JP2013167731A - Actinic ray-sensitive or radiation-sensitive resin composition and pattern forming method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an actinic ray-sensitive or radiation-sensitive resin composition capable of suppressing pattern collapse and improving LWR (line width roughness) and storage stability, and a pattern forming method using the composition.SOLUTION: An actinic ray-sensitive or radiation-sensitive resin composition comprises: (A) resin having a repeating unit expressed by the following general formula (1) and a repeating unit that is decomposed by an action of an acid to increase the solubility in an alkali developing solution; (B) a compound Rincluding at least one nitrogen atom or a compound which is an ionic compound including a basic moiety Rincluding at least one nitrogen atom, both having such a property that R-Hor R-Has conjugated acids thereof has a pKa of 8 or lower; and (C) a compound that generates an acid by irradiation with actinic rays or radiation. In the general formula (1), L represents a single bond or a divalent connecting group; Rrepresents a hydrogen atom or an alkyl group; and Z represents a cyclic acid anhydride structure.

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition and a pattern forming method using the same. More specifically, the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition suitably used for ultra-microlithography processes such as the production of VLSI and high-capacity microchips, and other photofabrication processes, and The present invention relates to the pattern forming method used. In particular, the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition particularly suitable when an ArF excimer laser or a KrF excimer laser is used as an irradiation source, and a pattern forming method using the same.

  The present invention also relates to an actinic ray-sensitive or radiation-sensitive film using the composition, an electronic device manufacturing method including the pattern forming method, and an electronic device manufactured by the method.

  Conventionally, in the manufacturing process of semiconductor devices such as IC and LSI, fine processing by lithography using a photoresist composition has been performed. In recent years, with the high integration of integrated circuits, the formation of ultrafine patterns in the submicron region and the quarter micron region has been required. Along with this, there is a tendency to shorten the exposure wavelength from g-line to i-line and further to KrF excimer laser light.

  As a resist composition for KrF exposure, a resist composition containing a resin having polyhydroxystyrene as a basic skeleton has been developed. As such a resin, for example, a copolymer of hydroxystyrene and a monomer containing an adamantyl group is known (see, for example, Patent Document 1).

  On the other hand, as a resist composition exposed mainly by an ArF light source, a composition containing a resin not containing an aromatic ring has been developed. As such a composition, for example, a composition containing a resin having a specific lactone structure is known (see, for example, Patent Document 2). Moreover, in order to improve hydrophilicity, the resist composition containing resin which has an acid anhydride structure is developed (for example, refer patent document 3 and 4).

  However, in the resist composition described above, further improvements are required for suppression of pattern collapse, pattern roughness such as Line Width Roughness (LWR), and storage stability of the resist solution.

US Patent Application Publication No. 2007/0121390 JP 2008-031298 A JP 2000-212221 A JP 2004-051995 A

  An object of the present invention is to solve the problem of the technology for improving performance in microfabrication of a semiconductor device using actinic rays or radiation, particularly ArF excimer laser light. In particular, it is to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of suppressing pattern collapse and improving LWR and storage stability, and a pattern forming method using the same.

  As a result of intensive studies to solve the above problems, the present inventors have completed the invention exemplified below.

[1] (A) a resin containing a repeating unit represented by the following general formula (1) and a repeating unit that decomposes by the action of an acid to increase the solubility in an alkali developer;
(B) an ionic compound comprising a basic moiety R _NN containing at least one nitrogen atom-containing compound R _N or at least one nitrogen atom, R _N -H ^+, or R is these conjugate acid _A compound having a pKa of _NN- H ⁺ of 8 or less;
(C) Actinic ray-sensitive or radiation-sensitive resin composition comprising a compound that generates acid upon irradiation with actinic ray or radiation:

In general formula (1),
L represents a single bond or a divalent linking group;
R ₁ represents a hydrogen atom or an alkyl group;
Z represents a cyclic acid anhydride structure.

[2] the at least compound R _N containing one nitrogen atom, characterized by being represented by the following general formula (b1) [1] ray- described or radiation-sensitive resin composition:

In general formula (b1):
n represents an integer of 0 to 2, m represents an integer of 1 to 3, and n + m = 3;
Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and when n = 2, the two Ras may be the same or different, and the two Ras are bonded to each other, and Ra May form a heterocyclic hydrocarbon group or a derivative thereof together with the nitrogen atom to which is bonded;
Rb independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group, and at least two Rb's are bonded to form an alicyclic hydrocarbon group or aromatic hydrocarbon. Groups, heterocyclic hydrocarbon groups or derivatives thereof may be formed.

[3] The actinic ray-sensitive or [1] as described in [1], wherein the ionic compound containing the basic moiety _RNN containing at least one nitrogen atom is represented by the following general formula (b2): Radiation sensitive resin composition:
_RNN- A ^- X ⁺ (b2)
In general formula (b2):
_RNN represents a monovalent basic compound residue containing at least one nitrogen atom, and the pKa of the conjugate acid _RNN- H ⁺ is 8 or less;
A ⁻ represents —SO ₃ ^— , —CO ₂ ^— or —X ₁ —N ^—— X ₂ —R ₁ , X ₁ and X ₂ each independently represent —CO— or —SO ₂ —; R ₁ represents a monovalent organic group;
X ⁺ represents a counter cation.

[4] The activity sensitive material according to any one of [1] to [3], wherein the resin (A) further contains at least one repeating unit represented by the following general formula (III): Light-sensitive or radiation-sensitive resin composition:

In general formula (III):
R ₈ and R ₉ represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms;
n represents an integer of 1 to 6.

[5] An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4].

[6] Forming a film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], exposing the film, and exposing the exposed film Developing a pattern.

[7] A method for manufacturing an electronic device, comprising the pattern forming method according to [6].

[8] An electronic device manufactured by the method for manufacturing an electronic device according to [7].

  According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of suppressing pattern collapse and improving LWR and storage stability, and a pattern forming method using the same.

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

  In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

  In the present invention, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, a deep ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (EUV light), an X-ray, an electron beam, an ion beam or other particle beam. Means. In the present invention, “light” means actinic rays or radiation.

  In addition, the term “exposure” in the present specification is not limited to exposure to far ultraviolet rays, X-rays, extreme ultraviolet rays (EUV light) and the like represented by mercury lamps and excimer lasers. It is also assumed that drawing by particle beams such as.

The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is decomposed by the action of (A) the repeating unit represented by the general formula (1) described later and an acid, thereby increasing the solubility in an alkali developer. a resin containing a repeating unit, (B) an ionic compound comprising a basic moiety R _NN containing at least one nitrogen atom-containing compound R _N or at least one nitrogen atom, in these conjugate acid A compound in which the pKa of a certain R _N —H ⁺ or R _NN —H ⁺ is 8 or less and (C) a compound that generates an acid upon irradiation with actinic rays or radiation are contained.

  The present inventors have found that the storage stability of the actinic ray-sensitive or radiation-sensitive resin composition can be improved by combining the resin (A) and the compound (B). Moreover, the repeating unit represented by the general formula (1) described later has an acid anhydride structure that is hydrolyzed with a developer to generate two carboxylic acid groups. Therefore, it is possible to suppress pattern collapse and improve line width roughness.

  Hereafter, each component mentioned above is demonstrated in order.

[1] Resin (A)
(1) Repeating unit represented by general formula (1) The resin (A) in the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention includes a repeating unit represented by the following general formula (1). .

In general formula (1),
L represents a single bond or a divalent linking group;
R ₁ represents a hydrogen atom or an alkyl group;
Z represents a cyclic acid anhydride structure (that is, a structure having —CO—O—CO—).

  The reason why the actinic ray-sensitive or radiation-sensitive composition of the present invention can suppress pattern collapse and improve LWR by including the repeating unit represented by the general formula (1) is estimated as follows. The

  The repeating unit represented by the general formula (1) has a cyclic acid anhydride structure containing —CO—O—CO—. Since the acid anhydride structure is hydrolyzed by the developer to generate two carboxylic acids, the solubility of the resin (A) in the developer can be improved. As a result, since the swelling of the pattern when the pattern is formed can be suppressed, it is considered that the pattern collapse can be suppressed and the LWR can be improved.

In the general formula (1), the alkyl group represented by R ₁ is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. The alkyl group of R ₁ may have a substituent, and preferred substituents include a hydroxyl group and a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

R ₁ 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.

  The divalent linking group as L is not particularly limited as long as it is a divalent linking group, but is preferably an alkylene group, a cycloalkylene group, an oxygen atom, a carbonyl group, a —NH— group, or a combination thereof. A combination of an oxygen atom and a carbonyl group is more preferable.

  The alkylene group may be linear or branched, preferably has 1 to 20 carbon atoms, more preferably has 1 to 10 carbon atoms, and still more preferably has 1 to 5 carbon atoms. The cycloalkylene group preferably has 3 to 20 carbon atoms, more preferably 4 to 10 carbon atoms, and 5 to 7 carbon atoms, which form a cyclic structure. Further preferred.

  The alkylene group and cycloalkylene group in L may have a substituent. Examples of the substituent include an alkyl group, a hydroxy group, and a cyano group.

  In the repeating unit represented by the general formula (1), since the linking group L exists between the main chain and the cyclic acid anhydride structure Z, the cyclic acid anhydride structure Z as the main chain and the hydrolysis site Can be released. Thereby, a cyclic acid anhydride structure can be rapidly hydrolyzed. As a result, a higher swelling suppression effect can be obtained, and further suppression of pattern collapse and improvement of line edge roughness can be achieved.

  Z represents a cyclic acid anhydride structure that is a cyclic structure containing —CO—O—CO—, and preferably has a polycyclic structure in which a plurality of rings are linked. When Z has a polycyclic structure, the storage stability when the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is stored in a solvent is further improved. This is because in the case of a polycyclic structure, the acid anhydride once hydrolyzed returns to the original state by a ring-closing reaction.

The carbon atom that forms the cyclic acid anhydride structure as Z may have a substituent, and the substituent is preferably a monovalent organic group. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, —OH, —NH ₂ , —SO ₂ NH ₂ , and —N (Rd 4) SO ₂ (Rd 5). Rd4 and Rd5 are each independently a hydrogen atom or an alkyl group. As the monovalent organic group, an alkyl group, an alkoxy group, and an alkoxycarbonyl group are preferable, and an alkyl group is more preferable. The alkyl group may be linear or branched, and the number of carbon atoms is preferably 1-20, more preferably 1-10, and even more preferably 1-5. 1-10 are preferable, as for the carbon atom number of an alkoxy group, 1-5 are more preferable, and 1-3 are more preferable. When there are a plurality of Z substituents, the substituents may be linked to each other to form a ring. The number of substituents is preferably 0 to 4, more preferably 0 to 2.

Z is more preferably a structure represented by the following general formula (2).

In general formula (2),
L represents L in the general formula (1);
W is absent or represents a methylene group, an ethylene group, an oxygen atom or a sulfur atom;
p represents an integer of 1 or more;
q represents an integer of 0 to 2;
m represents the integer of 0-2 each independently.

W is preferably a methylene group, an ethylene group or an oxygen atom, more preferably a methylene group or an oxygen atom, and even more preferably a methylene group.
p is preferably an integer of 1 to 2, more preferably 1.
Both m are preferably 0.
q is preferably 0 or 1.

Of the structure represented by the general formula (2), the structure represented by the following general formula (3) is more preferable.

In general formula (3),
L represents L in the general formula (1);
p represents 1 or 2.

  In the above general formulas (2) and (3), L is bonded to any carbon atom that forms a cyclic acid anhydride structure.

Although the specific example of the repeating unit which has a structure represented by General formula (1) is given below, it is not limited to these.

  The content of the repeating unit having the structure represented by the general formula (1) is preferably 5 to 50 mol%, and preferably 10 to 40 mol% with respect to all the repeating units in the resin (A). Is more preferable, and it is still more preferable that it is 15-35 mol%.

(2) Repeating unit that decomposes by the action of an acid and increases the solubility in an alkaline developer Resin (A) further comprises a repeating unit that decomposes by the action of an acid and increases the solubility in an alkaline developer. Including. A repeating unit that decomposes by the action of an acid and increases the solubility in an alkali developer (hereinafter also referred to as a repeating unit having an acid-decomposable group) is a group that decomposes and leaves by the action of an acid. Preferably has a protected structure.

  Alkali-soluble groups include phenolic hydroxyl groups, carboxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl) imides. Group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, etc. Is mentioned.

  Preferred alkali-soluble groups include carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), and sulfonic acid groups.

A preferable group as the acid-decomposable group is a group obtained by substituting the hydrogen atom of these alkali-soluble groups with a group capable of leaving with an acid.
As the acid eliminable group, there can be, for _{example, -C (R 36) (R} 37) (R 38), - C (R 36) (R 37) (OR 39), - C (R 01) (R 02 ) (OR ₃₉ ) and the like.
In the formula, R _{36 to} R ₃₉ each 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 and R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

  The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.

The repeating unit having an acid-decomposable group that can be contained in the resin (A) is preferably a repeating unit represented by the following general formula (AI).

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 ₁₁ . R ₁₁ represents a hydroxy group or a monovalent organic group, and examples of the monovalent organic group include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, preferably 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 represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic). Two of Rx _{1 to} Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the divalent linking group for 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, more preferably a —CH ₂ — group, — (CH ₂ ) ₂ — group, or — (CH ₂ ) ₃ — group.

Examples of the alkyl group rx ₁ to Rx _3, methyl, ethyl, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group, those having 1 to 4 carbon atoms such as t- butyl group.

Examples of the cycloalkyl group represented by Rx _{1 to} Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. Groups are preferred.

Examples of the cycloalkyl group formed by combining two of Rx _{1 to} Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group A polycyclic cycloalkyl group such as a group is preferred. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.

_{One of} the methylene groups constituting the ring of the cycloalkyl group formed by combining two of Rx _{1 to} Rx ₃ may be replaced with an oxygen atom.
An embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-described cycloalkyl group is preferable.

  Each of the above groups may have a substituent. 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, An alkoxycarbonyl group (C2-C6) etc. are mentioned, C8 or less is preferable.

  The total content of repeating units having an acid-decomposable group is preferably from 20 to 70 mol%, more preferably from 30 to 60 mol%, based on all repeating units in the resin (A).

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

In specific examples, Rx and Xa ₁ represent a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms. Z represents a substituent containing a polar group, and when there are a plurality of Z, the plurality of Z may be the same as or different from each other. p represents 0 or a positive integer. Specific examples and preferred examples of Z are the same as the specific examples and preferred examples of R ₁₀ in formula (II-1) described later.

The resin (A) has at least one of the repeating unit represented by the following general formula (I) and the repeating unit represented by the general formula (II) as the repeating unit represented by the general formula (AI). A resin is preferable, and a resin having a repeating unit represented by the general formula (I) is more preferable.

In the general formulas (I) and (II),
R ₁ and R ₃ each independently represent a hydrogen atom, a methyl group which may have a substituent, or a group represented by —CH ₂ —R ₁₁ . R ₁₁ represents a hydroxyl group or a monovalent organic group.
R ₂ , R ₄ , R ₅ and R ₆ each independently represents an alkyl group or a cycloalkyl group.
R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom, and an oxygen atom may be contained in the ring member of the alicyclic structure.

R ₁ and R ₃ preferably represent a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. Specific examples and preferred examples of the monovalent organic group in R ₁₁ are the same as those described for R ₁₁ in formula (AI).

