WO2006082856A1

WO2006082856A1 - Negative resist composition and method of forming resist pattern

Info

Publication number: WO2006082856A1
Application number: PCT/JP2006/301679
Authority: WO
Inventors: Takako Hirosaki; Taku Hirayama; Daiju Shiono
Original assignee: Tokyo Ohka Kogyo Co., Ltd.
Priority date: 2005-02-02
Filing date: 2006-02-01
Publication date: 2006-08-10
Also published as: TW200632550A; TWI294557B; KR100996398B1; KR20070090268A; JP4327107B2; JP2006215164A

Abstract

A negative resist composition that is highly sensitive and is capable of forming a resist pattern of high resolution; and a relevant method of forming a resist pattern. The negative resist composition comprises alkali-soluble base material component (A), acid generator component (B) capable of generating an acid upon exposure and crosslinking agent (C), wherein the base material component (A) contains polyhydric phenol compound (A1) of 300 to 2500 molecular weight having two or more phenolic hydroxyls and represented by the following general formula (I).

Description

Negative resist composition and resist pattern forming method

Technical field

The present invention relates to a negative resist composition and a resist pattern forming method.

This application claims priority on February 2, 2005 based on Japanese Patent Application No. 2005-026266 filed in Japan, the contents of which are incorporated herein by reference.

Background art

In recent years, in the manufacture of semiconductor elements and liquid crystal display elements, pattern miniaturization has rapidly progressed due to advances in lithography technology.

As a technique for miniaturization, the wavelength of an exposure light source is generally shortened. Specifically, the power used in the past, typically ultraviolet rays such as g-line and i-line, has now begun mass production of semiconductor devices using KrF excimer laser and ArF excimer laser. In addition, these excimer lasers have shorter wavelength excimer lasers, electron beams, EUV (

2

Extreme ultraviolet rays) and X-rays are also being studied.

[0003] Further, as one of the pattern forming materials capable of forming a pattern with a fine dimension, a chemical amplification type containing a base material component having a film forming ability and an acid generator component that generates an acid upon exposure to light. Resists are known. Chemically amplified resists are classified into a negative type in which alkali solubility is reduced by exposure and a positive type in which alkali solubility is increased by exposure.

Conventionally, polymers have been used as the base component of chemically amplified resists. For example, polyhydroxystyrene (PHS) and PHS-based resins such as resins in which a part of the hydroxyl groups are protected with acid dissociable, dissolution inhibiting groups. Fatty acid, copolymers derived from (meth) acrylic acid esters, and rosin or the like in which a part of its force oxy group is protected with an acid dissociable, dissolution inhibiting group are used. For example, negative-type chemically amplified resists are generally used that contain an alkali-soluble resin such as PHS, an acid generator component, and a cross-linking agent. By the action of the acid generated from the components, cross-linking occurs between the resin and the cross-linking agent, which changes from alkali-soluble to alkali-insoluble.

However, when a pattern is formed using such a pattern forming material, There is a problem that roughness occurs on the surface of the upper surface or the side wall. For example, the roughness of the resist pattern side wall surface, that is, the line edge roughness (LER), causes distortion around the hole in the hole pattern and variations in the line width in the line and space pattern. It may adversely affect Such a problem becomes more serious as the pattern size is smaller. For this reason, for example, in lithography using an electron beam or EUV, an extremely low roughness exceeding the current pattern roughness is required due to the ability to form a fine pattern of several lOnm.

However, polymers generally used as substrates have a large molecular size (average square radius per molecule) of around several nm. In the patterning development process, the dissolution behavior of the resist in the developing solution is usually carried out in units of one molecular component of the base material. Therefore, as long as a polymer is used as the base material component, further reduction in roughness is extremely difficult.

To solve these problems, resists using low molecular weight materials as base materials have been proposed as materials aiming for extremely low roughness. For example, Patent Documents 1 and 2 propose a low molecular weight material having an alkali-soluble group such as a hydroxyl group and partially or entirely protected with an acid dissociable, dissolution inhibiting group.

Patent Document 1: JP 2002-099088

Patent Document 2: JP 2002-099089 A

Disclosure of the invention

Problems to be solved by the invention

Currently, in order to cope with the ever-increasing power of pattern miniaturization and the reduction of light source intensity due to the shorter wavelength of the exposure light source, as well as the ability to improve throughput, resists are required to have higher sensitivity. It has been. In particular, improvement of sensitivity is important for processes using electron beams and EUV.

However, with conventional technology, it is difficult to achieve both high sensitivity and high resolution. For example, as a method for realizing high sensitivity of the resist, a method of increasing the concentration of the acid generator in the chemically amplified resist can be considered. However, in conventional chemical amplification type resists, there is a tendency for the resolution to decrease when a high concentration acid generator is added, so it is difficult to add a high concentration acid generator. Has its limits. The present invention has been made in view of the above circumstances, and an object thereof is to provide a resist composition and a resist pattern forming method capable of forming a resist pattern with high sensitivity and high resolution.

Means for solving the problem

As a result of intensive studies, the present inventors have found that the above problems can be solved by a negative resist composition containing a polyvalent phenolic compound having a specific structure and molecular weight, and completed the present invention. I let you.

That is, the first aspect (aspect) of the present invention includes an alkali-soluble substrate component (A), an acid generator component (B) that generates an acid by exposure, and a crosslinking agent component (C). A negative resist composition comprising:

The substrate component (A) contains a polyvalent phenol compound A1) represented by the following general formula (I), having two or more phenolic hydroxyl groups and having a molecular weight of 300 to 2500. A negative resist composition.

[0007] [Chemical 1]

(I)

[In the formula (I), R "to R" each independently represents an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group, and may contain a hetero atom in the structure thereof; Each independently represents an integer of 1 or more, k, q is 0 or an integer of 1 or more, and g + j + k + q is 5 or less; h is an integer of 1 or more, and 1, m is Each independently 0 or an integer greater than or equal to 1 and less than h + 1 + m force; i is an integer greater than or equal to 1, n and o are each independently 0 or 1 And i + n + o is 4 or less; p is 0 or 1; X is a group represented by the following general formula (la) or (lb). ]

[Chemical 2]

((l)

[In the formula (la), R 1 and R ¹⁹ are each independently an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group, and may contain a hetero atom in the structure thereof; r, y, z Are each independently an integer of 0 or 1 and r + y + z is 4 or less]

[0009] A second aspect of the present invention includes a step of forming a resist film on a substrate using the negative resist composition of the first aspect, a step of exposing the resist film, and developing the resist film. And a resist pattern forming method including a step of forming a resist pattern.

