JP5427436B2 - Actinic ray-sensitive or radiation-sensitive resin composition and pattern forming method using the composition - Google Patents

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition suitably used in a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, and a photolithographic lithography process. And a pattern forming method using the composition. In particular, the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition suitable for exposure with an immersion type projection exposure apparatus that uses far ultraviolet light having a wavelength of 300 nm or less as a light source, and pattern formation using the same Regarding the method.

  In the present invention, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays, X-rays, electron beams, and the like. In the present invention, light means actinic rays or radiation.

  In a pattern forming process using a photosensitive composition, particularly a semiconductor pattern forming process using a resist composition, an image forming method called chemical amplification is used as a resist image forming method after the resist for KrF excimer laser (248 nm). Then, a chemically amplified resist for ArF excimer laser (193 nm) is becoming mainstream. Furthermore, in order to form a finer pattern than ever, a pattern formation process by so-called immersion exposure, in which the space between the projection lens and the sample is filled with a high refractive index liquid (hereinafter also referred to as “immersion liquid”), is also performed. It has been actively studied.

  An example of a positive chemical amplification image forming method will be described. After exposure, the acid generator in the exposed area is decomposed to generate an acid, and then the acid is generated by post exposure bake (PEB). By removing an acid-decomposable protective group (hereinafter also referred to as an acid-decomposable group) in the composition as a reaction catalyst, the property is changed from alkali-insoluble to alkali-soluble, and the exposed area is removed by alkali development. Thus, an image is formed.

  Various studies have been made on the protecting group, and for example, Patent Document 1 and Patent Document 2 disclose a resin having an acid-decomposable group having a polar substituent as a composition suitable for an ArF excimer laser. And a composition using the same, and it is disclosed that excellent effects are exhibited in terms of line edge roughness (LER), sensitivity, resolution, substrate adhesion, and the like.

  However, the resist compositions disclosed in the above prior art documents have problems of insufficient exposure latitude (EL) and pattern profile degradation, particularly when trying to form ultrafine patterns of 30 nm or less. Therefore, it is required to improve the resist performance.

JP 2006-16379 A JP 2006-104353 A

  In view of the above problems, the present invention provides a pattern with a good exposure latitude (EL: Exposure Latitude) and pattern profile, not only in normal exposure (dry exposure) but also in immersion exposure, particularly in pattern formation by excimer laser light. It is an object of the present invention to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of obtaining the above and a pattern forming method using the composition.

As a result of intensive studies to solve the above problems, the present inventors have reached the present invention shown below.
(1) (A) a resin whose protective group is eliminated by the action of an acid and the solubility in an alkali developer increases,
(B) a compound that generates an acid upon irradiation with actinic rays or radiation;
The actinic ray-sensitive or radiation-sensitive resin composition, wherein the protecting group of the resin (A) has a polar group, and the acid generated from the compound (B) is represented by the following general formula (I) object.

Where
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ¹ and R ² each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or a group selected from an alkyl group substituted with at least one fluorine atom, and R ¹ and R ² in the case where a plurality of R ¹ and R ^{2 are present.} May be the same or different.

L represents a single bond or a divalent linking group, and when there are a plurality of L, they may be the same or different.
A represents a group having a cyclic structure.
x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

  (2) The actinic ray-sensitive or radiation-sensitive resin composition according to (1), wherein in general formula (I), A is an alicyclic group.

  (3) The actinic ray-sensitive or radiation-sensitive property according to (1) or (2), wherein in general formula (I), at least one L is a —COO— group or a —OCO— group. Resin composition.

  (4) The polar group of the protective group of the resin (A) is any one of a hydroxyl group, a ketone group, a cyano group, an amide group, an alkylamide group, a sulfonamide group, a lower ester group, and a lower sulfonate group. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (3).

  (5) Further, (I) has at least a fluorine atom or a silicon atom group, or a linear or branched alkyl group having 8 or more carbon atoms, and exhibits the property of increasing the contact angle of the film surface by the addition thereof. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (4), comprising a hydrophobic resin.

  (6) A step of forming a film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (5), and exposing and developing the film. Pattern forming method.

  According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern having a good EL and pattern profile not only in normal exposure (dry exposure) but also in pattern formation by immersion exposure. became.

Hereinafter, the present invention will be described in detail.
In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have 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).

[1] Resin (A) in which the protecting group is eliminated by the action of an acid and the solubility in an alkali developer increases
<Repeating unit containing a protecting group having a polar group>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention comprises at least (A) a resin (hereinafter referred to as “resin (A)” in which the protective group is eliminated by the action of an acid and the solubility in an alkali developer is increased. The resin (A) is characterized by having a repeating unit containing an acid-decomposable protecting group having a polar group.

Specific examples of the “repeating unit containing an acid-decomposable protecting group having a polar group” include units represented by the following general formula (1).

In general formula (1),
Xa ₁ represents a hydrogen atom, a methyl group or a group represented by —CH ₂ —R ₉ . R ₉ represents a hydroxyl group or a monovalent organic group. Rx _{1 to} Rx ₃ each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic). Any two of Rx _{1 to} Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).
The acid-decomposable group represented by —C (Rx ₁ ) (Rx ₂ ) (Rx ₃ ) in the general formula (1) has at least one group represented by — (L) _n1 —P as a substituent. .
L represents a divalent linking group. n ₁ is 0 or 1. P represents a polar group.

The general formula (1) will be described in more detail.
The methyl group of Xa ₁ may be substituted with a halogen atom (preferably a fluorine atom) or the like.
Examples of the monovalent organic group represented by R ₉ include an alkyl group having 5 or less carbon atoms and an acyl group, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group.
Xa ₁ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

The alkyl group of Rx ₁ ~Rx _3, preferably a straight-chain or branched having 1 to 4 carbon atoms.

Examples of the cycloalkyl group represented by Rx _{1 to} Rx ₃ include a monocyclic or polycyclic cycloalkyl group having 3 to 15 carbon atoms.
The cycloalkyl group formed by combining any two of Rx _{1 to} Rx ₃ is preferably a monocyclic or polycyclic cycloalkyl group having 3 to 15 carbon atoms.
An embodiment in which at least one of Rx _{1 to} Rx ₃ is a cycloalkyl group and a — (L) _n1 —P group is bonded to the cycloalkyl group, or Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and It is preferable that Rx ₃ is bonded to form the cycloalkyl group described above, and the-(L) _n1 -P group is bonded to the cycloalkyl group.

Examples of the polar group of P include heteroatoms such as a hydroxyl group, a ketone group, a cyano group, an amino group, an amide group (—CONH ₂ ), an alkylamide group, a sulfonamide group, a lower ester group, and a lower sulfonate group. The group to do can be mentioned. Here, the lower group is preferably a group having 2 to 3 carbon atoms. Preferred polar groups are a hydroxyl group, a cyano group, and an amide group, and more preferably a hydroxyl group.

Examples of the divalent linking group for L include a linear or branched alkylene group and a cycloalkylene group. The number of atoms of the divalent linking group as L is preferably 20 or less, and preferably 15 or less. More preferred. Each group of the above linear or branched alkylene group and cycloalkylene group preferably has 8 or less carbon atoms and may have a substituent. The substituent preferably has 8 or less carbon atoms, for example, 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 (2 carbon atoms). ~ 6) and the like.
The group represented by — (L) _n1 —P is, for example, a linear or branched group having a hydroxyl group, a cyano group, an amino group, an alkylamide group, an acid amide group, or a sulfonamide group, when n1 = 1. Examples include an alkyl group (preferably having 1 to 10 carbon atoms) and a cycloalkyl group (preferably having 3 to 15 carbon atoms), preferably an alkyl group having a hydroxyl group (preferably having 1 to 5 carbon atoms, more preferably C1-C3, and most preferably isopropyl group).
Specific examples of the group represented by-(L) _n1 -P are given below.

Among these, it is preferable that P is a hydroxyl group, n1 is 0 or 1, and L is a linear or branched alkylene group (preferably having 1 to 5 carbon atoms).
The group represented by —C (Rx ₁ ) (Rx ₂ ) (Rx ₃ ) in the general formula (1) preferably has 1 to 3 groups represented by — (L) _n1 —P. Or it is more preferable to have two, and it is most preferable to have one.
The repeating unit represented by the general formula (1) is preferably a repeating unit represented by the following general formula (1-1).