The alkyl group in R ₂ may be linear or branched, and may have a substituent. The cycloalkyl group in R ₂ may be monocyclic or polycyclic and may have a substituent.
R ₂ is preferably an alkyl group, more preferably 1 to 10 carbon atoms, still more preferably 1 to 5 carbon atoms, and examples thereof include a methyl group and an ethyl group.

  R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom. The alicyclic structure formed by R together with the carbon atom is preferably a monocyclic alicyclic structure, and the carbon number thereof is preferably 3 to 7, more preferably 5 or 6.

R ₃ is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.

The alkyl group in R ₄ , R ₅ , and R ₆ may be linear or branched and may have a substituent. As the alkyl group, those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group are preferable.

The cycloalkyl group in R ₄ , R ₅ and R ₆ may be monocyclic or polycyclic and may have a substituent. The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group.

The repeating unit represented by the general formula (I) is preferably a repeating unit represented by the following general formula (AIII).

In the general formula (AIII),
R ₈ represents a hydrogen atom or an alkyl group. R ₉ represents an alkyl group. n represents an integer of 1 to 6.
The alkyl group for R ₈ is preferably an alkyl group having 1 to 10 carbon atoms, and may have a substituent.
n is preferably an integer of 1 to 3, and more preferably 1 or 2.

  Examples of the substituent that each of the above groups may have include the same groups as those described above as the substituent that each of the groups in the general formula (AI) may have.

The repeating unit represented by the general formula (II) is preferably a repeating unit represented by the following general formula (II-1).

In the general formula (II-1),
R _{3 to} R ₅ are respectively synonymous with those in the general formula (II).
R ₁₀ represents a substituent containing a polar group. When a plurality of R ₁₀ are present, they may be the same as or different from each other. Examples of the substituent containing a polar group include a hydroxyl group, a cyano group, an amino group, an alkylamide group or a sulfonamide group itself, or a linear or branched alkyl group or cycloalkyl group having at least one of them. An alkyl group having a hydroxyl group is preferable. More preferably, it is a branched alkyl group having a hydroxyl group. As the branched alkyl group, an isopropyl group is particularly preferable.
p represents an integer of 0 to 15. p is preferably 0 to 2, more preferably 0 or 1.

  The resin (A) is a resin containing at least two types of repeating units represented by the general formula (I) as the repeating unit having an acid-decomposable group, or a repeating unit represented by the general formula (I) And a resin containing a repeating unit represented by the general formula (II).

One type of repeating unit having an acid-decomposable group contained in the resin (A) may be used, or two or more types may be used in combination. As the combination in the case of using together, the following are preferable. In the following formula, each R independently represents a hydrogen atom or a methyl group.

(3) Repeating unit having lactone structure or sultone structure The resin (A) may further contain a repeating unit having a lactone structure or a sultone (cyclic sulfonate ester) structure.

Any lactone group or sultone group can be used as long as it has a lactone structure or sultone structure, but a lactone structure or sultone structure having a 5- to 7-membered ring is preferable, and a lactone having a 5- to 7-membered ring is preferable. A structure in which another ring structure is condensed to form a bicyclo structure or a spiro structure in the structure or sultone structure is preferable. It is more preferable to have a repeating unit having a lactone structure or a sultone structure represented by any of the following general formulas (LC1-1) to (LC1-17) and (SL1-1) to (SL1-3). A lactone structure or a sultone structure may be directly bonded to the main chain. Preferred lactone structures or sultone structures are (LC1-1), (LC1-4), (LC1-5), and (LC1-8), more preferably (LC1-4). By using a specific lactone structure or sultone structure, LWR is improved and development defects can be suppressed.

The lactone structure portion or the sultone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (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 2 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferably, they are a C1-C4 alkyl group, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0-4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different, and a plurality of substituents (Rb ₂ ) may be bonded to form a ring. .

The resin (A) preferably contains a repeating unit having a lactone structure or a sultone structure represented by the following general formula (VI).

In general formula (VI),
B represents an ester bond (a group represented by —COO—) or an amide bond (a group represented by —CONH—).
R ₀ represents an alkylene group, a cycloalkylene group, or a combination thereof independently when there are a plurality of R ₀ .
Z is independently a single bond, an ether bond, an ester bond, an amide bond, or a urethane bond when there are a plurality of Zs.

Or urea bond

Represents. Here, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group each independently.
R ₈ represents a monovalent organic group having a lactone structure or a sultone structure.
n _is the repetition number of the structure represented by -R 0 -Z-, represents an integer of 0 to 2. n is preferably 1 or 2.
R ₇ represents a hydrogen atom, a halogen atom or an alkyl group.

The alkylene group and cycloalkylene group represented by R ₀ may have a substituent.
Z is preferably an ether bond or an ester bond, and particularly preferably an ester bond.

The alkyl group for R ₇ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. The alkylene group of R ₀ , the cycloalkylene group, and the alkyl group in R ₇ may each be substituted. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom, a mercapto group, and a hydroxy group. Group, alkoxy group such as methoxy group, ethoxy group, isopropoxy group, t-butoxy group and benzyloxy group, and acetoxy group such as acetyloxy group and propionyloxy group. R ₇ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

The chain alkylene group for R ₀ is preferably a chain alkylene having 1 to 10 carbon atoms, more preferably a chain alkylene having 1 to 5 carbon atoms, such as a methylene group, an ethylene group, or a propylene group. Etc. A preferable cycloalkylene group is a cycloalkylene group having 3 to 20 carbon atoms, and examples thereof include a cyclohexylene group, a cyclopentylene group, a norbornylene group, and an adamantylene group. In order to exhibit the effect of the present invention, a chain alkylene group is more preferable, and a methylene group is particularly preferable.

The monovalent organic group having a lactone structure or a sultone structure represented by R ₈ is not limited as long as it has a lactone structure or a sultone structure, and the general formula (LC1-1) described above as a specific example A lactone structure or a sultone structure represented by (LC1-17) and (SL1-1) to (SL1-3) is exemplified, and a structure represented by (LC1-4) is particularly preferable. In addition, n ₂ in (LC1-1) to (LC1-17) and (SL1-1) to (SL1-3) is more preferably 2 or less.

R ₈ is preferably a monovalent organic group having an unsubstituted lactone structure or sultone structure, or a monovalent organic group having a lactone structure or sultone structure having a methyl group, a cyano group or an alkoxycarbonyl group as a substituent. A monovalent organic group having a lactone structure (cyanolactone) or a sultone structure (cyanosultone) having a cyano group as a substituent is more preferable.

  Specific examples of the repeating unit having a group having a lactone structure or a sultone structure represented by the general formula (VI) are shown below, but the present invention is not limited thereto.

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

As the repeating unit having a lactone structure or a sultone structure, a repeating unit represented by the following general formula (VI-1) or (VI-1 ′) is more preferable.

In the general formulas (VI-1) and (VI-1 ′),
R ₇ , B, R ₀ , Z, and n have the same meanings as in general formula (VI).
R ₇ ′, B ′, R ₀ ′, Z ′ and n ′ have the same meanings as R ₇ , B, R ₀ , Z and n in the general formula (VI), respectively.
R ₉ independently represents 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, and} when there are a plurality of R _{9 s} , May be formed.
R ₉ ′ independently represents an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, a cyano group, a hydroxyl group or an alkoxy group, and when there are a plurality of R ₉ ′, two R ₉ ′ are bonded to each other. , May form a ring.
X and X ′ each independently represents an alkylene group, an oxygen atom or a sulfur atom.
m and m ′ are the number of substituents, and each independently represents an integer of 0 to 5. m and m ′ are preferably each independently 0 or 1.

The alkyl group for R ₉ and R ₉ ′ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and most preferably a methyl group. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, and a t-butoxycarbonyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group. These groups may have a substituent, and examples of the substituent include an alkoxy group such as a hydroxy group, a methoxy group, and an ethoxy group, and a halogen atom such as a cyano group and a fluorine atom. R ₉ and R ₉ ′ are more preferably a methyl group, a cyano group or an alkoxycarbonyl group, and even more preferably a cyano group.

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

When m and m ′ are 1 or more, at least one of R ₉ and R ₉ ′ is preferably substituted at the α-position or β-position of the carbonyl group in the lactone, and particularly preferably substituted at the α-position.

Specific examples of the group having a lactone structure represented by the general formula (VI-1) or (VI-1 ′) or the repeating unit having a sultone structure are shown below, but the present invention is not limited thereto. . In the following specific examples, R represents a hydrogen atom, an alkyl group which may have a substituent, or a halogen atom, preferably a hydrogen atom, a methyl group, a hydroxymethyl group or an acetoxymethyl group.

In one embodiment, the unit represented by the general formula (VI) may be a repeating unit represented by the following general formula (AII ′).

In general formula (AII ′),
Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. Preferable substituents that the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb ₀ 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.
V represents a group having a structure represented by any one of formulas (LC1-1) to (LC1-17) and (SL1-1) to (SL1-3).

  The resin (A) may contain a repeating unit having a lactone structure or a sultone structure in addition to the unit represented by the general formula (VI).

Specific examples of the repeating unit having a lactone group or a sultone group include the following in addition to the specific examples given above, but the present invention is not limited thereto.

Among the specific examples, particularly preferred repeating units include the following repeating units. By selecting an optimal lactone group or sultone group, the pattern profile and the density dependency are improved.

  The repeating unit having a lactone group or a sultone group usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90% or more, more preferably 95% or more.

  The resin (A) may have two or more repeating units having a lactone structure or a sultone structure. In particular, it is preferable to use two or more types selected from the lactone repeating units in which n is 1 in the general formula (VI).

  The content of the repeating unit having a lactone structure or a sultone structure is preferably 10 to 60 mol%, more preferably 15 to 50 mol%, based on the total repeating units in the resin (A) when a plurality of types are contained. More preferably, it is 20-40 mol%.

(4) Repeating unit having hydroxyl group or cyano group The resin (A) preferably further has a repeating unit having a hydroxyl group or a cyano group. Thereby, the substrate adhesion and the developer compatibility are improved. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and preferably has no acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diamantyl group, or a norbornane group. As the alicyclic hydrocarbon structure substituted with a preferred hydroxyl group or cyano group, partial structures represented by the following general formulas (VIIa) to (VIId) are preferred.

In general formulas (VIIa) to (VIIc),
R ₂ c to R ₄ c each independently represents a hydrogen atom, a hydroxyl group, or a cyano group. However, at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c are a hydroxyl group and the rest are hydrogen atoms. In general formula (VIIa), it is more preferable that _two members out of R ₂ c to R ₄ c are hydroxyl groups and the remaining are hydrogen atoms.

Examples of the repeating unit having a partial structure represented by the general formulas (VIIa) to (VIId) include the repeating units represented by the following general formulas (AIIa) to (AIId).

In the general formulas (AIIa) to (AIId),
R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.
R ₂ c to R ₄ c are in the general formula (VIIa) ~ _(VIIc), same meanings as R 2 c~R ₄ c.

  The resin (A) may or may not contain a repeating unit having a hydroxyl group or a cyano group. However, when it is contained, the content of the repeating unit having a hydroxyl group or a cyano group is the total number of repeating units in the resin (A). 5-40 mol% is preferable with respect to a unit, More preferably, it is 5-30 mol%, More preferably, it is 10-25 mol%.

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

(5) Repeating unit having alkali-soluble group The resin (A) may further have a repeating unit having an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol (for example, hexafluoroisopropanol group) substituted with an electron-withdrawing group at the α-position. It is more preferable to have a repeating unit. By containing a repeating unit having an alkali-soluble group, the resolution in contact hole applications is increased. The repeating unit having an alkali-soluble group includes a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an alkali in the main chain of the resin through a linking group. Any repeating unit to which a soluble group is bonded may be used, and further, a polymerization initiator or a chain transfer agent having an alkali-soluble group may be introduced at the end of the polymer chain at the time of polymerization. The linking group may have a monocyclic or polycyclic hydrocarbon structure. Particularly preferred are repeating units of acrylic acid and methacrylic acid.

  The resin (A) may or may not contain a repeating unit having an alkali-soluble group, but when it is contained, the content of the repeating unit having an alkali-soluble group is based on all repeating units in the resin (A). On the other hand, 1-20 mol% is preferable, More preferably, it is 3-15 mol%, More preferably, it is 5-10 mol%.

Specific examples of the repeating unit having an alkali-soluble group are shown below, but the present invention is not limited thereto.
In specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

(6) Repeating unit having an alicyclic hydrocarbon structure having no polar group The resin (A) further has an alicyclic hydrocarbon structure having no polar group (for example, the alkali-soluble group, hydroxyl group, cyano group, etc.). And may have a repeating unit that does not exhibit acid decomposability. As such a repeating unit, the repeating unit represented by the following general formula (IV) is mentioned.

In the general formula (IV), R ₅ represents a hydrocarbon group having at least one cyclic structure and having no polar group.
Ra 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. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

The cyclic structure possessed by R ₅ includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include cycloalkenyl having 3 to 12 carbon atoms such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like, and cycloalkyl groups having 3 to 12 carbon atoms and cyclohexenyl group. Groups. The preferred monocyclic hydrocarbon group is a monocyclic hydrocarbon group having 3 to 7 carbon atoms, more preferably a cyclopentyl group or a cyclohexyl group.

The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group, and examples of the ring assembly hydrocarbon group include a bicyclohexyl group and a perhydronaphthalenyl group. As the bridged cyclic hydrocarbon ring, for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Hydrocarbon rings and tricyclic hydrocarbon rings such as homobredan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [4.3.1.1 ^2,5 ] undecane ring, tetracyclo [ 4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene. A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring are condensed is also included.

Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5,2,1,0 ^2,6 ] decanyl group, and the like. More preferable examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.

  These alicyclic hydrocarbon groups may have a substituent. Preferred examples of the 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. It is done. Preferred halogen atoms include bromine, chlorine and fluorine atoms, and preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups. The alkyl group described above may further have a substituent, and examples of the substituent that may further include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom. The group can be mentioned.

  Examples of the group in which the hydrogen atom is substituted include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group. Preferred alkyl groups include alkyl groups having 1 to 4 carbon atoms, preferred substituted methyl groups include methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl groups, and preferred substituted ethyl groups. 1-ethoxyethyl, 1-methyl-1-methoxyethyl, preferred acyl groups include formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, pivaloyl groups, etc., aliphatic acyl groups having 1 to 6 carbon atoms, alkoxycarbonyl Examples of the group include an alkoxycarbonyl group having 1 to 4 carbon atoms.

  The resin (A) has an alicyclic hydrocarbon structure having no polar group, and may or may not contain a repeating unit that does not exhibit acid decomposability. The content of is preferably from 1 to 40 mol%, more preferably from 2 to 20 mol%, based on all repeating units in the resin (A).

Specific examples of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  Resin (A) adjusts dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc., which are general necessary properties of resist, in addition to the above repeating units. It can have various repeating units for the purpose.

  Examples of such a repeating unit include, but are not limited to, repeating structural units corresponding to the following monomers.

  As a result, the performance required for the resin (A), in particular, (1) solubility in coating solvents, (2) film-forming properties (glass transition point), (3) alkali developability, (4) film slipping (familiarity) Fine adjustments such as (selection of aqueous and alkali-soluble groups), (5) adhesion of unexposed portions to the substrate, and (6) dry etching resistance are possible.