[0010] In the present invention, "exposure" is a concept including general irradiation of excimer laser, electron beam, ultraviolet ray, X-ray and other radiation.

The invention's effect

With the negative resist composition and the resist pattern forming method of the present invention, a resist pattern with high sensitivity and high resolution can be formed.

BEST MODE FOR CARRYING OUT THE INVENTION

[0012] [Negative resist composition]

The negative resist composition of the present invention comprises (A) an alkali-soluble substrate component (hereinafter sometimes referred to as (A) component) and (B) an acid generator component (hereinafter referred to as “acid generator”) that generates an acid upon exposure. (B) component) and (C) crosslinker component (hereinafter also referred to as component (C)).

In such a negative resist composition, when an acid is generated from the component (B) by exposure (radiation irradiation) during the formation of the resist pattern, the acid acts to react the components (A), (C) and Between Cross-linking occurs and becomes insoluble in alkali. Therefore, in the formation of a resist pattern, when the resist film having the negative resist composition strength is selectively exposed, or when exposed to heat after exposure, the exposed portion turns to insoluble force while the unexposed portion is Since the Al force remains soluble and does not change, a negative resist pattern can be formed by alkali development.

[0013] <Component (A)>

In the negative resist composition of the present invention, the component (A) is a polyhydric phenol compound having two or more phenolic hydroxyl groups and a molecular weight of 300 to 2500 represented by the general formula (I) ( A1) must be contained.

In the polyhydric phenol compound (A1), it is preferable to have 3 or more phenolic hydroxyl groups, and more preferably 4 to: LO. Thereby, good alkali solubility can be obtained.

In the general formula (I), R ^{U to} R ¹⁷ are each independently a linear, branched or cyclic alkyl group or aromatic hydrocarbon group having 1 to 10 carbon atoms.

As the alkyl group, a linear or branched lower alkyl group having 1 to 5 carbon atoms or a cyclic alkyl group having 5 to 6 carbon atoms is preferable. Examples of the lower alkyl group include linear or branched alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, and neopentyl group. Examples include an alkyl group. Examples of the cyclic alkyl group include a cyclohexyl group and a cyclopentyl group.

The aromatic hydrocarbon group preferably has 6 to 15 carbon atoms, for example, a phenyl group, a tolyl group, a xylyl group, a mesityl group, a phenethyl group, a naphthyl group, etc. These alkyl groups or The aromatic hydrocarbon group may contain a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom in its structure.

R ″ to R ¹⁷ are preferably a methyl group or a cyclohexyl group from the viewpoint of excellent effects of the present invention.

[0015] g and j are each independently an integer of 1 or more, preferably an integer of 1 or 2, and k and q are respectively Independently 0 or 1 or more, preferably an integer not exceeding 2, and g + j + k + q is 5 or less.

h is an integer of 1 or more, preferably 1 or 2, and 1, and m are each independently 0 or 1 or more, preferably an integer not exceeding 2, and less than or equal to h + 1 + m force.

i is an integer of 1 or more, preferably 1 or 2, n and o are each independently 0 or 1 or more, preferably an integer not exceeding 2, and i + n + o is 4 or less.

p is 0 or 1, preferably 1.

[0016] X is a group represented by the above general formula (la) or (lb).

Wherein (la), the alkyl group or aromatic hydrocarbon group R ^18, R ^19, the same alkyl group or an aromatic hydrocarbon group of the ¹ ~! ^ ¹ ⁷ and the like. Among these, as R ¹⁸ and R ¹⁹ , a methyl group is preferable from the viewpoint of excellent effects of the present invention.

r, y and z are each independently 0 or an integer of 1 or more, and r + y + z is 4 or less. Among these, it is preferable that r is 1 and y + z is 1.

Among these, since a high-resolution pattern with reduced roughness can be formed, it is p force, R ¹¹ is a lower alkyl group or a cycloalkyl group, and j force ^, and R ¹² is Preference is given to compounds (A1-1) which are lower alkyl groups, k is 1 and g is 1! /. In particular, a compound in which q, 1, m, n and o in compound (Al-1) are 0 and h and i are both 1 is preferable.

[0018] Examples of the polyhydric phenol compound (A1) include the following formulas (1-11), (1-12), (1-13)

) Or (1-14).

[0019] [Chemical 3]

[0020] In the present invention, the polyvalent phenolic compound (Al) has a necessary force S having a molecular weight of 300 to 2500 for the effect of the present invention, preferably ί 450 to 1500, and more preferably ί. 500-1200. In addition, when the molecular weight is within the above range, a pattern with reduced roughness can be formed, and the profile shape of the resist pattern is good.

[0021] The polyvalent phenolic compound (A1) is a material capable of forming an amorphous film by a spin coating method. Here, the spin coating method is one of commonly used thin film forming methods, and an amorphous film means an optically transparent film that does not crystallize.

Whether a polyvalent phenolic compound is a material that can form an amorphous film by spin coating depends on whether the coating formed by spin coating on an 8-inch silicon wafer is completely transparent. Can be determined. More specifically, for example, it can be determined as follows. First, for the polyhydric phenol compound, a solvent generally used as a resist solvent is used, for example, a mixed solvent of lactate ethylpropylene glycol monoethyl etherate = 40Z60 (mass ratio) , Abbreviated as ΕΜ) to a concentration of 14% by mass, and then subjected to ultrasonic treatment (dissolution treatment) using an ultrasonic cleaner, and the solution is spun onto the wafer at 1500 rpm. Coat and optionally dry beta (PAB, Post

Applied Bake) is performed at 110 ° C for 90 seconds, and in this state, whether or not an amorphous film is formed is visually determined by determining whether or not a transparent film is obtained. . A cloudy film that is not transparent is not an amorphous film.

Furthermore, it is preferable that the polyvalent phenolic compound (A1) has a stable amorphous film formed as described above. For example, after PAB, it is allowed to stand at room temperature for 2 weeks. It is preferable that a transparent state, that is, an amorphous state is maintained even after the treatment.

