0 g, 200 mmol) was dissolved in ethanol (45 mL) and hydrochloric acid (15 mL) was added. This solution was ice-cooled to 5 ° C. while stirring, and 10.0 g (50 mmol) of a 50% aqueous solution of glutaraldehyde was slowly added dropwise. Then, it heated at 80 degreeC for 48 hours, and obtained yellow suspension. The suspension was poured into methanol and then filtered to isolate the precipitate. The isolated precipitate was washed with methanol three times and dried under reduced pressure at room temperature for 24 hours to obtain a powdery pale yellow solid (S) (yield: 11.2 g (yield: 79%)).

The structure of the obtained pale yellow solid (S) was confirmed by ¹ H-NMR analysis of mass spectrometry, infrared absorption spectrum, and nuclear magnetic resonance spectrum. These results are shown below.
Mass spectrometry: it was shown that only a compound with a molecular weight of 1705 was obtained.
Infrared absorption spectrum (film method, (cm ⁻¹ )): 3406 (ν _OH ); 2931 (ν _C—H ); 1621, 1505, 1436 (ν _{C═C (aromatic)} )
¹ H-NMR (500 MHz, solvent DMSO-d ₆ , internal standard TMS): δ (ppm) = 0.86 to 2.35 (b, 12H), 3.98 to 4.22 (m, 4H), 6 0.09 to 7.42 (m, 8H), 8.65 to 9.56 (m, 8H)

  3.5 g of the obtained pale yellow solid (S) and 0.8 g of tetrabutylammonium bromide were added to 40 g of 1-methyl-2-pyrrolidone and dissolved by stirring at 70 ° C. for 4 hours. After dissolution, 3.3 g of potassium carbonate was added and stirred at 70 ° C. for 1 hour. A solution prepared by dissolving 6.9 g of 2-methyl-2-adamantyl bromoacetate in 20 g of 1-methyl-2-pyrrolidone was gradually added, followed by stirring at 70 ° C. for 6 hours. The mixture was cooled to room temperature and extracted with water and methylene chloride. The organic layer was washed 3 times with 100 mL of a 3% oxalic acid aqueous solution and twice with 100 mL of water, and the organic layer was dried over magnesium sulfate. Then, the compound (A-1) was obtained by refine | purifying with silica gel column chromatography by using hexane: ethyl acetate = 1: 4 (vol / vol) as an eluent (yield 3.2g).

The obtained compound (A-1) was subjected to ¹ H-NMR analysis of nuclear magnetic resonance spectrum analysis. As a result, compound (A-1) was selected as R among the compounds represented by general formula (6). 40 mol% of the represented group was a group represented by the formula (R-1) (2-methyl-2-adamantyloxycarbonylmethyl group), and the rest was a hydrogen atom.

In addition, the result of ¹ H-NMR is shown below.
¹ H-NMR (500 MHz, solvent DMSO-d ₆ , internal standard TMS): δ (ppm) = 0.82 to 2.40 (m, 66.4H), 3.80 to 4.52 (m, 10. 4H), 6.08-7.41 (m, 8.0H), 8.62-9.54 (m, 3.2H)

(Synthesis Example 2)
As in Synthesis Example 1, except that 4.7 g of t-butyl bromoacetate was used instead of 6.9 g of 2-methyl-2-adamantyl bromoacetate and that it was not washed with 100 mL of 3% oxalic acid aqueous solution. Compound (A-2) was obtained (yield 3.8 g).

The obtained compound (A-2) was subjected to ¹ H-NMR analysis of nuclear magnetic resonance spectrum analysis. As a result, compound (A-2) was selected as R among the compounds represented by general formula (6). 40 mol% of the group represented was a group represented by the formula (R-2) (tert-butyl-oxycarbonylmethyl group), and the rest was a hydrogen atom.