  As such a monomer, for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.

  In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating units may be copolymerized.

  In the resin (A), the content molar ratio of each repeating structural unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, heat resistance, and sensitivity, which are general required performance of the resist. It is set appropriately in order to adjust etc.

  When the composition of the present invention is for ArF exposure, the resin (A) preferably has substantially no aromatic group from the viewpoint of transparency to ArF light. More specifically, the repeating unit having an aromatic group is preferably 5% by mole or less, more preferably 3% by mole or less, and more ideally, during the entire repetition of the resin (A). More preferably, it is 0 mol%, that is, it does not have a repeating unit having an aromatic group. The resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

  In addition, it is preferable that resin (A) does not contain a fluorine atom and a silicon atom from a compatible viewpoint with the hydrophobic resin mentioned later.

  The resin (A) is preferably one in which all of the repeating units are composed of (meth) acrylate repeating units. In this case, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are methacrylate repeating units and acrylate repeating units. Although it can be used, the acrylate-based repeating unit is preferably 50 mol% or less of the total repeating units. Moreover, the alicyclic hydrocarbon substituted by the (meth) acrylate type repeating unit 20-50 mol% which has an acid-decomposable group, the (meth) acrylate type repeating unit 20-50 mol% which has a lactone group, and a hydroxyl group or a cyano group. A copolymer containing 5 to 30 mol% of a (meth) acrylate-based repeating unit having a structure and further containing 0 to 20 mol% of another (meth) acrylate-based repeating unit is also preferred.

  When the composition of the present invention is irradiated with KrF excimer laser light, electron beam, X-ray, high energy light beam (EUV, etc.) having a wavelength of 50 nm or less, the resin (A) further has a hydroxystyrene-based repeating unit. It is preferable. More preferably, it has an acid-decomposable repeating unit such as a hydroxystyrene-based repeating unit, a hydroxystyrene-based repeating unit protected with an acid-decomposable group, and a (meth) acrylic acid tertiary alkyl ester.

  Preferred examples of the hydroxystyrene-based repeating unit protected with an acid-decomposable group include t-butoxycarbonyloxystyrene, 1-alkoxyethoxystyrene, (meth) acrylic acid tertiary alkyl ester repeating units, and the like. it can. More preferred are repeating units of 2-alkyl-2-adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate.

  The resin (A) in the present invention can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide and dimethylacetamide, Furthermore, the solvent which melt | dissolves the composition of this invention like the below-mentioned propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone is mentioned. More preferably, the polymerization is performed using the same solvent as the solvent used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.

  The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, more preferably from 60 ° C to 100 ° C.

  After completion of the reaction, the mixture is allowed to cool to room temperature and purified. Purification is a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water washing and an appropriate solvent, a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less, Reprecipitation method that removes residual monomer by coagulating resin in poor solvent by dropping resin solution into poor solvent, purification in solid state such as washing filtered resin slurry with poor solvent A normal method such as a method can be applied. For example, the resin is precipitated as a solid by contacting a solvent (poor solvent) in which the resin (A) is hardly soluble or insoluble in a volume amount of 10 times or less, preferably 10 to 5 times that of the reaction solution. .

  The solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent for the polymer, and may be a hydrocarbon, halogenated hydrocarbon, nitro, depending on the type of polymer. A compound, ether, ketone, ester, carbonate, alcohol, carboxylic acid, water, a mixed solvent containing these solvents, and the like can be appropriately selected for use.

  The amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency, yield, and the like, but generally 100 to 10000 parts by mass, preferably 200 to 2000 parts by mass with respect to 100 parts by mass of the polymer solution, More preferably, it is 300-1000 mass parts.

  The temperature for precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.). The precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.

  The precipitated or re-precipitated polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed using a solvent-resistant filter medium, preferably under pressure. Drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure).

  In addition, once the resin is deposited and separated, it may be dissolved again in a solvent, and the resin may be brought into contact with a hardly soluble or insoluble solvent. That is, after completion of the radical polymerization reaction, a solvent in which the polymer is hardly soluble or insoluble is contacted to precipitate a resin (step a), the resin is separated from the solution (step b), and dissolved again in the solvent to obtain a resin solution A. (Step c), and then, the resin solution A is brought into contact with a solvent in which the resin is hardly soluble or insoluble in a volume amount less than 10 times that of the resin solution A (preferably 5 times or less volume). Thus, a method including depositing a resin solid (step d) and separating the deposited resin (step e) may be used.

  In order to prevent the resin from aggregating after the preparation of the composition, for example, as described in JP-A-2009-037108, the synthesized resin is dissolved in a solvent to form a solution. A step of heating at about 30 ° C. to 90 ° C. for about 30 minutes to 4 hours may be added.

  The weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, and even more preferably 3,000 to 15 in terms of polystyrene by GPC method. 1,000, particularly preferably 3,000 to 11,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, developability is deteriorated, and viscosity is increased, resulting in deterioration of film forming property. Can be prevented.

  The dispersity (molecular weight distribution) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and particularly preferably 1.4 to 2.0. Those in the range are used. The smaller the molecular weight distribution, the better the resolution and the resist shape, and the smoother the side wall of the resist pattern, the better the roughness.

In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the blending amount of the resin (A) is preferably 30 to 99% by mass, more preferably 60 to 95% by mass in the total solid content of the composition. .
Moreover, resin (A) may be used by 1 type and may be used together.

  In addition, you may use other resin other than resin (A) together in the range which does not impair the effect of this invention. Examples of the resin other than the resin (A) include an acid-decomposable resin that may contain a repeating unit that can be contained in the resin (A), and other known acid-decomposable resins. .

[2] compounds containing at least one nitrogen atom R _N or ionic compounds containing a basic moiety R _NN containing at least one nitrogen atom (B)
Next, a compound R _N containing at least one nitrogen atom (hereinafter also referred to as compound (B1)) and an ionic compound containing a basic moiety R _NN containing at least one nitrogen atom (hereinafter referred to as compound (B2) (Hereinafter also referred to as nitrogen-containing compound (B)).

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention improves storage stability by including the nitrogen-containing compound (B) described here in addition to the resin (A) described above.

(1) Compound (B1)
The compound (B1) is a compound containing at least one nitrogen atom and having a pKa of R _N —H ⁺ that is a conjugate acid of 8 or less. The pKa of the conjugate acid is more preferably −3 to 8, and even more preferably −2.5 to 5.0. When it is smaller than −3, the basicity becomes weak, so that it becomes impossible to suppress the diffusion of the acid generated by the exposure to the unexposed portion, which may cause a decrease in LWR. On the other hand, when it is larger than 8, the basicity becomes strong, causing hydrolysis of the acid anhydride monomer, which is an essential component of the resin in the present invention, and storage stability is lowered. In the present invention, the pKa value is expressed as a value calculated by ACD / ChemSketch (ACD / Labs 8.00 Release Product Version: 8.08).

Examples of the compound (B1) include the following compounds, but the present invention is not limited thereto.

As the compound (B1), a compound represented by the following general formula (b1) is preferable.

In general formula (b1):
n represents an integer of 0 to 2, m represents an integer of 1 to 3, and n + m = 3.
Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When n = 2, the two Ras may be the same or different, and the two Ras are bonded to each other, and together with the nitrogen atom to which Ra is bonded, a heterocyclic hydrocarbon group (preferably having a carbon number of 20 or less Or a derivative thereof.
Rb independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group, and at least two Rb's are bonded to form an alicyclic hydrocarbon group or aromatic hydrocarbon. Groups, heterocyclic hydrocarbon groups or derivatives thereof may be formed.

  In general formula (b1), the alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Ra may have a substituent. Preferred substituents include a hydroxy group, a cyano group, and an alkoxy group.

  Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group of Ra (these alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with the above groups) include: Examples thereof include a methyl group, an ethyl group, a cyclohexyl group, a phenyl group, and a benzyl group.

  In addition, examples of the heterocyclic hydrocarbon group (preferably having 1 to 20 carbon atoms) formed by a combination of Ra to each other and a nitrogen atom to which Ra is bonded or derivatives thereof include, for example, pyrrolidine, piperidine, morpholine, , 4,5,6-tetrahydropyrimidine, 1,2,3,4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, 1H-1,2,3-triazole, 1,4,7-triazacyclononane, tetrazole, 7-azaindole, indazole, benzimidazole, imidazo [1,2-a] pyridine, (1S, 4S)-( +)-2,5-diazabicyclo [2.2.1] heptane, 1,5,7-triazabicyclo [4.4 0] groups derived from heterocyclic compounds such as dec-5-ene, indole, indoline, 1,2,3,4-tetrahydroquinoxaline, perhydroquinoline, 1,5,9-triazacyclododecane, these A group derived from a heterocyclic compound is a group derived from a linear or branched alkane, a group derived from a cycloalkane, a group derived from an aromatic compound, a group derived from a heterocyclic compound, a hydroxyl group, a cyano group , Groups substituted with one or more functional groups such as amino group, pyrrolidino group, piperidino group, morpholino group, oxo group and the like.

  The alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkoxyalkyl group as Rb may have a substituent. Examples of such a substituent include a methoxy group, a hydroxy group, a cyano group, and an alkoxy group.

  Examples of the alkyl group for Rb include a methyl group, an ethyl group, and an isopropyl group. A cyclohexyl group is mentioned as a cycloalkyl group of Rb. A phenyl group is mentioned as an aryl group of Rb. Examples of the aralkyl group for Rb include a benzyl group and a phenethyl group. Examples of the alkoxyalkyl group for Rb include a methoxymethyl group and 2-methoxyethoxymethyl.

  Examples of the alicyclic hydrocarbon group formed by combining at least two Rb include a cyclopentyl group and a cyclohexyl group.

Specific examples of the compound represented by formula (b1) that are particularly preferred in the present invention are shown below, but are not limited thereto.

The compound represented by the general formula (b1) can be synthesized based on JP2007-298869A, JP2009-199021A, and the like.
In the present invention, the compound (B1) can be used singly or in combination of two or more.

  In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the content of the compound (B1) is usually 0.001 to 20% by mass, preferably 0.001 based on the total solid content of the composition. -10 mass%, More preferably, it is 0.01-5 mass%.

(2) Compound (B2)
As the ionic compound (B2) containing a basic moiety _RNN containing at least one nitrogen atom, a compound represented by the following general formula (b2) is preferably used.

_RNN- A ^- X ⁺ (b2)
In general formula (b2),
_RNN means a monovalent basic compound residue containing at least one nitrogen atom, and the pKa of the conjugate acid _RNN- H ⁺ is 8 or less.
A ⁻ represents —SO ₃ ^— , —CO ₂ ^— , or —X ₁ —N ^—— X ₂ —R ₁ , X ₁ and X ₂ each independently represent —CO— or —SO ₂ —; R ₁ represents a monovalent organic group.
X ⁺ represents a counter cation.

In the general formula (b2), A ⁻ is preferably —X ₁ —N ^—— X ₂ —R ₁ .
More preferably, at least one of X ₁ and X ₂ is —SO ₂ —.

The organic group as R ₁ is preferably an organic group having 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 ₁ may have a substituent, preferably a linear or branched alkyl group having 1 to 30 carbon atoms, and has an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain. It may be. Specifically, 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. And a branched alkyl group such as isopropyl group, isopropyl group, isobutyl group, t-butyl group, neopentyl group, 2-ethylhexyl group.

The cycloalkyl group as R ₁ may have a substituent, preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom or a nitrogen atom in the ring. Specific examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like.

The aryl group as R ₁ may have a substituent, and is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

The aralkyl group as R ₁ may have a substituent, preferably an aralkyl group having 7 to 20 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group. .

The alkenyl group as R ₁ may have a substituent, and examples thereof include a group having a double bond at an arbitrary position of the alkyl group.

  Examples of the substituent that each group may have include, for example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), and an aryl group (preferably Has 6 to 14 carbon atoms, an alkoxy group (preferably 1 to 10 carbon atoms), an acyl group (preferably 2 to 20 carbon atoms), an acyloxy group (preferably 2 to 10 carbon atoms), an alkoxycarbonyl group (preferably C2-C20), an aminoacyl group (preferably C2-C10) etc. are mentioned. As for the cyclic structure in the aryl group, cycloalkyl group and the like, examples of the substituent further include an alkyl group (preferably having 1 to 10 carbon atoms). As for the aminoacyl group, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 10). Examples of the alkyl group having a substituent include perfluoroalkyl groups such as a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, and a perfluorobutyl group.

In the general formula (b2), R _NN is a monovalent basic compound residue containing at least one nitrogen atom, and is also referred to as “basic site R _NN ” below. The basic site _RNN has a pKa representing an acid dissociation constant of its conjugate acid _RNNH ⁺ of 8 or less, more preferably -3 or more and 8 or less, more preferably -2.5 or more and 5 or less. .

The basic site _RNN is preferably represented by the following general formula (ii).

In general formula (ii),
R ₂₁ represents a monovalent organic group, and R ₂₂ represents a divalent organic group. R ₂₁ and R ₂₂ may combine with each other to form a ring.
L represents a functional group having a Hammett's rule σ _p value of −0.1 or more excluding a hydrogen atom.
* The A ^- indicates the binding site of the.

The general formula (ii) will be described in detail.
L is a functional group having a Hammett's rule substituent constant σ _p value (reference document Hansch et al., Chemical Reviews, 1991, Vol, 91, No. 2, 165-195) of −0.1 or more, preferably Is a functional group having a σ _p value of −0.05 or more, more preferably a functional group having a σ _p value of −0.03 or more and 0.5 or less. The Hammett's rule constant σ is a numerical value representing the effect of the substituent on the acid dissociation equilibrium constant of the substituted benzoic acid, and is a parameter indicating the electron withdrawing and electron donating strength of the substituent. The σp value means the substituent constant σ when the substituent is located at the para position of benzoic acid.

For functional groups not described in the references, the σ _p value can be calculated from the difference from the pKa of benzoic acid using ACD / ChemSketch (ACD / Labs 8.00 Release Product Version: 8.08) separately. Examples of functional groups having a σ _p value of −0.1 or more include aryl groups (such as phenyl groups), acyl groups (such as acetyl groups), alkoxycarbonyl groups (such as methoxycarbonyl groups and t-butoxycarbonyl groups), and alkyl groups. Examples thereof include a carbonyloxy group (such as a methylcarbonyloxy group), a carboxyl group, an alkoxy group (such as a methoxy group), a cyano group, a nitro group, a halogen atom, and an alkyl group substituted with these functional groups.

Note that L may have a structure that is decomposed by an acid generated from a compound (acid generator) that generates an acid upon irradiation with actinic rays or radiation described below. For example, when L has a structure having an alkoxycarbonyl group, if the alkyl group of the alkoxycarbonyl group is a structure represented by —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), generation from an acid generator Decomposes with acids. In the formula, R _{36 to} R ₃₈ each 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.

  The number of atoms (excluding hydrogen atoms) possessed by L is not particularly limited, but is usually 1 to 20, preferably 1 to 15, and more preferably 1 to 10.

As the organic group for R _21, the same groups as those for R ₁ in formula (b2) can be exemplified.

The divalent organic group represented by R ₂₂ is preferably represented by the following general formula (iii), in which case the basic moiety R _NN is represented by the following general formula (iv).