[0022] In the component (A), the polyhydric phenol compound (A1) may be used alone or in combination of two or more. For example, the number of hydroxyl groups and the types and numbers of substituents differ from each other. You may use a compound together. When two or more compounds are included as the polyvalent phenolic compound (A1), the closer the structure (number of hydroxyl groups, types and number of substituents, etc.) of each of a plurality of different multivalent phenolic compounds is preferred. Good.

Thereby, the effect of this invention is exhibited and roughness is also reduced.

[0023] The proportion of the polyhydric phenolic compound (A1) in component (A) is preferably more than 40% by mass, more preferably more than 50% by mass, and more preferably more than 80% by mass. There still more preferably tool rather most preferred is 100 mass ^_0/0.

[0024] The polyhydric phenolic compound (A1) can be generally produced by a well-known method, for example, by the method described in JP-A-11 199533. [0025] The component (A) further contains any resin component that has been proposed as a base material component of the chemical amplification type resist layer so far as it does not impair the effects of the present invention. . Examples of strong resin components include those proposed as base resins such as conventional chemically amplified negative resist compositions for KrF and negative resist compositions for ArF, and resist pattern formation. It can be suitably selected according to the type of exposure light source used sometimes.

[0026] In the negative resist composition of the present invention, the content of the component (A) should be adjusted according to the resist film thickness to be formed.

[0027] <Component (B)>

The component (B) is not particularly limited, and those that have been proposed as acid generators for chemical amplification resists can be used. Examples of such acid generators include onium salt-based acid generators such as ododonium salts and sulfo-um salts, oxime sulfonate-based acid generators, bisalkyl or bisarylsulfonyldiazomethanes. A wide variety of acid generators such as diazomethane acid generators such as poly (bissulfol) diazomethanes, nitrobenzilsulfonate acid generators, iminosulfonate acid generators, and disulfone acid generators are known.

[0028] Examples of the form salt-based acid generator include compounds represented by the following general formula (b-1) or (b-2).

[0029]

[Wherein R ¹ "^ ³ ", R ⁵ "to R ⁶ " each independently represents an aryl group or an alkyl group; R ⁴ "represents a linear, branched or cyclic alkyl group or a fluorinated alkyl. Represents at least one of,, ~ "represents an aryl group, and at least one of R ⁵ " to R ⁶ "represents an aryl group. ]

[0030] In formula (b-1),,, and ~ each independently represent an aryl group or an alkyl group. Among R ¹ "to R ³ ", at least one represents an aryl group. 2 or more of them are It is most preferable that all of R ^{lw to} R ³ "are aryl groups. The aryl group of R ^{lw to} R ³ " is not particularly limited, for example, it has 6 to 20 carbon atoms. An aryl group in which some or all of the hydrogen atoms may or may not be substituted with an alkyl group, an alkoxy group, a halogen atom, or the like. The aryl group is preferably an aryl group having 6 to L0 carbon atoms because it can be synthesized at a low cost. Specific examples include a phenyl group and a naphthyl group.

Examples of the alkyl group that may be substituted with the hydrogen atom of the aryl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group, which are preferably alkyl groups having 1 to 5 carbon atoms. Most preferred to be.

The alkoxy group which may be substituted with the hydrogen atom of the aryl group is most preferably a methoxy group or an ethoxy group, preferably an alkoxy group having 1 to 5 carbon atoms.

The halogen atom that may be substituted with the hydrogen atom of the aryl group is preferably a fluorine atom.

The “˜” alkyl group is not particularly limited, and examples thereof include a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. From the viewpoint of excellent resolution, the number of carbon atoms is preferably 1 to 5. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a nonyl group, A decanyl group and the like can be mentioned, and a methyl group can be mentioned as a preferable one because it is excellent in resolution and can be synthesized at low cost.

Among these, it is most preferable that all of “˜” are a phenol group.

R ⁴ ″ represents a linear, branched or cyclic alkyl group or a fluorinated alkyl group. The linear alkyl group preferably has 1 to 10 carbon atoms. Most preferably, it is 1 to 4 carbon atoms.

The cyclic alkyl group is a cyclic group as shown by the above R ¹ ″, preferably a carbon number of 4 to 15 carbon atoms, more preferably a carbon number of 4 to 10 carbon atoms. Most preferably, the number is from 6 to 10.

The fluorinated alkyl group is most preferably 1 to 4 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms. Also. The fluorination The fluorination rate of the alkyl group (ratio of fluorine atoms in the alkyl group) is preferably 10 to: L0 0%, more preferably 50 to 100%, and in particular, all hydrogen atoms are substituted with fluorine atoms However, it is preferable because the strength of the acid is increased.

R ⁴ ″ is most preferably a linear or cyclic alkyl group or a fluorinated alkyl group.

In the formula (b-2), R ⁵ ″ to R ⁶ ″ each independently represents an aryl group or an alkyl group. Of R 5, ˜˜R ⁶ , at least one represents an aryl group. All of R ⁵ ″ to R ⁶ , are preferably aryl groups.

Examples of the aryl group of R ⁵ "to R ⁶ " include the same as the aryl group of,, ~ "

Examples of the alkyl group for R ⁵ ″ to R ⁶ ″ include the same as the alkyl group for R ¹ ″ to R ³ ″. Among these, R ⁵ ″ to R ⁶ ″ are all phenyl groups. Most preferred. Those similar to - "(1 b) R ⁴ in the formula is as" the like R ⁴ of formula (b-2) in.

[0033] Specific examples of the acid salt-based acid generator include trifluoromethane sulfonate or nonafluorobutane sulfonate of diphenylodium, trifluoromethanesulfonate or nona of bis (4-tertbutylbutyl) ododonium. Fluorobutane sulfonate, triphenyl sulfone trifluoromethane sulfonate, heptafluoropropane sulfonate or nonafluorobutane sulfonate, tri (4-methylphenol) snorephonium trifanololomethane sulphonate , Its heptafluororenopropane sulfonate or its nonafluorobutane sulfonate, dimethyl (4-hydroxynaphthyl) snorephonium trifanololemethane sulfonate, its heptafluororenopropane sulfonate Or its nonafluorobutane sulfonate, monophenyl dimethyl sulfone trifluorolone methane sulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, diphenyl monomethyl sulfone. Trifluoromethane sulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, (4 methylphenol) diphenylsulfotrifluoromethane sulfonate, its heptafluoropropane sulfonate or its nonafluoro Butane sulfonate, trifluoromethane sulfonate of (4-methoxyphenyl) diphenyl sulfone, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, tri (4-tert-butyl) phenol sulfone trifluoro Chloromethane sulfonate, its heptafluoropropane sulfonate, or its nonafluorobutane sulfonate, diphenyl (1- (4-methoxy) naphthyl) sulfo-trifluoromethane sulfonate, its heptafluoropropane sulfonate or Nonafluorobutane sulfonate and the like can be mentioned. In addition, ohmic salts in which the ionic part of these ohmic salts is replaced with methane sulfonate, n-propane sulfonate, n-butane sulfonate, or n-octane sulfonate can be used.