(Synthesis Example 3)
0.85 g of the pale yellow solid (S) obtained in Synthesis Example 1 and 0.19 g of tetrabutylammonium bromide were added to 6 mL of dehydrated pyridine and stirred for 1 hour. Thereafter, 5.2 g of di-t-butyl dicarbonate was gradually added and stirred at room temperature for 48 hours. After cooling to room temperature, the reaction solution was poured into 300 mL of a 3% aqueous oxalic acid solution to precipitate a solid. The obtained solid was dissolved in methylene chloride, washed three times with 100 mL of 3% aqueous oxalic acid, and then twice with 100 mL of water, and the organic layer was dried over magnesium sulfate. Then, the compound (A-3) was obtained by refine | purifying with a silica gel column chromatography by using hexane: ethyl acetate = 1: 1 (vol / vol) as an eluent (yield 1.7g).

When ¹ H-NMR analysis of nuclear magnetic resonance spectrum analysis was performed on the obtained compound (A-3), the compound (A-3) was represented as R among the compounds represented by the general formula (6). All the groups to be formed were compounds represented by the formula (R-3) (t-butoxycarbonyl group).

(Synthesis Example 4)
100 g of commercially available anthracene-9-carboxylic acid and 55 g of potassium t-butoxy were dissolved in 500 g of dimethylformamide, 100 g of t-butyl bromoacetate was further added, and the mixture was reacted at 23 ° C. for 2 hours. Thereafter, 200 g of ethyl acetate and 500 g of water were added to separate into two phases, the aqueous layer was discarded, the ethyl acetate layer was taken out and washed with water, the solvent was distilled off, and anthracene-9-carboxylic acid t- 112 g of butoxycarbonylmethyl was obtained as a yellow solid. This compound is referred to as (E-1).

(Synthesis Example 5)
140 g of p-acetoxystyrene, 50 g of pt-butoxystyrene, 9 g of 2,5-dimethylhexane-2,5-diacrylate, 8 g of azobisisobutyronitrile, and 6 g of t-dodecyl mercaptan are added with 240 g of propylene glycol monomethyl ether. The polymer was polymerized for 16 hours while maintaining the reaction temperature at 70 ° C. in a nitrogen atmosphere. After the polymerization, the reaction solution was dropped into 2,000 g of n-hexane for reprecipitation, and the precipitate was dried at 50 ° C. under reduced pressure for 3 hours. After 190 g of the dried precipitate was dissolved again in 150 g of propylene glycol monomethyl ether, 300 g of methanol, 100 g of triethylamine, and 15 g of water were added, and a hydrolysis reaction was performed for 8 hours while refluxing at the boiling point. After the reaction, the solvent and triethylamine were distilled off under reduced pressure, and the resulting solid was redissolved in acetone so that the solid concentration was 20%, and then dropped into 2,000 g of water to reprecipitate and precipitate. The white powder was filtered off, and then dried at 50 ° C. under reduced pressure overnight to obtain (C-1) resin.

The obtained (C-1) resin had Mw of 40,000 and Mw / Mn of 2.6. As a result of ¹³ C-NMR analysis of nuclear magnetic resonance spectrum analysis, p-hydroxystyrene, p- It was a copolymer in which the molar ratio of repeating units derived from t-butoxystyrene and 2,5-dimethylhexane-2,5-diacrylate was 67: 30: 3.

(Synthesis Example 6)
100 g of p-acetoxystyrene, 25 g of tert-butyl acrylate, 18 g of styrene, 6 g of azobisisobutyronitrile, 1 g of t-dodecyl mercaptan, and 260 g of propylene glycol monomethyl ether were used for the polymerization reaction, and the hydrolysis reaction was dried. (C-2) resin was obtained in the same manner as in Synthesis Example 5, except that 135 g of the precipitate, 150 g of propylene glycol monomethyl ether, 300 g of methanol, 80 g of triethylamine, and 15 g of water were used.

The obtained (C-2) resin had Mw of 11,500 and Mw / Mn of 1.6. As a result of ¹³ C-NMR analysis of nuclear magnetic resonance spectrum analysis, p-hydroxystyrene, acrylic acid The copolymer had a molar ratio of repeating units derived from t-butyl and styrene of 61:19:20.

