KR20120104950A - Resist composition, and resist film and pattern forming method for using the same - Google Patents

Abstract

PURPOSE: A resist composition, a resist film using the composition, and a pattern forming method using the composition are provided to include a resin, of which dissolution speed to a developer is changed by the action of acid. CONSTITUTION: A resist composition includes a resin with a cycloaliphatic structure, a compound generating acid by the irradiation of active rays or radiation rays, and a compound represented by chemical formula EA. The dissolution speed of the resin to a developer is changed by the action of acid. In chemical formula EA, o, p, and q are the integer of 1 or more; n is the integer of 3 or more; r and s are the integer of 1 or more; t is the integer of 0 or more; R1 and R2 are respectively hydrogen groups, alkyl groups, aryl groups, or aralkyl groups; R3 is a hydrogen group, an alkyl group, an aryl group, or an aralkyl group if t is 1 or more; R3 is an alkyl group, an aryl group, or an aralkyl group if t is 0.

Description

Resist composition, resist film and pattern formation method using the same {RESIST COMPOSITION, AND RESIST FILM AND PATTERN FORMING METHOD FOR USING THE SAME}

The present invention relates to a resist composition, a resist film and a pattern forming method using the same. More specifically, the present invention relates to a resist composition applicable to, for example, semiconductor manufacturing processes such as ICs, production of circuit boards such as liquid crystals and thermal heads, and other lithography processes of photofabrication, and resist films using the same; It relates to a pattern forming method.

The photosensitive composition for pattern formation typically contains the compound which generate | occur | produces an acid by irradiation of light, and resin which changes the solubility to a developing solution by the action of an acid. By adopting such a configuration, the solubility in the developer of the composition can be changed by the exposed portion and the non-exposed portion. That is, in this way, the fine pattern according to the shape of an exposed part or a non-exposed part can be formed comparatively easily.

This photosensitive composition may further contain a basic compound. For example, Patent Document 1 describes the use of a tertiary amine having an aliphatic hydroxyl group as the basic compound. In addition, Patent Document 2 describes the use of a tertiary amine or secondary amine having a specific structure containing an ether group as a basic compound. In addition, Patent Document 3 describes a method of developing and patterning a developer with a developer containing a solvent using a photosensitive composition using a tertiary amine or a secondary amine having a specific structure containing an ether group.

Japanese Patent Laid-Open No. 10-177250 Japanese Patent Laid-Open No. 11-084639 Japanese Patent Publication No. 2009-258585

The present invention is to provide a resist composition capable of forming a pattern having a favorable shape, a resist film and a pattern forming method using the same.

The present invention is as follows, for example.

[1] A compound having (A) an alicyclic structure and having a dissolution rate in a developer due to the action of an acid, (B) a compound generating an acid by irradiation with actinic rays or radiation, and (C) A resist composition containing the compound represented by general formula (EA).

Wherein,

o, p and q each independently represent an integer of 1 or more.

n represents an integer of 3 or more.

r and s each independently represent an integer of 1 or more.

t represents an integer of 0 or more.

R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.

R <_3> represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group when t≥1, and when t = 0, represents an alkyl group, an aryl group, or an aralkyl group.

[2] The composition according to [1], in which the resin is provided with a lactone group containing the alicyclic structure.

[3] The composition of [2], wherein the lactone group is not provided with a cyano group.

[4] (A) The repeating unit (a) represented by the following general formula (Ia) or the general formula (Ib), the repeating unit (b) represented by the following general formula (II), and the following general formula ( Resin containing repeating unit (d) represented by III), (B) the compound which generate | occur | produces an acid by irradiation of actinic light or radiation, and (C) the compound represented by following General formula (EA) A resist composition containing the.

Wherein,

R ₁ represents a hydrogen atom or a methyl group.

R ₂ each independently represents an alkyl group when q ≧ ₂ .

R ₃ represents a hydrogen atom or an alkyl group.

q represents the integer of 0-3.

s represents the integer of 1-3.

Wherein,

R ₄ represents a hydrogen atom or a methyl group.

R ₅ , R ₆ and R ₇ each independently represent an alkyl group or a monocyclic cycloalkyl group. Two of R ₅ , R ₆ and R ₇ may be bonded to each other to form a monocyclic ring.

Wherein,

R ₉ represents a hydrogen atom or a methyl group.

m represents 1 or 2.

Wherein,

o, p and q each independently represent an integer of 1 or more.

n represents an integer of 3 or more.

r and s each independently represent an integer of 1 or more.

t represents an integer of 0 or more.

R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.

R <_3> represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group when t≥1, and when t = 0, represents an alkyl group, an aryl group, or an aralkyl group.

[5] The composition according to [4], wherein the resin (A) is different from the repeating unit (b) and further includes a repeating unit (c) having a group decomposed by the action of an acid.

[6] The resin (A) has a content of the repeating unit (a) of 30 to 55 mol%, a content of the repeating unit (b) of 20 to 50 mol%, and a content of the repeating unit (c). It is 5-30 mol%, and the composition as described in [5] whose content of the said repeating unit (d) is 1-20 mol%.

[7] The composition according to any one of [1] to [6], wherein the weight average molecular weight of the resin (A) is in a range of 5000 to 30000.

[8] The composition according to any one of [1] to [7], further comprising a solvent containing propylene glycol monomethyl ether acetate and cyclohexanone.

[9] A resist film formed using the composition according to any one of [1] to [8].

[10] forming a film using the composition according to any one of [1] to [8], exposing the film, and developing the exposed film using a developer containing an organic solvent to form a negative pattern. Pattern formation method including the one.

[11] The pattern formation method according to [10], wherein the developer contains an ester solvent as the organic solvent.

[12] The pattern forming method according to [10] or [11], further comprising rinsing the negative pattern.

[13] A method for producing an electronic device, comprising the pattern forming method according to any one of [10] to [12].

[14] An electronic device manufactured by the method for producing an electronic device according to [13].

(Effects of the Invention)

According to this invention, it becomes possible to provide the resist composition which enables formation of the pattern of a favorable shape, and the resist film and pattern formation method using the same.

Hereinafter, embodiments of the present invention will be described in detail.

In addition, group and atom group which do not specify a substitution or unsubstitution here shall include both the thing which does not have a substituent, and the thing which has a substituent. For example, the "alkyl group" which does not specify a substituted or unsubstituted shall include not only the alkyl group (unsubstituted alkyl group) which does not have a substituent, but the alkyl group (substituted alkyl group) which has a substituent.

In addition, "active light" or "radiation" means here the light spectrum of a mercury lamp, the far ultraviolet rays represented by an excimer laser, an extreme ultraviolet (EUV) ray, an X ray, or an electron beam (EB), for example. "Light" means actinic light or radiation. "Exposure" means not only light irradiation by mercury lamps, far ultraviolet rays, X-rays and EUV light, but also drawing by particle beams such as electron beams and ion beams.

The resist composition according to the present invention is a resin (A), in which the dissolution rate in a developer is changed by the action of an acid (hereinafter also referred to as an acid-decomposable resin), and (B) an acid generated by irradiation with actinic light or radiation. A compound [hereinafter also referred to as a photoacid generator] and (C) a basic compound are contained.

MEANS TO SOLVE THE PROBLEM This inventor discovered that the pattern of a favorable shape can be formed by using resin (A) which has alicyclic structure as acid-decomposable resin, and using compound (C) which has a specific structure as basic compound.

Hereinafter, the said component (A)-(C) is demonstrated in detail.

(A) acid-decomposable resin

The resist composition which concerns on this invention contains the acid-decomposable resin (A) which has alicyclic structure. This alicyclic structure may have a monocyclic structure and may have a polycyclic structure. In addition, this alicyclic structure may further have a substituent. In addition, an aromatic ring is not contained in the "alicyclic" here.

It is preferable that resin (A) contains the repeating unit provided with the said alicyclic structure. As an example of such a repeating unit, what has an alicyclic structure among the repeating units demonstrated below is mentioned.

It is preferable that resin (A) is equipped with the lactone group containing the said alicyclic structure. The lactone structure contained in the lactone group is preferably a 5 to 7 membered ring lactone structure, and more preferably the other ring structure is condensed in the form of forming a bicyclo structure and a spiro structure to the 5 to 7 membered ring lactone structure. It is preferable that this lactone group is equipped with the lactone structure represented by either of the following general formula (LC1-1)-general formula (LC1-13). Among these, the structure represented by general formula (LC1-2), general formula (LC1-3), general formula (LC1-4), or general formula (LC1-11) is more preferable, and general formula (LC1-2) Or the structure represented by general formula (LC1-3) is more preferable, and the structure represented by general formula (LC1-2) is especially preferable.

In the formula, Rb ₂ represents a substituent and n ₂ represents an integer of 0-4. It is preferable that n <_2> is an integer of 0-2.

Preferred examples of Rb ₂ include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, and an acid-decomposable group described later. Can be mentioned. Among these, an alkyl group having 1 to 4 carbon atoms or an acid decomposable group is particularly preferable. In addition, n may be a plurality of Rb ₂ are equal to each other if ₂ ≥2 one or different each other. Further, the plurality of Rb ₂ these may be bonded to each other to form a ring.

In addition, although an optical isomer exists normally in a lactone group, what kind of optical isomer may be used as mentioned above. Moreover, 1 type of optical isomers may be used independently, and several optical isomers may be mixed and used. When mainly using one type of optical isomer, it is preferable that the optical purity is 90% ee or more, and it is more preferable that it is 95% ee or more.

It is more preferable that the said lactone group does not have the cyano group. That is, the lactone group having the alicyclic structure is more preferably a lactone group not having a cyano group. By adopting such a configuration, it is possible to further improve at least one of sensitivity, exposure latitude (EL), line width roughness (LWR), local dimensional uniformity (Local CDU), and pattern shape, for example. Become.

It is preferable that resin (A) contains the repeating unit provided with alicyclic structure as mentioned above. As this repeating unit, the repeating unit provided with the lactone group containing an alicyclic structure is mentioned, for example. As this lactone group, what was mentioned above is mentioned, for example.

As a repeating unit provided with the lactone group containing an alicyclic structure, what is represented by following General formula (L) is mentioned, for example.

In formula (L)

A represents an ester bond (group represented by -COO-) or an amide bond (group represented by -CONH-).

When there are a plurality of R _{0 's} , each independently represents an alkylene group, a cycloalkylene group, or a combination thereof.

In the case where there are a plurality of Z's, they are each independently an ether bond, an ester bond, an amide bond, or a urethane bond.

Or urea bond

. R represents a hydrogen atom, an alkyl group, a cycloalkyl group, and an aryl group here.

R ₈ represents a monovalent organic group having a lactone structure including an alicyclic structure.

n is a repeating number of the structure represented by -R ₀ -Z-, and represents the integer of 1-5.

R ₇ represents a hydrogen atom, a halogen atom or an alkyl group.

The alkylene group and cycloalkylene group of R ₀ may have a substituent.

Z is preferably an ether bond or an ester bond, particularly preferably an ester bond.

The alkyl group of R ₇ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group and an ethyl group, and particularly preferably a methyl group. The alkyl group in R ₇ may be substituted, and examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, a mercapto group, a hydroxy group, a methoxy group, an ethoxy group, an isopropoxy group and t-butoxy Acetoxy groups, such as alkoxy groups, such as a time period and a benzyloxy group, an acetyl group, and a propionyl group, are mentioned. R ₇ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

As a preferable linear alkylene group in R <_0> , C1-C10 linear alkylene is preferable, More preferably, it is C1-C5, For example, a methylene group, ethylene group, a propylene group, etc. are mentioned. . Preferable cycloalkylene is C1-C20 cycloalkylene, for example, cyclohexylene, cyclopentylene, norbornylene, adamantylene, etc. are mentioned. In order to express the effect of this invention, a linear alkylene group is more preferable, and a methylene group is especially preferable.

The substituent having a lactone structure represented by R ₈ is not limited as long as it has a lactone structure, and examples thereof include lactone structures represented by general formulas (LC1-1) to (LC1-13). The structure represented by general formula (LC1-2) is especially preferable. Moreover, it is more preferable that n <_2> in general formula (LC1-1)-general formula (LC1-13) is 2 or less.

Although the specific example of the repeating unit which has group which has a lactone structure containing the alicyclic structure represented by general formula (L) below is shown, this invention is not limited to this.

In the following specific examples, R represents a hydrogen atom, an alkyl group or a halogen atom which may have a substituent, and preferably a hydrogen atom, a methyl group, a hydroxymethyl group or an acetoxymethyl group.

As a repeating unit which has a lactone structure containing an alicyclic structure, the repeating unit represented with the following general formula (L-1) is more preferable.

In general formula (L-1),

R <_7> , A, R <_0> , Z, and n are synonymous with the said general formula (L).

When there are a plurality of R _{9 's} , they each independently represent an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, a cyano group, a hydroxyl group or an alkoxy group. When there are a plurality of R _{9' s} , two R ₉ 's may be bonded to each other to form a ring.

X represents an alkylene group, an oxygen atom or a sulfur atom.

m is the number of substituents and represents the integer of 0-5. It is preferable that m is 0 or 1.

As an alkyl group of R <_9> , a C1-C4 alkyl group is preferable, a methyl group and an ethyl group are more preferable, and a methyl group is the most preferable. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl groups. Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, and the like. As an alkoxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, butoxy group etc. are mentioned. These groups may have a substituent, and examples of the substituent include halogen atoms such as alkoxy groups such as hydroxy groups, methoxy groups and ethoxy groups, and fluorine atoms. R ₉ is more preferably a methyl group or an alkoxycarbonyl group.

Examples of the alkylene group of X include a methylene group and an ethylene group. X is preferably an oxygen atom or a methylene group, and more preferably a methylene group.

When m is 1 or more, it is preferable that at least 1 R <_9> is substituted by the (alpha) position or (beta) position of the carbonyl group of lactone, and it is especially preferable to substitute by the (alpha) position.

Although the specific example of the repeating unit which has group which has a lactone structure represented by general formula (L-1) is shown, this invention is not limited to this. In the following specific examples, R represents a hydrogen atom, an alkyl group or a halogen atom which may have a substituent, and preferably a hydrogen atom, a methyl group, a hydroxymethyl group or an acetoxymethyl group.

As a repeating unit which has a lactone structure containing an alicyclic structure, the repeating unit represented with the following general formula (AII ') is also preferable.

In general formula (AII '),

Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. The preferable substituent which the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom of Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Preferably, they are a hydrogen atom, a methyl group, a hydroxymethyl group, and a trifluoromethyl group, and a hydrogen atom and a methyl group are especially preferable.