In general formula (1-1),
R ₃ is the same as X _a1 in the general formula (1).

R ₄ and R ₅ are the same as Rx ₁ and Rx _{2 in} the general formula (1).

- (L) group represented by _n1 -P has the general formula (1) for - (L) is the same as the group represented by _n1 -P.

  p represents an integer of 1 to 3. p is preferably 1 or 2, more preferably 1.

  The monomer corresponding to the repeating unit of the general formula (1) can be synthesized, for example, by the method described in JP-A-2006-16379.

  As for the content rate of the repeating unit represented by General formula (1), 5-50 mol% is preferable with respect to all the repeating units in resin (A), More preferably, it is 10-30 mol%.

  Moreover, you may have 2 or more types of repeating units represented by General formula (1). 2 or more types include one or more repeating units represented by the general formula (1) and one or more repeating units represented by the general formula (1) that are not exactly the same repeating units as the repeating unit. It means to do. The molar ratio of the repeating units represented by the two general formulas (1) at that time is preferably 90/10 to 10/90, more preferably 80/20 to 20/80.

Although the preferable specific example is shown below about the repeating unit represented by General formula (1), it is not limited to these.
In the following structural formulas, Q represents a group represented by-(L) _n1 -P. (L, P, and n1 are synonymous with those in the general formula (1).)
Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH.

  Rxa and Rxb each independently represents an alkyl group having 1 to 4 carbon atoms.

  When there are a plurality of each, they may be the same or different.

p represents an integer of 1 to 3.

<Repeating units having other acid-decomposable groups>
In addition to the repeating unit represented by the general formula (1), the resin (A) may further have a repeating unit having an acid-decomposable group other than the general formula (1). Examples of the acid-decomposable group include a repeating unit having an acid-decomposable group selected from the following general formulas (pI) to (pV).

In the general formulas (pI) to (pV),
R ₁₁ represents an alkyl group or a cycloalkyl group.
Z represents an atomic group necessary for forming a cycloalkyl group together with a carbon atom.
R _{12 to} R ₁₄ each independently represents an alkyl group or a cycloalkyl group. However, at least one of R _{12 to} R ₁₄ represents a cycloalkyl group.
R ₁₅ and R ₁₆ each independently represents an alkyl group or a cycloalkyl group. However, either R ₁₅ or R ₁₆ represents a cycloalkyl group.
R _{17 to} R ₂₁ each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group. However, at least one of R _{17 to} R ₂₁ represents a cycloalkyl group. Moreover, any of R ₁₉ and R ₂₁ represents an alkyl group or a cycloalkyl group.
R _{22 to} R ₂₅ each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group. However, at least one of R _{22 to} R ₂₅ represents a cycloalkyl group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

In the general formulas (pI) to (pV), the alkyl group in R _{11 to} R ₂₅ is preferably a linear or branched alkyl group having 1 to 8 carbon atoms.
The cycloalkyl group in R _{11 to} R ₂₅ or the cycloalkyl group formed by Z and the carbon atom may be monocyclic or polycyclic. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 4 or more carbon atoms. The carbon number is preferably 4 to 30, and particularly preferably 5 to 25. The cycloalkyl group may have an unsaturated double bond in the ring. The cycloalkyl group may have a substituent.

Further, the cycloalkyl group in R _{11 to} R ₂₅ or the cycloalkyl group formed by Z and the carbon atom is more preferably monocyclic, and the cycloalkyl group preferably has 4 to 10 carbon atoms, most preferably. Has 5 to 7 carbon atoms.

  These alkyl groups and cycloalkyl groups may further have a substituent. As further substituents for alkyl groups and cycloalkyl groups, alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, alkoxycarbonyl groups (2 to 2 carbon atoms). 6). The above alkyl group, alkoxy group, alkoxycarbonyl group and the like may further have a substituent. Examples of the substituent that the alkyl group, alkoxy group, alkoxycarbonyl group and the like may further have include a hydroxyl group, a halogen atom, and an alkoxy group.

  The groups represented by the general formulas (pI) to (pV) can form an acid-decomposable group when used for protecting an alkali-soluble group. Examples of the alkali-soluble group include various groups known in this technical field. A structure in which a hydrogen atom of a carboxylic acid group or a sulfonic acid group is substituted with a group represented by general formulas (pI) to (pV) is preferable.

The repeating unit having a group represented by general formulas (pI) to (pV) is preferably a repeating unit represented by the following general formula (pA).

In the general formula (pA), R represents a hydrogen atom, a halogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of R may be the same or different.
A is a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a group of two or more groups selected from the group consisting of a ureylene group. Represents. A single bond is preferable.
Rp ₁ represents any one of the general formulas (pI) to (pV).
Hereinafter, although the specific example of the repeating unit which has an acid-decomposable group is shown, this invention is not limited to this.

In the above structural formulas, Rx represents H, CH ₃ , CF ₃ or CH ₂ OH, and Rxa and Rxb each independently represents an alkyl group having 1 to 4 carbon atoms.
The content of the repeating unit having an acid-decomposable group other than the repeating unit represented by the general formula (1), such as the repeating unit having an acid-decomposable group represented by the general formula (pA), is in the resin (A). The total repeating unit is preferably 20 to 70 mol%, more preferably 30 to 50 mol%.

  Moreover, you may have 2 or more types of repeating units which have an acid-decomposable group represented by general formula (pA). The molar ratio of the repeating unit having an acid-decomposable group represented by the two general formulas (pA) at that time is preferably 90/10 to 10/90, more preferably 80/20 to 20/80. It is.

<Repeating unit having a lactone group>
The resin (A) preferably contains a repeating unit having a lactone group.
Any lactone group can be used as long as it has a lactone structure, but it is preferably a 5- to 7-membered ring lactone structure, and forms a bicyclo structure or a spiro structure in the 5- to 7-membered ring lactone structure. The other ring structure is preferably condensed. It is more preferable to have a repeating unit having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-16). The lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), and a specific lactone structure is used. LWR and development defects are improved.

The lactone structure moiety 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. .

As the repeating unit having a lactone structure, a repeating unit represented by the following general formula (AII) is also preferable.

In general formula (AII),
Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group represented by 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. Preferred are a hydrogen atom, a methyl group, a hydroxymethyl group, and a trifluoromethyl group, and a hydrogen atom and a methyl group are particularly preferred.

Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, or a divalent linking group obtained by combining these. Preferably a single bond, -Ab ₁ -CO ₂ - is a divalent linking group represented by.

Ab ₁ is a linear, branched alkylene group, monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.

V represents an atomic group containing a lactone structure. Specific examples include groups having a structure represented by any of the general formulas (LC1-1) to (LC1-16).
Among the units represented by the general formula (AII), the following repeating units are particularly preferable as the repeating unit having a lactone group when Ab is a single bond. In specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ . By selecting an optimal lactone group, the pattern profile and the density dependency are improved.

The resin (A) contains a repeating unit having a lactone structure represented by the following general formula (2) separately from the lactone unit in which Ab is a single bond in the general formula (AII) or together with the left lactone unit. Is preferred.

In general formula (2),
A represents an ester bond (—COO—) or an amide bond (—CONH—).
R ₀ represents an alkylene group, a cycloalkylene group, or a combination thereof, and when there are a plurality of R _{0 s} , they may be the same or different.
Z represents an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond, and when there are a plurality thereof, they may be the same or different.
R ₈ represents a monovalent organic group having a lactone structure.
n ₂ has the general formula is a repeating number of the structure represented by _-R 0 -Z- in the repeating a unit represented by (2), represents an integer of 1 to 5. n ₂ 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 alkyl group in R ₇ may be substituted. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom, mercapto group, hydroxy group, methoxy group, ethoxy group, isopropoxy group, t -Acetoxy groups such as alkoxy groups such as butoxy group and benzyloxy group, acetyl groups and propionyl groups. R ₇ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

A preferable alkylene group in R ₀ is preferably a linear or branched alkylene having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group. . Preferable cycloalkylene is cycloalkylene having 1 to 20 carbon atoms, and examples thereof include cyclohexylene, cyclopentylene, norbornylene, adamantylene and the like. In order to exhibit the effect of the present invention, an alkylene group is more preferable, and a methylene group is further preferable.