(Synthesis Example 7)
154 g of p-acetoxystyrene, 7 g of styrene, 53 g of pt-butoxystyrene, 9 g of azobisisobutyronitrile, 7 g of t-dodecyl mercaptan, and 260 g of propylene glycol monomethyl ether were used for the polymerization reaction, and the hydrolysis reaction was performed. Resin (C-3) was obtained in the same manner as in Synthesis Example 5 except that 215 g of dried precipitate, 260 g of propylene glycol monomethyl ether, 300 g of methanol, 80 g of triethylamine, and 15 g of water were used.

The obtained (C-3) resin had Mw of 16,000 and Mw / Mn of 1.7. As a result of ¹³ C-NMR analysis of nuclear magnetic resonance spectrum analysis, p-hydroxystyrene, styrene, It was a copolymer having a molar ratio of repeating units derived from pt-butoxystyrene of 72: 5: 23.

(Synthesis Example 8)
24 g of poly (p-hydroxystyrene) having an Mw of 12,000 was dissolved in 100 g of dioxane, and bubbled with nitrogen gas for 30 minutes. Thereafter, 5 g of ethyl vinyl ether and 1 g of p-toluenesulfonic acid pyridinium salt as a catalyst were added to this solution and reacted at room temperature for 12 hours. Next, the reaction solution was dropped into a 1% aqueous ammonia solution to precipitate a polymer, filtered, and then dried at 50 ° C. under reduced pressure overnight to obtain (C-4) resin.

The obtained (C-4) resin had Mw of 15,000 and Mw / Mn of 1.7. As a result of ¹³ C-NMR analysis of nuclear magnetic resonance spectrum analysis, poly (p-hydroxystyrene) was obtained. It was a copolymer having a structure in which 35 mol% of hydrogen atoms in the phenolic hydroxyl group were substituted with 1-ethoxyethyl group.

Example 1
10 parts of the compound (A-1) obtained in Synthesis Example 1, 9 parts of N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, Synthesis Example 7 100 parts of (C-3) resin and 0.5 part of N- (t-butoxycarbonyl) 2-phenylbenzimidazole obtained in 1 above were dissolved in 990 parts of ethyl lactate and 420 parts of propylene glycol monomethyl ether acetate to obtain a homogeneous solution. Then, it was filtered through a membrane filter having a pore diameter of 200 nm to prepare a composition solution. Next, in the trade name “Clean Track ACT-8” (manufactured by Tokyo Electron Co., Ltd.), the prepared composition solution was spin-coated on a silicon wafer, and PB was performed under the conditions shown in Table 2 so that the film thickness was 250 nm. A resist film was formed. Thereafter, the product name “scanner NSR-S203B” (manufactured by Nikon Corporation, numerical aperture = 0.68, σ = 0.75) was used for exposure through a binary mask, and PEB was performed under the conditions shown in Table 2. After the exposure, a 2.38% tetramethylammonium hydroxide aqueous solution was used and developed by a paddle method using an LD nozzle at 23 ° C. for 30 seconds, washed with pure water, and dried to form a resist pattern.

The sensitivity of the formed resist pattern was 35 mJ / cm ² , the resolution was 0.15 μm, the depth of focus was 0.9 μm, and the line width variation value was 75 nm.

(Examples 2-5 and Comparative Examples 1-2)
A resist pattern was formed in the same manner as in Example 1 except that the components and blending amounts shown in Table 1 were used and the resist pattern formation conditions shown in Table 2 were used. Table 2 shows the resist pattern formation conditions and the evaluation results of the resist pattern.

  Details of (B) the radiation sensitive acid generator, (D) the acid diffusion controller, and (F) the solvent described in Table 1 are as follows.

Radiation sensitive acid generator (B)
B-1: Bis (p-fluorophenyl) iodonium 10-camphorsulfonate B-2: N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide B -3: triphenylsulfonium trifluoromethanesulfonate B-4: N-[(5-methyl-5-carboxymethylbicyclo [2.2.1] heptan-2-yl) sulfonyloxy] succinimide B-5: bis (1 , 4-Dioxaspiro [4.5] decane-7-sulfonyl) diazomethane

(D) Acid diffusion controller D-1: N- (t-butoxycarbonyl) 2-phenylbenzimidazole D-2: Trioctylamine

(F) Solvent S-1: Ethyl lactate S-2: Propylene glycol monomethyl ether acetate

  The positive-type radiation-sensitive resin composition of the present invention can be used very suitably in the field of microfabrication represented by the manufacture of integrated circuit elements that are expected to be further miniaturized in the future.