[0034] Further, in the general formula (b-1) or (b-2), the anion part is replaced with a caron part represented by the following general formula (b-3) or (b-4) (The cation moiety is the same as (b-1) or (b-2)).

[0035] [Chemical 5] so ₂ o ₂ s—Y "

/ ヽ /

"N. X" (b-3) _-N ~ (b— 4)

s ° 2 0 ₂ S—Z "

[Wherein X "represents a C 2-6 alkylene group in which at least one hydrogen atom is replaced by a fluorine atom; Υ", Ζ "each independently represents at least one hydrogen atom is fluorine. Represents an alkyl group having 1 to 10 carbon atoms substituted with an atom.

[0036] X "is a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkylene group has 2 to 6 carbon atoms, preferably 3 to 3 carbon atoms. 5 and most preferably 3 carbon atoms.

Υ "and Ζ" are each independently a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkyl group has 1 to 10 carbon atoms, preferably It is C1-C7, More preferably, it is C1-C3.

The carbon number of the alkylene group of X "or the carbon number of the alkyl group of Υ" and Ζ "should be small for reasons such as good solubility in the resist solvent within the above carbon number range. Do you like ヽ?

In addition, in the alkylene group of X "or the alkyl group of Υ" and Ζ ", the greater the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength and the higher the energy of 200 nm or less. And U is preferred because of its improved transparency to electron beams, and the proportion of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to L00%. Most preferably, it is a perfluoroalkylene group or a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.

In the present invention, the oxime sulfonate-based acid generator is a compound having at least one group represented by the following general formula (B-1), which generates an acid upon irradiation with radiation. It is what has. Such oxime sulfonate acid generators are frequently used for chemically amplified resist compositions, and can be arbitrarily selected from those used.

[0038] [Chemical 6]

… (1)

(In the formula (B-1), R ²¹ and R ²² each independently represents an organic group.)

[0039] In the present invention, the organic group is a group containing a carbon atom, and an atom other than a carbon atom (for example, a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom (a fluorine atom, a chlorine atom, etc.)). Etc. may be included.

As the organic group for R ²¹ , a linear, branched or cyclic alkyl group or aryl group is preferable. These alkyl groups and aryl groups may have a substituent. The substituent is not particularly limited, and examples thereof include a fluorine atom and a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. Here, “having a substituent” means that part or all of the hydrogen atoms of the alkyl group or aryl group are substituted with a substituent. As the alkyl group, those having 1 to 20 carbon atoms are preferred, those having 1 to 10 carbon atoms are more preferred, those having 1 to 8 carbon atoms are more preferred, and those having 1 to 6 carbon atoms are particularly preferred. Carbon The number 1 to 4 are most preferable. As the alkyl group, a partially or completely halogenated alkyl group (hereinafter sometimes referred to as a halogenated alkyl group) is particularly preferable. The partially halogenated alkyl group means an alkyl group in which a part of hydrogen atoms is substituted with a halogen atom, and the completely halogenated alkyl group means that all of the hydrogen atoms are halogen atoms. An alkyl group substituted with an atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is particularly preferable. That is, the halogenated alkyl group is preferably a fluorinated alkyl group.

The aryl group preferably has 4 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and more preferably 6 to carbon atoms: LO. As the aryl group, a partially or completely halogenated aryl group is particularly preferable. The partially halogenated aryl group means an aryl group in which a part of the hydrogen atom is substituted with a halogen atom, and the fully halogenated aryl group means a hydrogen atom. An aryl group substituted entirely with halogen atoms.

R ²¹ is particularly preferably an alkyl group having 1 to 4 carbon atoms having no substituent or a fluorinated alkyl group having 1 to 4 carbon atoms.

[0040] The organic group represented by R ²² is preferably a linear, branched or cyclic alkyl group, aryl group or cyan group. Examples of the alkyl group and aryl group for R ²² include the same alkyl groups and aryl groups as those described above for R ²¹ .

R ²² is particularly preferably a cyano group, an alkyl group having 1 to 8 carbon atoms having no substituent, or a fluorinated alkyl group having 1 to 8 carbon atoms.

[0041] More preferable examples of the oxime sulfonate acid generator include compounds represented by the following general formula (B-2) or (B-3).

[0042] [Chemical 7]

R ³² _C = N— 0—SO. -R ³³

( ^B - ²⁾

[In the formula (B-2), R ³¹ represents a cyano group, an alkyl group having no substituent, or a halogenalkyl group. R ³² is an aryl group. R ³³ is an alkyl group having no substituent or A halogenated alkyl group; ]

[0043] [Chemical 8]

[In the formula (B-3), R ³⁴ represents a cyano group, an alkyl group having no substituent, or a halogenalkyl group. R ³⁵ is a divalent or trivalent aromatic hydrocarbon group. R ³⁶ is an alkyl group having no substituent or a halogenated alkyl group. p is 2 or 3. ]

[0044] In the general formula (B-2), the alkyl group or the halogenated alkyl group having no substituent of R ³¹ is preferably a carbon having 1 to 10 carbon atoms. Those having a number of 18 are more preferred, those having a carbon number of 16 being most preferred.

R ³¹ is more preferably a fluorinated alkyl group, preferably a halogenated alkyl group.

The fluorinated alkyl group for R ³¹ preferably has 50% or more of the hydrogen atom of the alkyl group, more preferably 70% or more, and even more preferably 90% or more.

[0045] As the aryl group of R ³² , aromatic carbonization such as a phenol group, a biphenyl group, a fluorenyl group, a naphthyl group, an anthracyl group, a phenanthryl group, etc. Hydrogen ring force A group with one hydrogen atom removed, and a heteroaryl group in which some of the carbon atoms constituting the ring of these groups are substituted with a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom. Etc. Among these, a fluorenyl group is preferable.