In general formulas (iii) and (iv),
R ₄₁ and R ₄₂ each independently represents a divalent linking group.
B represents a single bond, an oxygen atom or -N (Rx)-.
Rx represents a hydrogen atom or a monovalent organic group.
When B is —N (Rx) —, R ₂₁ and Rx may combine to form a ring.
X ₃ represents —CO— or —SO ₂ —.
* The A ^- indicates the binding site of the.
R ₂₁ and L are synonymous with each group in the general formula (ii).

In the general formulas (iii) and (iv), the divalent linking group as R ₄₁ is preferably a divalent linking group having a fluorine atom having 1 to 8 carbon atoms, such as fluorine having 1 to 8 carbon atoms. Examples thereof include an alkylene group having an atom and a phenylene group having a fluorine atom. An alkylene group having a fluorine atom is more preferable, and a preferable carbon number is 2 to 6, more preferably 2 to 4. The alkylene chain may have a linking group such as an oxygen atom or a sulfur atom. The alkylene group is preferably an alkylene group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms, more preferably a perfluoroalkylene group, and particularly preferably a perfluoroethylene group, a perfluoropropylene group, or a perfluorobutylene group. .

Preferred examples of the divalent linking group as R ₄₂ include an alkylene group and a phenylene group, with an alkylene group being particularly preferred.

B is preferably -N (Rx)-, and the monovalent organic group as Rx preferably has 1 to 8 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. Examples include groups. Examples of the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group are the same as those described above.
X ₃ is preferably —SO ₂ —.

In one embodiment, the basic site _RNN is represented by the following general formula (V).

In the general formula (V), R ₄₁ , X ₃ , L and * have the same meanings as those in the general formula (iv).

In the general formula (b2), the counter cation represented by X ⁺ is preferably onium, more preferably sulfonium or iodonium.
The sulfonium and iodonium that can be used here are sulfonium and iodonium in the compounds represented by the general formulas (ZI) and (ZII) in a compound (acid generator) that generates an acid upon irradiation with actinic rays or radiation described later. It is the same, and the same examples as sulfonium and iodonium in (z1) to (z70) described later can be given as specific examples.

Hereinafter, although the specific example of a compound (B2) represented by general formula (b2) is shown, this invention is not limited to this. The pKa value shown below is a value calculated by the method shown below for the pKa of the conjugate acid of the basic site _RNN .

The content of the compound (B2) in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably 0.1% by mass to 20% by mass, more preferably 0.00%, based on the solid content of the composition. It is 1 to 15% by mass, and more preferably 2 to 10% by mass.
Compound (B2) can be synthesized by a method similar to the method described in JP-A-2006-330098.

[Calculation method of pKa]
The acid dissociation constant (pKa) of the conjugate acid (R _N —H ⁺ ) of the compound (B1) and the conjugate acid (R _NN —H ⁺ ) of the basic site R _NN in the compound (B2) was calculated by the following means. .
In the case of compound (B1), the equilibrium constant of the following structure was calculated to determine the pKa of the conjugate acid. (PKa = −log ₁₀ (Ka))

In the compound (B2), particularly when basic moiety R _NN is represented by the general formula (ii) described above, pKa of the conjugate acid of the basic site R _NN was determined by calculating the equilibrium constant of the following.

In particular, when R _NN is represented by the general formula (iv) described above, the following equilibrium constant is calculated:

At that time, when R ₂₁ and R x form a ring, the following equilibrium constant was calculated by substituting a nitrogen atom with a methylene group so as not to change the number of ring members.

[3] Compound (C) that generates acid upon irradiation with active light or radiation
The composition of the present invention contains a compound that generates an acid upon irradiation with actinic rays or radiation (hereinafter also referred to as “acid generator”).

Although it will not specifically limit as an acid generator if it is a well-known thing, Preferably the compound represented by the following general formula (ZI), (ZII), (ZIII) can be mentioned.

In the general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents 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.
Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R _{201 to} R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group).

In addition, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, at least one of R _{201 to} R ₂₀₃ of the compound represented by the general formula (ZI) is a single bond or at least one of R _{201 to} R ₂₀₃ of another compound represented by the general formula (ZI) It may be a compound having a structure bonded through a linking group.

Z ⁻ represents a non-nucleophilic anion (an anion having an extremely low ability to cause a nucleophilic reaction).
Examples of Z ⁻ include a sulfonate anion (an aliphatic sulfonate anion, an aromatic sulfonate anion, a camphor sulfonate anion, etc.), a carboxylate anion (an aliphatic carboxylate anion, an aromatic carboxylate anion, an aralkyl carboxylate anion). Etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.

  The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate 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 carbon number. 3-30 cycloalkyl groups are mentioned.

  The aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group.

  The alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. Specific examples thereof include nitro groups, halogen atoms such as 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). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7), an alkylthio group (preferably 1 to 15 carbon atoms), an alkylsulfonyl group (preferably 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably 2 to 15 carbon atoms), an aryloxysulfonyl group (preferably carbon) Number 6-20), alkylaryloxysulfonyl group (preferably C7-20), cycloalkylary Examples thereof include an oxysulfonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like. . About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) can further be mentioned as a substituent.

The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.
Examples of the sulfonylimide anion include saccharin anion.

  The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of 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. A fluorine atom or an alkyl group substituted with a fluorine atom is preferred.

Examples of other Z ⁻ include fluorinated phosphorus (for example, PF ₆ ⁻ ), fluorinated boron (for example, BF ₄ ⁻ ), fluorinated antimony (for example, SbF ₆ ⁻ ), and the like.

Z ^- The at least α-position by an aliphatic sulfonate anion substituted with a fluorine atom, a fluorine atom or a fluorine atom is substituted with a group having a aromatic sulfonate anion of a sulfonic acid, an alkyl group substituted with a fluorine atom Bis (alkylsulfonyl) imide anions and tris (alkylsulfonyl) methide anions in which the alkyl group is substituted with a fluorine atom are preferred. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (more preferably 4 to 8 carbon atoms), a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, or perfluorooctane. A sulfonate anion, a pentafluorobenzenesulfonate anion, and a 3,5-bis (trifluoromethyl) benzenesulfonate anion.

  From the viewpoint of acid strength, the pKa of the generated acid is preferably −1 or less in order to improve sensitivity.

_Examples of the organic group for R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include an aryl group (preferably having 6 to 15 carbon atoms), a linear or branched alkyl group (preferably having 1 to 10 carbon atoms), and a cycloalkyl group (having 3 carbon atoms). ~ 15 are preferred).
Of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , at least one is preferably an aryl group, more preferably all three are aryl groups. As the aryl group, in addition to a phenyl group, a naphthyl group, and the like, a heteroaryl group such as an indole residue and a pyrrole residue can be used.

These aryl groups, alkyl groups and cycloalkyl groups as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ 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). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7) and the like, but are not limited thereto.

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.

Preferred structures when at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is not an aryl group include paragraphs 0046 and 0047 of JP-A-2004-233661, paragraphs 0040 to 0046 of JP-A-2003-35948, US Compounds exemplified as formulas (I-1) to (I-70) in Patent Publication No. 2003 / 0224288A1, and Formulas (IA-1) to (I) in U.S. Patent Publication No. 2003 / 0077540A1 IA-54) and cation structures such as compounds exemplified as formulas (IB-1) to (IB-24).

In particular, when at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is not an aryl group, the following aspect (1) or (2) is particularly preferable.

(1) At least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ has a structure represented by Ar—CO—X—, and the remaining group is a linear or branched alkyl group or a cycloalkyl group. If. At this time, when there are two remaining groups, two linear or branched alkyl groups or cycloalkyl groups may be bonded to each other to form a ring structure.
Here, Ar represents an aryl group which may have a substituent, and is specifically the same as the aryl group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ . A phenyl group which may have a substituent is preferable.
X represents an alkylene group which may have a substituent. Specifically, it is an alkylene group having 1 to 6 carbon atoms. Preferably it is a C1-C3 linear or branched alkylene group.
The remaining linear or branched alkyl group or cycloalkyl group preferably has 1 to 6 carbon atoms. These atomic groups may further have a substituent. Moreover, when the remaining groups are two, it is preferable that they are bonded to each other to form a ring structure (preferably a 5- to 7-membered ring).

(2) One or two of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ are an aryl group which may have a substituent, and the remaining group is a linear or branched alkyl group or a cycloalkyl group If there is.
In this case, the aryl group is specifically the same as the aryl group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , and is preferably a phenyl group or a naphthyl group. The aryl group preferably has any one of a hydroxyl group, an alkoxy group, and an alkyl group as a substituent. More preferably, it is a C1-C12 alkoxy group as a substituent, More preferably, it is a C1-C6 alkoxy group.
The remaining linear or branched alkyl group or cycloalkyl group preferably has 1 to 6 carbon atoms. These atomic groups may further have a substituent. When the remaining groups are two, the two may be bonded to each other to form a ring structure.

More preferable examples of the (ZI) component include compounds (ZI-3) and (ZI-4) described below.
The compound (ZI-3) is a compound represented by the following general formula (ZI-3), and is a compound having a phenacylsulfonium salt structure.

In general formula (ZI-3),
R _{1c to} R _5c are each independently a hydrogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen atom, hydroxyl group Represents a nitro group, an alkylthio group or an arylthio group.
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
R _x and R _y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

Any two or more of R _{1c to} R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y may be bonded to form a ring structure. The ring structure may include an oxygen atom, a sulfur atom, a ketone group, an ester bond, and an amide bond.
Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, or a polycyclic fused ring formed by combining two or more of these rings. Examples of the ring structure include 3 to 10 membered rings.

Zc ^- represents a non-nucleophilic anion, in the general formula (ZI) Z ^- and include the same non-nucleophilic anion.

The alkyl group as R _{1c to} R _7c may be either linear or branched, and examples thereof include linear or branched alkyl groups having 1 to 20 carbon atoms. Examples of cycloalkyl groups include Examples thereof include a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group and a cyclohexyl group).

The aryl group as R _{1c to} R _5c preferably has 5 to 15 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

The alkoxy group as R _{1c to} R _{5c may} be linear, branched or cyclic, and examples thereof include linear and branched alkoxy groups having 1 to 10 carbon atoms and cyclic alkoxy groups having 3 to 10 carbon atoms. be able to.

Specific examples of the alkoxy group in the alkoxycarbonyl group as R _1c to R _5c are the same as specific examples of the alkoxy group of _R 1c _{to R 5c.}
Specific examples of the alkyl group in the alkylcarbonyloxy group and alkylthio group as R _1c to R _5c are the same as specific examples of the alkyl group of _R 1c _{to R 5c.}

Specific examples of the cycloalkyl group in the cycloalkyl carbonyl group as R _1c to R _5c are the same as specific examples of the cycloalkyl group of _R 1c _{to R 5c.}
Specific examples of the aryl group in the aryloxy group and arylthio group as R _1c to R _5c are the same as specific examples of the aryl group of _R 1c _{to R 5c.}
Preferably, any of R _{1c to} R _5c is a linear or branched alkyl group, a cycloalkyl group, or a linear, branched or cyclic alkoxy group.

The ring structure that any two or more of R _{1c to} R _5c may be bonded to each other is preferably a 5-membered or 6-membered ring.
The ring structure which may be formed by R _5c and R _6c are bonded to each other, bonded R _5c and R _6c are each other a single bond or an alkylene group (methylene group, ethylene group, etc.) by configuring the generally Examples thereof include a carbonyl carbon atom in formula (ZI-3) and a 4-membered ring (particularly preferably a 5- to 6-membered ring) formed together with the carbon atom.

The aryl group as R _6c and R _7c preferably has 5 to 15 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.
As an aspect of R _6c and R _7c , it is preferable that both of them are alkyl groups.
The ring formed by combining R _6c and R _7c may have a hetero atom such as an oxygen atom in the ring.

_Examples of the alkyl group and cycloalkyl group as R _x and R _y include the same alkyl group and cycloalkyl group as in R _{1c to} R _7c .

_Examples of the 2-oxoalkyl group and 2-oxocycloalkyl group as R _x and R _y include a group having> C═O at the 2-position of the alkyl group and cycloalkyl group as R _{1c to} R _7c. .

As for the alkoxy group in the alkoxycarbonylalkyl group as R _x and R _y , the same alkoxy group as in R _{1c to} R _5c can be exemplified, and the alkyl group is, for example, a linear chain having 1 to 12 carbon atoms. An alkyl group can be mentioned.

The allyl group as R _x and R _y is not particularly limited, but is preferably an unsubstituted allyl group or an allyl group substituted with a monocyclic or polycyclic cycloalkyl group.
The vinyl group as R _x and R _y is not particularly limited, but is preferably an unsubstituted vinyl group or a vinyl group substituted with a monocyclic or polycyclic cycloalkyl group.

The ring structure which may be formed by R _5c and R _x are bonded to each other by R _5c and R _x constitutes a bond to a single bond or an alkylene group with one another, formula (ZI-3) in the Examples thereof include a 5-membered ring (particularly preferably a 5-membered ring) formed with a sulfur atom and a carbonyl carbon atom.

As the ring structure which R _x and R _y may combine with each other, a 5-membered or 6-membered ring formed by divalent R _x and R _y together with a sulfur atom in the general formula (ZI-3) Is mentioned.
R _x and R _y are preferably an alkyl group or a cycloalkyl group having 4 or more carbon atoms.

R _{1c to} R _7c , R _x and R _y may further have a substituent, and examples of such a substituent include a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cyclo group. Alkyl group, aryl group, alkoxy group, aryloxy group, acyl group, arylcarbonyl group, alkoxyalkyl group, aryloxyalkyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, etc. Can be mentioned.

Next, the compound (ZI-4) will be described.
The compound (ZI-4) is represented by the following general formula (ZI-4).

In general formula (ZI-4),
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group. These groups may have a substituent.
When there are a plurality of R _{14 s,} each independently represents a group having a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group. Represent. These groups may have a substituent.
R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R ₁₅ may be bonded to each other to form a ring. These groups may have a substituent.
l represents an integer of 0-2.
r represents an integer of 0 to 8.
Z ^- represents a non-nucleophilic anion, in the general formula (ZI) Z ^- and include the same non-nucleophilic anion.

In General Formula (ZI-4), the alkyl groups represented by R ₁₃ , R _14, and R ₁₅ are linear or branched and preferably have 1 to 10 carbon atoms.
Examples of the cycloalkyl group represented by R ₁₃ , R ₁₄ and R ₁₅ include a monocyclic or polycyclic cycloalkyl group.

The alkoxy group for R ₁₃ and R ₁₄ is linear or branched and preferably has 1 to 10 carbon atoms.
The alkoxycarbonyl group for R ₁₃ and R ₁₄ is linear or branched and preferably has 2 to 11 carbon atoms.

Examples of the group having a cycloalkyl group of R ₁₃ and R ₁₄ include a group having a monocyclic or polycyclic cycloalkyl group. These groups may further have a substituent.
The alkyl group of the alkyl group of R _14, include the same specific examples as the alkyl group as R ₁₃ to R ₁₅ described above.
The alkylsulfonyl group and cycloalkylsulfonyl group for R ₁₄ are linear, branched, or cyclic, and preferably have 1 to 10 carbon atoms.

  Examples of the substituent that each of the above groups may have include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group. Etc.