Claims (9)

(A) a compound represented by the following general formula (1),
A positive-type radiation-sensitive resin composition containing (B) a radiation-sensitive acid generator, and (C) an alkali-insoluble or alkali-insoluble resin having an acid-dissociable group.

(In the general formula (1), R independently represents a hydrogen atom or a monovalent acid-dissociable group. X independently represents a substituted or unsubstituted alkylene having 1 to 8 carbon atoms. Y represents, independently of each other, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, or a substituted or unsubstituted group having 2 to 10 carbon atoms. An alkynyl group, a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenoxy group, q independently of each other , 0 or 1) The resin (C) has a repeating unit represented by the following general formula (2) and a repeating unit represented by at least one of the following general formula (3) and the following general formula (4). The positive radiation sensitive resin composition described in 1.

(In the general formula (2), R ¹ represents a hydrogen atom or a methyl group, R ² independently represents a monovalent organic group, m represents an integer of 0 to 3, and n represents 1 Represents an integer of ˜3, wherein R ² excludes a group corresponding to —OR ⁵ in the general formula (3), and R ³ represents a hydrogen atom or a methyl group in the general formula (3). R ⁴ independently represents a monovalent organic group, R ⁵ independently represents a monovalent acid-dissociable group, p represents an integer of 0 to 3, and r represents shows 1-3 integers. However, ^{R 4} excluding a group corresponding to -OR ^5. Furthermore, in the general formula (4), ^{R 6} represents a hydrogen atom or a methyl group, ^{R 7} is a monovalent Indicates an acid dissociable group.) The monovalent acid dissociable group represented by R in the general formula (1) is a group represented by the following general formula (5-1) or (5-2). A positive-type radiation-sensitive resin composition.

(In the general formula (5-1), R ⁸ represents a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 40 carbon atoms, which may contain a hetero atom, and s is Represents an integer of 0 to 3. In the general formula (5-2), R ⁹ is a linear or branched group having 1 to 40 carbon atoms which is substituted or unsubstituted by a substituent which may contain a hetero atom, or A cyclic alkyl group, and R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) The positive radiation sensitive resin composition according to any one of claims 1 to 3, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (6).

(In the general formula (6), R independently represents a hydrogen atom or a monovalent acid-dissociable group.) 5. The positive electrode according to claim 4, wherein in the general formula (6), the monovalent acid-dissociable group represented by R is a group represented by the following general formula (5-1) or (5-2). Type radiation sensitive resin composition.

(In the general formula (5-1), R ⁸ represents a substituted or unsubstituted linear, branched or cyclic alkyl group having 1 to 40 carbon atoms, which may contain a hetero atom, and s is Represents an integer of 0 to 3. In the general formula (5-2), R ⁹ is a linear or branched group having 1 to 40 carbon atoms which is substituted or unsubstituted by a substituent which may contain a hetero atom, or A cyclic alkyl group, and R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.) In the general formula (5-1), R ⁸ is a t-butyl group, a 2-methyl-2-adamantyl group, a 2-ethyl-2-adamantyl group, a 1-ethylcyclopentyl group, or a 1-methylcyclopentyl group. The positive radiation sensitive resin composition according to claim 3 or 5, wherein s is 0 or 1. In the general formula (5-2), R ⁹ is an adamantyl group and R ¹⁰ is a hydrogen atom or a methyl group, or R ⁹ is a 2-methyl-2-adamantyl group or 2-ethyl-2-adamantyl group. The positive radiation-sensitive resin composition according to claim 3, wherein R is a group and R ¹⁰ is a methyl group. The radiation sensitive acid generator (B) is
The positive radiation-sensitive resin composition according to claim 1, which is at least one compound selected from the group consisting of an onium salt, a diazomethane compound, and a sulfonimide compound.   (D) The positive radiation sensitive resin composition according to any one of claims 1 to 8, further comprising an acid diffusion controller.