The aryl group of R ³² may have a substituent such as an alkyl group having 110 carbon atoms, a halogenated alkyl group, or an alkoxy group, and the alkyl group or halogenated alkyl group in the substituent may have a carbon number. A carbon number of 1 to 8 is preferred, and a carbon number of 14 is more preferred. Further, the halogenoalkyl group is preferably a fluorinated alkyl group.

[0046] The alkyl group having no substituent for R ³³ or the halogenated alkyl group has 1 carbon atom. Most preferred are those having 1 to 8 carbon atoms, preferably 10 to 10 carbon atoms.

R ³³ is preferably a partially or fully fluorinated alkyl group, preferably a halogenated alkyl group.

The fluorinated alkyl group in R ³³ preferably has 50% or more of the hydrogen atoms of the alkyl group fluorinated, more preferably 70% or more, and even more preferably 90% or more. This is preferable because the strength of the acid is increased. Most preferably, it is a fully fluorinated alkyl group in which a hydrogen atom is 100% fluorine-substituted.

In the general formula (B-3), the alkyl group or halogenated alkyl group having no substituent of R ^{34 is} an alkyl group having no substituent of R ^31. Examples thereof are the same as the group or the halogenalkyl group.

Examples of the divalent or trivalent aromatic hydrocarbon group for R ³⁵ include groups in which the aryl group strength of R ³² is one or two hydrogen atoms.

Do no substituent of R ^36, the alkyl group or Harogeni spoon alkyl group, the same alkyl group or Harogeni spoon alkyl group containing no substituent group of the ³ mentioned et be.

p is preferably 2.

[0048] Specific examples of the oxime sulfonate-based acid generator include α- (ρ-toluenesulfo-luoximino) -benzyl cyanide, α- (ρ-chlorobenzenebenzenesulfo-luminoximino) -benzil cyanide, _α- (4-Nitrobenzenesulfo-luoximino) -benzyl cyanide, α- (4-Nitro-2-trifluoromethylbenzenesulfo-luoximino) -benzyl cyanide, a- (benzenesulfo-ruximino) -4 -Chronobenzyl cyanide, a-(Benzenesulfo-ruximino)-2, 4-dichlorobenzil cyanide, α-(Benzenesulfo-ruxinomino) -2, 6-dichlorobenzil cyanide, α-( Benzenesulfo-luoxyimino) -4-methoxybenzyl cyanide, α- (2-chlorobenzenesulfo-roximino) -4-methoxybenzil cyanide, a- (benzenesulfo-luo) Xyimino) -Chen-2-ylacetonitrile, a- (4-dodecylbenzenesulfo-ruximino) -benzyl cyanide, α-[(p-toluenesulfo-ruxiimino) -4-methoxyphenyl] acetonitrile, (X -[(Dodecylpen Zensulfo-Luoxyimino) -4-Methoxyphenyl] acetonitrile, α- (Tosyloxy Mino) -4-Chelocyanide, _α- (Methylsulfo-Luoxyimino) -1 -Cyclopentaylacetonitrile, (X- (Methylsulfo-Luoximino) ) - 1 - xenon cyclohexane - Ruasetonitoriru, alpha - (Mechirusuruho - Ruokishiimino) - 1 - cycloheptenylidenephenyl Saturation Rua Seto nitrile, alpha - (methylsulfonyl - Ruokishiimino) - 1 - cyclopropyl OTA Saturation Rua Seto nitrile, _alpha - (Torifuruo R-methylsulfo-luoxyimino)-1 -cyclopente-rucetonitrile, α-(trifluoromethylsulfo-luximino) -cyclohexylhexonitrile, α-(ethylsulfo-roximino)-ethylacetonitrile, _α -(Propylsulfo-luximino) -propylacetonitol, α -(Cyclohexylsulfonyloximino) -Cyclopentylacetonitrile, α-(Cyclohexylsulfo-Luximinomino) -Cyclohexylacetonitrile, H-(Cyclohexylsulfo-Luximinomino)-1 -Cyclopente-Luacetonitrile, α- (Ethylsulfo-Luoxyimino)-1 -Cyclopentaylacetonitrile, H-(Isopropylsulfoloxymino)-1 -Cyclopente-Luacetonitrile, (X-(η-Butylsulfo-Luoxyimino))-1 -Cyclopenta-Lucetonitrile, at -(Ethylsulfo-Luoxyimino)-1 -Cyclohexyl-Luacetonitrile, OC-(Isopropylsulfo-Luoxyimino)-1 -Cyclohexe-Luaceto-Tolyl, α-(η-Butylsulfo-Luoxyimino)-1 -Cyclohexi Ruase _Tonitoriru, α - (methyl (Rufo-Luoxyimino) Phenylacetonitrile, α (Methylsulfonyloximino) -ρ-methoxyphenylacetonitrile, α (Trifluoromethylsulfo-Luoxyimino) Phenylacetonitrile, α (Trifluoromethylsulfo-Luoxyimino) ρ-Methoxyphene- Examples include rubetonitrile, ひ (ethylsulfo-luoxyimino) -ρ-methoxyphenylacetonitrile, (X- (propylsulfo-luoxyimino) ρ methylphenol-nitronitrile, α (methylsulfo-luoxyimino) -ρ bromophenyl-acetonitrile.

Further, compounds represented by the following chemical formula (compound groups (i) to (iii)) can be mentioned.

(Compound group (i))

[Chemical 9] CH ₃ — 0 ₂ S— Ο—— /) ~ C ^ N—— O S0 ₂ —— CH

NC CH

C ₄ H ₉ —. ₂ S—— O—— N = C- C = N- 0—— S. ₂ ——C ₄ H ₉

CN CN

[0050] Of the compounds represented by the general formula (B--2) or (B-3), preferred examples of the compounds are shown below.

[0051] (Compound group (ii))

[Chemical 10]

(Compound group (iii))

[Chemical 11]

C = N— 0— S0 ₂ — C ₄ F _g

[0053] Among the above exemplified compounds, the following three compounds (iv), (v) and (vi) are preferable.