As a ring structure that two R ₁₅ may be bonded to each other, a 5-membered or 6-membered ring formed by two R ₁₅ together with a sulfur atom in the general formula (ZI-4) is particularly preferable. Includes a 5-membered ring (that is, a tetrahydrothiophene ring), and may be condensed with an aryl group or a cycloalkyl group. The divalent R ₁₅ may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxy group. Examples thereof include a carbonyl group and an alkoxycarbonyloxy group. There may be a plurality of substituents for the ring structure, or they may be bonded to each other to form a ring.

R ₁₅ in the general formula (ZI-4) is preferably a methyl group, an ethyl group, a naphthyl group, a divalent group in which two R ^15s are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom.

The substituent that R ₁₃ and R ₁₄ may have is preferably a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, or a halogen atom (particularly a fluorine atom).

l is preferably 0 or 1, and more preferably 1.
As r, 0-2 are preferable.

  Specific examples of the cation structure possessed by the compounds (ZI-3) and (ZI-4) described above include the above-mentioned JP-A Nos. 2004-233661, 2003-35948, and US Patent Application Publication No. 2003. In addition to cation structures such as compounds exemplified in the specification of U.S. Pat. No. 0224288A1 and U.S. Patent Application Publication No. 2003 / 0077540A1, for example, paragraphs 0046, 0047, 0072 to 0077, 0107 Cation structure in the chemical structure and the like exemplified in .about.0110, and the cation structure in the chemical structure and the like exemplified in paragraphs 0135 to 0137, 00151, and 0196 to 0199 in JP2011-53430A.

In general formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents 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, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ in the aforementioned compound (ZI).

The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ may have a substituent. Even the substituent, an aryl group of R ₂₀₁ to R ₂₀₃ in the above compound (ZI), alkyl groups include those which may have a cycloalkyl group.

Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} formula (ZI).

Examples of the acid generator further include compounds represented by the following general formulas (ZIV), (ZV), and (ZVI).

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents an aryl group.
R ₂₀₈ , R ₂₀₉ and R ₂₁₀ each independently represents an alkyl group, a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.
Specific examples of the aryl group represented by Ar ₃ , Ar ₄ , R ₂₀₈ , R _209, and R ₂₁₀ include the same examples as the specific examples of the aryl group as R _{201 to} R ₂₀₃ in the general formula (ZI). it can.

Specific examples of the alkyl group and cycloalkyl group of R ₂₀₈ , R ₂₀₉ and R ₂₁₀ are the same as the specific examples of the alkyl group and cycloalkyl group as R _{201 to} R ₂₀₃ in the general formula (ZI), respectively. Can be mentioned.

  The alkylene group of A is an alkylene group having 1 to 12 carbon atoms (for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, etc.), and the alkenylene group of A is 2 carbon atoms. ˜12 alkenylene groups (for example, vinylene group, propenylene group, butenylene group, etc.), and as the arylene group for A, arylene groups having 6 to 10 carbon atoms (for example, phenylene group, tolylene group, naphthylene group, etc.) Each can be mentioned.

  Moreover, in the composition of this invention, it is preferable that the structure of the cation part of an acid generator is the same as the structure of the cation part of a compound (A). As described above, by making the cation structure of the acid generator the same as the cation structure of the compound (A), an unintended ion exchange reaction can be prevented.

More specifically, one preferred embodiment of the present invention is that the acid generator is represented by the following general formula (I ′). By being represented by the following general formula (I ′), the light transmittance of the exposed film is improved, which can contribute to the improvement of LWR and DOF.

In the general formula (I ′),
X ′ represents an oxygen atom, a sulfur atom or —N (Rx ′) —.
R ₁ ′ to R ₉ ′ and Rx ′ have the same meanings as R _{1 to} R ₉ and Rx in the general formula (I), respectively.
R ₁ ′ and R ₂ ′ may be connected to each other to form a ring. In addition, any two or more of R ₆ ′ to R ₉ ′, R ₃ ′ and R ₉ ′, R ₄ ′ and R ₅ ′, R ₅ ′ and Rx ′, R ₆ ′ and Rx ′, They may be connected to each other to form a ring.
Z ^- represents a non-nucleophilic anion, in the general formula (ZI) Z ^- and include the same non-nucleophilic anion.

Among acid generators, particularly preferred examples are given below.

An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the acid generator in the composition is preferably 0.1 to 30% by mass, more preferably 3 to 25% by mass, and still more preferably 7 to 20% by mass, based on the total solid content of the composition. is there.

[4] Hydrophobic resin The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a hydrophobic resin having at least one of a fluorine atom and a silicon atom (hereinafter referred to as “hydrophobic”), particularly when applied to immersion exposure. (Also referred to as a “resin (HR)”). As a result, the hydrophobic resin (HR) is unevenly distributed on the surface layer of the film, and when the immersion medium is water, the static / dynamic contact angle of the resist film surface with water is improved, and the immersion liquid followability is improved. be able to.

  Hydrophobic resin (HR) is unevenly distributed at the interface as described above, but unlike a surfactant, it does not necessarily have a hydrophilic group in the molecule, and polar / nonpolar substances should be mixed uniformly. It does not have to contribute to

  The hydrophobic resin typically contains fluorine atoms and / or silicon atoms. The fluorine atom and / or silicon atom in the hydrophobic resin (HR) may be contained in the main chain of the resin or may be contained in the side chain.

  When the hydrophobic resin contains a fluorine atom, it may be a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom. preferable.

  The alkyl group having a fluorine atom is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, You may have the substituent of.

  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 another substituent.

  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 the aryl group may further have another substituent.

As the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, or the aryl group having a fluorine atom, a group represented by any one of the following general formulas (F2) to (F4) is preferable. However, the present invention is not limited to this.

In general formulas (F2) to (F4),
R _{57 to} R ₆₈ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group (straight 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 are a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. (Preferably having 1 to 4 carbon atoms).
R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are preferably all fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably a fluoroalkyl group (preferably having 1 to 4 carbon atoms), and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. When R ₆₂ and _{R 63} is a perfluoroalkyl _group, it is preferred that _{R 64} is a hydrogen atom. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

  Specific examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.

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

Specific examples of the group represented by the general formula (F4) include, 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 preferred.

  The partial structure containing a fluorine atom may be directly bonded to the main chain, and further from the group consisting of 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 ureylene bond. You may couple | bond with the principal chain through the group selected or the group which combined these 2 or more.

Suitable examples of the repeating unit having a fluorine atom include those shown below.

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, which may have a substituent, and examples of the alkyl group having a substituent include a fluorinated alkyl group. it can.
W _{3 to} W ₆ each independently represents an organic group containing at least one fluorine atom. Specific examples include the atomic groups (F2) to (F4).

In addition to these, the hydrophobic resin may have a unit as shown below as a repeating unit having a fluorine atom.

In the formula, R _{4 to} R ₇ each 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, which may have a substituent, and examples of the alkyl group having a substituent include a fluorinated alkyl group. it can.
However, 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. Specific examples include the atomic groups (F2) to (F4).
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—, —N (R )-(Wherein R represents a hydrogen atom or alkyl), —NHSO ₂ — or a divalent linking group in which a plurality of these are combined.

  Q represents an alicyclic structure. The alicyclic structure may have a substituent, may be monocyclic, may be polycyclic, and may be bridged in the case of polycyclic. As the monocyclic type, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. Examples of the polycyclic type include groups having a bicyclo, tricyclo or 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. , Tricyclodecanyl group, tetocyclododecyl group and the like. Note that at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom. Particularly preferred examples of Q include a norbornyl group, a tricyclodecanyl group, a tetocyclododecyl group, and the like.

The hydrophobic resin may contain a silicon atom.
The partial structure having a silicon atom preferably has an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure.
Specific examples of the alkylsilyl structure or the cyclic siloxane structure include groups represented by the following general formulas (CS-1) to (CS-3).

In general formulas (CS-1) to (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 > -L < ₅ > represents a single bond or a bivalent coupling group. The divalent linking group includes an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond, or a group of two or more groups selected from the group consisting of a ureylene bond. A combination is mentioned.
n represents an integer of 1 to 5. n is preferably an integer of 2 to 4.

The repeating unit having at least either a fluorine atom or a silicon atom is preferably a (meth) acrylate-based repeating unit.
Hereinafter, although the specific example of the repeating unit which has at least any one of a fluorine atom and a silicon atom is given, this invention is not limited to this. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ , and X ₂ represents —F or —CF ₃ .

  The hydrophobic resin preferably has a repeating unit (b) having at least one group selected from the group consisting of the following (x) to (z).

(X) Alkali-soluble group (y) A group that decomposes by the action of an alkali developer and increases the solubility in an alkali developer (hereinafter also referred to as a polar conversion group).
(Z) A group that decomposes by the action of an acid to increase the solubility in an alkali developer. Examples of the repeating unit (b) include the following types.

A repeating unit (b ′) having at least one of a fluorine atom and a silicon atom and at least one group selected from the group consisting of the above (x) to (z) on one side chain
A repeating unit (b *) having at least one group selected from the group consisting of (x) to (z) and having no fluorine atom and no silicon atom
A fluorine atom and silicon on one side chain having at least one group selected from the group consisting of (x) to (z) above and on a side chain different from the side chain in the same repeating unit Repeating unit (b ″) having at least one of atoms
It is more preferable that the hydrophobic resin has a repeating unit (b ′) as the repeating unit (b). That is, it is more preferable that the repeating unit (b) having at least one group selected from the group consisting of the above (x) to (z) has at least one of a fluorine atom and a silicon atom.

  When the hydrophobic resin has a repeating unit (b *), a repeating unit having at least one of a fluorine atom and a silicon atom (a repeating unit different from the repeating units (b ′) and (b ″)) In addition, in the repeating unit (b ″), a side chain having at least one group selected from the group consisting of the above (x) to (z), and at least one of a fluorine atom and a silicon atom Are preferably bonded to the same carbon atom in the main chain, that is, in a positional relationship as shown in the following formula (K1).

In the formula, B1 represents a partial structure having at least one group selected from the group consisting of the above (x) to (z), and B2 represents a partial structure having at least one of a fluorine atom and a silicon atom.

  The group selected from the group consisting of the above (x) to (z) is preferably (x) an alkali-soluble group or (y) a polar conversion group, and more preferably (y) a polar conversion group.

  Examples of the alkali-soluble group (x) include phenolic hydroxyl group, carboxylic acid group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) ( Alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) ) And a methylene group.

  Preferred alkali-soluble groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (carbonyl) methylene groups.

  As the repeating unit (bx) having an alkali-soluble group (x), a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a linking group is used. Examples include a repeating unit in which an alkali-soluble group is bonded to the main chain of the resin. Furthermore, a polymerization initiator or a chain transfer agent having an alkali-soluble group can be used at the time of polymerization to be introduced at the end of the polymer chain, Either case is preferred.

  In the case where the repeating unit (bx) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, corresponding to the repeating unit (b ′) or (b ″)), the repeating unit (bx) Examples of the partial structure having a fluorine atom include the same ones as mentioned in the repeating unit having at least one of the fluorine atom and the silicon atom, and preferably represented by the general formulas (F2) to (F4). In this case, the partial structure having a silicon atom in the repeating unit (bx) is the same as that described in the repeating unit having at least one of the fluorine atom and the silicon atom. Preferably, groups represented by the general formulas (CS-1) to (CS-3) can be exemplified.

  The content of the repeating unit (bx) having an alkali-soluble group (x) is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, still more preferably from 5 to 20 mol, based on all repeating units in the hydrophobic resin. %.

Specific examples of the repeating unit (bx) having an alkali-soluble group (x) are shown below, but the present invention is not limited thereto. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ .

Examples of the polar conversion group (y) include a lactone group, a carboxylic acid ester group (—COO—), an acid anhydride group (—C (O) OC (O) —), an acid imide group (—NHCONH—), A carboxylic acid thioester group (—COS—), a carbonic acid ester group (—OC (O) O—), a sulfate ester group (—OSO ₂ O—), a sulfonic acid ester group (—SO ₂ O—), and the like. A lactone group is preferred.

  The polarity converting group (y) is, for example, introduced into the side chain of the resin by being included in a repeating unit of acrylic acid ester or methacrylic acid ester, or a polymerization initiator or chain having the polarity converting group (y). Any form in which a transfer agent is introduced at the end of the polymer chain using the polymerization is preferred.

  Specific examples of the repeating unit (by) having a polar conversion group (y) include a repeating unit having a lactone structure represented by formulas (KA-1-1) to (KA-1-17) described later. Can do.

  Further, the repeating unit (by) having the polarity converting group (y) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, the repeating unit (b ′), (b ″) corresponds to the repeating unit (b ′)). The resin having the repeating unit (by) is hydrophobic, but is particularly preferable from the viewpoint of reducing development defects.

As the repeating unit (by), for example, a repeating unit represented by the formula (K0) can be given.

In the formula, R _k1 represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group, or a group containing a polarity converting group.
R _k2 represents an alkyl group, a cycloalkyl group, an aryl group, or a group containing a polarity converting group.
However, at least one of R _k1 and R _k2 represents a group containing a polarity converting group.

The polarity converting group represents a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer as described above. The polar conversion group is preferably a group represented by X in the partial structure represented by the general formula (KA-1) or (KB-1).

X in the general formula (KA-1) or (KB-1) is a carboxylic acid ester group: —COO—, an acid anhydride group: —C (O) OC (O) —, an acid imide group: —NHCONH—, Carboxylic acid thioester group: —COS—, carbonate ester group: —OC (O) O—, sulfate ester group: —OSO ₂ O—, sulfonate ester group: —SO ₂ O—.
Y ¹ and Y ² may be the same or different and each represents an electron-withdrawing group.

The repeating unit (by) has a group that increases the solubility in a preferable alkali developer by having a group having a partial structure represented by the general formula (KA-1) or (KB-1). Are bonded to each other as in the case of the partial structure represented by the general formula (KA-1) and the partial structure represented by (KB-1) when Y ¹ and Y ² are monovalent When it does not have a hand, the group having the partial structure is a group having a monovalent or higher group obtained by removing at least one arbitrary hydrogen atom in the partial structure.

  The partial structure represented by the general formula (KA-1) or (KB-1) is linked to the main chain of the hydrophobic resin through a substituent at an arbitrary position.

The partial structure represented by the general formula (KA-1) is a structure that forms a ring structure together with the group as X.
X in the general formula (KA-1) is preferably a carboxylic acid ester group (that is, when a lactone ring structure is formed as KA-1), an acid anhydride group, or a carbonic acid ester group. More preferably, it is a carboxylic acid ester group.
The ring structure represented by the general formula (KA-1) may have a substituent, for example, may have nka substituents Z _ka1 .

Z _ka1 independently represents a halogen atom, an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group, or an electron-withdrawing group, when there are a plurality of Z _ka1 .
Z _ka1 may be linked to form a ring. Examples of the ring formed by connecting Z _{ka1 to} each other include a cycloalkyl ring and a hetero ring (a cyclic ether ring, a lactone ring, etc.).

  nka represents an integer of 0 to 10. Preferably it is an integer of 0 to 8, more preferably an integer of 0 to 5, more preferably an integer of 1 to 4, and most preferably an integer of 1 to 3.

The electron withdrawing group as Z _{ka1 is the same} as the electron withdrawing group as Y ¹ and Y ² described later. The electron withdrawing group may be substituted with another electron withdrawing group.

Z _ka1 is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, or an electron withdrawing group, and more preferably an alkyl group, a cycloalkyl group, or an electron withdrawing group. In addition, as an ether group, the thing substituted by the alkyl group or the cycloalkyl group, ie, the alkyl ether group, etc. are preferable. The electron withdrawing group has the same meaning as described above.

Examples of the halogen atom as Z _ka1 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

The alkyl group as Z _ka1 may have a substituent and may be linear or branched. As a linear alkyl group, Preferably it is C1-C30, More preferably, it is 1-20, for example, a methyl group, an ethyl group, n-propyl group, n-butyl group, sec-butyl group, t-butyl. Group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group and the like. As a branched alkyl group, Preferably it is C3-C30, More preferably, it is 3-20, for example, i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group, Examples include i-hexyl group, t-hexyl group, i-heptyl group, t-heptyl group, i-octyl group, t-octyl group, i-nonyl group, t-decanoyl group and the like. C1-C4 things, such as a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, are preferable.

The cycloalkyl group as Z _ka1 may have a substituent, and may be monocyclic or polycyclic. In the case of a polycyclic type, the cycloalkyl group may be a bridged type. That is, in this case, the cycloalkyl group may have a bridged structure. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. Examples of the polycyclic type include groups having a bicyclo, tricyclo, tetracyclo structure or the like 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, isobornyl group, Examples thereof include a camphanyl group, a dicyclopentyl group, an α-pinel group, a tricyclodecanyl group, a tetocyclododecyl group, and an androstanyl group. As the cycloalkyl group, the following structure is also preferable. Note that at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.

  Preferred examples of the alicyclic moiety include adamantyl group, noradamantyl group, decalin group, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecanyl group. And cyclododecanyl group. More preferred are an adamantyl group, a decalin group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, a cyclododecanyl group, and a tricyclodecanyl group.

  Examples of the substituent of these alicyclic structures include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group, and more preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group. Preferred examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the substituent that the alkyl group and the alkoxy group may have include a hydroxyl group, a halogen atom, and an alkoxy group (preferably having 1 to 4 carbon atoms).

  Further, the above group may further have a substituent, and examples of the further substituent include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the above alkyl group, and a methoxy group. , Alkoxy groups such as ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and t-butoxy group, alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, Aralkyl groups such as benzyl, phenethyl and cumyl groups, aralkyloxy groups, formyl groups, acetyl groups, butyryl groups, benzoyl groups, cyanyl groups, acyl groups such as valeryl groups, acyloxy groups such as butyryloxy groups, vinyl groups, propenyls Group, alkenyl group such as allyl group, vinyloxy group, propenyl Alkoxy group include an allyloxy group, an alkenyloxy group such as a butenyloxy group, a phenyl group, an aryl group such as a naphthyl group, an aryloxy group such as phenoxy group, aryloxycarbonyl group such as benzoyloxy group.

  X in the general formula (KA-1) is a carboxylic acid ester group, and the partial structure represented by the general formula (KA-1) is preferably a lactone ring, and more preferably a 5- to 7-membered lactone ring.

  In addition, as in the following (KA-1-1) to (KA-1-17), a 5- to 7-membered lactone ring as a partial structure represented by the general formula (KA-1) has a bicyclo structure, a spiro It is preferred that other ring structures are condensed in a form that forms the structure.

  As for the peripheral ring structure to which the ring structure represented by the general formula (KA-1) may be bonded, for example, those in the following (KA-1-1) to (KA-1-17), or The thing according to can be mentioned.

As a structure containing a lactone ring structure represented by the general formula (KA-1), a structure represented by any one of the following (KA-1-1) to (KA-1-17) is more preferable. The lactone structure may be directly bonded to the main chain. Preferred structures include (KA-1-1), (KA-1-4), (KA-1-5), (KA-1-6), (KA-1-13), (KA-1- 14) and (KA-1-17).

The structure containing the lactone ring structure may or may not have a substituent. Preferable substituents include those similar to the substituent Z _ka1 that the ring structure represented by the general formula (KA-1) may have.

  Preferred examples of X in the general formula (KB-1) include a carboxylic acid ester group (—COO—).

Y ¹ and Y ² in formula (KB-1) each independently represent an electron-withdrawing group.
The electron withdrawing group is a partial structure represented by the following formula (EW). * In the formula (EW) represents a bond directly connected to (KA-1) or a bond directly connected to X in (KB-1).

In formula (EW),
R _ew1 and R _ew2 each independently represent an arbitrary substituent, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
n _ew is the repeating number of the linking group represented by —C (R _ew1 ) (R _ew2 ) — and represents an integer of 0 or 1. When n _ew is 0, it represents a single bond, indicating that Y _ew1 is directly bonded.

Y _ew1 is a halogen atom, a cyano group, a nitrile group, a nitro group, a halo (cyclo) alkyl group or a haloaryl group represented by —C (R _f1 ) (R _f2 ) —R _f3 , an oxy group, a carbonyl group, a sulfonyl group Examples thereof include a group, a sulfinyl group, and a combination thereof. The electron-withdrawing group may have the following structure, for example. The “halo (cyclo) alkyl group” represents an alkyl group and a cycloalkyl group that are at least partially halogenated, and the “haloaryl group” represents an aryl group that is at least partially halogenated. In the following structural formula, R _ew3 and R _ew4 each independently represent an arbitrary structure. R _ew3 and R _ew4 may have any structure, and the partial structure represented by the formula (EW) may have an electron withdrawing property, and may be linked to, for example, the main chain of the resin. An alkyl group and a fluorinated alkyl group;

When Y _ew1 is a divalent or higher group, the remaining bond forms a bond with an arbitrary atom or substituent. At least one group of Y _ew1 , R _ew1 , and R _ew2 may be connected to the main chain of the hydrophobic resin through a further substituent.

Y _ew1 is preferably a halogen atom, or a halo (cyclo) alkyl group or haloaryl group represented by —C (R _f1 ) (R _f2 ) —R _f3 .

At least two of R _ew1 , R _ew2 and Y _ew1 may be connected to each other to form a ring.

Here, R _f1 represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group, or a perhaloaryl group, more preferably a fluorine atom, a perfluoroalkyl group, or a perfluorocycloalkyl group, still more preferably a fluorine atom or a trialkyl group. Represents a fluoromethyl group.

R _f2 and R _f3 each independently represent a hydrogen atom, a halogen atom or an organic group, and R _f2 and R _f3 may be linked to form a ring. Examples of the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group. More preferably, R _f2 represents the same group as R _f1 or is linked to R _f3 to form a ring.

R _{f1 to} R _f3 may be linked to form a ring, and examples of the ring formed include a (halo) cycloalkyl ring and a (halo) aryl ring.
Examples of the (halo) alkyl group in R _{f1 to} R _f3 include the alkyl group in Z _ka1 described above and a structure in which this is halogenated.

Examples of the (per) halocycloalkyl group and the (per) haloaryl group in R _{f1 to} R _f3 or in the ring formed by linking R _f2 and R _f3 include, for example, the aforementioned cycloalkyl group in Z _ka1 is a halogen atom. And a perfluoroaryl group represented by -C _(n) F _(n-1) and more preferably a fluorocycloalkyl group represented by -C _(n) F _(2n-2) H Can be mentioned. Although carbon number n is not specifically limited here, the thing of 5-13 is preferable and 6 is more preferable.

The ring that may be formed by linking at least two of R _ew1 , R _ew2 and Y _ew1 preferably includes a cycloalkyl group or a heterocyclic group, and the heterocyclic group is preferably a lactone ring group. Examples of the lactone ring include structures represented by the above formulas (KA-1-1) to (KA-1-17).

  In the repeating unit (by), a plurality of partial structures represented by the general formula (KA-1), a plurality of partial structures represented by the general formula (KB-1), or a general formula (KA) It may have both a partial structure represented by -1) and a partial structure represented by the general formula (KB-1).

Note that part or all of the partial structure of the general formula (KA-1) may also serve as an electron withdrawing group as Y ¹ or Y ² in the general formula (KB-1). For example, when X in the general formula (KA-1) is a carboxylic acid ester group, the carboxylic acid ester group functions as an electron withdrawing group as Y ¹ or Y ² in the general formula (KB-1). There is also a possibility.

  In addition, when the repeating unit (by) corresponds to the repeating unit (b *) or the repeating unit (b ″) and has a partial structure represented by the general formula (KA-1), the general formula (KA) As for the partial structure represented by -1), it is more preferable that the polarity conversion group is a partial structure represented by -COO- in the structure represented by the general formula (KA-1).

The repeating unit (by) can be a repeating unit having a partial structure represented by the general formula (KY-0).

In the general formula (KY-0),
R ₂ represents a chain or cyclic alkylene group, and when there are a plurality of R ₂ groups, they may be the same or different.
R ₃ represents a linear, branched or cyclic hydrocarbon group in which part or all of the hydrogen atoms on the constituent carbons are substituted with fluorine atoms.
R ₄ is a halogen atom, cyano group, hydroxy group, amide group, alkyl group, cycloalkyl group, alkoxy group, phenyl group, acyl group, alkoxycarbonyl group, or R—C (═O) — or R—C ( = O) A group represented by O- (R represents an alkyl group or a cycloalkyl group). If R ₄ is a plurality may be the same or different, and two or more R ₄ are attached, may form a ring.
X represents an alkylene group, an oxygen atom, or a sulfur atom.
Z and Za represent a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality of them, they may be the same or different.
* Represents a bond to the main chain or side chain of the resin.
o is the number of substituents and represents an integer of 1 to 7.
m is the number of substituents and represents an integer of 0 to 7.
n represents the number of repetitions and represents an integer of 0 to 5.

The structure represented by —R ₂ —Z— is preferably a structure represented by — (CH ₂ ) ₁ —COO— (l represents an integer of 1 to 5).
The preferred carbon number range and specific examples of the chain or cyclic alkylene group as R ₂ are the same as those described for the chain alkylene group and cyclic alkylene group in Z ₂ of the general formula (bb).

The linear, branched or cyclic hydrocarbon group as R ₃ has preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and preferably 3 carbon atoms when branched. -30, more preferably 3-20, and in the case of a ring, it is 6-20. Specific examples of R ₃ include specific examples of the alkyl group and cycloalkyl group as Z _ka1 described above.

Preferable carbon numbers and specific examples in the alkyl group and cycloalkyl group as R ₄ and R are the same as those described for the alkyl group and cycloalkyl group as Z _ka1 described above.

The acyl group as R ₄ is preferably one having 1 to 6 carbon atoms, and examples thereof include a formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, and pivaloyl group.

Examples of the alkyl moiety in the alkoxy group and alkoxycarbonyl group as R ₄ include a linear, branched or cyclic alkyl moiety, and the preferred carbon number of the alkyl moiety and specific examples thereof are those described above for Z _ka1. The same as those described in the alkyl group and cycloalkyl group.

Examples of the alkylene group as X include a chain or cyclic alkylene group, and preferred carbon numbers and specific examples thereof are the same as those described for the chain alkylene group and cyclic alkylene group as R ₂ .

  When the polarity conversion group is decomposed by the action of the alkali developer and the polarity is changed, the receding contact angle with water of the resist film after alkali development can be lowered. It is preferable from the viewpoint of suppressing development defects that the receding contact angle with water of the film after alkali development is lowered.

  The receding contact angle with water of the resist film after alkali development is preferably 50 ° or less at a temperature of 23 ± 3 ° C. and a humidity of 45 ± 5%, more preferably 40 ° or less, still more preferably 35 ° or less. Most preferably, it is 30 ° or less.

  The receding contact angle is a contact angle measured when the contact line at the droplet-substrate interface recedes, and is useful for simulating the ease of movement of the droplet in a dynamic state. It is generally known. In simple terms, it can be defined as the contact angle when the droplet interface recedes when the droplet discharged from the needle tip is deposited on the substrate and then sucked into the needle again. It can be measured by using a contact angle measuring method generally called an expansion / contraction method.

  The hydrolysis rate of the hydrophobic resin with respect to the alkaline developer is preferably 0.001 nm / second or more, more preferably 0.01 nm / second or more, still more preferably 0.1 nm / second or more, Most preferably, it is 1 nm / second or more.

  Here, the hydrolysis rate of the hydrophobic resin with respect to the alkaline developer was 23 ° C. when TMAH (tetramethylammonium hydroxide aqueous solution) (2.38 mass%) was used to form the resin film with only the hydrophobic resin. This is the rate at which the film thickness decreases.

  The repeating unit (by) is more preferably a repeating unit having at least two or more polar conversion groups.

When the repeating unit (by) has at least two polar conversion groups, the repeating unit (by) preferably has a group having a partial structure having two polar conversion groups represented by the following general formula (KY-1). Note that when the structure represented by the general formula (KY-1) does not have a bond, it is a group having a monovalent or higher valent group in which at least one arbitrary hydrogen atom in the structure is removed.

In general formula (KY-1),
R _ky1 and R _ky4 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, carbonyl group, carbonyloxy group, oxycarbonyl group, ether group, hydroxyl group, cyano group, amide group, or aryl group Represents. Alternatively, R _ky1 and R _ky4 may be bonded to the same atom to form a double bond. For example, R _ky1 and R _ky4 are bonded to the same oxygen atom to form a part of a carbonyl group (═O). May be formed.

R _ky2 and R _ky3 are each independently an electron withdrawing group, or R _ky1 and R _ky2 are linked to form a lactone ring and R _ky3 is an electron withdrawing group. As the lactone ring to be formed, the structures (KA-1-1) to (KA-1-17) are preferable. Examples of the electron withdrawing group include the same groups as those described above for Y ₁ and Y ₂ in the formula (KB-1), and preferably a halogen atom or the aforementioned —C (R _f1 ) (R _f2 ) —R _f3. A halo (cyclo) alkyl group or a haloaryl group represented by the formula: Preferably _{R ky3} halogen atom, or the _{-C (R f1)} (R f2) is represented by the halo (cyclo) alkyl groups or haloaryl groups _{-R f3,} lactone _{R ky2} is linked to _{R ky1} An electron withdrawing group that forms a ring or has no halogen atom.

R _ky1 , R _ky2 , and R _ky4 may be connected to each other to form a monocyclic or polycyclic structure.
Specific examples of R _ky1 and R _ky4 include the same groups as Z _ka1 in formula (KA-1).

As the lactone ring formed by linking R _ky1 and R _ky2 , the structures (KA-1-1) to (KA-1-17) are preferable. Examples of the electron withdrawing group include those similar to Y ₁ and Y ₂ in the formula (KB-1).

The structure represented by the general formula (KY-1) is more preferably a structure represented by the following general formula (KY-2). Note that the structure represented by the general formula (KY-2) is a group having a monovalent or higher group obtained by removing at least one arbitrary hydrogen atom in the structure.

In formula (KY-2),
R _{ky6 to} R _ky10 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, carbonyl group, carbonyloxy group, oxycarbonyl group, ether group, hydroxyl group, cyano group, amide group, or aryl. Represents a group.
Two or more of R _{ky6 to} R _ky10 may be connected to each other to form a monocyclic or polycyclic structure.
R _ky5 represents an electron withdrawing group. Examples of the electron withdrawing group include the same groups as those described above for Y ₁ and Y ₂ , and preferably a halogen atom or a halo (cyclo (cyclo) represented by —C (R _f1 ) (R _f2 ) —R _f3 ) An alkyl group or a haloaryl group.
Specific examples of R _{ky5 to} R _ky10 include the same groups as Z _ka1 in formula (KA-1).

The structure represented by the formula (KY-2) is more preferably a partial structure represented by the following general formula (KY-3).

In formula (KY-3), Z _ka1 and nka have the same meanings as those in formula (KA-1). R _ky5 has the same _{meaning as} in formula (KY-2).
L _ky represents an alkylene group, an oxygen atom or a sulfur atom. _Examples of the alkylene group for L _ky include a methylene group and an ethylene group. L _ky is preferably an oxygen atom or a methylene group, and more preferably a methylene group.

  The repeating unit (b) is not limited as long as it is a repeating unit obtained by polymerization such as addition polymerization, condensation polymerization, addition condensation, etc., but is a repeating unit obtained by addition polymerization of a carbon-carbon double bond. Preferably there is. Examples include acrylate-based repeating units (including those having substituents at the α-position and β-position), styrene-based repeating units (including those having substituents at the α-position and β-position), vinyl ether-based repeating units, norbornene-based Repeating units, maleic acid derivatives (maleic anhydride and derivatives thereof, maleimides, etc.), and the like, acrylate-based repeating units, styrene-based repeating units, vinyl ether-based repeating units, norbornene-based repeating units Preferred are acrylate repeat units, vinyl ether repeat units, and norbornene repeat units, with acrylate repeat units being most preferred.

  When the repeating unit (by) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, when the repeating unit (by) corresponds to the repeating unit (b ′) or (b ″)), the repeating unit (by) Examples of the partial structure having a fluorine atom include the same ones as mentioned in the repeating unit having at least one of the fluorine atom and the silicon atom, and preferably represented by the general formulas (F2) to (F4). In this case, the partial structure having a silicon atom in the repeating unit (by) has the same structure as that described in the repeating unit having at least one of the fluorine atom and the silicon atom. Preferably, groups represented by the general formulas (CS-1) to (CS-3) can be exemplified.

  The content of the repeating unit (by) in the hydrophobic resin is preferably from 10 to 100 mol%, more preferably from 20 to 99 mol%, still more preferably from 30 to 97 mol%, based on all repeating units in the hydrophobic resin. Most preferably, it is 40-95 mol%.

Specific examples of the repeating unit (by) having a group capable of increasing the solubility in an alkali developer are shown below, but are not limited thereto.
In the specific examples shown below, Ra represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

  Examples of the method for synthesizing the monomer corresponding to the repeating unit (by) having the polar conversion group (y) as described above include the method described in International Publication No. 2010/069705, International Publication No. 2010/069705, or the like. Can be synthesized with reference to

  Examples of the repeating unit (bz) having a group (z) capable of decomposing by the action of an acid in the hydrophobic resin include the same repeating units having an acid-decomposable group as mentioned for the resin (A).

  In the case where the repeating unit (bz) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, corresponding to the repeating unit (b ′) or (b ″)), the repeating unit (bz) Examples of the partial structure having a fluorine atom include the same ones as mentioned in the repeating unit having at least one of the fluorine atom and the silicon atom, and preferably represented by the general formulas (F2) to (F4). In this case, the partial structure having a silicon atom in the repeating unit (by) has the same structure as that described in the repeating unit having at least one of the fluorine atom and the silicon atom. Preferably, groups represented by the general formulas (CS-1) to (CS-3) can be exemplified.

  In the hydrophobic resin, the content of the repeating unit (bz) having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol%, more preferably based on all repeating units in the hydrophobic resin. It is 10-80 mol%, More preferably, it is 20-60 mol%.

  Hereinabove, the repeating unit (b) having at least one group selected from the group consisting of the above (x) to (z) has been described, but the content of the repeating unit (b) in the hydrophobic resin is hydrophobic. It is preferably 1 to 98 mol%, more preferably 3 to 98 mol%, still more preferably 5 to 97 mol%, and most preferably 10 to 95 mol% with respect to all repeating units in the conductive resin.

  The content of the repeating unit (b ′) is preferably 1 to 100 mol%, more preferably 3 to 99 mol%, still more preferably 5 to 97 mol%, and most preferably 10 to 10 mol% with respect to all repeating units in the hydrophobic resin. 95 mol%.

  The content of the repeating unit (b *) is preferably from 1 to 90 mol%, more preferably from 3 to 80 mol%, still more preferably from 5 to 70 mol%, most preferably from 10 to 10%, based on all repeating units in the hydrophobic resin. 60 mol%. The content of the repeating unit having at least one of a fluorine atom and a silicon atom used together with the repeating unit (b *) is preferably 10 to 99 mol%, more preferably 20 with respect to all repeating units in the hydrophobic resin. It is -97 mol%, More preferably, it is 30-95 mol%, Most preferably, it is 40-90 mol%.

  The content of the repeating unit (b ″) is preferably 1 to 100 mol%, more preferably 3 to 99 mol%, still more preferably 5 to 97 mol%, and most preferably 10 to 10 mol% based on all repeating units in the hydrophobic resin. 95 mol%.

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

In general formula (CIII):
R _c31 represents a hydrogen atom, an alkyl group (which may be substituted with a fluorine atom or the like), 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, 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 fluorine atom, a group containing a silicon atom, or the like.
L _c3 represents a single bond or a divalent linking group.

In general formula (CIII), the alkyl group represented by R _c32 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 a phenyl group or naphthyl group having 6 to 20 carbon atoms, 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 of L _c3 is preferably an alkylene group (preferably having 1 to 5 carbon atoms), an oxy group, a phenylene group, or an ester bond (a group represented by —COO—).

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

In the formula (BII-AB),
R _c11 ′ and R _c12 ′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group.
Zc ′ represents an atomic group for forming an alicyclic structure containing two bonded carbon atoms (C—C).

  When each group in the repeating unit represented by the general formulas (CIII) and (BII-AB) is substituted with a group containing a fluorine atom or a silicon atom, the repeating unit includes at least the fluorine atom and the silicon atom. It corresponds also to the repeating unit which has either.

Specific examples of the repeating unit represented by the general formulas (CIII) and (BII-AB) are shown below, but the present invention is not limited to these. In the formula, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN. Note that the repeating unit in the case where Ra is CF ₃ also corresponds to the repeating unit having at least one of the fluorine atom and the silicon atom.

  As in the case of the resin (A) described above, the hydrophobic resin naturally has few impurities such as metals, and the residual monomer or oligomer component is preferably 0 to 10% by mass, more preferably 0. -5 mass%, 0-1 mass% is still more preferable. Thereby, a resist composition having no change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 3, more preferably 1 to 2, and still more preferably, in terms of resolution, resist shape, resist pattern side walls, roughness, and the like. It is in the range of 1 to 1.8, most preferably 1 to 1.5.

  As the hydrophobic resin, various commercially available products can be used, and can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable.

  The reaction solvent, the polymerization initiator, the reaction conditions (temperature, concentration, etc.) and the purification method after the reaction are the same as those described for the resin (A) described above.

Specific examples of the hydrophobic resin (HR) are shown below. Table 1 below shows the molar ratio of repeating units in each resin (the positional relationship of each repeating unit in each resin shown in the specific example corresponds to the positional relationship of the composition ratio numbers in Table 1), weight average Indicates molecular weight and degree of dispersion.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains an actinic ray-sensitive or radiation-sensitive resin composition by containing a hydrophobic hydrophobic resin containing at least one of a fluorine atom and a silicon atom. When the hydrophobic resin is unevenly distributed in the surface layer of the film formed from the material and the immersion medium is water, the receding contact angle of the film surface after baking to water and before exposure is improved, and the immersion liquid followability is improved. Can be made.

  After baking the coating film comprising the actinic ray-sensitive or radiation-sensitive resin composition of the present invention and before exposure, the receding contact angle of the film is the temperature at the time of exposure, usually room temperature 23 ± 3 ° C., humidity 45 ± 5%. 60 ° to 90 °, more preferably 65 ° or more, still more preferably 70 ° or more, and particularly preferably 75 ° or more.

  The hydrophobic resin is unevenly distributed at the interface as described above, but unlike the surfactant, it does not necessarily have a hydrophilic group in the molecule and contributes to uniform mixing of polar / nonpolar substances. It is not necessary.

  In the immersion exposure process, the immersion head needs to move on the wafer following the movement of the exposure head to scan the wafer at high speed to form the exposure pattern. In this case, the contact angle of the immersion liquid with respect to the resist film is important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.

  Hydrophobic resins are hydrophobic, so that development residues (scum) and BLOB defects are likely to deteriorate after alkali development, but they have three or more polymer chains via at least one branch, compared to linear resins. Further, since the alkali dissolution rate is improved, development residue (scum) and BLO defect performance are improved.

  When the hydrophobic resin has a fluorine atom, the fluorine atom content is preferably 5 to 80% by mass and more preferably 10 to 80% by mass with respect to the molecular weight of the hydrophobic resin. Moreover, it is preferable that the repeating unit containing a fluorine atom is 10-100 mol% with respect to all the repeating units in hydrophobic resin, and it is more preferable that it is 30-100 mol%.

  When the hydrophobic resin has a silicon atom, the content of the silicon atom is preferably 2 to 50% by mass and more preferably 2 to 30% by mass with respect to the molecular weight of the hydrophobic resin. Moreover, it is preferable that it is 10-90 mol% with respect to all the repeating units of hydrophobic resin, and, as for the repeating unit containing a silicon atom, it is more preferable that it is 20-80 mol%.

  The weight average molecular weight of the hydrophobic resin is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and still more preferably 3,000 to 35,000. Here, the weight average molecular weight of the resin indicates a molecular weight in terms of polystyrene measured by GPC (carrier: tetrahydrofuran (THF)).

  The content of the hydrophobic resin in the actinic ray-sensitive or radiation-sensitive resin composition can be appropriately adjusted and used so that the receding contact angle of the actinic ray or radiation-sensitive resin film falls within the above range. Is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, still more preferably 0.1 to 10% by mass, based on the total solid content of the light-sensitive or radiation-sensitive resin composition. And particularly preferably 0.2 to 8% by mass.

  Hydrophobic resins can be used alone or in combination of two or more.

[5] Surfactant The composition of the present invention may further contain a surfactant or may not contain a surfactant. As the surfactant, fluorine-based and / or silicon-based surfactants are preferable.

  As surfactants corresponding to these, Megafac F176, Megafac R08 manufactured by DIC Corporation, PF656, PF6320 manufactured by OMNOVA, Troisol S-366 manufactured by Troy Chemical Co., Ltd., manufactured by Sumitomo 3M Co., Ltd. Fluorado FC430, polysiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

  Further, other surfactants other than fluorine-based and / or silicon-based surfactants can also be used. More specific examples include polyoxyethylene alkyl ethers and polyoxyethylene alkyl aryl ethers.

In addition, known surfactants can be used as appropriate. Examples of the surfactant that can be used include surfactants described in [0273] et seq. Of US Patent Application Publication No. 2008 / 0248425A1.
Surfactants may be used alone or in combination of two or more.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may or may not contain a surfactant, but when it is contained, the amount of surfactant used is the total solid content of the composition. Preferably it is 0-2 mass% with respect to a minute, More preferably, it is 0.0001-2 mass%, Most preferably, it is 0.0005-1 mass%.

  On the other hand, it is also preferable that the addition amount of the surfactant is 10 ppm or less or not contained. This increases the uneven distribution of the surface of the hydrophobic resin, whereby the resist film surface can be made more hydrophobic, and the water followability during immersion exposure can be improved.

[6] Solvent The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention usually further contains a solvent.

  Examples of the solvent include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), and monoketone which may contain a ring. Examples include organic solvents such as compounds (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.

  Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), 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.

  Examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether (PGME, also known as 1-methoxy-2-propanol), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene Preferred is glycol monoethyl ether.

  Preferred examples of the alkyl lactate include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.

  Preferable examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-methoxypropionate.

  Examples of the cyclic lactone include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, and γ-octano. Preferred are iclactone and α-hydroxy-γ-butyrolactone.

  Examples of the monoketone compound which may contain a ring include 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-tetramethyl-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, -Penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3-methyl Cyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methylcyclo A preferred example is heptanone.

  Preferred examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.

  Examples of the alkyl alkoxyacetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy-acetate. 2-propyl is preferred.

  Preferred examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.

  As a solvent which can be preferably used, a solvent having a boiling point of 130 ° C. or higher under normal temperature and normal pressure can be mentioned. Specifically, cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, ethyl pyruvate, 2-ethoxyethyl acetate, acetic acid -2- (2-ethoxyethoxy) ethyl and propylene carbonate are mentioned.

In the present invention, the above solvents may be used alone or in combination of two or more.
In this invention, you may use the mixed solvent which mixed the solvent which contains a hydroxyl group in a structure, and the solvent which does not contain a hydroxyl group as an organic solvent.

  As the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, the above-mentioned exemplary compounds can be selected as appropriate, but as the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate, etc. are preferable, propylene glycol monomethyl ether, More preferred is ethyl lactate. Further, as the solvent not containing a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, monoketone compound which may contain a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene glycol monomethyl ether Acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone and butyl acetate are particularly preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxypropionate and 2-heptanone are most preferred.

  The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. . A mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.

  The solvent is preferably a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.

[7] Other components In addition to the components described above, the composition of the present invention comprises a carboxylic acid onium salt, a dissolution inhibiting compound having a molecular weight of 3000 or less, a dye, described in Proceeding of SPIE, 2724, 355 (1996), etc. A plasticizer, a photosensitizer, a light absorber and the like can be appropriately contained.

[8] Pattern Forming Method The pattern forming method of the present invention includes steps of exposing and developing a resist film.
The resist film is formed from the actinic ray-sensitive or radiation-sensitive resin composition of the present invention described above, and more specifically, is preferably formed on a substrate. In the pattern forming method of the present invention, the step of forming a film of a resist composition on the substrate, the step of exposing the film, and the developing step can be performed by generally known methods.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably used at a film thickness of 30 to 250 nm, more preferably at a film thickness of 30 to 200 nm, from the viewpoint of improving resolution. preferable. By setting the solid content concentration in the actinic ray-sensitive or radiation-sensitive resin composition to an appropriate range to have an appropriate viscosity, and improving the coating property and film forming property, such a film thickness is obtained. Can do.

  The total solid concentration in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is generally 1 to 10% by mass, more preferably 1 to 8.0% by mass, and still more preferably 1.0 to 6.0% by mass.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is used by dissolving the above components in a solvent, filtering the solution, and applying the solution to a support. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon having a pore size of 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less. Note that a plurality of types of filters may be connected in series or in parallel. The composition may be filtered multiple times. Furthermore, you may perform a deaeration process etc. with respect to a composition before and after filter filtration.

  The composition is applied by a suitable application method, such as a spinner, onto a substrate (eg, silicon / silicon dioxide coating) as used in the manufacture of integrated circuit devices. Thereafter, it can be dried to form a photosensitive resist film.

The film is irradiated with actinic rays or radiation through a predetermined mask, preferably baked (heated), developed and rinsed. Thereby, a good pattern can be obtained. Note that in electron beam irradiation, drawing (direct drawing) without using a mask is common.
It is also preferable to include a preheating step (PB; Prebake) after the film formation and before the exposure step.
It is also preferable to include a post-exposure heating step (PEB; Post Exposure Bake) after the exposure step and before the development step.

The heating temperature is preferably 70 to 120 ° C., more preferably 80 to 110 ° C. for both PB and PEB.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds.

Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.
The reaction of the exposed part is promoted by baking, and the sensitivity and pattern profile are improved.

  Although it does not specifically limit as actinic light or a radiation, For example, they are a KrF excimer laser, ArF excimer laser, EUV light, an electron beam, etc., ArF excimer laser, EUV light, and an electron beam are preferable.

As the alkali developer in the development step, a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used. An aqueous solution can also be used.
Furthermore, an appropriate amount of alcohol or surfactant may be added to the alkaline developer.

The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
The pH of the alkali developer is usually from 10.0 to 15.0.
As the rinsing liquid, pure water can be used, and an appropriate amount of a surfactant can be added.

  As a developing method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc. can be applied.

  In the rinsing step, the developed wafer is cleaned using a rinsing liquid. The cleaning method is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid on the substrate surface (spray method), and the like can be applied. Among them, a cleaning treatment is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. The developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking. The heating step after the rinsing step is usually 40 to 160 ° C., preferably 70 to 95 ° C., and usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

  Moreover, the process which removes the developing solution or rinse liquid adhering on a pattern with a supercritical fluid can be performed after a image development process or a rinse process.

Before forming the photosensitive film (resist film), an antireflection film may be coated on the substrate in advance.
As the antireflection film, any of an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon, and an organic film type made of a light absorber and a polymer material can be used. In addition, as the organic antireflection film, commercially available organic antireflection films such as DUV30 series, DUV-40 series manufactured by Brewer Science, AR-2, AR-3, AR-5 manufactured by Shipley, etc. may be used. it can.

Exposure (immersion exposure) may be performed by filling a liquid (immersion medium) having a higher refractive index than air between the film and the lens during irradiation with actinic rays or radiation. Thereby, resolution can be improved. The immersion medium used is preferably water. Water is also suitable in terms of a small temperature coefficient of refractive index, ease of availability, and ease of handling.
A medium having a refractive index of 1.5 or more can also be used in that the refractive index can be improved. This medium may be an aqueous solution or an organic solvent.

  When water is used as the immersion liquid, an additive for the purpose of improving the refractive index may be added in a small proportion. Examples of additives are detailed in Chapter 12 of CMC Publishing "Processes and Materials for Immersion Lithography". On the other hand, the presence of impurities that are opaque to 193 nm light and impurities whose refractive index is significantly different from that of water causes distortion of the optical image projected on the film, and therefore, distilled water is preferred as the water to be used. Further, pure water purified with an ion exchange filter or the like may be used. The electric resistance of pure water is desirably 18.3 MQcm or more, the TOC (organic substance concentration) is desirably 20 ppb or less, and deaeration treatment is desirably performed.

  An immersion liquid poorly soluble film (hereinafter also referred to as “top coat”) may be provided between the resist film and the immersion liquid in order to avoid contact between the resist film and the immersion liquid. Functions necessary for the top coat include suitability for application on a resist film, transparency to radiation, particularly radiation having a wavelength of 193 nm, and poor immersion liquid solubility. As the top coat, it is preferable to use a top coat that can be uniformly coated on the resist film without being mixed with the resist film.

  From the viewpoint of transparency at 193 nm, the topcoat is preferably a polymer that does not contain aromatics. Examples of such polymers include hydrocarbon polymers, acrylic ester polymers, polymethacrylic acid, polyacrylic acid, polyvinyl ether, silicon-containing polymers, and fluorine-containing polymers. The hydrophobic resin described above is also suitable as a top coat. When impurities are eluted from the top coat into the immersion liquid, the optical lens is contaminated. Therefore, it is preferable that the residual monomer component of the polymer contained in the top coat is small.

  When peeling the top coat, a developer may be used, or a separate release agent may be used. As the release agent, a solvent having a small penetration into the resist film is preferable. It is preferable that the peeling process can be performed with an alkali developer in that the peeling process can be performed simultaneously with the resist development process. The top coat is preferably acidic from the viewpoint of peeling with an alkali developer, but may be neutral or alkaline from the viewpoint of non-intermixability with the resist.

  There is preferably no or small difference in refractive index between the top coat and the immersion liquid. In this case, the resolution can be improved. When the exposure light source is an ArF excimer laser (wavelength: 193 nm), it is preferable to use water as the immersion liquid. Therefore, the top coat for ArF immersion exposure is close to the refractive index of water (1.44). preferable.

  Moreover, it is preferable that a topcoat is a thin film from a viewpoint of transparency and a refractive index. The top coat is preferably not mixed with the resist film and further not mixed with the immersion liquid. From this point of view, when the immersion liquid is water, the solvent used in the top coat is hardly soluble in the solvent used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention and is not water-soluble. It is preferable that the medium be a sex medium. Further, when the immersion liquid is an organic solvent, the top coat may be water-soluble or water-insoluble.

The present invention also relates to an electronic device manufacturing method including the above-described pattern forming method of the present invention, and an electronic device manufactured by this manufacturing method.
The electronic device of the present invention is suitably mounted on electrical and electronic equipment (home appliances, OA / media related equipment, optical equipment, communication equipment, etc.).

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

(Acid-decomposable resin (A))
The following resins (A-1) to (A-6) and (AX) were synthesized as shown below.

[Synthesis of acid-decomposable resin A-5]
Under a nitrogen stream, 4.2 g of cyclohexanone was placed in a three-necked flask and heated to 85 ° C. In this way, solvent 1 was obtained. Next, the following monomer-1 (1.85 g), monomer-2 (2.00 g), monomer-3 (1.64 g) and monomer-4 (1.57 g) were dissolved in cyclohexanone (17.0 g). A monomer solution was prepared. Furthermore, a solution in which 6.5 mol% of a polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added and dissolved with respect to the total amount of monomers was added dropwise to the solvent 1 over 6 hours. After completion of dropping, the reaction was further continued at 85 ° C. for 2 hours. The reaction solution was allowed to cool and then added dropwise to a mixed solvent of 173 g of heptane / 74 g of ethyl acetate, and the precipitated powder was collected by filtration and dried to obtain 5.0 g of Resin (A-5). The obtained resin (A-5) has a weight average molecular weight of 8,300, a dispersity (Mw / Mn) of 1.55, and a composition ratio measured by ¹³ C-NMR of 30/20/30/20. there were.

  Resins (A-1) to (A-4), (A-6), and (AX) were synthesized in the same manner as the resin (A-5).

[Synthesis example of monomer-1]

  Anhydrous 5-norbornene-2,3-dicarboxylic acid (65.66 g, 0.4 mol) and chloroacetic acid (75.60 g, 0.8 mol) were put into a three-necked flask and heated and melted at 80 ° C. to obtain a uniform solution. . Trifluorosulfonic acid (3.5 ml, 40 mmol) was added dropwise thereto, and the mixture was stirred at 100 ° C. for 3 hours. After completion of the reaction, the reaction solution was cooled to 50 ° C., 500 ml of toluene was added, and the mixture was cooled to 25 ° C. This solution was added to a solution of 40 g of sodium hydrogen carbonate, 320 ml of distilled water, and 160 ml of saturated brine with stirring to carry out liquid separation purification. Thereafter, the organic layer was washed with 480 ml of saturated saline, and then the solvent was distilled off under reduced pressure to obtain 80 g of an oily compound.

  The obtained oil was put into a three-necked flask, 550 ml of dimethylacetamide was added, methacrylic acid (34.61 g, 0.402 mol), sodium hydrogen carbonate (33.77 g, 0.402 mol), potassium iodide (12.82 g). 0.077 mol) was added and the mixture was stirred at 60 ° C. for 4 hours. After adding 1.5 L of toluene and cooling to 25 ° C., 1N hydrochloric acid was added until pH = 3, and a liquid separation operation was performed. The organic layer was washed with an aqueous sodium hydrogen carbonate solution and saturated brine, and then the solvent was distilled off under reduced pressure to obtain 50 g of an oily compound.

  The obtained oil was subjected to column purification (hexane / ethyl acetate = 2/1), and the obtained oil was crystallized from ethyl acetate / heptane to obtain 26.4 g of monomer-1 (white crystals).

¹ H-NMR (400 MHz in (CD ₃ ) ₂ CO): δ (ppm) = 1.17-2.31 (m, 7H), 2.70-3.44 (m, 4H), 4.58- 5.18 (m, 3H), 6.22 (s, 1H), 7.27 (s, 1H)
(Acid generator (C))
The acid generator was appropriately selected from the acid generators z1 to z114 listed above.

(Nitrogen-containing compound (B))
The pKa values shown below are values calculated by the method shown above as the pKa calculation method.

(Hydrophobic resin (HR))
The hydrophobic resin was appropriately selected from the hydrophobic resins (B-1) to (B-55) listed above.

(Surfactant)
W-1: Mega-Fuck F176 (manufactured by DIC Corporation; fluorine-based)
W-2: Megafuck R08 (manufactured by DIC Corporation; fluorine and silicon-based)
W-3: Troisol S-366 (manufactured by Troy Chemical Co .; fluorine type)
W-4: PF656 (manufactured by OMNOVA; fluorine-based)
W-5: PF6320 (manufactured by OMNOVA; fluorine-based)
(solvent)
A1: Propylene glycol monomethyl ether acetate (PGMEA)
A2: Cyclohexanone A3: γ-butyrolactone B1: Propylene glycol monomethyl ether (PGME)
B2: Ethyl lactate [Exposure conditions: ArF immersion exposure]
<Preparation of actinic ray-sensitive or radiation-sensitive resin composition>
The components shown in Table 2 below are dissolved in a solvent, and a solution having a solid content concentration of 4% by mass is prepared for each, and this is filtered through a polyethylene filter having a pore size of 0.1 μm, and an actinic ray-sensitive or radiation-sensitive resin. A composition (positive photosensitive resin composition) was prepared. The prepared positive photosensitive resin composition was evaluated by the following method, and the results are shown in Table 2.

<Image performance test>
An organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied on a silicon wafer (12 inch diameter), and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 98 nm. The positive photosensitive resin composition prepared thereon was applied and baked at 120 ° C. for 60 seconds to form a photosensitive film (resist film) having a thickness of 100 nm. Using the ArF excimer laser immersion scanner (XT1700i, NA1.20, C-Quad, outer sigma 0.981, inner sigma 0.895, XY deflection, manufactured by ASML), the resulting wafer is a 1: 1 line and space pattern with a line width of 45 nm. And exposed through a 6% halftone mask. Ultra pure water was used as the immersion liquid. Thereafter, heating was performed at 120 ° C. for 60 seconds, followed by development with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds, rinsing with pure water, and spin drying to obtain a resist pattern.

<Pattern collapse>
The exposure amount that reproduces the mask pattern of a line and space (1: 1) with a line width of 45 nm is set as the optimal exposure amount, and the line width of the line pattern formed by further increasing the exposure amount from the optimal exposure amount is reduced. In this case, the line width (nm) is defined so that the pattern is resolved without falling down. A smaller value indicates that a finer pattern is resolved without falling, and pattern falling is less likely to occur.

<Line width roughness (LWR)>
The line width roughness (nm) is measured by using a length-measuring scanning electron microscope (SEM) to observe a line-and-space (1: 1) pattern with a line width of 45 nm, and the edge of the line pattern in the longitudinal direction is 2 μm. The distance from the reference line that should have an edge in the range of 50 was measured with a length measurement SEM (Hitachi, Ltd. S-8840), and the standard deviation was determined for the measurement variation, and 3σ was calculated. A smaller value indicates better performance.

<Storage stability>
Evaluation was made based on the line width difference between a resist that was aged for 30 days at 5 ° C., 25 ° C., 40 ° C., and 60 ° C., and a resist that was aged for 30 days at 0 ° C. (reference resist). Specifically, first, an exposure amount E ₁ for reproducing a mask pattern having a line width of 45 nm (line / space = 1/1) was determined for a resist that was aged at 0 ° C. for 30 days. Next, the four types of resist films heated for 30 days were exposed for E ₁ minute. The line width of the obtained pattern was measured with a scanning electron microscope (Hitachi, Ltd. S-9380), and the variation value of the pattern line width with respect to the line width (45 nm) obtained with the reference resist was determined. Based on the obtained four points of data, the reciprocal of the temperature over time (absolute temperature) on the X axis and the line width fluctuation value per year on the Y axis (that is, the line width fluctuation value after 30 days multiplied by 12) Was plotted on a semilogarithmic graph and approximated by a straight line. The value of the Y coordinate corresponding to the time-lapse temperature of 25 ° C. of the straight line thus obtained was read. This value was expressed as a line width variation value (nm) when left at 25 ° C. for 1 year. A smaller value indicates better storage stability.

Claims (8)

(A) a resin containing a repeating unit represented by the following general formula (1) and a repeating unit that decomposes by the action of an acid and increases the solubility in an alkali developer;
(B) an ionic compound comprising a basic moiety R _NN containing at least one nitrogen atom-containing compound R _N or at least one nitrogen atom, R _N -H ^+, or R is these conjugate acid _A compound having a pKa of _NN- H ⁺ of 8 or less;
(C) Actinic ray-sensitive or radiation-sensitive resin composition comprising a compound that generates acid upon irradiation with actinic ray or radiation:

In general formula (1),
L represents a single bond or a divalent linking group;
R ₁ represents a hydrogen atom or an alkyl group;
Z represents a cyclic acid anhydride structure. Wherein at least one nitrogen atom-containing compound R _N is, the actinic ray-sensitive according to claim 1, characterized by being represented by the following general formula (b1) or radiation-sensitive resin composition:

In general formula (b1):
n represents an integer of 0 to 2, m represents an integer of 1 to 3, and n + m = 3;
Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and when n = 2, the two Ras may be the same or different, and the two Ras are bonded to each other, and Ra May form a heterocyclic hydrocarbon group or a derivative thereof together with the nitrogen atom to which is bonded;
Rb independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group, and at least two Rb's are bonded to form an alicyclic hydrocarbon group or aromatic hydrocarbon. Groups, heterocyclic hydrocarbon groups or derivatives thereof may be formed. 2. The actinic ray-sensitive or radiation-sensitive property according to claim 1, wherein the ionic compound containing a basic moiety _RNN containing at least one nitrogen atom is represented by the following general formula (b2). Resin composition:
_RNN- A ^- X ⁺ (b2)
In general formula (b2):
_RNN represents a monovalent basic compound residue containing at least one nitrogen atom, and the pKa of the conjugate acid _RNN- H ⁺ is 8 or less;
A ⁻ represents —SO ₃ ^— , —CO ₂ ^— or —X ₁ —N ^—— X ₂ —R ₁ , X ₁ and X ₂ each independently represent —CO— or —SO ₂ —; R ₁ represents a monovalent organic group;
X ⁺ represents a counter cation. The actinic ray-sensitive or sensation according to any one of claims 1 to 3, wherein the resin (A) further contains at least one type of repeating unit represented by the following general formula (III). Radiation resin composition:

In general formula (III):
R ₈ and R ₉ represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms;
n represents an integer of 1 to 6.   An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4.   Forming a film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, irradiating the film with an actinic ray or radiation, and the actinic ray Or developing a film irradiated with radiation.   The manufacturing method of an electronic device containing the pattern formation method of Claim 6.   An electronic device manufactured by the method for manufacturing an electronic device according to claim 7.