The monovalent organic group having a lactone structure represented by R ₈ is not limited as long as it has a lactone structure. Specific examples thereof include those represented by the general formulas (LC1-1) to (LC1-16). The lactone structure represented is mentioned, Of these, the structure represented by (LC1-4) is particularly preferable. Further, n ₂ in (LC1-1) to (LC1-16) is more preferably 2 or less.
R ₈ is more preferably a monovalent organic group having a lactone structure (cyanolactone) having a cyano group as a substituent.

Specific examples of the repeating unit having a group having a lactone structure represented by the general formula (2) 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.

As the repeating unit having a lactone structure, a repeating unit represented by the following general formula (2-1) is more preferable.

In general formula (2-1),
_{R 7, A, R 0,} Z, and n ₂ are as defined in the general formula (2) in _{R 7, A, R 0,} Z, and the n _2.
Rb 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 Rb, two Rb's are bonded to form a ring. You may do it.
X represents an alkylene group, an oxygen atom, or a sulfur atom.
m is the number of substituents and represents an integer of 0 to 5. m is preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1.
When m = 1, Rb preferably has at least one at the α-position or β-position of the carbonyl group of the lactone, and particularly preferably at the α-position.

The alkyl group for Rb 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. Examples of the cycloalkyl group include those having 3 to 6 carbon atoms. 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, an n-butoxy group, and a t-butoxy group.
The alkyl group, cycloalkyl group, alkoxycarbonyl group, and alkoxy group of Rb may have a substituent. Examples of the substituent include an alkoxy group such as a hydroxy group, a methoxy group, and an ethoxy group, a cyano group, and a fluorine atom. Can be mentioned.

  Rb is preferably a methyl group or a cyano group, and more preferably a cyano group.

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

Specific examples of the repeating unit having a group having a lactone structure represented by General Formula (2-1) 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.

The repeating unit having a lactone group usually has an optical isomer, but any optical isomer may be used.
As for the content rate of the repeating unit which has a lactone group, 15-60 mol% is preferable with respect to all the repeating units in resin (A), More preferably, it is 20-50 mol%, More preferably, it is 30-50 mol%.
The resin (A) may contain a plurality of repeating units represented by the general formula (AII).

  The resin (A) preferably has a repeating unit having a hydroxyl group or a cyano group. This improves the substrate adhesion and developer compatibility. 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. 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 norbornyl group. Preferred examples of the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group include a monohydroxyadamantyl group, a dihydroxyadamantyl group, a monohydroxydiamantyl group, a dihydroxyadamantyl group, and a norbornyl group substituted with a cyano group.

Examples of the repeating unit having the atomic group include 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 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 remaining is a hydrogen atom. In general formula (VIIa), more preferably, _two of R ₂ c to R ₄ c are hydroxyl groups and the remaining are hydrogen atoms.

  The content of the repeating unit having a hydroxyl group or a cyano group is preferably from 5 to 40 mol%, more preferably from 5 to 30 mol%, still more preferably from 10 to 25 mol%, based on all repeating units in the resin (A).

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.

<Repeating unit having alkali-soluble group>
Resin (A) may 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 bisulsulfonylimide group, and an aliphatic alcohol (for example, hexafluoroisopropanol group) substituted with an electron-attracting group at the α-position. It is more preferable to have a repeating unit. By containing the 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. Either a repeating unit to which a soluble group is bonded, or a polymerization initiator or chain transfer agent having an alkali-soluble group is used at the time of polymerization and introduced at the end of the polymer chain, and the linking group is monocyclic or polycyclic. It may have a cyclic hydrocarbon structure. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

As for the content rate of the repeating unit which has an alkali-soluble group, 0-20 mol% is preferable with respect to all the repeating units in resin (A), 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.

<Repeating unit having non-acid-decomposable and alkali-insoluble group>
The resin (A) of the present invention preferably further has a repeating unit that has an alicyclic hydrocarbon structure having no polar group and does not exhibit acid decomposability. Thereby, the elution of low molecular components from the actinic ray-sensitive or radiation-sensitive resin composition film to the immersion liquid during immersion exposure can be reduced. An example of such a repeating unit is a repeating unit represented by the following general formula (3).

In general formula (3), R ₅ represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group.
Ra represents a hydrogen atom, an alkyl group (which may be substituted with a fluorine atom) 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 trifluoromethyl group, or a hydroxymethyl 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.

The content of the repeating unit represented by the general formula (3) having neither a hydroxyl group nor a cyano group is preferably from 0 to 40 mol%, more preferably based on all repeating units in the resin (A). 0 to 20 mol%.
Specific examples of the repeating unit represented by the general formula (3) are listed below, but the present invention is not limited to these. 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 required characteristics of resist, in addition to the above repeating structural units. For this purpose, various repeating structural units can be included.

  Examples of such repeating structural units 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 structural units may be copolymerized.

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

  Resin used for the actinic ray-sensitive or radiation-sensitive resin composition of the present invention from the viewpoint of transparency to ArF light when the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is for ArF exposure (A) preferably has no aromatic group.

  Moreover, when using resin (A) as a composition for immersion exposure, it is preferable not to contain a fluorine atom and a silicon atom from a compatible viewpoint with hydrophobic resin (HR) mentioned later.

  The resin (A) is preferably one in which all of the repeating units are composed of (meth) acrylate-based 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. More preferably, the (meth) acrylate repeating unit having an acid-decomposable group is 20 to 50 mol%, the (meth) acrylate repeating unit having a lactone group is 20 to 50 mol%, and the alicyclic ring is substituted with a hydroxyl group or a cyano group. It is a copolymer containing 5 to 30 mol% of a (meth) acrylate-based repeating unit having a hydrocarbon structure and further 0 to 20 mol% of another (meth) acrylate-based repeating unit.

The glass transition temperature (Tg) of the resin (A) contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is preferably 110 to 200 ° C, more preferably 130 to 170 ° C. For this purpose, the above-mentioned repeating unit can be used as appropriate. For example, by introducing the repeating unit represented by the general formula (2), the Tg of the resin (A) can be lowered, the ratio of the repeating unit represented by the general formula (1), and the resin (A) The Tg of the resin (A) can be adjusted by appropriately changing the molecular weight of the resin and the ratio of the repeating units that may be contained in the resin (A).
The resin (A) of 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 the polymerization is performed by heating, 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, 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 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, more preferably 60-100 ° C.

  The weight average molecular weight of the resin (A) of the present invention is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, still more preferably 3, as a polystyrene conversion value by GPC method. 000 to 15,000, particularly preferably 3,000 to 10,000. By setting it as the above range, it is possible to improve heat resistance and prevent deterioration of dry etching resistance, and it is also possible to prevent deterioration of developability and film forming property due to increase in viscosity.

  The degree of dispersion (molecular weight distribution) is usually 1 to 3, preferably 1 to 2.6, more preferably 1 to 2, particularly preferably 1.4 to 2.0. 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.

The blending amount of the resin (A) in the entire actinic ray-sensitive or radiation-sensitive resin composition is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass in the total solid content.
Moreover, the resin (A) of the present invention may be used alone or in combination.

[2] Compound (B) that generates acid upon irradiation with actinic rays or radiation
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a compound that generates an acid represented by the general formula (I) upon irradiation with actinic rays or radiation (hereinafter also referred to as “acid generator”). To do.

Where
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ¹ and R ² each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or a group selected from an alkyl group substituted with at least one fluorine atom, and R ¹ and R ² in the case where a plurality of R ¹ and R ^{2 are present.} May be the same or different.
L represents a single bond or a divalent linking group, and when there are a plurality of L, they may be the same or different.
A represents a group having a cyclic structure.
x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

General formula (I) will be described in more detail.
The alkyl group in the alkyl group substituted with the fluorine atom of Xf preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specifically, fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , CH ₂ CH ₂ C ₄ F ₉ is mentioned, among which fluorine atom and CF ₃ are preferable.

The alkyl group in R ¹ and R ^{2 and} the alkyl group substituted with at least one fluorine atom are preferably those having 1 to 4 carbon atoms. More preferably, it is a C1-C4 perfluoroalkyl group. Specifically, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , CH ₂ CH ₂ C ₄ F _9. Among these CF ₃ are preferred.

y is preferably 0 to 4, and more preferably 0. x is preferably from 1 to 8, and preferably from 1 to 4. z is preferably 0 to 8, particularly preferably 0 to 4.
The divalent linking group of L is not particularly limited, and is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group, a cycloalkylene group, Examples include alkenylene groups. Of these, —COO—, —OCO—, —CO—, and —O— are preferable, and —COO— and —OCO— are more preferable.