[0054] [Chemical 12]

(iv)

[0055] [Chemical 13]

(v)

[0056] [Chemical 14]

~ (Vi)

[0057] Among diazomethane acid generators, specific examples of bisalkyl or bisarylsulfol diazomethanes include bis (isopropylsulfol) diazomethane, bis (p-toluenesulfol) diazomethane, bis ( 1,1-dimethylethylsulfol) diazomethane, bis (cyclohexylsulfol) diazomethane, bis (2,4-dimethylphenylsulfol) diazomethane and the like.

Examples of poly (bissulfonyl) diazomethanes include 1,3-bis (phenylsulfodiazomethylsulfo) propane (A = 3) having the following structure (vii) or (viii): ), 1, 4-bis (phenylsulfol diazomethylsulfol) butane (when A = 4), 1,6-bis (phenolsulfol diazomethylsulfol) Xane (when A = 6), 1,10-bis (phenylsulfol diazomethylsulfo) decane (when A = 10), 1,2-bis (cyclohexylsulfol diazomethyl) Sulfo-l) ethane (when B = 2), 1,3-bis (cyclohexylsulfodiazomethylsulfol) propan (when B = 3), 1,6-bis (cyclohexylsulfo) -Luazomethylsulfol) Hexane (when B = 6), 1,10-bis (cyclohexylsulfoldiazo) Chirusuru e - Le) if the decane (B = 10) and the like.

[0058] [Chemical 15]

[0059] In the present invention, it is preferable to use, as the component (B), a fluorinated alkyl sulfonate ion or an aluminum salt having an alkyl sulfonate ion as a cation.

[0060] As the component (B), one type of acid generator may be used alone, or two or more types may be used in combination.

The content of the component (B) is 0.5 to 30 parts by mass, preferably 1 to 15 parts by mass, and most preferably 5 to LO parts by mass with respect to 100 parts by mass of the component (A). By setting the above range, the pattern is sufficiently formed. Further, it is preferable because a uniform solution can be obtained and the storage stability becomes good.

[0061] <Component (C)>

The component (C) is not particularly limited, and can be arbitrarily selected from cross-linking agents used in conventionally known chemically amplified negative resist compositions.

Specifically, for example, 2, 3 dihydroxy 5 hydroxymethylnorbornane, 2 hydroxy-1,5-bis (hydroxymethyl) norbornane, cyclohexanedimethanol, 3, 4, 8 (or 9) -trihydroxytricyclo Aliphatic cyclic hydrocarbons having a hydroxyl group and / or a hydroxyalkyl group such as decane, 2-methyl-2-adamantanol, 1,4 dioxane-1,2,3 diol, 1,3,5 trihydroxycyclohexane And elemental oxygen-containing derivatives thereof.

[0062] Further, an amino group-containing compound such as melamine, acetateguanamine, benzoguanamine, urea, ethylene urea, propylene urea, glycoluril is reacted with formaldehyde or formaldehyde and a lower alcohol, and the hydrogen atom of the amino group is converted to a hydroxymethyl group. Or a compound substituted with a lower alkoxymethyl group.

Of these, those using melamine are melamine-based crosslinking agents, and those using urea are urea-based A cross-linking agent using an alkylene urea such as ethylene urea or propylene urea is called an alkylene urea cross-linking agent, and a glycoluril using a glycoluril cross-linking agent.

Component (C) is preferably at least one selected from the group consisting of melamine crosslinking agents, urea crosslinking agents, alkylene urea crosslinking agents, and glycoluril crosslinking agents. An agent or a glycoluril-based crosslinking agent is more preferable, and a glycoluril-based crosslinking agent is particularly preferable.

[0063] As the melamine-based cross-linking agent, melamine and formaldehyde are reacted, and a compound in which the hydrogen atom of the amino group is substituted with a hydroxymethyl group, melamine, formaldehyde and lower alcohol are reacted. Examples thereof include compounds in which a hydrogen atom of an amino group is substituted with a lower alkoxymethyl group. Specific examples include hexamethoxymethyl melamine, hexethoxymethyl melamine, hexapropoxymethyl melamine, hexasuboxybutyl melamine, etc. Among them, hexamethoxymethyl melamine is preferred!

[0064] The urea-based cross-linking agent includes a compound in which urea and formaldehyde are reacted to replace the hydrogen atom of the amino group with a hydroxymethyl group, and urea, formaldehyde and lower alcohol are reacted to form a hydrogen in the amino group. And compounds in which the atom is substituted with a lower alkoxymethyl group. Specific examples include bismethoxymethylurea, bisethoxymethylurea, bispoxoxymethylurea, bisbutoxymethylurea, and the like. Among them, bismethoxymethylurea is preferable.

[0065] Examples of the alkylene urea crosslinking agent include compounds represented by the following general formula (III).

[0066] [Chemical 16]

(III)

(Wherein R ¹ ′ and R ² ′ are each independently a hydroxyl group or a lower alkoxy group, R ³ ′ R ⁴ ′ are each independently a hydrogen atom, a hydroxyl group or a lower alkoxy group, and V is 0, 1 or In 2 is there. )

[0067] When R ¹ 'and R ² ' are lower alkoxy groups, they are preferably alkoxy groups having 1 to 4 carbon atoms, which may be linear or branched. R ¹ ′ and R ² may be the same or different from each other. More preferably, they are the same.

When R ³ ′ and are lower alkoxy groups, they are preferably alkoxy groups having 1 to 4 carbon atoms, which may be linear or branched. R ³ 'and R ⁴ may be the same or different from each other. More preferably, they are the same.

V is 0, 1 or 2, preferably 0 or 1.

As the alkylene urea cross-linking agent, a compound in which V is 0 (ethylene urea cross-linking agent) and a compound in which Z or V is 1 (propylene urea cross-linking agent) are particularly preferable!

[0068] The compound represented by the general formula (III) can be obtained by a condensation reaction of alkylene urea and formaldehyde, and by reacting this product with a lower alcohol.

[0069] Specific examples of the alkylene urea-based crosslinking agent include, for example, mono- and Z- or dihydroxymethyl-modified styrene urea, mono- and Z- or dimethoxymethyl-modified styrene urea, mono- and Z- or diethoxymethyl-modified styrene urea, mono- and z or dipropoxymethylated ethylene urea, mono and Z or dibutoxymethyl ethylene ethylene urea and other crosslinking agents; mono and Z or dihydroxymethyl propylene urea, mono and Z or dimethoxymethylated propylene urea, Propylene urea crosslinkers such as mono and z or diethoxymethylated propylene urea, mono and Z or dipropoxymethylated propylene urea, mono and Z or dibutoxymethylated propylene urea; 1,3-di (methoxymethyl) -4,5-dihydroxyl 2-imidazolidinone, 1,3-di (methoxy Methyl) -1,4,5-dimethoxy-1-2-imidazolidinone.