V represents a group having a structure represented by any one of General Formulas (LC1-1) to General Formula (LC1-13).

Although the specific example of the repeating unit which has a lactone group containing alicyclic structure other than the unit represented by general formula (L) is given to the following, this invention is not limited to these.

The following repeating unit is mentioned as a repeating unit which has lactone groups other than the unit represented by especially preferable general formula (L). By selecting the optimal lactone group, the pattern profile and the roughness dependency are improved.

As a repeating unit which has an alicyclic structure, the repeating unit (a) represented by the following general formula (I-a) or general formula (I-b) is especially preferable. It is more preferable that resin (A) contains the unit represented by following General formula (I-a) as a repeating unit (a). In this way, the solubility of resin (A) can be improved further.

Wherein,

R ₁ represents a hydrogen atom or a methyl group.

R ₂ each independently represents an alkyl group when q ≧ ₂ .

R ₃ represents a hydrogen atom or an alkyl group.

q represents the integer of 0-3.

s represents the integer of 1-3.

The alkyl group represented by R ₂ or R ₃ may be linear or branched. It is preferable that it is 1-5, and, as for carbon number of this alkyl group, it is more preferable that it is 1-3. As such an alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group are mentioned, for example.

The alkyl group represented by R ₂ or R ₃ may further have a substituent. As such a substituent, a halogen atom, a hydroxyl group, an alkoxy group, a cyano group, a nitro group, a sulfonyl group, and a silyl group are mentioned, for example.

It is preferable that q is an integer of 0-2. s is preferably 1 or 2.

The specific example of a repeating unit (a) is given to the following.

Resin (A) may contain two or more types of repeating units (a).

It is preferable that it is 30-55 mol%, and, as for content of the repeating unit (a) which occupies for resin (A) based on all the repeating units of resin (A), it is more preferable that it is 35-55 mol%.

Resin (A) is comprised so that the dissolution rate with respect to a developing solution may change with the action of an acid as mentioned above. Resin (A) is typically provided with a group (henceforth an acid-decomposable group) which decomposes | dissolves by the action of an acid and produces | generates an alkali-soluble group. This resin may be provided with an acid-decomposable group in one of a main chain and a side chain, and may be provided in both of these. It is preferable that this resin is equipped with the acid-decomposable group in the side chain.

The acid-decomposable group preferably has a structure protected by a group that decomposes and detaches the alkali-soluble group by the action of an acid.

Examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (Alkylcarbonyl) methylene group, a bis (alkylcarbonyl) methylene group, a bis (alkylcarbonyl) methylene group, a bis Alkylsulfonyl) methylene group and the like.

Preferred examples of the alkali-soluble group include a carboxyl group, a fluorinated alcohol group (preferably, hexafluoroisopropanol), and a sulfonic acid group.

A group preferable as an acid-decomposable group is group which substituted the hydrogen atom of these alkali-soluble groups by the group detach | desorbed by an acid.

Examples of the group that is released by an acid include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), and -C (R ₀₁ ) (R ₀₂ (OR ₃₉ ), and the like.

In the formula, each of R _{36 to} R ₃₉ independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

R _{01 to} R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

As an acid-decomposable group, Preferably it is a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group, etc. More preferably, it is a tertiary alkyl ester group.

As a repeating unit which has an acid-decomposable group which resin (A) may contain, the repeating unit represented with the following general formula (AI) is preferable.

In general formula (AI),

Xa ₁ represents a hydrogen atom, a methyl group which may have a substituent, or a group represented by -CH ₂ -R ₉ . R ₉ represents a hydroxy group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and an acyl group, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. Xa ₁ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

T represents a single bond or a divalent linking group.

Rx _{1 to} Rx ₃ each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic).

At least two of Rx _{1 to} Rx ₃ may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the divalent linking group of T include an alkylene group, -COO-Rt- group, -O-Rt- group and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.

T is preferably a single bond or a -COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a -CH ₂ -group and a-(CH ₂ ) ₃ -group.

That the _first Rx? Alkyl group of Rx ₃ methyl group, ethyl group, n- propyl group, a C 1?, Such as an isopropyl group, n- butyl group, an isobutyl group, a t- butyl group 4 are preferable.

As the cycloalkyl group of Rx _1? Rx ₃ cyclopentyl group, a cyclohexyl ah such monocyclic cycloalkyl group, norbornyl group, tetracyclo decamethylene group, a tetracyclododecanyl group, in the group just a polycyclic cycloalkyl group such as a group are preferred .

Examples of the cycloalkyl group formed by bonding at least two of Rx _{1 to} Rx ₃ include a monocyclic cycloalkyl group such as cyclopentyl group and cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group Polycyclic cycloalkyl groups are preferred. Particularly preferred is a monocyclic cycloalkyl group having 5 to 6 carbon atoms.

It is preferable that Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the cycloalkyl group described above.

Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (2 to 6 carbon atoms). And C8 or less is preferable.

Although the specific example of the repeating unit which has an acid-decomposable group is shown below, this invention is not limited to this.

In the specific examples, Rx and Xa ₁ represent a hydrogen atom, CH ₃ , CF ₃ or CH ₂ OH. Rxa and Rxb each represent an alkyl group having 1 to 4 carbon atoms. Z represents a substituent including a polar group, and when a plurality of groups are present, they are each independently. p represents 0 or a positive integer.

It is more preferable that resin (A) contains the repeating unit (b) represented by following General formula (II) as a repeating unit which has an acid-decomposable group.

Wherein,

R ₄ represents a hydrogen atom or a methyl group.

R ₅ , R ₆ and R ₇ each independently represent an alkyl group or a monocyclic cycloalkyl group. Two of R ₅ , R ₆ and R ₇ may be bonded to each other to form a monocyclic ring.

The alkyl group represented by R ₅ , R ₆ or R ₇ may be linear or branched. It is preferable that carbon number of this alkyl group is 1-7, It is more preferable that it is 1-5, It is still more preferable that it is 1-3. As such an alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group are mentioned, for example.

It is preferable that the monocyclic cycloalkyl group represented by R <_5> , R <_6> or R <_7> is a 3-8 membered ring, It is more preferable that it is a 5 or 6 membered ring, It is especially preferable that it is a 6 membered ring. As such a cycloalkyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group are mentioned, for example.

It is preferable that it is a 3-8 membered ring, and, as for two of R <_5> , R <_6> and R <_7> combine with each other, it is more preferable that it is a 5 or 6 membered ring.

The alkyl group represented by R <_5> , R <_6> or R <_7> and monocyclic cycloalkyl group, and the monocyclic which two of these couple | bond together and may form may further have a substituent. As such a substituent, a halogen atom, a hydroxyl group, an alkoxy group, a cyano group, a nitro group, a sulfonyl group, and a silyl group are mentioned, for example.

In formula (II), it is preferable that two of R ₅ , R ₆ and R ₇ are bonded to each other to form a monocyclic ring. That is, the repeating unit (b) is preferably represented by the following general formula (II-1). By adopting such a configuration, it is possible to further improve the film density.

Wherein,

R ₄ represents a hydrogen atom or a methyl group.

R ₅ represents an alkyl group.

R _S represents a substituent.

m represents the integer of 0-3.

n represents the integer of 1-3.

As an alkyl group represented by R <_5> , the same thing as what was demonstrated previously about General formula (II) is mentioned, for example.

Examples of the substituent represented by R _S include a halogen atom, a hydroxyl group, an alkoxy group, a cyano group, a nitro group, a sulfonyl group, and a silyl group.

It is preferable that it is an integer of 0-2, and, as for m, it is more preferable that it is 0 or 1.

It is preferable that it is 1 or 2, and, as for n, it is more preferable.

Below, the specific example of a repeating unit (b) is given.

Resin (A) may contain two or more types of repeating units (b).

It is preferable that it is 20-50 mol%, and, as for content of the repeating unit (b) which occupies for resin (A) based on all the repeating units of resin (A), it is more preferable that it is 30-50 mol%.

As for resin (A), it is more preferable that it contains two or more types of repeating units which have an acid-decomposable group. It is especially preferable that resin (A) differs from the repeating unit (b) and the said repeating unit (b) and contains the repeating unit (c) provided with an acid-decomposable group. By adopting such a configuration, more excellent lithographic performance can be achieved.

The repeating unit (c) is preferably represented by the following general formula (IV).

Wherein,

R ₈ represents a hydrogen atom or a methyl group.

R ₉ , R ₁₀ and R ₁₁ each independently represent an alkyl group or a cycloalkyl group. Provided that at least one of R ₉ , R ₁₀ and R ₁₁ represents a polycyclic cycloalkyl group. Two of R ₉ , R ₁₀ and R ₁₁ may be bonded to each other to form a polycyclic hydrocarbon structure.

The alkyl group represented by R ₉ , R ₁₀ or R ₁₁ may be linear or branched. It is preferable that carbon number of this alkyl group is 1-7, It is more preferable that it is 1-5, It is still more preferable that it is 1-3. As such an alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group are mentioned, for example.

The monocyclic cycloalkyl group represented by R ₉ , R ₁₀ or R ₁₁ is preferably a 3-8 membered ring, preferably a 5 or 6 membered ring, and preferably a 6 membered ring. As such a cycloalkyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group are mentioned, for example.

The polycyclic cycloalkyl group represented by R ₉ , R ₁₀ or R ₁₁ preferably has 7 to 25 carbon atoms, and particularly preferably an adamantyl group.

The alkyl group and cycloalkyl group represented by R ₉ , R ₁₀ or R ₁₁ , and the ring which can be formed by bonding two of them to each other may further have a substituent. As such a substituent, a halogen atom, a hydroxyl group, an alkoxy group, a cyano group, a nitro group, a sulfonyl group, and a silyl group are mentioned, for example.

In general formula (IV), it is preferable that two of R <_9> , R <_10> and R <_11> is an alkyl group, and the other one is a polycyclic cycloalkyl group. Moreover, it is more preferable that two of R <_9> , R <_10> and R <_11> is a linear alkyl group and the other one is an adamantyl group. Moreover, it is more preferable that two of R <_9> , R <_10> and R <_11> is a methyl group and the other one is an adamantyl group.

Below, the specific example of the repeating unit (c) is given.

Resin (A) may contain two or more types of repeating units (c).

When resin (A) contains the repeating unit (c), it is preferable that it is 5-30 mol%, and, as for the content, based on all the repeating units of resin (A), it is more preferable that it is 5-25 mol%. Do.

As above-mentioned, resin (A) may contain two or more types of repeating units which have an acid-decomposable group.

As for the content rate as the sum total of the repeating unit which has an acid-decomposable group, 20-70 mol% is preferable with respect to all the repeating units in resin (A), More preferably, it is 30-60 mol%.

It is preferable that resin (A) further contains the repeating unit which has a hydroxyl group or a cyano group other than the above-mentioned repeating unit.

The repeating unit having a hydroxyl group or cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or cyano group, and preferably has no acid-decomposable group. As an alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted by the hydroxyl group or the cyano group, an adamantyl group, a diamantyl group, and a norbornane group are preferable. As an alicyclic hydrocarbon structure substituted by the preferable hydroxyl group or cyano group, the partial structure represented by the following general formula (VIIa)-general formula (VIId) is preferable.

In general formula (VIIa)-general formula (VIIc),

R ₂ c? R ₄ c each independently represent a hydrogen atom, a hydroxyl group or a cyano group. Provided that at least one of R ₂ c? R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c? R ₄ c is a hydroxyl group, and the rest are hydrogen atoms. In general formula (VIIa), More preferably, _two of R <_2> C-R <_4> C are hydroxyl groups, and the remainder is a hydrogen atom.

As a repeating unit which has a partial structure represented by general formula (VIIa)-general formula (VIId), the repeating unit represented by the following general formula (AIIa)-general formula (AIId) is mentioned.

In general formula (AIIa)-general formula (AIId),

R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

R ₂ c? R ₄ c is R ₂ c? R ₄ c and agreement in the formula (VIIa)? Formula (VIIc).

Specific examples of the repeating unit having a hydroxyl group or a cyano group are shown below, but the present invention is not limited thereto.

It is especially preferable that resin (A) is a repeating unit which has a hydroxyl group or a cyano group, and contains the repeating unit (d) represented by following General formula (III). By adopting such a configuration, it is possible to reduce the diffusion length of acid generated from the photoacid generator described later.

Wherein,

R ₉ represents a hydrogen atom or a methyl group.

m represents 1 or 2. It is preferable that m is 1.

The repeating unit (d) is more preferably represented by the following general formula (III-1) or general formula (III-2).

In formula, R <_9> represents a hydrogen atom or a methyl group.

Resin (A) may contain two or more types of repeating units (d).

When resin (A) contains the repeating unit (d), it is preferable that it is 1-20 mol%, and, as for the content, based on all the repeating units of resin (A), it is more preferable that it is 1-10 mol%. Do.

Resin (A) may contain two or more types of repeating units which have a hydroxyl group or a cyano group.

It is preferable that it is 1-20 mol%, and, as for the content rate as the sum total of the repeating unit which has a hydroxyl group or a cyano group, based on all the repeating units in resin (A), it is more preferable that it is 1-10 mol%.

It is especially preferable that resin (A) contains a repeating unit (a), a repeating unit (b), and a repeating unit (d). It is also preferable that resin (A) contains the repeating unit (a), the repeating unit (b), the repeating unit (c), and the repeating unit (d). In these cases, the pattern of especially favorable shape can be formed.

When resin (A) contains a repeating unit (a), a repeating unit (b), a repeating unit (c), and a repeating unit (d), content of a repeating unit (a) is 30-55 mol% and repeats It is preferable that content of a unit (b) is 20-50 mol%, content of a repeating unit (c) is 5-30 mol%, and content of a repeating unit (d) is 1-20 mol%.

In this case, the content of the repeating unit (a) is 35 to 55 mol%, the content of the repeating unit (b) is 30 to 50 mol%, the content of the repeating unit (c) is 5 to 25 mol%, and the repetition. As for content of a unit (d), it is more preferable that it is 1-10 mol%. Employing such a structure improves etching resistance and solubility.

The resin (A) may further include a repeating unit (hereinafter also referred to as repeating unit (e)) having an acid group. By further including the repeating unit (e) in the resin (A), the resolution in contact hole applications can be further improved.