  The group having a cyclic structure of A is not particularly limited as long as it has a cyclic structure. The group having an alicyclic group, an aryl group, or a heterocyclic structure (not only those having an aromatic attribute, but also having an aromatic attribute And the like).

  The alicyclic group may be monocyclic or polycyclic, and may be a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, or a tetracyclododecane group. A polycyclic cycloalkyl group such as a nyl group and an adamantyl group is preferred. Among them, an alicyclic group having a bulky structure having 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group is used in the PEB (post-exposure heating) step. The diffusibility in the film can be suppressed, which is preferable from the viewpoint of improving MEEF.

  Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring. Of these, naphthalene having low absorbance is preferred from the viewpoint of light absorbance at 193 nm.

  Examples of the group having a heterocyclic structure include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Of these, a furan ring, a thiophene ring, and a pyridine ring are preferable.

  The group having the cyclic structure may have a substituent, and the substituent may be an alkyl group (which may be linear, branched or cyclic, preferably having 1 to 12 carbon atoms), Examples include aryl groups (preferably having 6 to 14 carbon atoms), hydroxy groups, alkoxy groups, ester groups, amide groups, urethane groups, ureido groups, thioether groups, sulfonamido groups, sulfonic acid ester groups, and the like.

Among the compounds that generate an acid represented by the general formula (I) upon irradiation with actinic rays or radiation, preferred compounds include compounds having an ionic structure such as sulfonium salts and iodonium salts, oxime esters, imide esters and the like. Those having an ionic compound structure are preferred. Examples of the compound having an ionic structure include compounds represented by the following general formulas (ZI) and (ZII).

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 1-30, preferably 1-20.
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. The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).
Z ⁻ represents an anion structure of the acid represented by the general formula (I).

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.

  More preferred (ZI) components include compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described below.

The compound (ZI-1) is at least one of the aryl groups R ₂₀₁ to R ₂₀₃ in formula (ZI), arylsulfonium compounds, namely, compounds containing an arylsulfonium as a cation.

In the arylsulfonium compound, all of R _{201 to} R ₂₀₃ may be an aryl group, or a part of R _{201 to} R ₂₀₃ may be an aryl group with the remaining being an alkyl group or a cycloalkyl group.

  Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

  The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.

  The alkyl group or cycloalkyl group that the arylsulfonium compound has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms, such as a methyl group, Examples thereof include an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

Aryl group, alkyl group of R ₂₀₁ to R _203, cycloalkyl group, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms) , An alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be substituted. Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, more preferably carbon. An alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted with any one of the three R _{201 to} R ₂₀₃ , or may be substituted with all three. When R _{201 to} R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

  Next, the compound (ZI-2) will be described.

Compound (ZI-2) is a compound in which R _{201 to} R ₂₀₃ in formula (ZI) each independently represents an organic group having no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.

The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, alkoxy group. A carbonylmethyl group, particularly preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group of R ₂₀₁ to R _203, preferably a linear or branched alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group). More preferred examples of the alkyl group include a 2-oxoalkyl group and an alkoxycarbonylmethyl group. More preferred examples of the cycloalkyl group include a 2-oxocycloalkyl group.

The 2-oxoalkyl group may be either linear or branched, and a group having> C = O at the 2-position of the above alkyl group is preferable.
The 2-oxocycloalkyl group is preferably a group having> C═O at the 2-position of the cycloalkyl group.

  The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group).

R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

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, a linear or branched alkyl group (preferably having 1 to 12 carbon atoms), a cycloalkyl group (preferably having 3 to 8 carbon atoms), a linear or branched alkoxy group. A group (C1-C12 is preferable in the case of a straight chain, C3-C8 is preferable in the case of a branch), or represents a halogen atom.

R _6c and R _7c each independently represent a hydrogen atom, a linear or branched alkyl group (preferably having 1 to 12 carbon atoms) or a cycloalkyl group (preferably having 3 to 8 carbon atoms).
R _x and R _y each independently represents a linear or branched alkyl group (preferably having 1 to 12 carbon atoms), a cycloalkyl group (preferably having 3 to 8 carbon atoms), an allyl group or a vinyl group.

Any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y may be bonded to each other to form a ring structure, and this ring structure includes an oxygen atom and a sulfur atom. , An ester bond and an amide bond may be included.
Zc ⁻ represents the anion structure of the acid represented by the general formula (I) similar to Z ⁻ .

  Preferable specific examples of the compound (ZI-3) include those described in JP-A-2004-233661, paragraphs 0047 and 0048, JP-A-2003-35948, paragraphs 0040 to 0046 and US2003 / 0224288A1. -1) to (I-70), exemplified as formulas (IA-1) to (IA-54) and formulas (IB-1) to (IB-24) in US2003 / 0077540A1 And the like.

Next, general formula (ZII) will be described.
In formula _{(ZII), R 204, R} 205 each independently represents an aryl group, an alkyl group or a cycloalkyl group.
The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ and R ₂₀₅ are the same as the groups described as the aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ in the aforementioned compound (ZI-1). is there.

Aryl group, alkyl group of R ₂₀₄ to R _205, cycloalkyl groups may have a substituent. Even the substituent, an aryl group of R ₂₀₄ to R ₂₀₅ in the compound of the aforementioned (ZI-1), an alkyl group, a cycloalkyl group are the same as those of the substituent which may have.
Zc ⁻ represents the anion structure of the acid represented by the general formula (I) similar to Z ⁻ .
The compound (ZI-4) is a compound 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, or an alkoxycarbonyl group.

When a plurality of R ₁₄ are present, each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group, or a cycloalkylsulfonyl group.

R ₁₅ each independently represents an alkyl group, a cycloalkyl group, a phenyl group or a naphthyl group. Two R ₁₅ may be bonded to each other to form a ring.

  l represents an integer of 0-2.

  r represents an integer of 0 to 10.

Z ⁻ represents the anion structure of the acid represented by the general formula (I).

In the general formula (ZI-4), the alkyl group of R ¹³ , R ¹⁴ and R ¹⁵ is linear or branched and preferably has 1 to 10 carbon atoms, and is preferably a methyl group, an ethyl group, n -Propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n -An octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group etc. can be mentioned. Of these alkyl groups, a methyl group, an ethyl group, an n-butyl group, a t-butyl group, and the like are preferable.

Examples of the cycloalkyl group of R ¹³ , R ¹⁴ and R ¹⁵ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecanyl, cyclobenenyl, cyclohexenyl, cyclooctadienyl and the like. In particular, cyclopropyl, cyclopentyl, cyclohexyl and cyclooctyl are preferred.

The alkoxy group of R ¹³ and R ¹⁴ is linear or branched and preferably has 1 to 10 carbon atoms, such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n -Butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group and the like can be mentioned. Of these alkoxy groups, a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, and the like are preferable.

The alkoxycarbonyl group for R ¹³ is linear or branched and preferably has 2 to 11 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, or an i-propoxycarbonyl group. N-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group, n-pentyloxycarbonyl group, neopentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyl Examples thereof include an oxycarbonyl group, an n-octyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, an n-nonyloxycarbonyl group, and an n-decyloxycarbonyl group. Of these alkoxycarbonyl groups, a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, and the like are preferable.

The alkylsulfonyl group and cycloalkylsulfonyl group of R ¹⁴ are linear, branched, or cyclic, and preferably those having 1 to 10 carbon atoms, such as methanesulfonyl group, ethanesulfonyl group, n-propanesulfonyl. Group, n-butanesulfonyl group, tert-butanesulfonyl group, n-pentanesulfonyl group, neopentanesulfonyl group, n-hexanesulfonyl group, n-heptanesulfonyl group, n-octanesulfonyl group, 2-ethylhexanesulfonyl group n -Nonanesulfonyl group, n-decanesulfonyl group, cyclopentanesulfonyl group, cyclohexanesulfonyl group, etc. can be mentioned. Of these alkylsulfonyl groups, a methanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, an n-butanesulfonyl group, a cyclopentanesulfonyl group, a cyclohexanesulfonyl group, and the like are preferable.
As r, 0-2 are preferable.

In the general formula (ZI-4), the phenyl group represented by R ¹⁵ may be substituted. For example, the phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-dimethylphenyl Group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,6-trimethylphenyl Group, 4-ethylphenyl group, 4-t-butylphenyl group, 4-cyclohexylphenyl group, 4-fluorophenyl group or the like phenyl group or linear, branched or cyclic alkyl group having 1 to 10 carbon atoms A phenyl group substituted with a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxy group. Examples include groups substituted with one or more groups such as an alkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group.

  Among the substituents for the phenyl group and the alkyl-substituted phenyl group, examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a 2-methylpropoxy group, 1- Examples thereof include linear, branched or cyclic alkoxy groups having 1 to 20 carbon atoms such as a methylpropoxy group, a t-butoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

  Examples of the alkoxyalkyl group include straight chain having 2 to 21 carbon atoms such as methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 2-methoxyethyl group, 1-ethoxyethyl group, and 2-ethoxyethyl group. Examples thereof include a chain, branched or cyclic alkoxyalkyl group. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, a 2-methylpropoxycarbonyl group, and a 1-methylpropoxycarbonyl group. , T-butoxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl and the like, and straight chain, branched or cyclic alkoxycarbonyl groups having 2 to 21 carbon atoms.

Examples of the alkoxycarbonyloxy group include methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i-propoxycarbonyloxy group, n-butoxycarbonyloxy group, t-butoxycarbonyloxy group, and cyclopentyloxy. Examples thereof include linear, branched or cyclic alkoxycarbonyloxy groups having 2 to 21 carbon atoms such as carbonyl group and cyclohexyloxycarbonyl. Examples of the optionally substituted phenyl group for R ^{15 in} the general formula (ZI-4) include a phenyl group, a 4-cyclohexylphenyl group, a 4-t-butylphenyl group, a 4-methoxyphenyl group, and 4-t-butoxy. A phenyl group and the like are preferable.

Examples of the optionally substituted naphthyl group for R ¹⁵ include 1-naphthyl group, 2-methyl-1-naphthyl group, 3-methyl-1-naphthyl group, 4-methyl-1-naphthyl group, 4- Methyl-1-naphthyl group, 5-methyl-1-naphthyl group, 6-methyl-1-naphthyl group, 7-methyl-1-naphthyl group, 8-methyl-1-naphthyl group, 2,3-dimethyl-1 -Naphthyl group, 2,4-dimethyl-1-naphthyl group, 2,5-dimethyl-1-naphthyl group, 2,6-dimethyl-1-naphthyl group, 2,7-dimethyl-1-naphthyl group, 2, 8-dimethyl-1-naphthyl group, 3,4-dimethyl-1-naphthyl group, 3,5-dimethyl-1-naphthyl group, 3,6-dimethyl-1-naphthyl group, 3,7-dimethyl-1- Naphthyl group, 3,8-dimethyl-1-naphthyl Group, 4,5-dimethyl-1-naphthyl group, 5,8-dimethyl-1-naphthyl group, 4-ethyl-1-naphthyl group, 2-naphthyl group, 1-methyl-2-naphthyl group, 3-methyl- A naphthyl group substituted with a naphthyl group such as a 2-naphthyl group, 4-methyl-2-naphthyl group or the like, or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms; And a group in which a naphthyl group is substituted with at least one group such as 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. it can.

Examples of the alkoxy group, alkoxyalkyl group, alkoxycarbonyl group, and alkoxycarbonyloxy group as the substituent include the groups exemplified for the phenyl group and the alkyl-substituted phenyl group. Examples of the optionally substituted naphthyl group of R ^{15 in} the general formula (ZI-4) include 1-naphthyl group, 1- (4-methoxynaphthyl) group, 1- (4-ethoxynaphthyl) group, 1- ( 4-n-propoxynaphthyl) group, 1- (4-n-butoxynaphthyl) group, 2- (7-methoxynaphthyl) group, 2- (7-ethoxynaphthyl) group, 2- (7-n-propoxynaphthyl) group ) Group, 2- (7-n-butoxynaphthyl) group and the like are preferable.

As the ring structure that two R ¹⁵ may be bonded to each other, a 5- or 6-membered ring, particularly preferably a 5-membered ring (that is, a 5-membered ring together with the sulfur atom in formula (ZI-4)) And a group that forms a tetrahydrothiophene ring). Examples of the substituent for the divalent group include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxy group exemplified as the substituent for the phenyl group and the alkyl-substituted phenyl group. Examples thereof include a carbonyl group and an alkoxycarbonyloxy group. As R ¹⁵ in the general formula (ZI-4), a methyl group, an ethyl group, a phenyl group, a 4-methoxyphenyl group, a 1-naphthyl group, and two R ¹⁵ are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom. A divalent group or the like that forms is preferable.
Preferred specific examples of the cation in the compound represented by the general formula (ZI-4) are shown below.

Specific examples of the compound capable of generating an acid represented by formula (I) are shown below.

  The content of the acid generator (B) that generates an acid represented by the general formula (I) in the actinic ray-sensitive or radiation-sensitive resin composition is 0.1 to 20% by mass with respect to the total solid content. Preferably, it is 1-15 mass%, More preferably, it is 2-10 mass%.

  The acid generator (B) which generates the acid represented by the general formula (I) can be used alone or in combination of two or more.

  Acids other than the acid generator (B) that generates an acid represented by the general formula (I) that can be used in combination with the acid generator (B) that generates an acid represented by the general formula (I) Examples of the generator include acid generators described in [0150] of US Patent Application Publication No. 2008/0248425.

[3] Solvent Examples of the solvent that can be used in preparing the actinic ray-sensitive or radiation-sensitive resin composition by dissolving the above components include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl. Ether, alkyl lactate ester, alkoxypropionate alkyl, cyclic lactone (preferably 4 to 10 carbon atoms), monoketone compound (preferably 4 to 10 carbon atoms) which may contain a ring, alkylene carbonate, alkyl alkoxyacetate, pyrubin Examples thereof include organic solvents such as acid alkyls.

  Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl Preferred examples include ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.

  Preferred examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.

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 usually 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. It is. 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.

[4] Basic Compound The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a basic compound in order to reduce a change in performance over time from exposure to heating.
Preferred examples of the basic compound include compounds having structures represented by the following formulas (A) to (E).

In general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and are a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (having a carbon number). 6-20), wherein R ²⁰¹ and R ²⁰² may combine with each other to form a ring. R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.

About the said alkyl group, as an alkyl group which has a substituent, a C1-C20 aminoalkyl group, a C1-C20 hydroxyalkyl group, or a C1-C20 cyanoalkyl group is preferable.
The alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.

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

  Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, and 1,8-diazabicyclo [5,4,0. ] Undec-7-ene etc. are mentioned. Examples of the compound having an onium hydroxide structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide, tris ( and t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, and the like. As the compound having an onium carboxylate structure, an anion portion of the compound having an onium hydroxide structure is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of the aniline compound include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris (methoxyethoxyethyl) amine. Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.

  Preferred examples of the basic compound further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group.

The amine compound having a phenoxy group, the ammonium salt compound having a phenoxy group, the amine compound having a sulfonate group, and the ammonium salt compound having a sulfonate group have at least one alkyl group bonded to a nitrogen atom. Is preferred. The alkyl chain preferably has an oxygen atom and an oxyalkylene group is formed. The number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6. -CH ₂ CH ₂ O Among the oxyalkylene group _{-, - CH (CH 3)} CH 2 O- or -CH ₂ CH ₂ CH ₂ O- structure is preferred.

Specific examples of the amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonate group, and an ammonium salt compound having a sulfonate group include US Patent Application Publication No. 2007/0224539. Examples thereof include, but are not limited to, compounds (C1-1) to (C3-3) exemplified in [0066] of the description.
These basic compounds are used alone or in combination of two or more.
The usage-amount of a basic compound is 0.001-10 mass% normally on the basis of solid content of actinic-ray-sensitive or radiation-sensitive resin composition, Preferably it is 0.01-5 mass%.
The use ratio of the acid generator and the basic compound in the composition is preferably acid generator / basic compound (molar ratio) = 2.5 to 300. That is, the molar ratio is preferably 2.5 or more from the viewpoints of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to pattern thickening over time until post-exposure heat treatment. The acid generator / basic compound (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

[4] Surfactant The actinic ray-sensitive or radiation-sensitive resin composition preferably further contains a surfactant, and a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant, silicon-based interface) It is more preferable to contain any one or two or more of an activator and a surfactant having both a fluorine atom and a silicon atom.

  When the composition of the present invention contains the above-mentioned surfactant, it is possible to give a pattern with less adhesion and development defects with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less. Become.

  Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in [0276] of US Patent Application Publication No. 2008/0248425. For example, Ftop EF301, EF303, (Shin-Akita Kasei Co., Ltd.) )), FLORARD FC430, 431, 4430 (manufactured by Sumitomo 3M Co., Ltd.), Megafac F171, F173, F176, F189, F113, F110, F177, F120, R08 (manufactured by Dainippon Ink & Chemicals, Inc.), Surflon S-382, SC101, 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), GF-300, GF-150 (Toagosei Chemical Co., Ltd.) ), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.), F-top EF121, EF122A EF122B, RF122C, EF125M, EF135M, EF351, 352, EF801, EF802, EF601 (manufactured by Gemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204G, 208G, 218G, 230G 208D, 212D, 218D, 222D (manufactured by Neos Co., Ltd.) and the like. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

  In addition to the known surfactants described above, the surfactant is derived from a fluoroaliphatic compound produced by a telomerization method (also called telomer method) or an oligomerization method (also called oligomer method). A surfactant using a polymer having a fluoroaliphatic group can be used. The fluoroaliphatic compound can be synthesized by the method described in JP-A-2002-90991.

  As the polymer having a fluoroaliphatic group, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable and distributed irregularly. Or may be block copolymerized. Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, and the like. A unit having different chain lengths in the same chain length, such as a block link) or poly (block link of oxyethylene and oxypropylene) may be used. Furthermore, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but also a monomer having two or more different fluoroaliphatic groups, Further, it may be a ternary or higher copolymer obtained by simultaneously copolymerizing two or more different (poly (oxyalkylene)) acrylates (or methacrylates).

For example, as a commercially available surfactant, Megafac F178, F-470, F-473, F-475, F-476, F-472 (manufactured by Dainippon Ink & Chemicals, Inc.), C ₆ F ₁₃ group Copolymer of acrylate (or methacrylate) and (poly (oxyalkylene)) acrylate (or methacrylate), acrylate (or methacrylate) and (poly (oxyethylene)) acrylate (or methacrylate) having C ₃ F ₇ groups And a copolymer of (poly (oxypropylene)) acrylate (or methacrylate).

In the present invention, surfactants other than fluorine-based and / or silicon-based surfactants described in [0280] of US Patent Application Publication No. 2008/0248425 can also be used.
These surfactants may be used alone or in several combinations.
The amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total amount of the actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent). is there.

[5] Other components In the composition of the present invention, a dissolution inhibiting compound having a molecular weight of 3000 or less, which is further decomposed by the action of an carboxylic acid onium salt and an acid to increase the solubility in an alkaline developer, if necessary. For example, alicyclic or aliphatic compounds containing acid-decomposable groups such as cholic acid derivatives containing acid-decomposable groups described in Proceeding of SPIE, 2724,355 (1996)), dyes, plasticizers , A photosensitizer, a light absorber, and a compound that promotes solubility in a developer (for example, a phenol compound having a molecular weight of 1000 or less, an alicyclic group having a carboxyl group, or an aliphatic compound). Good.

[6] Hydrophobic resin (I)
When the composition of the present invention is applied to immersion exposure described later, the composition preferably further contains a hydrophobic resin (HR) as the component (I).
As a hydrophobic resin (HR), by adding it to an actinic ray-sensitive or radiation-sensitive resin composition, it is unevenly distributed on the film surface and increases the contact angle, thereby suppressing watermark defects and sensitivity during immersion exposure. The compound is not particularly limited as long as it is a compound (also referred to as “compound (U ′)”) capable of forming a protective layer that suppresses elution of the actinic ray-sensitive or radiation-sensitive resin composition into the immersion medium. Further, unlike a surfactant, it is not always necessary to have a hydrophilic group in the molecule, and it does not have to contribute to uniform mixing of polar / nonpolar substances.

From the viewpoint of uneven distribution on the film surface, the compound (U ′) has (i) a fluorine atom in the main chain or side chain of the resin, (ii) a silicon atom in the main chain or side chain of the resin, or (iii) It preferably has at least one feature of having a hydrocarbon group in the side chain of the resin.
When the compound (U ′) has a fluorine atom in the main chain or side chain of the resin (i), as the partial structure having a fluorine atom, an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or a fluorine atom A resin having an aryl group with
The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, It may have a substituent.

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 may further have another substituent.

Preferred examples of the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, or the aryl group having a fluorine atom include groups represented by the following general formulas (F2) to (F4). The present invention is not limited to this.

In general formulas (F2) to (F4),
R _{57 to} R ₆₈ each independently represents a hydrogen atom, a fluorine atom or an alkyl group. 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 having at least one hydrogen atom substituted with a fluorine atom. Represents a group (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 an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. 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 1,3,3-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.
Preferred examples of the repeating unit having a fluorine atom include those shown below.

In the formula, R ₁₀ and R ₁₁ are each independently a hydrogen atom, a fluorine atom, or an alkyl group (preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and particularly as an alkyl group having a substituent, Fluorinated alkyl group can be mentioned).
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).
Besides these, resins having units as shown below are also applicable.

In the formula, R _{4 to} R ₇ are each independently a hydrogen atom, a fluorine atom, or an alkyl group (preferably a linear or branched alkyl group having 1 to 4 carbon atoms, and the alkyl group having a substituent is In particular, a fluorinated alkyl group can be mentioned).
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 )-Or a divalent linking group in which a plurality of these are combined.

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

When the compound (U ′) has a silicon atom in the main chain or side chain of the resin (ii), a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure as a partial structure having a silicon atom It is preferable that
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 represents 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. As the divalent linking group, an alkylene group, a phenylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a urethane group, or a urea group is used alone or in combination of two or more groups. A combination is mentioned.
n represents an integer of 1 to 5.

Examples of the repeating unit having a silicon atom include the repeating units shown in the above (C-Ia) to (C-Id) and (C-III). (However, W ₂ and W _{3 to} W ₆ are represented by “an atomic group containing at least one or more silicon atoms, specifically, an atomic group represented by (CS-1) to (CS-3)”). "Represents")
Hereinafter, although the specific example of the repeating unit which has group represented by general formula (CS-1)-(CS-3) is given, this invention is not limited to this. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ .

When the compound (U ′) has a hydrocarbon group in the side chain of (iii) resin, it preferably has a hydrocarbon group having 4 or more carbon atoms in the side chain, and a hydrocarbon group having 6 or more carbon atoms in the side chain. More preferably, it has.
Further, in another aspect, preferably has a hydrocarbon group having a -CH ₃ structure at one or more side chains, and more preferably has a hydrocarbon group having a -CH ₃ structure two or more side chains. In this respect, the hydrocarbon group is preferably a branched alkyl group.
Specific examples of the repeating unit include the repeating units represented by the general formulas (C-Ia) to (C-Id). (However, W _{3 to} W ₆ are read as “represents a hydrocarbon group”)
Examples of the side chain hydrocarbon group include an alkyl group, an alkyloxy group, an alkyl-substituted cycloalkyl group, an alkenyl group, an alkyl-substituted alkenyl group, an alkyl-substituted cycloalkenyl group, an alkyl-substituted aryl group, and an alkyl-substituted aralkyl group. Group, an alkyl-substituted cycloalkyl group is preferred.

As the alkyl group, a linear alkyl group having 1 to 20 carbon atoms or a branched alkyl group having 3 to 20 carbon atoms is preferable. Specific examples of preferable branched alkyl groups include isopropyl, isobutyl, t-butyl, 3-pentyl, 2-methyl-3-butyl, 3-hexyl, and 2-methyl-3-pentyl. 3-methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, isooctyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5 -Dimethyl-3-heptyl group, 2,3,5,7-tetramethyl-4-heptyl group and the like.
Specific examples of preferable linear alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl groups.

  More preferably, it is a linear or branched alkyl group having 8 or more carbon atoms, specifically 3,5-dimethyl-4-pentyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2, 6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3,5,7-tetramethyl-4-heptyl group.

Examples of the alkyloxy group include a group in which an ether group is bonded to the above-described alkyl group.
The cycloalkyl group may be monocyclic or polycyclic. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The carbon number is preferably 6-30, and particularly preferably 7-25. Preferred cycloalkyl groups include adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, A cyclodecanyl group and a cyclododecanyl group can be mentioned. More preferable examples include an adamantyl group, norbornyl group, cyclohexyl group, cyclopentyl group, tetracyclododecanyl group, and tricyclodecanyl group. More preferably, they are a norbornyl group, a cyclopentyl group, and a cyclohexyl group.