[0070] Examples of the glycoluril-based crosslinking agent include glycoluril derivatives in which the N-position is substituted with one or both of a hydroxyalkyl group and an alkoxyalkyl group having 1 to 4 carbon atoms. Powerful glycoluril derivatives can be obtained by the condensation reaction of glycoluril and formaldehyde and by reacting this product with a lower alcohol. Specific examples of the glycoluril-based crosslinking agent include, for example, mono, di, tri and z or tetrahydroxymethyl glycol glycol, mono, di, tri and / or tetramethoxymethyl glycoluril, mono, di, Examples include tri- and / or tetraethoxymethylated glycoluril, mono-, di-, tri- and / or tetrapropoxymethylethyl glycoluril, mono-, di-, tri- and / or tetrabutoxymethyl-glycoluril and the like.

[0071] As the component (C), one type may be used alone, or two or more types may be used in combination.

The blending amount of the component (C) is most preferably 3 15 parts by mass, more preferably 5 15 parts by mass, more preferably 3 30 parts by mass with respect to 100 parts by mass of component (A). When the content of component (C) is at least the lower limit value, crosslinking formation proceeds sufficiently and a good resist pattern can be obtained. On the other hand, if it is less than or equal to this upper limit, the storage stability of the resist coating solution is good, and the deterioration of sensitivity over time is suppressed.

[0072] <Other optional components>

The negative resist composition of the present invention is further optional in order to improve the resist pattern shape, post exposure stability of the latent image formed oy the pattern-wise exposure of the resist layer, etc. As the component, nitrogen-containing organic compound (D) (hereinafter referred to as component (D)) can be blended.

A variety of components (D) have already been proposed, and any known component can be used arbitrarily. For example, n-hexylamine, n-ptylamine, n-octylamine, n-norlamin, n- Monoalkylamines such as decylamine; dialkylamines such as jetylamine, di-n-propylamine, di-n-ptylamine, di-n-octylamine, dicyclohexyl-lamine; trimethylamine, triethylamine, tri- _n -propylamine, trie Trialkylamines such as _n- butylamine, tri- _n- xylamine, tri- _n- pentylamine, tri- _n- ptylamamine, tri- _n- octylamine, tri- _n- nonylamine, tri- _n -de-force-lamine, tri- _n -dodecylamine; diethanolamine Min, Triethanolamine, Diisopropanol Min, triisopropanolamine § Min, di one n- OTA Tanoruamin, alkyl alcohols § Min such tree n- O click pentanol § Min like et be. Of these, secondary aliphatic amines are especially preferred for tertiary aliphatic amines. Tri-n-octylamine is most preferred, with trialkylamines having a prime number of 5 to 10 being more preferred.

These can be used alone or in combination of two or more.

Component (D) is usually used in the range of 0.01 to 5.0 parts by mass per 100 parts by mass of component (A).

[0073] In the negative resist composition of the present invention, the deterioration of sensitivity due to the blending of the component (D) is prevented, and the resist pattern shape and stability over time (post exposure stability of the late nt image formed by the pattern) For the purpose of improving -wise exposure of the resist layer), an organic carboxylic acid or oxo acid of phosphorus or a derivative thereof (E) (hereinafter referred to as (E) component) can be further contained as an optional component. . The component (D) and the component (E) can be used together, or one of them can be used.

As the organic carboxylic acid, for example, malonic acid, citrate, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable.

Phosphoric acid or its derivatives include phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid diphenol ester and other phosphoric acid or derivatives such as those esters, phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid Phosphonic acid such as n-butyl ester, phenol phosphonic acid, diphosphoric phosphonic acid ester, dibenzyl phosphonic acid ester and derivatives thereof, phosphinic acid such as phosphinic acid, phenol phosphinic acid and the like And derivatives such as esters, of which phosphonic acid is particularly preferred.

Component (E) is used in a proportion of 0.01 to 5.0 parts by mass per 100 parts by mass of component (A).

[0074] In the negative resist composition of the present invention, there are further additives that are miscible as desired, for example, an additional grease for improving the performance of the resist film, and a surfactant for improving the coating property. Further, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, an antihalation agent, a dye, and the like can be appropriately added and contained.

[0075] Organic solvent>

The negative resist composition of the present invention can be produced by dissolving the components (A), (B) and (C), and various optional components in an organic solvent. Any organic solvent can be used as long as it can dissolve each component used to form a uniform solution. Any conventionally known solvent for chemically amplified resists can be used.

One type or two or more types can be appropriately selected and used.

For example, latones such as γ-butyrolatatane, ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol Polyhydric alcohols such as monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, or monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether of dipropylene glycol monoacetate and derivatives thereof, Cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, pyrubi Acid Echiru, methyl methoxypropionate, and the like esters such as ethoxy propyl propionic acid Echiru.

These organic solvents can be used alone or as a mixed solvent of two or more. A mixed solvent obtained by mixing propylene glycol monomethyl ether acetate (PGMEA) and a polar solvent is preferable. The mixing ratio (mass ratio) may be appropriately determined in consideration of the compatibility between PGMEA and the polar solvent, but is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2. Within range.

More specifically, when EL is blended as a polar solvent, the mass ratio of PGMEA: EL is preferably 1: 9 to 9: 1, more preferably 2: 8 to 8: 2.

In addition, as the organic solvent, a mixed solvent of at least one selected from among PGMEA and EL and γ-petit-mouth rataton is also preferable. In this case, the mixing ratio of the former and the latter is preferably 70: 30-95: 5.

The amount of the organic solvent used is not particularly limited, but it is a concentration that can be applied to a substrate and the like, and is appropriately set according to the coating film thickness. Generally, the solid content concentration of the resist composition is 2 to 20 mass. %, Preferably 5-15% by mass.

[Resist pattern formation method]

The resist pattern forming method of the present invention uses the negative resist composition of the present invention. Forming a resist film on the substrate, exposing the resist film, and developing the resist film to form a resist pattern.