As an acidic group, a carboxyl group, a sulfonamide group, a sulfonyl imide group, a bissulfonyl imide group, and the aliphatic alcohol (for example, hexafluoroisopropanol group) by which the (alpha) position was substituted by the electron withdrawing group are mentioned, for example. . It is more preferable that the repeating unit (e) has a carboxyl group.

Examples of the repeating unit having an acid group include a repeating unit in which the group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a repeating unit in which the group is bonded to the main chain of the resin through a linking group. The polymerization initiator or the chain transfer agent may be used at the time of polymerization to introduce into the terminal of the polymer chain, and the linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure. Especially preferably, it is a repeating unit by acrylic acid and methacrylic acid.

Resin (A) may contain two or more types of repeating units (e).

When resin (A) contains the repeating unit (e), it is preferable that it is 10 mol% or less, and, as for the content, based on all the repeating units of resin (A), it is more preferable that it is 5 mol% or less. In this case, the content of the repeating unit (e) is usually 1 mol% or more.

Below, the specific example of the repeating unit (e) is shown. In the formula, Rx represents H, CH ₃ or CF ₃ .

Resin (A) may further contain the repeating unit (henceforth a repeating unit (f) hereafter) which has an alicyclic hydrocarbon structure which does not have a polar group and does not show acid decomposability. Thereby, the elution of the low molecular weight component from the resist film to the immersion liquid at the time of immersion exposure can be reduced, and the solubility of resin (A) can be suitably adjusted at the time of image development using the developing solution containing the organic solvent.

As a repeating unit (f), the repeating unit represented by following General formula (V) is mentioned, for example.

Wherein,

R ₁₂ represents a hydrogen atom, an alkyl group or a —CH ₂ —O—Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group or an acyl group.

R ₁₃ represents a hydrocarbon group having at least one cyclic structure and having neither of a hydroxyl group nor a cyano group.

R ₁₂ is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and more preferably a hydrogen atom or a methyl group.

The cyclic structure of R ₁₃ includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. As a monocyclic hydrocarbon group, C3-C12 cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, have a C3-C12 cyclo etc. Alkenyl group is mentioned. As a preferable monocyclic hydrocarbon group, a C3-C7 monocyclic hydrocarbon group is mentioned. Cyclopentyl group and cyclohexyl group are mentioned as a more preferable monocyclic hydrocarbon group.

The polycyclic hydrocarbon group includes a ring group hydrocarbon group and a temporary exchange hydrocarbon group, and examples of the ring group hydrocarbon group include a bicyclohexyl group and a perhydronaphthrenyl group. Examples of the temporary-exchange hydrocarbon ring include 2, such as refuge, boran, norfinan, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.). Cyclic hydrocarbon rings and tricyclic hydrocarbon rings such as homobredan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane and tricyclo [4.3.1.1 ^2,5 ] undecane ring, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane, 1,4-dihydro-flops meth furnace -5,8 there may be mentioned 4-cyclic hydrocarbon ring such as a naphthalene ring meta furnace. In addition, condensed cyclic hydrocarbon rings include, for example, perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydrophenylene ring. Condensed rings in which a plurality of 5- to 8-membered cycloalkane rings such as these are condensed are also included.

As a preferable crosslinkable hydrocarbon ring, norbornyl group, adamantyl group, bicyclooctanyl group, tricyclo [5, 2, 1, 0 ^2,6 ] decanyl group, etc. are mentioned. Norbornyl group and an adamantyl group are mentioned as a more preferable crosslinkable hydrocarbon ring.

These alicyclic hydrocarbon groups may have a substituent, and a preferable substituent includes a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, an amino group substituted with a hydrogen atom, and the like. Preferred halogen atoms include bromine, chlorine and fluorine atoms, and preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups. The alkyl group may further have a substituent, and examples of the substituent which may have a substituent include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom.

As a substituent of the said hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group is mentioned, for example. As a preferable alkyl group, it is a C1-C4 alkyl group, As a preferable substituted methyl group, As a methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl group, As a preferable substituted ethyl group, 1-ethoxyethyl And 1-methyl-1-methoxyethyl, and preferred acyl groups include aliphatic acyl and alkoxycarbonyl groups having 1 to 6 carbon atoms such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl group, and the like. C1-C4 alkoxycarbonyl group etc. are mentioned.

Resin (A) may contain two or more types of repeating units (f).

When resin (A) contains the repeating unit (f), it is preferable that it is 1-40 mol%, and it is more preferable that it is 5-20 mol%.

Below, the specific example of the repeating unit (f) is shown. In the formula, Ra represents H, CH ₃ or CF ₃ .

In addition to the repeating unit, the resin (A) may have various repeating units for the purpose of adjusting dry etching resistance, standard developer aptitude, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc. which are general necessary properties of the resist.

As such a repeating unit, the repeating unit corresponded to the following monomer, for example. That is, for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, and vinyl esters may be mentioned. have.

In addition, it may be copolymerized as long as it is an addition-polymerizable unsaturated compound copolymerizable with the monomer corresponding to the said various repeating unit.

It is more preferable that resin (A) contains only repeating unit (a), repeating unit (b), repeating unit (c), and repeating unit (d) substantially. It is preferable that content of repeating units other than a repeating unit (a), a repeating unit (b), a repeating unit (c), and a repeating unit (d) is 3 mol% or less with respect to all the repeating units of resin (A), and it is 1 mol It is more preferable that it is% or less.

In addition, resin (A) may contain two or more types of repeating units provided with an alicyclic structure.

Preferably the weight average molecular weight of resin (A) is 5000-30000 as polystyrene conversion value by GPC method, More preferably, it is 7000-15000. This makes it possible to reduce the occurrence of defects.

The degree of dispersion of the resin (A) is usually 1 to 3, preferably 1 to 2.6, more preferably 1 to 2, and particularly preferably 1.4 to 2.0. The smaller the molecular weight distribution, the better the resolution and resist shape, the smoother the sidewall of the resist pattern, and the better the roughness.

Resin (A) may be used individually by 1 type, and may be used in combination of 2 or more type.

It is preferable that it is 30-99 mass% with respect to the total solid, and, as for the compounding rate which occupies the whole composition of resin (A), it is more preferable that it is 60-95 mass%.

The resist composition which concerns on this invention may further contain resin other than resin (A) as acid-decomposable resin in the range which does not impair the effect of this invention. In this case, the ratio of the resin (A) in the total amount of the acid-decomposable resin is, for example, 80 to 99% by mass, and typically 90 to 99% by mass. Moreover, it is preferable that it is 30-99 mass% with respect to the total solid, and, as for the compounding rate which occupies the whole composition of acid-decomposable resin, it is more preferable that it is 60-95 mass%.

(B) photoacid generator

The composition according to the present invention contains a photoacid generator.

As a photo-acid generator, the compound represented by the following general formula (ZI), general formula (ZII), or general formula (ZIII) is mentioned, for example.

In the general formula (ZI),

R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.

The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.

In addition, two of R _{201 to} R _{203 may be} bonded to each other to form a ring structure, and the ring may include an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbonyl group. Examples of the group formed by bonding of two of R _{201 to} R ₂₀₃ include an alkylene group (for example, butylene group and pentylene group).

Z ⁻ represents a non-nucleophilic anion (anion that is significantly less capable of causing nucleophilic reactions).

As Z ⁻ , for example, sulfonic acid anions (aliphatic sulfonic acid anions, aromatic sulfonic acid anions, camphor sulfonic acid anions, etc.), carboxylic acid anions (aliphatic carboxylic acid anions, aromatic carboxylic acid anions, aralkylcarboxylic acid anions, etc.), Sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methed anion and the like.

The aliphatic moiety in the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms.

As an aromatic group in an aromatic sulfonic acid anion and aromatic carboxylic acid anion, Preferably, a C6-C14 aryl group, for example, a phenyl group, a tolyl group, a naphthyl group, etc. are mentioned.

Each of the alkyl group, cycloalkyl group, and aryl group described above may have a substituent. Specific examples thereof include halogen atoms such as nitro groups and fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms), and aryl groups (preferably Preferably, 6 to 14 carbon atoms, alkoxycarbonyl group (preferably 2 to 7 carbon atoms), acyl group (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), alkylthio group (Preferably having 1 to 15 carbon atoms), alkylsulfonyl group (preferably having 1 to 15 carbon atoms), alkyliminosulfonyl group (preferably having 2 to 15 carbon atoms), and aryloxysulfonyl group (preferably having 6 to 6 carbon atoms); 20), an alkylaryloxysulfonyl group (preferably having 7 to 20 carbon atoms), a cycloalkylaryloxysulfonyl group (preferably having 10 to 20 carbon atoms), and an alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms) And a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms). About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) is mentioned as a substituent.

As an aralkyl group in an aralkyl carboxylic acid anion, Preferably, a C6-C12 aralkyl group, for example, a benzyl group, a phenethyl group, a naphthyl methyl group, a naphthyl ethyl group, a naphthyl butyl group, etc. are mentioned.

The sulfonylimide anion includes, for example, a saccharin anion.

The alkyl group in the bis (alkylsulfonyl) imide anion and the tris (alkylsulfonyl) methed anion is preferably an alkyl group having 1 to 5 carbon atoms. Substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like. Fluorine atoms or fluorine Preferred are alkyl groups substituted by atoms.

As other Z <^-> , phosphorus fluoride, a boron fluoride, antimony fluoride, etc. are mentioned, for example.

Z ⁻ is an aliphatic sulfonic anion in which at least the α position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonic acid anion substituted with a fluorine atom or a group having a fluorine atom, a bis (alkylsulfonyl) imide anion in which an alkyl group is substituted with a fluorine atom, and an alkyl group is fluorine Preference is given to tris (alkylsulfonyl) methed anions substituted with atoms. As the non-nucleophilic anion, more preferably a perfluoro aliphatic sulfonic acid anion (more preferably 4 to 8 carbon atoms), a benzene sulfonic acid anion having a fluorine atom, more preferably a nonafluorobutane sulfonic acid anion and a perfluorooctane sulfonic acid anion Pentafluorobenzenesulfonic acid anion and 3,5-bis (trifluoromethyl) benzenesulfonic acid anion.

From the viewpoint of acid strength, pKa of the generated acid is preferably -1 or less for the purpose of sensitivity improvement.

R _201, R _202, and aryl group organic group of R ₂₀₃ (C 6? Is 15 is preferable), a straight-chain or (it is C 1? 10 is preferable), branched alkyl group, a cycloalkyl group (it is the carbon number of 3? 15 is preferable) Etc. can be mentioned.

At least one of R ₂₀₁ , R _202, and R ₂₀₃ is preferably an aryl group, and more preferably all three are aryl groups. As an aryl group, heteroaryl groups, such as an indole residue and a pyrrole residue, besides a phenyl group, a naphthyl group, etc. are possible. These aryl groups may further have a substituent. Examples of the substituent include halogen atoms such as nitro groups and fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms), and aryl groups (preferably Preferable examples include C6-14, alkoxycarbonyl group (preferably C2-7), acyl group (preferably C2-12), alkoxycarbonyloxy group (preferably C2-7), and the like. However, it is not limited to these.

In addition, two selected from R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may be bonded via a single bond or a linking group. Examples of the linking group include an alkylene group (preferably having 1 to 3 carbon atoms), -O-, -S-, -CO-, -SO ₂ -and the like, but are not limited thereto.

As a preferable structure when at least 1 of R <_201> , R <_202> and R <_203> is not an aryl group, Paragraph 0047, 0048 of Unexamined-Japanese-Patent No. 2004-233661, Paragraph 0040-0046 of Unexamined-Japanese-Patent No. 2003-35948, US Compounds exemplified in the 2003 / 0224288A1 specification as formulas (I-1) to (I-70), formulas (IA-1) to (IA-54) and formula (IB-1) in US 2003 / 0077540A1 specification. And cation structures such as compounds exemplified as? (IB-24).

In general formula (ZII), general formula (ZIII),

R _{204 to} R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group.

The aryl group, alkyl group and cycloalkyl group of R _{204 to} R ₂₀₇ are the same as the aryl group described as the aryl group, alkyl group and cycloalkyl group of R _{201 to} R _{203 in} the compound (ZI-1) described above.

The aryl group, alkyl group and cycloalkyl group of R _{204 to} R ₂₀₇ may have a substituent. As this substituent, what may have the aryl group, alkyl group, and cycloalkyl group of R <_201> -R <_{203> in} the above-mentioned compound (ZI-1) is mentioned.

Z <^-> represents a non-nucleophilic anion and the same thing as the non-nucleophilic anion of Z <^-> in general formula (ZI) is mentioned.

As a photo-acid generator, the compound represented by the following general formula (ZIV), general formula (ZV), and general formula (ZVI) is also mentioned.

In general formula (ZIV) to general formula (ZVI),

Ar ₃ and Ar ₄ each independently represent an aryl group.

R ₂₀₈ , R ₂₀₉ and R ₂₁₀ independently represent an alkyl group, a cycloalkyl group or an aryl group.

A represents an alkylene group, an alkenylene group or an arylene group.

As a specific example of a photo-acid generator, the following are mentioned, for example.

It is particularly preferable that the photoacid generator is represented by the following general formula (III-a) or general formula (III-b).

Wherein,

m represents the integer of 1-5.

r represents the integer of 0-3.

R _A and R _B each independently represent a hydrogen atom or an alkyl group. R _A and R _B may be bonded to each other to form a ring.

p represents the integer of 1-5.

In general formula (III-a), it is preferable that m is an integer of 1-3, It is more preferable that it is 1 or 2, It is especially preferable that it is 1. In addition, it is preferable that r is 1 or 2, and it is especially preferable that it is 1.

In General Formula (III-b), the alkyl group represented by R _A or R _B may be linear or branched. It is preferable that it is 1-5, and, as for carbon number of this alkyl group, it is more preferable that it is 1-3. As such an alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group are mentioned, for example.

The ring which R _A and R _B may combine with each other to form may be monocyclic or polycyclic. It is preferable that this ring is mono-cyclic, It is more preferable that it is a 5- or 6-membered ring, It is especially preferable that it is a 6-membered ring.

The alkyl group represented by R _A or R _B and the ring which can be formed by bonding to each other may further have a substituent. As such a substituent, a halogen atom, a hydroxyl group, an alkoxy group, a cyano group, a nitro group, a sulfonyl group, and a silyl group are mentioned, for example.

In general formula (III-b), it is preferable that p is an integer of 1-3, and it is especially preferable that it is 3.

In general formula (III-b), it is more preferable that R _<A> and R <_B> combine with each other and form the ring.

Below, the specific example of a compound represented by general formula (III-a) or general formula (III-b) is shown.

Photo-acid generators may be used individually by 1 type, and may be used in combination of 2 or more type.

It is preferable that it is 0.1-20 mass% with respect to the total solid, The compounding ratio which occupies the whole composition of a photo-acid generator is more preferable, It is more preferable that it is 0.5-15 mass%, It is further more preferable that it is 3-15 mass%.

(C) basic compound

The resist composition which concerns on this invention contains the compound represented by the following general formula (EA) as a basic compound.

Wherein,

o, p and q each independently represent an integer of 1 or more.

n represents an integer of 3 or more.

r and s each independently represent an integer of 1 or more.

t represents an integer of 0 or more.

R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.

R <_3> represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group when t≥1, and when t = 0, represents an alkyl group, an aryl group, or an aralkyl group.

o, p and q are each independently preferably an integer of 1-5, More preferably, it is 2 or 3, Especially preferably, it is 2.

n represents an integer of 3 or more as mentioned above. n is preferably an integer of 3-10, More preferably, it is 3-6, More preferably, it is 3.

When n is set to 0-2, the boiling point of a basic compound becomes low, and when it develops using the developing solution containing the organic solvent, for example, T-top of pattern shape arises. When n is made excessively large, the hydrophobicity of a basic compound may become excessively high, and also in this case, T-topization of a pattern shape may arise. In addition, excessively increasing n may increase steric hindrance around the amine nitrogen, which may lower the nucleophilicity of the basic compound. Therefore, in this case, the exposure latitude of the composition may decrease.

Each of r and s represents an integer of 1 or more as described above. r and s are each independently preferably an integer of 1-5, More preferably, it is 1 or 2.

t represents an integer of 0 or more as described above. t becomes like this. Preferably it is an integer of 0-5, More preferably, it is an integer of 0-2.

Each of R ₁ and R ₂ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group as described above. R ₁ and R ₂ are each independently preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom. In addition, the said alkyl group, an aryl group, and an aralkyl group may further have a substituent.

The alkyl group as R ₁ or R ₂ is, for example, a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group or dodecyl group. The alkyl group of R ₁ or R ₂ is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

The aryl group as R ₁ or R ₂ is, for example, a phenyl group, tolyl group, naphthyl group or anthryl group. The aryl group of R ₁ or R ₂ is preferably an aryl group having 6 to 15 carbon atoms.

Aralkyl groups as R ₁ or R _{2 are} , for example, benzyl groups or phenethyl groups. The aralkyl group as R ₁ or R ₂ is preferably an aralkyl group having 6 to 20 carbon atoms.

As a substituent which these alkyl group, an aryl group, and an aralkyl group may have, it is a hydroxyl group, for example; Halogen atoms such as fluorine, chlorine, bromine and iodine atoms; A nitro group; Cyano; Amide group; Sulfonamide groups; Alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group; Alkoxy groups such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group and butoxy group; Alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; Acyl groups such as formyl group, acetyl group and benzoyl group; Acyloxy groups, such as an acetoxy group and a butyryloxy group, and a carboxy group are mentioned.

R ₃ is a hydrogen atom, an alkyl group, an aryl group or an aralkyl group when t ≧ 1. In this case, R ₃ is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group. In addition, the said alkyl group, an aryl group, and an aralkyl group may further have a substituent. R ₃ as alkyl, aryl, aralkyl, and the substituent which they may further have includes, for example, the front, such as those described for R ₁ and R _2.

R <_3> is an alkyl group, an aryl group, or an aralkyl group when t = 0. In this case, R ₃ is preferably an alkyl group, more preferably a methyl group. In addition, the said alkyl group, an aryl group, and an aralkyl group may further have a substituent. R ₃ as alkyl, aryl, aralkyl, and the substituent which they may further have includes, for example, the front, such as those described for R ₁ and R _2.

The basic compound represented by formula (EA) is a tertiary amine in which a group containing R ₁ , a group containing R _2, and a group containing R ₃ are bonded to a nitrogen atom.

Groups containing R ₃ are typically different from groups containing R ₁ and groups containing R ₂ .

For example, t is typically smaller compared to r and s. n is typically greater compared to l and m. By adopting such a configuration, for example, it becomes possible to further improve at least one of sensitivity, exposure latitude EL, line width roughness LWR, local dimensional uniformity (Local CDU), and pattern shape.

Also, groups comprising R ₁ and groups containing R ₂ are typically identical to each other.

Each of R ₁ and R ₂ is preferably a hydrogen atom. In particular, it is preferable that both of R ₁ and R ₂ are hydrogen atoms. That is, it is preferable that the said basic compound is a compound represented with the following general formula (EA-2).

In the formula, the definitions of n, o, p, q, r, s, t, and R ₃ are the same as those described for general formula (EA). Moreover, these preferable examples are also the same as what was mentioned before about general formula (EA).

By adopting such a configuration, for example, the pattern shape can be further improved.

As a basic compound represented by general formula (EA), the following are mentioned, for example.

The basic compound represented by general formula (EA) may be used individually by 1 type, and may be used in combination of 2 or more type.

It is preferable that the content of the basic compound represented by general formula (EA) is 0.01-8.0 mass% on the basis of the total solid of a composition, It is more preferable that it is 0.1-5.0 mass%, It is 0.1-4.0 mass% Particularly preferred.

The basic compound represented by general formula (EA) is synthesize | combined as follows, for example.

First, the monoamine provided with the group containing R <_3> is prepared. Subsequently, the monoamine and the halide corresponding to the group containing R ₁ and the group containing R ₂ are reacted in the presence of a base in an organic solvent. Subsequently, the obtained salt is separated and purified to obtain the desired basic compound.

In addition, the composition according to the present invention may further contain other basic compounds in addition to the basic compound represented by General Formula (EA). That is, this composition may further contain basic compounds other than the compound represented by general formula (EA).

As a basic compound which can be used together with the compound represented by general formula (EA), the compound which has a structure represented by following formula (A)-(E) is mentioned, for example.

In general formula (A) and general formula (E),

R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and represent a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (having 6 to 20 carbon atoms) In this case, R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring. R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and represent an alkyl group having 1 to 20 carbon atoms.

As an alkyl group which has a substituent with respect to the said alkyl group, a C1-C20 aminoalkyl group, a C1-C20 hydroxyalkyl group, or a C1-C20 cyanoalkyl group is preferable.

As for the alkyl group in these general formula (A) and general formula (E), it is more preferable that it is unsubstituted.

Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and more preferred compounds include imidazole structure, diazabicyclo structure, Compounds having an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, an aniline derivative having a hydroxyl group and / or an ether bond, and the like. Can be mentioned.

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzoimidazole, and the like. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] nona-5-ene and 1,8-diazabi Cyclo [5,4,0] undec-7-ene and the like. Examples of the compound having an onium hydroxide structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium (T-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, . As a compound which has an onium carboxylate structure, the anion part of the compound which has an onium hydroxide structure consists of carboxylates, For example, acetate, adamantane-1-carboxylate, perfluoroalkyl carboxylate, etc. Can be mentioned. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine, tri (n-octyl) amine and the like. Examples of the aniline compound include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline, and the like. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyl diethanolamine, tris (methoxyethoxyethyl) amine, and the like. Examples of the aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline and the like.

As a preferable basic compound, the amine compound which has a phenoxy group, the ammonium salt compound which has a phenoxy group, the amine compound which has a sulfonic acid ester group, and the ammonium salt compound which has a sulfonic acid ester group are mentioned.

The amine compound having a phenoxy group, the ammonium salt compound having a phenoxy group, the amine compound having a sulfonic acid ester group and the ammonium salt compound having a sulfonic acid ester group preferably have at least one alkyl group bonded to a nitrogen atom. Moreover, it is preferable to have an oxygen atom in the said alkyl chain, and the oxyalkylene group is formed. The number of oxyalkylene groups is 1 or more in a molecule | numerator, Preferably it is 3-9, More preferably, it is 4-6. Among the oxyalkylene groups, the structures of —CH ₂ CH ₂ O—, —CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O— are preferred.

Specific examples of the amine compound having a phenoxy group, the ammonium salt compound having a phenoxy group, the amine compound having a sulfonic acid ester group and the ammonium salt compound having a sulfonic acid ester group include compounds exemplified in US Patent Application Publication No. 2007/0224539. Although (C1-1)-(C3-3) is mentioned, it is not limited to these.

As a basic compound which can be used together with the compound represented by general formula (EA), it has a proton acceptor functional group and decomposes | disassembles by irradiation of actinic light or a radiation, and the proton acceptor property falls, disappears, or from proton acceptor property. The compound (PDA) which produces the compound changed into acidity is also mentioned.

A proton acceptor functional group is a functional group which has a group or an electron which can electrostatically interact with a proton, For example, the functional group which has a macrocyclic structure, such as a cyclic polyether, or nitrogen which has a non-covalent electron pair which does not contribute to (pi) conjugate | conjugate. It means the functional group which has an atom. The nitrogen atom which has a lone pair which does not contribute to (pi) conjugation is a nitrogen atom which has a partial structure shown by following formula, for example.

As a preferable partial structure of a proton acceptor functional group, a crown ether, an aza crown ether, a primary tertiary amine, a pyridine, an imidazole, a pyrazine structure, etc. are mentioned, for example.

Here, the decrease or loss of proton acceptor property or the change from proton acceptor to acidic acid is a change in proton acceptor property due to the addition of protons to the proton acceptor functional group, specifically, the proton acceptor functional group. When a proton adduct is produced from a compound (PDA) having a proton and a proton, it means that the equilibrium constant in the chemical equilibrium is reduced.

Proton acceptor property can be confirmed by performing a pH measurement.

In the present invention, it is preferable that the acid dissociation constant (pKa) satisfies -13 <pKa <-8, and the compound produced by decomposition of compound (PDA) by irradiation of actinic light or radiation, and -12 <pKa <- 9 is more preferable.

In the present invention, the acid dissociation constant (pKa) refers to an acid dissociation constant (pKa) in an aqueous solution, and is, for example, to a chemical handbook (II) (Rev. 4, 1993, Japanese Chemical Sculpture, Maruzen Co., Ltd.). The lower the value, the greater the acid strength. The acid dissociation constant (pKa) in the aqueous solution can be actually measured by measuring the acid dissociation constant at 25 ° C. using an infinite dilution aqueous solution, and further, a database of Hammet's substituent constants and known literature values using the following software package 1 The value can also be obtained by calculation. All the values of pKa described in this specification represent the value calculated | required by calculation using this software package.

Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs)

As a compound (PDA), a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt, an imide sulfonate, an oxime sulfonate, a diazo disulfone, a disulfone, and o-nitrobenzyl sulfonate is mentioned, for example. . It is preferable that a compound (PDA) is at least 1 sort (s) chosen from the group which consists of a sulfonium salt, an iodonium salt, a diazo sulfone, a disulfone, an imide sulfonate, and an oxime sulfonate.

It is preferable that a compound (PDA) is represented by the following general formula (PDA-1).

Wherein,

R _f represents an alkyl group, a cycloalkyl group or an aryl group.

W ₁ and W ₂ each independently represent —SO ₂ — or —CO—.

A represents a single bond or a divalent linking group.

X represents -SO ₂ -or -CO-.

n represents 0 or 1.

B represents a single bond, an oxygen atom, or -N (R _x ) R _y- . Here, R _x represents a hydrogen atom or a monovalent organic group, and R _y represents a single bond or a divalent organic group. R _x may be bonded to R _y to form a ring, or R _x may be bonded to R to form a ring.

R represents a monovalent organic group having a proton accepting functional group.

[C] ⁺ represents a counter cation. As this counter cation, the thing similar to what was demonstrated previously with the combined photoacid generator is mentioned, for example. As the counter cation, a triarylsulfonium cation is preferable. As an aryl group of a triarylsulfonium cation, a phenyl group is preferable.

W ₁ and W ₂ is at least one -SO ₂ - which is preferred, and both -SO ₂ - is particularly preferred in.

R _f is preferably an alkyl group which may have a fluorine atom of 1 to 6 carbon atoms, more preferably a perfluoroalkyl group of 1 to 6 carbon atoms, still more preferably a perfluoroalkyl group of 1 to 3 carbon atoms.

As a bivalent coupling group in A, Preferably it is a C2-C12 bivalent coupling group, For example, an alkylene group, a phenylene group, etc. are mentioned. More preferably, it is an alkylene group which has at least 1 fluorine atom, Preferably carbon number is 2-6, More preferably, it is C2-C4. You may have coupling groups, such as an oxygen atom and a sulfur atom, in an alkylene chain. The alkylene group is particularly preferably an alkylene group in which 30 to 100% of the number of hydrogen atoms is replaced with a fluorine atom, and more preferably a carbon atom bonded to the Q moiety has a fluorine atom. Moreover, a perfluoroalkylene group is preferable and a perfluoroethylene group, a perfluoropropylene group, and a perfluoro butylene group are more preferable.

When B represents -N (R _x ) R _y- , the monovalent organic group for R _x preferably has 1 to 30 carbon atoms, for example, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group. Etc. can be mentioned. These groups may further have a substituent.

The alkyl group for R _x may have a substituent, preferably a straight chain and branched alkyl group having 1 to 20 carbon atoms, and may have an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain.

In addition, examples of the alkyl group having a substituent include groups in which a cycloalkyl group is substituted (for example, adamantylmethyl group, adamantylethyl group, cyclohexylethyl group, camphor residue, etc.).

As a cycloalkyl group in R <_x> , you may have a substituent, Preferably it is a C3-C20 cycloalkyl group, and may have an oxygen atom in a ring.

As the aryl group R _x may have a substituent in, and is preferably an aryl group having 6? 14.

The aralkyl group in R _x may have a substituent, and preferably an aralkyl group having 7 to 20 carbon atoms is mentioned.

As an alkenyl group in R <_x> , you may have a substituent, For example, the group which has a double bond in the arbitrary position of the alkyl group mentioned as R <_x> is mentioned.

When B represents -N (R _x ) R _y- , preferably an alkylene group is mentioned as a divalent organic group in R _y . In this case, as the ring structure in which R _x and R _y may be bonded to each other, a 5- to 8-membered ring containing a nitrogen atom, and particularly preferably a 6-membered ring, may be mentioned.

When B represents -N (R _x ) R _y- , it is preferable that R and R _x combine with each other to form a ring. Stability improves by forming ring structure, and storage stability of the composition using this improves. 4-20 are preferable, as for carbon number which forms a ring, monocyclic or polycyclic may be sufficient and an oxygen atom, a sulfur atom, and a nitrogen atom may be included in the ring.

Examples of the monocyclic structure include a 4-membered ring, 5-membered ring, 6-membered ring, 7-membered ring, and 8-membered ring containing a nitrogen atom. As a polycyclic structure, the structure which consists of a combination of 2 or 3 or more monocyclic structures is mentioned. Each of the monocyclic structure and the polycyclic structure may have a substituent, for example, a halogen atom, a hydroxyl group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (preferably C 3 to 10), and an aryl group (preferably carbon number). 6-14), alkoxy group (preferably 1 to 10 carbon atoms), acyl group (preferably 2 to 15 carbon atoms), acyloxy group (preferably 2 to 15 carbon atoms), alkoxycarbonyl group (preferably 2 carbon atoms) ? 15), an aminoacyl group (preferably having 2 to 20 carbon atoms), and the like. About a cyclic structure in an aryl group, a cycloalkyl group, an alkyl group (preferably C1-C15) is mentioned as a substituent. About an aminoacyl group, an alkyl group (preferably C1-C15) is mentioned as a substituent.

As a proton acceptor functional group in R, a crown ether, an aza crown ether, a primary-tertiary amine, a pyridine, imidazole, a pyrazine structure, etc. are mentioned, for example.

As a group containing such a structure, preferable carbon number is 4-30, An alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, etc. are mentioned.

R represents an alkyl group, a cycloalkyl group including a proton acceptor functional group or an ammonium group in the aryl group, an aralkyl group, an alkyl group in groups alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, alkenyl group group either as the above R _x And a cycloalkyl group, an aryl group, an aralkyl group and an alkenyl group.

As a substituent which each said group may have, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably C3-C10), an aryl group (preferably C6-C14) , An alkoxy group (preferably having 1 to 10 carbon atoms), an acyl group (preferably having 2 to 20 carbon atoms), an acyloxy group (preferably having 2 to 10 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms), Amino acyl group (preferably C2-C20) etc. are mentioned. About the cyclic structure and aminoacyl group in an aryl group, a cycloalkyl group, an alkyl group (preferably C1-C20) is mentioned as a substituent.

It is preferable that a compound (PDA) is an ionic compound, and it is especially preferable that it is a sulfonium salt or an iodonium salt. When the compound (PDA) is an ionic compound, the proton acceptor functional group may be included in any of the anion site and the cation site.

Moreover, the following structure is preferable as one form of atom group R of the said General formula (PDA-1).

In general formula (PB-II),

R ₂₁ represents a hydrogen atom or a monovalent organic group, and R ₂₂ represents a divalent organic group. R ₂₁ and R ₂₂ may be bonded to each other to form a ring. In addition, the B in the formula (PDA-1) -N (R x) R y - when, R ₂₁ and R _x may be bonded to form a ring structure.

L represents a functional group having a σ _p value of −0.1 or more in the Hammett equation excluding hydrogen atoms.

* Represents a binding site to A ⁻ .

General formula (PB-II) is demonstrated in detail.

L is a functional group of -0.1 or more, and preferably a functional group of -0.05 or more, in the σ _p value of Hammett's formula (Ref .: Hansch et al., Chemical Reviews, 1991, Vol, 91, No. 2, 165-195), More preferably, they are -0.03 or more and 0.5 or less functional group. For functional groups not described in the reference, σ _p values can be calculated from the difference from pKa of benzoic acid in separate ACD / ChemSketch (ACD / Labs 8.00 Release Product Version: 8.08). As a functional group whose (sigma) _p value is -0.1 or more, an aryl group (phenyl group etc.), an acyl group (acetyl group etc.), an alkoxycarbonyl group (methoxycarbonyl group, t-butoxycarbonyl group etc.), an alkylcarbonyloxy group (methyl Carbonyloxy group etc.), a carboxyl group, an alkoxy group (methoxy group etc.), a cyano group, a nitro group, a halogen atom, and the group containing the alkyl group and lactone structure substituted by these functional groups, etc. are mentioned. By selecting such a group, it becomes possible to make the base strength of the nitrogen atom in the formula (PB-II) an appropriate range.

Especially as a substituted alkyl group, the alkyl group substituted by the acyl group, the alkoxycarbonyl group, the alkoxy group, and the cyano group is preferable.

It is more preferable to include the following lactone structure among the above-mentioned.

In addition, L may have a structure decomposed by an acid generated from the photoacid generator described above. For example, when L is a structure having an alkoxycarbonyl group, the structure in which the alkyl group of the alkoxycarbonyl group is represented by -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ) can decompose by the acid generated from the photoacid generator have. In the formula, each of R _{36 to} R ₃₈ independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

Although the number of atoms (except hydrogen atoms) which L has is not specifically limited, Usually, it is 1-20, Preferably it is 1-15, More preferably, it is the range of 1-10.

The organic group as R ₂₁ preferably has 1 to 40 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and an alkenyl group.

The alkyl group as R ₂₁ may have a substituent, Preferably it is a C1-C30 linear and branched alkyl group, and may have an oxygen atom, a sulfur atom, and a nitrogen atom in an alkyl chain. Specifically, such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group, etc. Branched alkyl groups, such as a linear alkyl group, isopropyl group, isobutyl group, t-butyl group, neopentyl group, and 2-ethylhexyl group, are mentioned.

The cycloalkyl group as R ₂₁ may have a substituent, Preferably it is a C3-C20 cycloalkyl group, and may have an oxygen atom and a nitrogen atom in a ring. Specifically, a cyclopropyl group, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group, etc. are mentioned.

The aryl group as R ₂₁ may have a substituent, Preferably it is a C6-C14 aryl group, For example, a phenyl group, a naphthyl group, etc. are mentioned.

The aralkyl group as R ₂₁ may have a substituent, Preferably, a C7-20 aralkyl group is mentioned, For example, a benzyl group, a phenethyl group, a naphthyl methyl group, a naphthyl ethyl group is mentioned.

The alkenyl group as R ₂₁ may have a substituent, and the group which has a double bond in arbitrary positions of the said alkyl group is mentioned.

As a substituent which each said group may have, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably C3-C10), an aryl group (preferably C6-C14) , An alkoxy group (preferably having 1 to 10 carbon atoms), an acyl group (preferably having 2 to 20 carbon atoms), an acyloxy group (preferably having 2 to 10 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms), Amino acyl group (preferably C2-C10) etc. are mentioned. About a cyclic structure in an aryl group, a cycloalkyl group, an alkyl group (preferably C1-C10) is mentioned as a substituent. About an aminoacyl group, an alkyl group (preferably C1-C10) is mentioned as a substituent. As an alkyl group which has a substituent, perfluoroalkyl groups, such as a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluoro butyl group, are mentioned, for example.

The divalent organic group of R ₂₂ is preferably an alkylene group, a phenylene group or the like, and an alkylene group is particularly preferable. 1-10 are preferable, as for carbon number of an alkylene group, 1-8 are more preferable, and 1-5 are more preferable.

Below, the specific example of a compound (PDA) is shown.

In addition, you may use what is described as compound (PA) in International Publication 2010/147228 pamphlet as a compound (PDA).

A compound (PDA) may be used individually by 1 type, and may be used in combination of 2 or more type.

When the composition by this invention contains a compound (PDA), it is preferable that the compounding ratio which occupies for the whole composition is 0.01-15 mass% with respect to whole solid content, It is more preferable that it is 0.1-12 mass%, It is 2? It is more preferable that it is 10 mass%.

The basic compound described above may be used individually by 1 type, and may be used in combination of 2 or more type.

When the composition according to the present invention contains a basic compound [containing a compound (PDA)], the blending ratio of the whole composition is preferably 0.01 to 15% by mass with respect to the total solids, and is 0.1 to 10% by mass. It is more preferable, and it is still more preferable that it is 0.5-7 mass%.

The content rate of a basic compound is 0.001-10 mass% normally based on the total solid of the composition of this invention, Preferably it is 0.01-7 mass%.

It is preferable that the content rate in the composition of a photo-acid generator and a basic compound is photo-acid generator / basic compound (molar ratio) = 0.5-300. That is, a molar ratio of 0.8 or more is preferable from the point of sensitivity and resolution, and 300 or less is preferable from the point of suppression of the fall of the resolution by thickening of the resist pattern over time until post-exposure heat processing. The photoacid generator / basic compound (molar ratio) is more preferably 0.8 to 200, still more preferably 0.8 to 150.

(D) hydrophobic resin

The resist composition according to the present invention particularly includes a hydrophobic resin (hereinafter, also referred to as "hydrophobic resin (D)" or only "resin (D)") having at least one of a fluorine atom and a silicon atom when applied to immersion exposure. You may contain it. As a result, when the hydrophobic resin (D) is localized in the film surface layer, and the immersion medium is water, the immersion liquid followability can be improved by improving the static / dynamic contact angle of the surface of the resist film with respect to water.

The hydrophobic resin (D) is preferably designed to be ubiquitous at the interface as described above. However, unlike the surfactant, the hydrophobic resin (D) does not necessarily have a hydrophilic group in the molecule, and does not necessarily contribute to uniformly mixing the polar / nonpolar material.

Hydrophobic resin (D) typically contains a fluorine atom and / or a silicon atom. The fluorine atom and / or silicon atom in hydrophobic resin (D) may be contained in the main chain of resin, and may be contained in the side chain.

When hydrophobic resin (D) contains a fluorine atom, it is preferable that it is resin which has the alkyl group which has a fluorine atom, the cycloalkyl group which has a fluorine atom, or the aryl group which has a fluorine atom as a partial structure which has a fluorine atom.

An alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a straight or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.

The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than the fluorine atom.

Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have a substituent other than the fluorine atom.

As an alkyl group which has a fluorine atom, the cycloalkyl group which has a fluorine atom, and the aryl group which has a fluorine atom, Preferably, group represented by the following general formula (F2)-general formula (F4) is mentioned, However, this invention adds to this. It is not limited.

In general formula (F2)-general formula (F4),

R _{57 to} R ₆₈ each independently represent a hydrogen atom, a fluorine atom or an alkyl group (linear or branched). Provided that at least one of R _{57 to} R ₆₁ , at least one of R _{62 to} R ₆₄ , and at least one of R _{65 to} R ₆₈ each independently represent an alkyl group having a fluorine atom or at least one hydrogen atom substituted with a fluorine atom ( Preferably C1-C4) is shown.

R _57? R ₆₁ and R _65? R ₆₇ are preferably both fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are each preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

As a specific example of group represented by general formula (F2), a p-fluorophenyl group, a pentafluorophenyl group, a 3, 5- di (trifluoromethyl) phenyl group, etc. are mentioned, for example.

Specific examples of the group represented by the general formula (F3) include a trifluoromethyl group, a pentafluoropropyl group, a pentafluoroethyl group, a heptafluorobutyl group, a hexafluoroisopropyl group, a heptafluoroisopropyl group, a hexafluoro (2-methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group , A perfluoro (trimethyl) hexyl group, a 2,2,3,3-tetrafluorocyclobutyl group, and a perfluorocyclohexyl group. Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group, perfluoroisopentyl group are preferable. , Hexafluoroisopropyl group, and heptafluoroisopropyl group are more preferable.

Specific examples of the group represented by formula (F4), for example, _{-C (CF 3) 2 OH,} -C (C 2 F 5) 2 OH, -C (CF 3) (CH 3) OH, -CH (CF ₃ ) OH, and the like, -C (CF ₃ ) ₂ OH is preferable.

The partial structure containing a fluorine atom may be directly bonded to the main chain, and may be selected from the group consisting of alkylene groups, phenylene groups, ether bonds, thioether bonds, carbonyl groups, ester bonds, amide bonds, urethane bonds and ureylene bonds. Or may be bonded to the main chain via a group of two or more thereof.

As a preferable repeating unit which has a fluorine atom, what is shown below is mentioned.

In the formula, R ₁₀ and R ₁₁ each independently represent a hydrogen atom, a fluorine atom or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and may have a substituent, and examples of the alkyl group having a substituent include a fluorinated alkyl group.

W _{3 to} W ₆ each independently represent an organic group containing at least one or more fluorine atoms. Specifically, the atom group of said (F2)-(F4) is mentioned.

In addition to these, hydrophobic resin (D) may have a unit shown below as a repeating unit which has a fluorine atom.

In the formula, each of R _{4 to} R ₇ independently represents a hydrogen atom, a fluorine atom, or an alkyl group. The alkyl group is preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and may have a substituent, and examples of the alkyl group having a substituent include a fluorinated alkyl group.

Provided that at least one of R _{4 to} R ₇ represents a fluorine atom. R ₄ and R ₅ or R ₆ and R ₇ may form a ring.

W ₂ represents an organic group containing at least one fluorine atom. Specifically, the atom group of said (F2)-(F4) is mentioned.

L ₂ represents a single bond or a divalent linking group. Examples of the divalent linking group include a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, -O-, -SO _2- , -CO-, and -N (R)-(formula In the above, R represents a hydrogen atom or alkyl), -NHSO ₂ -or a divalent linking group in which a plurality thereof are combined.

Q represents an alicyclic structure. The alicyclic structure may have a substituent, may be monocyclic, may be polycyclic, and in the case of polycyclic, it may be Conjugated. As monocyclic type, a C3-C8 cycloalkyl group is preferable and a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, a cyclooctyl group etc. are mentioned, for example. Examples of the polycyclic type include groups having a bicyclo, tricyclo and tetracyclo structure having 5 or more carbon atoms, and a cycloalkyl group having 6 to 20 carbon atoms is preferable, for example, an adamantyl group, norbornyl group, dicyclopentyl group, Tricyclo decanyl group, tetracyclo dodecyl group, etc. are mentioned. In addition, a part of carbon atoms in a cycloalkyl group may be substituted by hetero atoms, such as an oxygen atom. Especially preferably, Q is a norbornyl group, a tricyclo decanyl group, a tetracyclo dodecyl group, etc. are mentioned.

Hereinafter, although the specific example of the repeating unit which has a fluorine atom is shown, this invention is not limited to this. In the specific examples, X ₁ represents a hydrogen atom, -CH ₃ , -F or -CF ₃ . X ₂ represents -F or -CF ₃ .

Hydrophobic resin (D) may contain a silicon atom. It is preferable that it is resin which has an alkylsilyl structure (preferably trialkylsilyl group) or cyclic siloxane structure as a partial structure which has a silicon atom.

Specific examples of the alkylsilyl structure or the cyclic siloxane structure include groups represented by general formulas (CS-1) to (CS-3) shown below.

In general formula (CS-1)-general formula (CS-3),

R _{12 to} R ₂₆ each independently represent a linear or branched alkyl group (preferably having 1 to 20 carbon atoms) or a cycloalkyl group (preferably having 3 to 20 carbon atoms).

L _{3 to} L ₅ represent a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond, and a combination of two or more (preferably total 12 carbon atoms). The following) is mentioned.

n represents the integer of 1-5. n becomes like this. Preferably it is an integer of 2-4.

Hereinafter, although the specific example of the repeating unit which has group represented by general formula (CS-1)-general formula (CS-3) is given, this invention is not limited to this. In the specific examples, X ₁ represents a hydrogen atom, -CH ₃ , -F or -CF ₃ .

In addition, hydrophobic resin (D) may have at least 1 group chosen from the group of following (x)-(z).

(x) diffuse

(y) a group having a lactone structure, an acid anhydride group, or an acid imide group,

(z) groups decomposed by the action of acids

As the acid group (x), a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonyl imide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkyl Carbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group And a tris (alkylsulfonyl) methylene group.

Preferred acid groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (alkylcarbonyl) methylene groups.

As the repeating unit having an acid group (x), a repeating unit in which an acid group is directly bonded to the main chain of the resin such as a repeating unit of acrylic acid or methacrylic acid, or a repeating unit in which the acid group is bonded to the main chain of the resin through a linking group And a polymerization initiator or a chain transfer agent having an acid group can be introduced at the end of the polymer chain at the time of polymerization, which is preferable in either case. The repeating unit having an acid group (x) may have at least one of a fluorine atom and a silicon atom.

As for content of the repeating unit which has an acidic radical (x), 1-50 mol% is preferable with respect to all the repeating units in hydrophobic resin (D), More preferably, it is 3-35 mol%, More preferably, it is 5-20 mol% to be.

Although the specific example of the repeating unit which has an acidic radical (x) is shown below, this invention is not limited to this. In the formula, Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH.

As a group which has a lactone structure, an acid anhydride group, or an acid imide group (y), the group which has a lactone structure is especially preferable.

The repeating unit containing these groups is a repeating unit in which the group is directly bonded to the main chain of the resin, such as, for example, a repeating unit by an acrylic acid ester or a methacrylic acid ester. Alternatively, the repeating unit may be a repeating unit in which the group is bonded to the main chain of the resin through a linking group. Alternatively, this repeating unit may be introduced at the terminal of the resin using a polymerization initiator or a chain transfer agent having this group at the time of polymerization.

It is preferable that it is 1-100 mol%, and, as for content of the repeating unit which has group which has a lactone structure, an acid anhydride group, or an acid imide group, based on all the repeating units in hydrophobic resin, it is more preferable that it is 3-98 mol% It is more preferable that it is 5 to 95 mol%.

The repeating unit having a group (z) decomposed by the action of an acid in the hydrophobic resin (D) is not particularly limited as long as it is a known one. The repeating unit having a group (z) decomposed by the action of an acid may have at least one of a fluorine atom and a silicon atom. As for content of the repeating unit which has group (z) decomposed by the action of the acid in hydrophobic resin (D), 1-80 mol% is preferable with respect to all the repeating units in resin (D), More preferably, it is 10 80 mol%, More preferably, it is 20-60 mol%.

The hydrophobic resin (D) may further have a repeating unit represented by the following general formula (III).

In general formula (III),

R _c31 represents a hydrogen atom, an alkyl group (may be substituted with a fluorine atom, etc.), a cyano group, or a -CH ₂ -O-Rac ₂ group. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group. R _c31 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

R _c32 represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group or an aryl group. These groups may be substituted with a group containing a fluorine atom or a silicon atom.

L _c3 represents a single bond or a divalent linking group.

The alkyl group of R _c32 in General Formula (III) is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.

The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.

The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.

The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably a phenyl group or a naphthyl group, and these may have a substituent.

R _c32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom.

The divalent linking group for L _c3 is preferably an alkylene group (preferably having 1 to 5 carbon atoms), an ether bond, a phenylene group, or an ester bond (group represented by -COO-).

It is preferable that content of the repeating unit represented by General formula (III) is 1-100 mol%, More preferably, it is 10-90 mol%, 30-70 mol% based on all the repeating units in hydrophobic resin. More preferably.

It is also preferable that hydrophobic resin (D) further has a repeating unit represented with the following general formula (CII-AB).

In formula (CII-AB),

R _c11 'and R _c12 ' each independently represent a hydrogen atom, a cyano group, a halogen atom or an alkyl group.

Zc 'includes two carbon atoms (C-C) bonded to each other and represents an atomic group for forming an alicyclic structure.

The content of the repeating unit represented by General Formula (CII-AB) is preferably 1 to 100 mol%, more preferably 10 to 90 mol%, more preferably 30 to 70 based on all the repeating units in the hydrophobic resin. It is more preferable that it is mol%.

Although the specific example of the repeating unit represented by general formula (III) and general formula (CII-AB) below is given to the following, this invention is not limited to these. In the formula, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN.

Below, the specific example of hydrophobic resin (D) is shown. In addition, the following table shows the molar ratio (it responds sequentially from each repeating unit and a left), the weight average molecular weight, and dispersion degree of the repeating unit in each resin.

When hydrophobic resin (D) has a fluorine atom, it is preferable that it is 5-80 mass% with respect to the weight average molecular weight of hydrophobic resin (D), and it is more preferable that it is 10-80 mass%. Moreover, it is preferable that it is 10-100 mol% among all the repeating units contained in hydrophobic resin (D), and, as for the repeating unit containing a fluorine atom, it is more preferable that it is 30-100 mol%.

When hydrophobic resin (D) has a silicon atom, it is preferable that it is 2-50 mass% with respect to the weight average molecular weight of hydrophobic resin (D), and it is more preferable that it is 2-30 mass%. Moreover, it is preferable that it is 10-100 mol%, and, as for the repeating unit containing a silicon atom, it is more preferable that it is 20-100 mol% in all the repeating units contained in hydrophobic resin (D).

The weight average molecular weight of standard polystyrene conversion of hydrophobic resin (D) becomes like this. Preferably it is 1,000-100,000, More preferably, it is 1,000-50,000, More preferably, it is 2,000-15,000. In addition, the molecular weight distribution (Mw / Mn, also referred to as dispersion degree) is preferably in the range of 1 to 5, more preferably 1 to 3, and even more preferably, in terms of resolution, resist shape, sidewall of the resist pattern, roughness, and the like. It is in the range of 1-2.

Hydrophobic resin (D) may be used by 1 type, and may be used together in plurality.

0.01-10 mass% is preferable with respect to the total solid in the composition of this invention, as for content in the composition of hydrophobic resin (D), 0.05-8 mass% is more preferable, 0.1-5 mass% is further more preferable.

(E) surfactant

The composition according to the present invention may further contain a surfactant. By containing surfactant, when the exposure light source whose wavelength is 250 nm or less, especially 220 nm or less is used, it becomes possible to form the pattern which is favorable sensitivity and resolution, and there are few adhesiveness and development defects.

As the surfactant, it is particularly preferable to use a fluorine-based and / or silicon-based surfactant.

Examples of the fluorine-based and / or silicon-based surfactants include the surfactants described in the specification of US Patent Application Publication No. 2008/0248425. Furthermore, F-top EF301 or EF303 (made by Shin-Akita Kasei Co., Ltd.); Fluoride FC430, 431 or 4430 (manufactured by Sumitomo Industries Co., Ltd.); Megapack F171, F173, F176, F189, F113, F110, F177, F120, or R08 (manufactured by Dainippon Ink & Chemicals Co., Ltd.); Circlon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by Asahi Glass Co., Ltd.); Troisol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 or GF-150 (made by Toagosei Kagaku Co., Ltd.), Sufflon S-393 (made by Seiko Chemical Co., Ltd.); EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 or EF601 (manufactured by Gemco); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA); Alternatively, FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D, or 222D (manufactured by Neos) may be used. Moreover, polysiloxane polymer KP-341 (made by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon type surfactant.

The surfactant may be synthesized using a fluoroaliphatic compound produced by the telomerization method (also called telomer method) or the oligomerization method (also called oligomer method) in addition to the known ones described above. Specifically, you may use the polymer provided with the fluoro aliphatic group guide | induced from this fluoro aliphatic compound as surfactant. This fluoro aliphatic compound can be synthesize | combined by the method of Unexamined-Japanese-Patent No. 2002-90991, for example.

As the polymer having a fluoro aliphatic group, a copolymer of a monomer having a fluoro aliphatic group with (poly (oxyalkylene)) acrylate or methacrylate and / or (poly (oxyalkylene)) methacrylate is preferable and is irregular. May be distributed, or may be block copolymerized.

As a poly (oxyalkylene) group, a poly (oxyethylene) group, a poly (oxypropylene) group, and a poly (oxybutylene) group are mentioned, for example. Moreover, the unit which has alkylene of different chain length in the same chain | strand may be sufficient, such as poly (block linkage of oxyethylene, oxypropylene, and oxyethylene) and poly (block linkage of oxyethylene and oxypropylene).

In addition, the copolymer of the monomer which has a fluoro aliphatic group, and (poly (oxyalkylene)) acrylate or methacrylate is a monomer which has another 2 or more types of fluoro aliphatic groups, and another 2 or more types (poly (oxyalkylene)) ) A tertiary or higher copolymer formed by copolymerizing acrylate or methacrylate at the same time may be used.

For example, as a commercially available surfactant, Megapack F178, F-470, F-473, F-475, F-476, and F-472 (made by Dainippon Ink, Kagaku Kogyo Co., Ltd.) are mentioned. Further, copolymers of acrylates or methacrylates having C ₆ F ₁₃ groups with (poly (oxyalkylene)) acrylates or methacrylates, acrylates or methacrylates having C ₆ F ₁₃ groups and (poly (oxy Ethylene)) acrylates or methacrylates and copolymers of (poly (oxypropylene)) acrylates or methacrylates, acrylates or methacrylates having C ₈ F ₁₇ groups and (poly (oxyalkylene)) acrylates Or a copolymer of methacrylate, and an acrylate or methacrylate having a C ₈ F ₁₇ group with (poly (oxyethylene)) acrylate or methacrylate with (poly (oxypropylene)) acrylate or methacrylate Copolymers, etc. may be mentioned.

Moreover, you may use surfactant other than the fluorine type and / or silicon type described in the specification of US Patent application publication 2008/0248425.

These surfactant may be used individually by 1 type, and may be used in combination of 2 or more type.

When the composition by this invention contains surfactant, the content becomes like this. Preferably it is 0.0001-2 mass% on the basis of the total solid of a composition, More preferably, it is 0.0001-1.5 mass%, More preferably, it is 0.0005? 1 mass%.

(F) carboxylic acid onium salt

The composition of this invention may contain carboxylic acid onium salt. As carboxylic acid onium salt, an iodonium salt and a sulfonium salt are preferable. As an anion part, a C1-C30 linear, branched, monocyclic or polycyclic cyclic alkylcarboxylic acid anion is preferable. More preferably, anions of carboxylic acids in which some or all of these alkyl groups are fluorine substituted. The alkyl chain may contain an oxygen atom. Thereby, transparency with respect to the light of 220 nm or less is ensured, a sensitivity and a resolution are improved, and a roughness dependency and exposure margin are improved.

Examples of the anion of the fluorine-substituted carboxylic acid include fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, nonafluoropentanoic acid, perfluorododecanoic acid, and perfluorotridecanoic acid. And anions of perfluorocyclohexanecarboxylic acid and 2,2-bistrifluoromethylpropionic acid.

The content rate in the composition of an onium salt of a carboxylic acid is generally 0.1-20 mass%, Preferably it is 0.5-10 mass%, More preferably, it is 1-7 mass% with respect to the total solid of a composition.

(G) other additives

The composition according to the present invention is a compound containing a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorbent, and / or a compound which promotes solubility in a developer (for example, a cycloaliphatic compound having a molecular weight of 1000 or less, or a carboxyl group or And an aliphatic compound).

The composition according to the present invention may further contain a dissolution inhibiting compound. Here, a "dissolution inhibiting compound" is a compound having a molecular weight of 3000 or less which is decomposed by the action of an acid and the solubility in a developer containing an organic solvent decreases.

As this dissolution inhibiting compound, an alicyclic group containing an acid-decomposable group such as a cholic acid derivative containing an acid-decomposable group described in Proceeding of SPIE, 2724, 355 (1996), in order not to lower the transmittance to light having a wavelength of 220 nm or less. Group or aliphatic compounds are preferred. As this acid-decomposable group and alicyclic structure, the thing similar to what was demonstrated previously is mentioned, for example.

In addition, when exposing the resist composition by this invention by KrF excimer laser or irradiating with an electron beam, the compound containing the structure which substituted the phenolic hydroxyl group of the phenol compound by the acid-decomposer as a dissolution inhibiting compound is preferable. As a phenolic compound, it is preferable to contain 1-9 phenol skeletons, and it is more preferable to contain 2-6 pieces.

When the composition by this invention contains the dissolution inhibiting compound, the content becomes like this. Preferably it is 3-50 mass%, More preferably, it is 5-40 mass% based on the total solid of a composition.

Specific examples of the dissolution inhibiting compound are given below.

The phenol compound having a molecular weight of 1,000 or less can be easily referred to, for example, by methods described in Japanese Patent Application Laid-Open No. 4-122938, Japanese Patent Application Laid-Open No. 2-28531, US Patent No. 4,916,210, and European Patent No. 219294. Can be synthesized.

Examples of the alicyclic or aliphatic compound containing a carboxyl group include carboxylic acid derivatives including steroid structures such as cholic acid, dioxycholic acid and lithocholic acid, adamantanecarboxylic acid derivatives, adamantanedicarboxylic acid and cyclo Hexanecarboxylic acid and cyclohexanedicarboxylic acid are mentioned.

(H) solvent

The resist composition which concerns on this invention may contain the solvent further. As this solvent, you may contain, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactic acid alkyl ester, alkyl alkoxypropionate, cyclic lactone having 4 to 10 carbon atoms, and ring having 4 to 10 carbon atoms. Organic solvents such as monoketone compounds, alkylene carbonates, alkyl alkoxyacetic acids and alkyl pyruvates.

Examples of the alkylene glycol monoalkyl ether carboxylates include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, and propylene glycol monomethyl ether propionate. , Propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate are preferable.

As the alkylene glycol monoalkyl ether, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether are preferable. Can be mentioned.

As lactic acid alkyl ester, methyl lactate, ethyl lactate, propyl lactic acid, and butyl lactate are mentioned preferably, for example.

As the alkyl alkoxypropionate, for example, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-methoxypropionate are preferably used.

Examples of the cyclic lactone having 4 to 10 carbon atoms include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, (gamma) -valerolactone, (gamma) -caprolactone, (gamma) -octanoic lactone, and (alpha) -hydroxy- (gamma) -butyrolactone are mentioned preferably.

As a monoketone compound which may contain the C4-10 ring, for example, 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone , 4-methyl-2-pentanone, 2-methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetra Methyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one, 3-penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclo Pentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2, 6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methyl A claw-heptanone, and 3-methyl-bicyclo-heptanone can be preferably mentioned.

As alkylene carbonate, a propylene carbonate, vinylene carbonate, ethylene carbonate, butylene carbonate is mentioned preferably, for example.

As an alkoxy acetic acid alkyl, for example, 2-methoxy ethyl acetate, 2-ethoxy ethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, Acetic acid-1-methoxy-2-propyl is mentioned preferably.

As the alkyl pyruvate, for example, methyl pyruvate, ethyl pyruvate and propyl pyruvate are preferably used.

As a solvent which can be used preferably, the solvent which is a boiling point of 130 degreeC or more under normal temperature normal pressure is mentioned. Specifically, cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, ethyl pyruvate, and ethyl acetate-2-e Oxyethyl, acetic acid-2- (2-ethoxyethoxy) ethyl, and propylene carbonate.

In this invention, the said solvent may be used independently and may use two or more types together.

In this invention, you may use the mixed solvent which mixed the solvent containing a hydroxyl group in the structure, and the solvent which does not contain a hydroxyl group as an organic solvent.

Examples of the solvent containing a hydroxyl group include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethyl lactate, and the like. Propylene glycol monomethyl ether and ethyl lactate are particularly preferred.

As a solvent which does not contain a hydroxyl group, For example, propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, (gamma) -butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, etc. are mentioned, Among these, a propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, (gamma) -butyrolactone, cyclohexanone, butyl acetate Especially preferred is propylene glycol monomethyl ether acetate, ethyl ethoxy propionate and 2-heptanone.

The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent containing no hydroxyl group is 1/99-99/1, Preferably it is 10/90-90/10, More preferably, it is 20/80-60/40. The mixed solvent which contains 50 mass% or more of solvents which does not contain a hydroxyl group is especially preferable at the point of coating uniformity.

The solvent is preferably a mixed solvent of propylene glycol monomethyl ether acetate and at least one other solvent.

It is preferable that especially a solvent contains propylene glycol monomethyl ether acetate and cyclohexanone. By adopting such a configuration, the in-plane uniformity and pattern shape of the film thickness at the time of coating can be further improved. In this case, the mass ratio of propylene glycol monomethyl ether acetate and cyclohexanone is preferably 60:40 to 90:10, and more preferably 60:40 to 80:20.

It is also preferable that a solvent further contains propylene glycol monomethyl ether in addition to propylene glycol monomethyl ether acetate and cyclohexanone. In this case, it is preferable that it is 5-40 mass%, and, as for content of the propylene glycol monomethyl ether in a solvent, it is more preferable that it is 5-25 mass%.

Solid content concentration of the resist composition which concerns on this invention is 1.0-10 mass% normally, Preferably it is 2.0-8.0 mass%. This further improves in-plane uniformity of the film thickness at the time of coating.

<Pattern Forming Method>

In the pattern formation method according to the present invention, (A) a film is formed using the resist composition described above, (B) the film is exposed, and (C) the exposed film is developed using a developer containing an organic solvent to form a negative type. It includes forming a pattern. In addition, this method may further include rinsing the negative pattern obtained using (D) rinse liquid.

It is also preferable to include an electric heat (PB; prebake) process before a post-film-forming exposure process. It is also preferable to include a post exposure bake (PEB) step after the exposure step and before the development step.

It is preferable to perform heating temperature at 40-130 degreeC in both a PB process and a PEB process, It is more preferable to carry out at 50-120 degreeC, It is still more preferable to carry out at 60-110 degreeC. In particular, when the PEB process is performed at a low temperature of 60 ° C. to 90 ° C., the exposure latitude (EL) and the resolution can be remarkably improved.

Moreover, 30-300 second is preferable, 30-180 second is more preferable, and 30-90 second is more preferable.

In the pattern forming method according to the present invention, the step of forming the film by the composition on the substrate, the step of exposing the film, the heating step, and the developing step can be carried out by a generally known method.

The wavelength of the light source used for the exposure, but are not limited to, for example, a KrF excimer laser wavelength (248㎚), ArF excimer laser wavelength (193㎚), and, F ₂ excimer laser wavelength (157㎚).

You may perform liquid immersion exposure with respect to the film | membrane formed using the composition by this invention. As a result, resolution can be further improved. As the liquid immersion medium to be used, any liquid can be used as long as the liquid has a refractive index higher than that of air, but is preferably pure water.

In this case, the above-described hydrophobic resin may be added to the composition in advance, or a liquid immersion liquid poorly soluble film (hereinafter also referred to as a "top coat") may be formed thereon. In addition, the performance required for the top coat, its usage, and the like are described in Chapter 7 of CMC Publication "Process and Materials of Immersion Lithography."

From the viewpoint of transparency to a laser having a wavelength of 193 nm, the top coat is preferably a polymer that does not contain abundant aromatics. For example, a hydrocarbon polymer, an acrylic ester polymer, polymethacrylic acid, polyacrylic acid, polyvinyl ether, silicon Containing polymers and fluorine-containing polymers. The hydrophobic resin described above is also preferable as a top coat. In addition, commercially available topcoat materials can be suitably used.

When peeling a top coat after exposure, you may use a developing solution and you may use a separate peeling agent. As a peeling agent, the solvent with small penetration into a film | membrane is preferable. It is preferable that it can peel with a developing solution from the point that a peeling process can be performed simultaneously with the image development process of a film | membrane.

There is no restriction | limiting in particular in the board | substrate which forms a film in this invention. As this board | substrate, the board | substrate generally used in the semiconductor manufacturing process, such as IC, the manufacturing process of circuit boards, such as a liquid crystal and a thermal head, and the lithography process of other photofabrication can be used. As such a substrate, for example, a coating of silicon-based inorganic substrate, such as SiN and SiO ₂ such as an inorganic substrate, and the SOG. In addition, an organic antireflection film may be formed between the film and the substrate as necessary.

As a developing solution containing an organic solvent, for example, a developing solution containing a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent, and a hydrocarbon solvent.

Examples of the ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, acetyl acetone, acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl Ketones, isophorone, and propylene carbonate.

Examples of the ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, n-pentyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and ethylene glycol mono Ethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate , Ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, methyl propionate, methyl 3-methoxypropionate (MMP), ethyl propionate, ethyl 3-ethoxypropionate (EEP), and propionic acid propyl. Can be. In particular, acetic acid alkyl esters, such as methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, and amyl acetate, or propionic acid alkyl esters, such as methyl propionate, ethyl propionate, and propyl propionate, are preferable.

As the alcohol solvent, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl Alcohols such as 2-pentanol, n-heptyl alcohol, n-octyl alcohol and n-decanol; Glycols such as ethylene glycol, diethylene glycol and triethylene glycol; And glycol ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol. have.

Examples of the ether solvents include dioxane, tetrahydrofuran and anisole in addition to the glycol ether.

Examples of the amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethyl phosphate triamide, and 1,3-dimethyl-2-imide. Dazolidinones.

As a hydrocarbon solvent, aromatic hydrocarbon solvents, such as toluene, xylene, and anisole, and aliphatic hydrocarbon solvents, such as a pentane, hexane, an octane, and a decane, are mentioned, for example.

You may use the said solvent in mixture of 2 or more types. Moreover, you may use in mixture with solvent and / or water of that excepting the above within the range which can exhibit sufficient performance. However, it is preferable that the moisture content as the whole developing solution is less than 10 mass%, and it is more preferable that a developing solution does not contain water substantially. That is, it is preferable that this developing solution is a developing solution which consists only of organic solvent substantially. Moreover, also in this case, a developing solution may contain surfactant mentioned later. In this case, the developer may contain inevitable impurities derived from the atmosphere.

It is preferable that the usage-amount of the organic solvent with respect to a developing solution is 80 mass% or more and 100 mass% or less with respect to whole quantity of a developing solution, It is more preferable that it is 90 mass% or more and 100 mass% or less, It is further more preferable that it is 95 mass% or more and 100 mass% or less. .

The organic solvent contained in the developer is preferably at least one selected from ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. The organic solvent contained in the developer is particularly preferably an ester solvent.

It is preferable that the vapor pressure of the developing solution containing the organic solvent is 5 kPa or less in 20 degreeC, It is more preferable that it is 3 kPa or less, It is especially preferable that it is 2 kPa or less. By setting the vapor pressure of the developing solution to 5 kPa or less, evaporation of the developing solution on the substrate or in the developing cup is suppressed, and the temperature uniformity in the wafer surface is improved, and as a result, the dimensional uniformity in the wafer surface is improved.

Specific examples of the developer having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methyl Ketone solvents such as cyclohexanone, phenylacetone and methyl isobutyl ketone; Butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxy Ester solvents such as butyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formic acid, ethyl lactate, butyl lactate and propyl lactic acid; n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl Alcohol solvents such as alcohols and n-decanol; Glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol; Glycol ether solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol; Ether solvents such as tetrahydrofuran; Amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide; Aromatic hydrocarbon solvents such as toluene and xylene; And aliphatic hydrocarbon solvents such as octane and decane.

Specific examples of the developer having a vapor pressure of 2 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, Ketone solvents such as methylcyclohexanone and phenylacetone; Butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxy Ester solvents such as butyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, and lactic acid propyl; alcohols such as n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol and n-decanol System solvents; Glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol; Glycol ether solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol; Amide solvents of N-methyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide; Aromatic hydrocarbon solvents such as xylene; And aliphatic hydrocarbon solvents such as octane and decane.

An appropriate amount of surfactant can be added to the developing solution as needed.

There is no restriction | limiting in particular in this surfactant, For example, an ionic or nonionic fluorine type and / or silicon type surfactant can be used. As these fluorine and / or silicon type surfactants, For example, Unexamined-Japanese-Patent No. 62-36663, Unexamined-Japanese-Patent No. 61-226746, Unexamined-Japanese-Patent No. 61-226745, and Japan Unexamined-Japanese-Patent No. 62- 170950, Japanese Patent Laid-Open No. 63-34540, Japanese Patent Laid-Open No. 7-230165, Japanese Patent Laid-Open No. 8-62834, Japanese Patent Laid-Open No. 9-54432, Japanese Patent Laid-Open No. 9- Surfactants described in Japanese Patent No. 5988, US Patent 5405720, US 5360692, US 5529881, US 5296330, US 5436098, US 5576143, US 5294511, US 5824451 Can be mentioned. It is preferable that this surfactant is nonionic. As the nonionic surfactant, it is more preferable to use a fluorine-based surfactant or a silicon-based surfactant.

In addition, the usage-amount of surfactant is 0.001-5 mass% normally with respect to whole quantity of a developing solution, Preferably it is 0.005-2 mass%, More preferably, it is 0.01-0.5 mass%.

As a developing method, for example, a method of immersing a substrate in a bath filled with a developer for a predetermined time (dip method), a method of developing a developer by raising the developer solution on the surface of the substrate by surface tension and stopping for a certain time (paddle method), a developer on the substrate surface The spraying method (spray method) and the method (dynamic dispensing method) which continuously discharge a developing solution, scanning the developer discharge nozzle at a fixed speed on the board | substrate which rotates at a fixed speed are mentioned.

When the above various developing methods include a step of discharging the developer from the developing nozzle of the developing apparatus toward the resist film, the discharge pressure (flow rate per unit area of the developer to be discharged) of the discharged developer is preferably 2 mL / sec / mm 2 or less. More preferably, it is 1.5 mL / sec / mm <2> or less, More preferably, it is 1 mL / sec / mm <2> or less. There is no particular lower limit for the flow rate, but considering the throughput, the lower limit is preferably 0.2 mL / sec / mm 2 or more.

By setting the discharge pressure of the developer to be discharged within the above range, defects in the pattern resulting from the resist residue after development can be significantly reduced.

Although the details of this mechanism are not clear, it is probably because the pressure applied to the resist film by the developer by reducing the discharge pressure is reduced, thereby preventing the resist film and / or the resist pattern from being inadvertently shaved or collapsed.

The discharge pressure (mL / sec / mm 2) of the developing solution is a value at the exit of the developing nozzle in the developing apparatus.

As a method of adjusting the discharge pressure of a developing solution, the method of adjusting discharge pressure with a pump etc., and the method of changing the discharge pressure of a developing solution by adjusting a pressure by supply from a pressurization tank are mentioned, for example.

Moreover, you may perform the process of stopping image development, replacing by another solvent after the process of image development.

It is preferable that the pattern formation method by this invention includes the rinse process (process of washing a film | membrane using the rinse liquid containing an organic solvent) after the said image development process.

There is no restriction | limiting in particular as a rinse liquid used for a rinse process, if the pattern after image development is not melt | dissolved, The solution containing the general organic solvent can be used.

Examples of the rinse liquid include those containing at least one organic solvent selected from a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent. The rinse liquid more preferably contains at least one organic solvent selected from ketone solvents, ester solvents, alcohol solvents and amide solvents, and more preferably alcohol solvents or ester solvents. .

As for this rinse liquid, it is more preferable that monohydric alcohol is included, and it is more preferable that monovalent alcohol containing 5 or more carbon atoms is included.

These monohydric alcohols may be linear, branched or cyclic. As these monohydric alcohols, for example, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2 -Pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, and 4 -Octanol. Examples of the monohydric alcohol having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, and 3-methyl-1-butanol.

Two or more types of said each component may be used in mixture, and may be used in mixture with the organic solvent of that excepting the above.

It is preferable that the water content of a rinse liquid is less than 10 mass%, It is preferable that it is less than 5 mass%, It is more preferable that it is less than 3 mass%. That is, it is preferable that the usage-amount of the organic solvent with respect to a rinse liquid is 90 mass% or more and 100 mass% or less with respect to whole quantity of a rinse liquid, It is more preferable that it is 95 mass% or more and 100 mass% or less, It is 97 mass% or more and 100 mass% or less Is particularly preferred. By making the water content of the rinse liquid less than 10 mass%, more favorable image development characteristics can be achieved.

The vapor pressure of the rinse liquid is preferably 0.05 kPa or more and 5 kPa or less at 20 ° C, more preferably 0.1 kPa or more and 5 kPa or less, and even more preferably 0.12 kPa or more and 3 kPa or less. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and the swelling caused by the penetration of the rinse liquid is suppressed and the dimensional uniformity in the wafer surface is improved.

Moreover, you may add an appropriate amount of surfactant to a rinse liquid.

In the rinse step, the developed wafer is cleaned using the rinse liquid. Although the method of a washing process is not specifically limited, For example, the method of continuing to discharge a rinse liquid on the board | substrate which rotates at a fixed speed (rotary coating method), and the method of immersing a board | substrate in the tank filled with the rinse liquid for a predetermined time. (Dip method) and the method (spray method) of spraying a rinse liquid on the board | substrate surface are mentioned. Among these, it is preferable to remove a rinse liquid from the board | substrate by rotating a board | substrate at the rotation speed of 2000 rpm-4000 rpm after performing a washing process by the rotation coating method.

The pattern forming method according to the present invention may include a developing step (a positive pattern forming step) using an alkaline developing solution in addition to the developing step with a developing solution containing an organic solvent. Although there is no restriction | limiting in particular in the order of the image development process using an alkaline developing solution, and the image development process using the developing solution containing the organic solvent, It is more preferable to perform image development using an alkaline developing solution before image development using the developing solution containing the organic solvent. Moreover, it is preferable to include a heating process before each developing process.

Although the kind of alkaline developing solution is not specifically limited, Usually, the aqueous solution of tetramethylammonium hydroxide is used. An appropriate amount of alcohols and / or surfactants may be added to the alkaline developer.

The alkali concentration of alkaline developing solution is 0.1-20 mass% normally. The pH of alkaline developing solution is 10.0-15.0 normally. As alkaline developing solution, it is especially preferable to use 2.38 mass% aqueous solution of the tetramethylammonium hydroxide.

When rinsing is performed after development using an alkaline developer, pure water is typically used as the rinse solution. You may add an appropriate amount of surfactant to this rinse liquid.

[Example]

Hereinafter, although an Example demonstrates this invention further in detail, the content of this invention is not limited by this.

<Acid degradable resin>

Synthesis Example 1

The following resin (P-1) was synthesize | combined as follows.

209.9 mass parts of cyclohexanone was heated to 80 degreeC under nitrogen stream. While stirring this liquid, the monomer represented by following structural formula (A): 44.5 mass parts, the monomer represented by following structural formula (B): 11.8 mass parts, the monomer represented by following structural formula (C): 36.5 mass parts, and the monomer represented by following structural formula (D): 13.1 Mass part, cyclohexanone: 389.8 mass part, 2,2'- azobisisobutyric acid dimethyl [V-601, Wako Pure Chemical Industries, Ltd.]: 4.61 mass part of the mixed solution was dripped over 3 hours. It stirred further at 80 degreeC after completion | finish of dripping. After cooling the reaction solution, it was reprecipitated with a large amount of hexane / ethyl acetate and 90.0 parts by mass of resin (P-1) was obtained by vacuum drying the filtered solid.

The weight average molecular weight (Mw: polystyrene conversion) calculated | required from GPC (carrier: tetrahydrofuran (THF)) of obtained resin (P-1) was 10600, and dispersion degree (Mw / Mn) was 1.59.

Similarly, resin (P-2) and resin (P-10) shown below were synthesize | combined. Table 3 shows the molar ratio, weight average molecular weight (Mw), and dispersion degree (Pd) of the repeating units constituting each resin. In addition, in the synthesis | combination of each resin, the weight average molecular weight was adjusted by changing the quantity of an initiator.

<Mine generator>

[Synthesis Example 2]

The following compound (A-1) was synthesize | combined similarly to the synthesis example 3 of Unexamined-Japanese-Patent No. 2008-060800, except that decahydroisoquinoline was used instead of piperidine.

The following compound (A-2) was synthesize | combined with reference to Unexamined-Japanese-Patent No. 2006-257078.

In the same manner, the following compound (A-3) and compound (A-4) were synthesized. In addition, WPAG-773 (made by Wako Pure Chemical) was used as following compound (A-5).

&Lt; Basic compound >

[Synthesis Example 3]

The following compound (B-1) was synthesize | combined as follows.

30.0 g (0.3365 mol) of 3-methoxypropylamine, 92.2 g (0.7404 mol) of ethylene glycol mono-2-chloroethyl ether, and 107.1 g (1.01 mol) of sodium carbonate were added to 200 mL of toluene. The reaction solution obtained thereafter was heated to reflux over 16 hours. The salt which precipitated after cooling was filtered, and toluene was distilled off under reduced pressure. Subsequently, purification was performed by silica gel chromatography. This obtained 38g basic compound (B-1) (yield 43%).

(B-1) ¹ H-NMR (300 MHz, CDCl ₃ ): δ 1.73-1.84 (m, 2H), 2.62-2.71 (m, 6H), 3.41 (t, 2H, 6.0 Hz), 3.33 (s , 3H), 3.58-3.80 (m, 12H).

In the same manner, the following compound (B-2) to compound (B-6) were synthesized. In addition, the following compound (B-7) and compound (B-8) were prepared for reference.

<Solvent>

As a solvent, the following were mixed suitably and used.

Y1: propylene glycol monomethyl ether acetate (PGMEA; alias 1-methoxy-2-acetoxypropane);

Y2: propylene glycol monomethyl ether (PGME; alias 1-methoxy-2-propanol);

Y3: cyclohexanone

<Surfactant>

The following were used as surfactant.

W-1: PF-6320 (made by OMNOVA Corporation)

&Lt; Hydrophobic resin &

As the hydrophobic resin, the followings were used.

Z1: the following compound (Mw = 4200, Mw / Mn = 1.31)

<Preparation of resist composition>

The component shown in following Table 4 was melt | dissolved in the solvent shown in the same table, and the solution whose solid content concentration was 6.5 mass% was prepared. Each of these was filtered through a polyethylene filter having a pore size of 0.03 µm to prepare a resist composition (Ar-01) to (Ar-17).

<Formation of pattern>

A silicon wafer, SiO ₂ was prepared by the deposited substrate 2200Å. This substrate was subjected to hexamethyldisilane (HMDS) treatment at 100 ° C. for 30 seconds. The resist composition shown in Table 4 was apply | coated on it, and baking was performed at 100 degreeC for 60 second, and the resist film with a film thickness of 220 nm was formed.

On the obtained wafer, an exposure mask (pitch 200 nm, Duty = 1: 1) using an ArF excimer laser scanner (PAS5500 / 1100, NA 0.75, Dipole 35, σo / σi = 0.89 / 0.65, Y-polarization) manufactured by ASML Pattern exposure was performed through. Then, it heated at 105 degreeC for 60 second. Subsequently, a paddle was developed for 30 seconds with a negative developer (butyl acetate), followed by development for 30 seconds with a rinse solution (methylisobutylcarbinol (MIBC)). Subsequently, by rotating the wafer for 30 seconds at a rotation speed of 4000 rpm, a 1: 1 line and space pattern having a line width of 100 nm was obtained.

<Evaluation method>

[E _opt ]

The pattern was observed by a side-scanning electron microscope (SEM Hitachi Seisakusho S-9380II), and the optimum exposure dose when resolving a 1: 1 line and space pattern with a line width of 100 nm was determined by sensitivity (E _opt ) ( mJ / cm 2). The smaller this value, the higher the sensitivity.

Exposure Latitude (EL)

Regarding the pattern formation of each Example and Comparative Example, when the exposure dose was changed from the optimum exposure dose, an exposure dose width allowing ± 10% of the pattern size in each Example and Comparative Example was obtained, and this value was determined as sensitivity (E _opt). Percent divided by). The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude EL (%).

[Linewidth roughness (LWR)]

A 1: 1 line and space pattern having a line width of 100 nm was observed using a side-scanning electron microscope (SEM Hitachi Seisakusho S-9380), and the range of the space pattern in the longitudinal direction of 2 μm was 50 at equal intervals. The line width was measured and measured by calculating 3σ from the standard deviation. Smaller values indicate better performance.

[Local CDU]

Using the exposure mask, the exposure dose and focus for forming a 1: 1 line-and-space pattern having a line width of 100 nm are the optimum exposure dose and the optimum focus, respectively, and the exposure dose is at an interval of 1 μm with the optimum exposure dose and the focus at the optimum focus. Space sizes of five arbitrary and 45 total systems were measured at nine locations, and their standard deviations were calculated to calculate 3σ. Smaller values indicate better performance.

[Pattern shape]

The cross-sectional shape of each pattern in the exposure amount which shows the said sensitivity was observed using the scanning electron microscope (Hitachi Seisakusho S-9380II), and the pattern shape was evaluated in accordance with the following references | standards.

5: When the cross-sectional shape is rectangular, there is no standing wave, and roughness is not observed on the pattern surface.

4: When the cross-sectional shape is almost rectangular, there is no standing wave, and roughness is not observed on the pattern surface.

3: When the cross-sectional shape is almost rectangular, standing waves are observed slightly, and roughness is observed on the pattern surface.

2: When cross-sectional shape is taper shape or inverse taper shape, when standing wave is observed a little and roughness is partially observed on pattern surface.

1: When the cross section is tapered or inverse tapered, standing waves are observed, and roughness is observed on the pattern surface.

The above evaluation results are shown in Table 5 below.

As can be seen from Table 5, when the composition according to the example was used, a pattern having a better shape could be formed as compared with the case where the composition according to the comparative example was used. In addition, the composition according to the Examples also exhibited excellent performance in sensitivity, exposure latitude, line width roughness (LWR), and uniformity of local pattern dimensions (Local CDU).

<Immersion exposure>

Pattern formation by liquid immersion exposure was performed on the resist compositions (Ar-01) to (Ar-17). In addition, content of resin (P-2) was 91.0 mass parts and content of hydrophobic resin (Z-1) was 0.5 mass part about resist composition (Ar-02) at this time.

Evaluation similar to the above was performed about the obtained pattern. As a result, the composition by the Example showed the outstanding performance compared with the composition by the comparative example also when immersion exposure was performed.

<Evaluation when using other developer>

A pattern was formed in the same manner as described above, except that EEP, MAK (methyl amyl ketone), amyl acetate, or a mixed solvent of butyl acetate and MAK (mass ratio 1: 1) was used as the developer. And the evaluation similar to the above was performed about the obtained pattern. As a result, it was confirmed that excellent performance can be achieved even when a developer other than butyl acetate is used.

<Evaluation when omitting rinse process>

The pattern was formed in the same manner as described above, except that the rinse step was omitted. And the evaluation similar to the above was performed about the obtained pattern. As a result, it was confirmed that excellent performance can be achieved even when the rinse step is omitted.

The resist composition of the present invention capable of providing a pattern having such a performance can be suitably used in a lithography process in the manufacture of electronic devices such as various semiconductor elements and recording media.

Claims (14)

(A) a resin which has an alicyclic structure and whose dissolution rate with respect to a developing solution changes by the action of an acid,
(B) a compound which generates an acid by irradiation of actinic light or radiation,
(C) The resist composition containing the compound represented by the following general formula (EA).

[Wherein,
o, p and q each independently represent an integer of 1 or more.
n represents an integer of 3 or more.
r and s each independently represent an integer of 1 or more.
t represents an integer of 0 or more.
R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.
R ₃ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group when t ≧ 1, and an alkyl group, an aryl group or an aralkyl group when t = 0; The method of claim 1,
The said resin is equipped with the lactone group containing the said alicyclic structure, The resist composition characterized by the above-mentioned. The method of claim 2,
The lactone group is not provided with a cyano group. (A) to the repeating unit (a) represented by the following general formula (Ia) or the general formula (Ib), the repeating unit (b) represented by the following general formula (II), and the following general formula (III) Resin containing the repeating unit (d) represented by,
(B) a compound which generates an acid by irradiation of actinic light or radiation,
(C) The resist composition containing the compound represented by the following general formula (EA).

[Wherein,
R ₁ represents a hydrogen atom or a methyl group.
R ₂ each independently represents an alkyl group when q ≧ ₂ .
R ₃ represents a hydrogen atom or an alkyl group.
q represents the integer of 0-3.
s represents an integer of 1 to 3]

[Wherein,
R ₄ represents a hydrogen atom or a methyl group.
R ₅ , R ₆ and R ₇ each independently represent an alkyl group or a monocyclic cycloalkyl group. Two of R ₅ , R ₆ and R ₇ may be bonded to each other to form a monocyclic ring]

[Wherein,
R ₉ represents a hydrogen atom or a methyl group.
m represents 1 or 2]

[Wherein,
o, p and q each independently represent an integer of 1 or more.
n represents an integer of 3 or more.
r and s each independently represent an integer of 1 or more.
t represents an integer of 0 or more.
R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.
R ₃ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group when t ≧ 1, and an alkyl group, an aryl group or an aralkyl group when t = 0; The method of claim 4, wherein
The said resin (A) is different from the said repeating unit (b), and further includes the repeating unit (c) provided with the group decomposed by the action of an acid. The method of claim 5, wherein
The resin (A) is,
Content of the said repeating unit (a) is 30-55 mol%,
Content of the said repeating unit (b) is 20-50 mol%,
Content of the said repeating unit (c) is 5-30 mol%,
Content of the said repeating unit (d) is 1-20 mol%, The resist composition characterized by the above-mentioned. The method according to claim 1 or 4,
The weight average molecular weight of the said resin (A) exists in the range of 5000-30000, The resist composition characterized by the above-mentioned. The method according to claim 1 or 4,
A resist composition, further comprising a solvent comprising propylene glycol monomethyl ether acetate and cyclohexanone. The resist film formed using the resist composition of Claim 1 or 4. Using the resist composition according to claim 1 or 4 to form a film,
Exposing the film;
And forming a negative pattern by developing the exposed film using a developer containing an organic solvent. 11. The method of claim 10,
The developing solution includes a pattern forming method comprising an ester solvent as the organic solvent. 11. The method of claim 10,
And rinsing the negative pattern. The manufacturing method of the electronic device containing the pattern formation method of Claim 10. It is manufactured by the manufacturing method of the electronic device of Claim 13, The electronic device characterized by the above-mentioned.