The cycloalkyl group may be substituted with an alkyl group, and examples thereof include 3,5-dimethylcyclohexyl group, 4-isopropylcyclohexyl group, 4-tbutylcyclohexyl group and the like.
As the alkenyl group, a linear or branched alkenyl group having 1 to 20 carbon atoms is preferable, and a branched alkenyl group is more preferable.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group, and a phenyl group is preferable.
The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

(iii) Preferred specific examples of the repeating unit having a hydrocarbon group in the side chain of the resin are given below. In addition, this invention is not limited to these. In specific examples, Rx represents a hydrogen atom or a methyl group, and Rxa to Rxc each represents an alkyl group having 1 to 4 carbon atoms.

  The total content of the repeating units having the characteristics of any one of (i) to (iii) is preferably 50 to 100 mol%, more preferably 80 to 100 mol%, based on all repeating units in the compound (U ′). More preferably, it is 90-100 mol%.

  The compound (U ′) may further have at least one group selected from the following groups (x) to (z).

(X) an alkali-soluble group,
(Y) a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer;
(Z) A group that decomposes by the action of an acid.

  (X) Alkali-soluble groups include phenolic hydroxyl groups, carboxylic acid groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (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.

  Examples of the repeating unit having an alkali-soluble group (x) include 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 main group of the resin via a linking group. Examples include repeating units in which an alkali-soluble group is bonded to the chain. 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. Is also preferable.

The content of the repeating unit 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 polymer.
Specific examples of the repeating unit having an alkali-soluble group (x) are shown below, but the present invention is not limited thereto.

  (Y) Examples of the group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer include a group having a lactone structure, an acid anhydride group, an acid imide group, and the like, and preferably a lactone A group having a structure.

  As the repeating unit having a group (y) that is decomposed by the action of an alkali developer and increases the solubility in the alkali developer, an alkali is added to the main chain of the resin, such as a repeating unit of an acrylate ester or a methacrylate ester. A polymerization initiator having a repeating unit to which a group (y) that decomposes by the action of the developer and increases the solubility in an alkali developer is bonded, or a group (y) that increases the solubility in an alkali developer And a chain transfer agent used at the time of polymerization are preferably introduced at the end of the polymer chain.

  The content of the repeating unit having a group (y) whose solubility in an alkali developer is increased is preferably 1 to 40 mol%, more preferably 3 to 30 mol%, still more preferably based on all repeating units in the polymer. 5 to 15 mol%.

  Specific examples of the group (y) whose solubility in an alkali developer increases can include the lactone structure exemplified for the resin (A).

  Examples of the repeating unit having a group (z) that can be decomposed by the action of an acid include the same repeating units having an acid-decomposable group as mentioned for the resin (P). In the compound (U ′), the content of the repeating unit having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, based on all repeating units in the polymer. More preferably, it is 20-60 mol%.

The weight average molecular weight in terms of standard polystyrene of the compound (U ′) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000. . The dispersity is preferably 1.0 to 2.0, and more preferably 1.1 to 1.6.
The compound (U ′) is preferably (x) to (z) having a group capable of decomposing by the action of (z) acid from the viewpoint of improving LWR.

  The compound (U ′), like the resin of the component (A), 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% and 0-1 mass% are still more preferable. Thereby, a resist 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 5, more preferably 1 to 3, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is the range of 1-2.

  The blending amount of the hydrophobic resin (HR) in the actinic ray-sensitive or radiation-sensitive resin composition as a whole is preferably 0.1 to 20% by mass, more preferably 0.2 to 10% by mass, based on the total solid content. More preferably, it is 0.3-2 mass%.

As the hydrophobic resin (HR), various commercially available products can be used, and can be synthesized and purified according to a conventional method (for example, radical polymerization). Of course, the synthesis / generation method described as the synthesis method of the resin of the component (A) can also be applied. As a detailed synthesis / purification method, the method described in the above-mentioned resin (A) or the description in Chapter 2 “Polymer Synthesis” of “5th edition Experimental Chemistry Course 26 Polymer Chemistry” published by Maruzen Co., Ltd. is used. I can do it.
Hereinafter, although the specific example of a compound (U ') is shown, this application is not limited to these.

(F, Si type)

(Hydrocarbon)

<Pattern formation method>
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. Such a film thickness can be obtained by setting the solid content concentration in the positive resist composition to an appropriate range to give an appropriate viscosity and improving the coating property and film forming property.
The total solid content concentration in the positive resist composition 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 prepared by dissolving the above components in a predetermined organic solvent, preferably the mixed solvent, filtering the solution, and then applying the solution on a predetermined support as follows. And use. The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less made of polytetrafluoroethylene, polyethylene, or nylon.

  For example, a positive resist composition is coated on a substrate (eg, silicon / silicon dioxide coating) used for manufacturing a precision integrated circuit element by an appropriate coating method such as a spinner or a coater, and dried to form a resist film. Form.

  The resist 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.

Examples of the actinic ray or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-ray, electron beam, etc., preferably 250 nm or less, more preferably 220 nm or less, particularly Preferably, far ultraviolet light having a wavelength of 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, electron beam, etc., ArF excimer Laser, F ₂ excimer laser, EUV (13 nm), and electron beam are preferable.

During exposure to actinic rays or radiation, exposure (immersion exposure) is performed by filling a liquid (immersion medium) having a refractive index higher than air between the actinic ray-sensitive or radiation-sensitive resin composition film and the lens. May be. 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 publication “Processes and Materials for Immersion Lithography”. On the other hand, the presence of an opaque substance with respect to 193 nm light and the presence of impurities whose refractive index is significantly different from that of water causes distortion of the optical image projected on the actinic ray-sensitive or radiation-sensitive resin composition film. As water, distilled water is preferred. 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.
In addition, as mentioned above, when performing immersion exposure, it is preferable that the composition of this invention contains the above-mentioned compound (U ') (addition polymer).
In addition, as another method for performing immersion exposure, an immersion-light-sensitive or radiation-sensitive resin composition film is not directly brought into contact with the immersion liquid. May also be provided.

  From the viewpoint of 193 nm transparency, the top coat is preferably a polymer that does not contain abundant aromatics. Specifically, the polymer contains a hydrocarbon polymer, an acrylate polymer, polymethacrylic acid, polyacrylic acid, polyvinyl ether, and silicon. Examples thereof include a polymer and a fluorine-containing polymer. The hydrophobic resin (HR) described above as the component (I) is also suitable as a top coat. Commercially available top coat materials can also be used as appropriate. The performance required for the top coat and how to use it are explained in chapter 7 of CM Publishing “Immersion Lithography Processes and Materials”.

Before forming the actinic ray-sensitive or radiation-sensitive resin composition 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 are also used. it can.

As the alkaline developer in the development step, a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used. In addition, inorganic alkali, primary amine, secondary amine, tertiary amine, alcohol amine are also used. An aqueous alkali solution such as a cyclic amine can also be used.
Furthermore, alcohols and surfactants can be added in appropriate amounts 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.
Furthermore, alcohols and surfactants can be added in appropriate amounts to the alkaline aqueous solution.
As the rinsing liquid, pure water can be used, and an appropriate amount of a surfactant can be added.

  Further, after the development process or the rinsing process, a process of removing the developer or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed.

<Synthesis of Resin (A)>
(Resin (A1))
Under a nitrogen stream, 78.1 g of cyclohexanone was placed in a three-necked flask and heated to 80 ° C. Monomer A 18.3 g, monomer B 3.8 g, monomer C 5.5 g, monomer D 11.8 g, polymerization initiator (dimethyl-2,2′-azobis (2-methylpropionate (V-601)) (Manufactured by Wako Pure Chemical Industries, Ltd.) A solution prepared by dissolving 2.418 g in 145.0 g of cyclohexanone was added dropwise over 6 hours, and further reacted for 2 hours at 80 ° C. After allowing the reaction solution to cool, heptane / The mixture was dropped into an ethyl acetate mixed solution (1290 g / 551 g) over 20 minutes, and the precipitated powder was collected by filtration and dried to obtain 35 g of the desired resin (A1) .The weight average molecular weight of the obtained resin was standard polystyrene. It was 12500 in terms of conversion, and the dispersity (Mw / Mn) was 1.70.

(Resin (A2) to (A9), Resin (AC))
Resins (A2) to (A9) and Resin (AC) were synthesized using the same method as the synthesis method of Resin (A1).
<Synthesis of photoacid generator>
B1 was synthesized according to the method described in JP-A No. 2004-2252 and B2 was synthesized according to the method described in JP-A No. 2007-161707. B3 to B9 were synthesized in the same manner.

<Resist composition preparation>
The components shown in Table 1 below are dissolved in a mixed solvent shown in the same table to prepare a solution having a solid content concentration of 4.4% by mass, and this is filtered through a polyethylene filter having a pore size of 0.03 μm to form a positive resist solution. Was prepared. The prepared positive resist solution was evaluated by the following method.

  Each component used is as follows.

[(A) Resin in which the protecting group is removed by the action of an acid and the solubility in an alkali developer increases]

[(B) Compound that generates acid upon irradiation with actinic ray or radiation]

(C) Basic compound

[(I) Hydrophobic resin]

[(W) Surfactant]
W1: Troisol S-366 (manufactured by Troy Chemical Co.)
W2: Megafuck F-177 (Dainippon Ink Chemical Co., Ltd.)
[(S) solvent]
S1: Propylene glycol methyl ether acetate
/ Propylene glycol methyl ether (60/40)
S2: Propylene glycol methyl ether acetate
/ Ethyl lactate (80/20)
<Immersion exposure evaluation>
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 78 nm. The prepared positive resist composition was applied thereon and baked at 130 ° C. for 60 seconds to form a resist film having a thickness of 110 nm. The obtained wafer was exposed through a 6% halftone mask of 45 nm (line and space pattern) using an ArF excimer laser immersion scanner (XT1700i, NA1.35 manufactured by ASML). Pure water was used as the immersion liquid. Thereafter, the mixture was heated at 90 ° C. for 60 seconds, developed with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds, rinsed with pure water, and spin-dried to obtain a resist pattern.

[Exposure latitude (EL)]
An exposure amount that reproduces a mask pattern of a line and space (1: 1) with a line width of 45 nm is set as an optimum exposure amount, and an exposure amount width that allows a pattern size of 85 nm ± 10% when the exposure amount is changed is obtained. This value was divided by the optimum exposure amount and displayed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude (EL).

(Pattern profile)
The profile of the pattern obtained with a line and space (1: 1) mask pattern with a line width of 45 nm was observed with a cross-sectional SEM.

[LWR evaluation]
In the standard resist evaluation, the line pattern finished to 75 nm is observed with a scanning microscope (S9260 manufactured by Hitachi, Ltd.), and the distance from the reference line where the edge should be in the range of 2 μm edge in the longitudinal direction of the line pattern is set to 50. Point measurement was performed to obtain a standard deviation, and 3σ was calculated. A smaller value indicates better performance.

As shown in Table 2, the positive resist composition of the present invention is excellent in all of exposure latitude, LWR, and line pattern profile as compared with the positive resist compositions shown in Comparative Examples 1 to 3. Was confirmed.

<Dry exposure evaluation>
The components shown in Table 3 below are dissolved in the mixed solvent shown in the table to prepare a solution having a solid content concentration of 4% by mass, and this is filtered through a polyethylene filter having a pore size of 0.03 μm to prepare a positive resist solution. did. The prepared positive resist solution was evaluated by the following method.

  An anti-reflective coating DUV-42 manufactured by Brewer Science Co., Ltd. was uniformly applied to 600 angstroms on a silicon substrate subjected to hexamethyldisilazane treatment with a spin coater, dried on a hot plate at 100 ° C. for 90 seconds, and then at 190 ° C. Heat drying was performed for 240 seconds. Thereafter, each positive resist solution was applied with a spin coater and dried at 120 ° C. for 60 seconds to form a resist film having a thickness of 160 nm.

  The resist film was exposed with an ArF excimer laser stepper (NA = 0.75, dipole manufactured by ASML) through a mask, and immediately after the exposure, it was heated on a hot plate at 120 ° C. for 60 seconds. Further, development was performed at 23 ° C. for 60 seconds using an aqueous 2.38 mass% tetramethylammonium hydroxide solution, rinsed with pure water for 30 seconds, and then dried to obtain a line pattern.

  The exposure latitude (EL) and the pattern profile evaluation were evaluated in the same manner as the immersion exposure evaluation except that the exposure amount for reproducing a line and space (1: 1) mask pattern having a line width of 70 nm was set as the optimal exposure amount.

As shown in Table 4 below, it was confirmed that all of the positive resist compositions of the present invention were superior in exposure latitude, LWR, and line pattern profile as compared with the compositions shown in Comparative Examples 4-6. It was.

Claims (10)

(A) a resin in which the protecting group is eliminated by the action of an acid and the solubility in an alkali developer increases,
(B) a compound that generates an acid upon irradiation with actinic rays or radiation,
Further, (I) a hydrophobic resin having at least a fluorine atom or a silicon atom group, or a linear or branched alkyl group having 8 or more carbon atoms, and having the property of increasing the contact angle of the film surface by the addition thereof
Containing
The actinic ray-sensitive or radiation-sensitive resin composition , wherein the protecting group of the resin (A) has a polar group, and the acid generated from the compound (B) is represented by the following general formula (I) object.

Where
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ¹ and R ² each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or a group selected from an alkyl group substituted with at least one fluorine atom, and R ¹ and R ² in the case where a plurality of R ¹ and R ^{2 are present.} May be the same or different.
L represents a single bond or a divalent linking group, and when there are a plurality of L, they may be the same or different.
A represents a group having a cyclic structure.
x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.   2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein A is an alicyclic group in the general formula (I).   The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein in the general formula (I), at least one L is a -COO- group or a -OCO- group.   The polar group of the protective group of the resin (A) is any one of a hydroxyl group, a ketone group, a cyano group, an amide group, an alkylamide group, a sulfonamide group, a lower ester group, and a lower sulfonate group. Item 4. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of Items 1 to 3. The amount of the hydrophobic resin (I) is 0.1 to 20% by mass in the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition, according to any one of claims 1 to 4. The actinic ray-sensitive or radiation-sensitive resin composition described. (A) a resin in which the protecting group is eliminated by the action of an acid and the solubility in an alkali developer increases,
(B) A compound that generates an acid upon irradiation with actinic rays or radiation
Containing
While the protecting group of the resin (A) has a polar group, the resin (A) contains a repeating unit represented by the following formula 15, and the acid generated from the compound (B) is represented by the following general formula (I) An actinic ray-sensitive or radiation-sensitive resin composition characterized by the following:

Where
Rx is H, CH _Three , CF _Three Or CH ₂ Represents OH.
Rxa represents an alkyl group having 1 to 4 carbon atoms.

Where
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ¹ , R ² Each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or a group selected from an alkyl group substituted with at least one fluorine atom, ¹ , R ² May be the same or different.
L represents a single bond or a divalent linking group, and when there are a plurality of L, they may be the same or different.
A represents a group having a cyclic structure.
x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10. (A) a resin in which the protecting group is eliminated by the action of an acid and the solubility in an alkali developer increases,
(B) A compound that generates an acid upon irradiation with actinic rays or radiation
Containing
The actinic ray-sensitive or radiation-sensitive resin composition, wherein the protecting group of the resin (A) has a polar group, and the acid generated from the compound (B) is represented by the following general formula (I) object.

Where
  Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ¹ , R ² Each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or a group selected from an alkyl group substituted with at least one fluorine atom, ¹ , R ² May be the same or different.
L represents a single bond or a divalent linking group, and when there are a plurality of L, L may be the same or different, and at least one L is a —COO— group.
A represents a group having a cyclic structure.
x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10. In the general formula (I), x, y and z are each 1, Xf represents a fluorine atom, R ¹ And R ² Each represents a hydrogen atom, The actinic-ray sensitive or radiation sensitive resin composition of Claim 7 characterized by the above-mentioned. In the general formula (I), x, y and z are each 1, Xf represents a fluorine atom, R ¹ Represents a hydrogen atom, R ² Represents a trifluoromethyl group, The actinic ray-sensitive or radiation-sensitive resin composition according to claim 7. Film is formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 9 exposing the film pattern forming method, which comprises a step of developing.