More specifically, for example, a resist pattern can be formed by the following resist pattern forming method. That is, first, a negative resist composition is applied onto a substrate such as a silicon wafer with a spinner or the like, and optionally pre-beta (PAB) is applied to form a resist film. The formed resist film can be selectively used, for example, by exposure through a mask pattern using an exposure apparatus such as an electron beam drawing apparatus or EUV exposure apparatus, or by drawing by direct irradiation of an electron beam without using a mask pattern. After exposure, apply PEB (post-exposure heating).

Subsequently, after developing with an alkali developer, a rinsing treatment is performed to wash away the image solution on the substrate and the resist composition dissolved by the developer, and dry to obtain a resist pattern.

These steps can be performed using a known method. The operating conditions and the like are preferably set as appropriate according to the composition and characteristics of the negative resist composition to be used.

The exposure light source is not particularly limited. ArF excimer laser, KrF excimer laser, F

2 Can be performed using radiation such as excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), electron beam, X-ray, soft X-ray. In particular, the negative resist composition useful in the present invention is effective for electron beams or EUV, particularly electron beams.

In some cases, a post-beta step after the alkali development may be included, and an organic or inorganic antireflection film may be provided between the substrate and the resist film.

As described above, according to the negative resist composition of the present invention and the resist pattern forming method using the negative resist composition, a resist pattern with high sensitivity and high resolution can be formed. The reason for this is that the polyhydric phenol compound (A1) has a high alkali solubility, the alkali solubility is not easily influenced by other components in the resist such as the component (B), and the polyhydric phenolic compound. It is conceivable that the cross-linking reactivity between the compound (A1) and the component (C) is high, and that the polyvalent phenolic compound (A1) has a self-crosslinking property.

That is, in the conventional resist using rosin as the (A) component, the (B) component is immediately affected by the (B) component etc. Increasing the blending amount of the resist tends to lower the resist solubility, lower the resolution, and make it impossible to form a resist pattern, and the limit on the amount of component (B) added is large. On the other hand, in the present invention, even if the amount of the component (B) having high alkali solubility is increased, sufficient resolution can be achieved because the resolution is sufficient, and crosslinking with the component (C) is possible. Because of its high reactivity and self-crosslinking property, the exposed area rapidly becomes alkali-insoluble. Therefore, it is estimated that a resist pattern with high sensitivity and high resolution can be formed.

Further, in the present invention, since the polyvalent phenolic compound (A1) is a low molecular compound, a reduction in roughness can be expected.

Example

Examples of the present invention will be described below, but the scope of the present invention is not limited to these examples.

Examples 1-6, Comparative Example 1

Each component shown in Table 1 was mixed and dissolved to obtain a negative resist composition solution.

[0079] [Table 1]

[0080] In Table 1, the values in [] indicate the blending amount (parts by mass).

Compound 1 (manufactured by Honshu Chemical Industry Co., Ltd.), compound 2 (manufactured by Honshu Chemical Industry Co., Ltd.), BINDER1-3 (manufactured by Sanwa Chemical Co., Ltd.): Compounds having the structure shown below. Average molecular weight 3600, dispersity 2.0, manufactured by Nippon Soda Co., Ltd.) PAG1: Triphenylsulfurumnonafluorobutanesulfone

Amine 1: Tory n—Octylamine

ADD 1: Salicylic acid

PGME: Propylene glycol monomethyl ether

[Chemical 17]

The following evaluation was performed using the obtained negative resist composition solution in B Γ K D E R 1 B I N D E R 2 B I N D E R 3

The negative resist composition solution was uniformly applied on an 8-inch silicon substrate using a spinner, and beta treatment (PAB) was performed at 100 ° C. for 90 seconds to form a resist film (thickness 125 nm).

The resist film is drawn (exposure) using an electron beam lithography machine HL-800D (VSB) (manufactured by Hitachi) at an acceleration voltage of 70 kV, and beta treatment (PEB for 90 seconds at 110 ° C). ) and have rows, tetramethylammonium - after development for 60 seconds using a 2.38 mass ^_0/0 aqueous solution of Umuhidorokishido (TMAH) (23 ° C) , were rinsed for 30 seconds with pure water .

As a result, in Examples 1 to 6, the 50 nm isolated space pattern and the 50 nm 1: 1 An in-and-space (LZS) pattern was formed.

On the other hand, in Comparative Example 1, the resist in the space portion was not completely removed, and an isolated space pattern of 50 nm could not be formed.

The exposure dose (μ C / crn) for forming an isolated space pattern of 50 nm was determined.

These results are shown in Table 2.

[Table 2]

As apparent from the above results, in Examples 1 to 6, a resist pattern with high sensitivity and high resolution could be formed. In particular, Examples 1, 3, 4, and 6 using BINDER 1 or 3 were particularly sensitive.

On the other hand, in Comparative Example 1 using rosin 1 as the component (A), a 50 nm pattern could not be formed.

Industrial applicability

The negative resist composition and the resist pattern forming method of the present invention can form a resist pattern having high sensitivity and high resolution, and can be applied to the formation of a negative resist composition and a resist pattern. .

Claims

Claims [1] A negative resist composition comprising an alkali-soluble substrate component (A), an acid generator component (B) that generates an acid upon exposure, and a crosslinking agent component (C), The base material component (A) contains a polyhydric phenol compound (A1) represented by the following general formula (I), having two or more phenolic hydroxyl groups and having a molecular weight of 300 to 2500. Features a negative resist composition.

[Chemical 1]

(I)

[In the formula (I), R ″ to R ¹⁷ are each independently an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group, and the structure thereof may contain a hetero atom; Each independently represents an integer of 1 or more, k, q is 0 or an integer of 1 or more, and g + j + k + q is 5 or less; h is an integer of 1 or more, and 1, m is Each independently an integer of 0 or 1 and less than or equal to h + 1 + m force; i is an integer of 1 or more, n and o are each independently an integer of 0 or 1 and i + n + o is 4 or less; p is 0 or 1; X is a group represented by the following general formula (la) or (lb).]

[Chemical 2]

[2] The negative resist composition according to claim 1, further comprising a nitrogen-containing organic compound (D).

[3] A step of forming a resist film on a substrate using the negative resist composition according to claim 1 or 2, a step of exposing the resist film, and developing the resist film to form a resist pattern A resist pattern forming method including the step of: