JP2012128383A - Actinic ray-sensitive or radiation-sensitive resin composition and pattern forming method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an actinic ray-sensitive or radiation-sensitive resin composition excellent in roughness characteristics, focus latitude, bridge defect preventing performance and dependency of sensitivity on post exposure baking (PEB) temperature, and a pattern forming method using the composition.SOLUTION: The actinic ray-sensitive or radiation-sensitive resin composition comprises: a resin, which contains a first repeating unit having a group that is decomposed by an action of an acid to produce an alcoholic hydroxyl group, and the solubility of which with a developing solution containing an organic solvent is decreased by the action of the acid; a first compound that generates an acid by irradiation with actinic rays or radiation; a solvent; and a second compound having at least one of a fluorine atom and a silicon atom and having basicity or increasing basicity by the action of the acid.

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition and a pattern forming method using the same. More specifically, the present invention relates to a composition suitable for a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal and a thermal head, and other photofabrication lithography processes, and a pattern forming method using the composition. . In particular, the present invention relates to an ArF exposure apparatus, an ArF immersion projection exposure apparatus, and a composition suitable for exposure in an EUV exposure apparatus using far ultraviolet light having a wavelength of 300 nm or less as a light source, and a pattern forming method using the same. About.

  Here, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV) rays, X rays or electron rays (EB). Yes. In the present invention, “light” means actinic rays or radiation.

  In addition, “exposure” means not only light irradiation with a mercury lamp, far ultraviolet rays, X-rays, EUV light, etc., but also drawing with particle beams such as electron beams and ion beams, unless otherwise specified. .

  Since the resist for KrF excimer laser (248 nm), a pattern formation method using chemical amplification has been used to compensate for the sensitivity reduction due to light absorption. For example, in the positive chemical amplification method, first, a photoacid generator contained in an exposed portion is decomposed by light irradiation to generate an acid. Then, in the post exposure bake (PEB) process or the like, the alkali-insoluble group contained in the photosensitive composition is changed to an alkali-soluble group by the catalytic action of the generated acid. Thereafter, development is performed using, for example, an alkaline solution. Thereby, an exposed part is removed and a desired pattern is obtained.

  In the above method, various alkali developers have been proposed. For example, as this alkaline developer, a 2.38 mass% TMAH (tetramethylammonium hydroxide aqueous solution) aqueous alkaline developer is generally used.

  To reduce the size of semiconductor elements, the exposure light source has become shorter and the projection lens has a higher numerical aperture (high NA). Currently, an exposure machine using an ArF excimer laser having a wavelength of 193 nm as a light source has been developed. ing. As a technique for further increasing the resolving power, a method of filling a liquid having a high refractive index (hereinafter also referred to as “immersion liquid”) between the projection lens and the sample (that is, an immersion method) has been proposed. In addition, EUV lithography in which exposure is performed with ultraviolet light having a shorter wavelength (13.5 nm) has also been proposed.

  However, in reality, it is extremely difficult to find an appropriate combination of a resist composition, a developing solution, a rinsing solution and the like necessary for forming a pattern having comprehensively excellent performance. In particular, as the resolution line width of the resist becomes finer, improvements in roughness performance of line patterns and in-plane uniformity of pattern dimensions are required.

  In recent years, various configurations have been proposed as positive resist compositions (see, for example, Patent Documents 1 to 4). Development of negative resist compositions in pattern formation by alkali development has also been carried out (see, for example, Patent Documents 5 to 8). This is because, in the manufacture of semiconductor elements and the like, there is a demand for pattern formation having various shapes such as lines, trenches, and holes, but there are patterns that are difficult to form with current positive resists. .

  In recent years, a pattern forming method using a negative developer, that is, a developer containing an organic solvent is being developed (see, for example, Patent Documents 9 to 11). For example, Patent Document 11 discloses a step of applying a positive resist composition on a substrate, which increases the solubility in a positive developer and decreases the solubility in a negative developer by irradiation with actinic rays or radiation. There is disclosed a pattern forming method including an exposure step and a step of developing using a negative developer. According to this method, a highly accurate fine pattern can be stably formed.

  However, in the above composition, further improvement is required for roughness characteristics, focus margin (DOF), bridge defect performance, and sensitivity post-exposure heating (PEB) temperature dependence. .

JP 2008-203639 A JP 2007-146613 A JP 2006-131739 A JP 2000-122295 A JP 2006-317803 A JP 2006-259582 A JP 2006-195050 A JP 2000-206694 A JP 2008-281974 A JP 2008-281975 A JP 2008-292975 A

  An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition excellent in roughness characteristics, focus margin, bridge defect performance, and post-exposure heating (PEB) temperature dependence of sensitivity, and the use thereof Another object of the present invention is to provide a pattern forming method.

For example, the present invention is as follows.
[1] A resin containing a first repeating unit having a group capable of decomposing by the action of an acid to generate an alcoholic hydroxy group and having reduced solubility in a developer containing an organic solvent by the action of an acid, actinic rays or radiation An active substance comprising a first compound that generates an acid upon irradiation, a solvent, and a second compound that contains at least one of a fluorine atom and a silicon atom and has basicity or increases basicity by the action of an acid. A light-sensitive or radiation-sensitive resin composition.

  [2] The composition according to [1], wherein the second compound is a nitrogen-containing compound.

  [3] The composition according to [1] or [2], wherein the second compound is a low molecular compound.

[4] The composition according to any one of [1] to [3], wherein the second compound is represented by the following general formula (1N).

In general formula (1N),
Ra, Rb ₁ , Rb ₂ and Rb ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. At least two of Rb ₁ , Rb ₂ and Rb ₃ may be bonded to each other to form a ring. However, the case where all of Rb ₁ , Rb ₂ and Rb ₃ are simultaneously hydrogen atoms is excluded.
Rc represents a single bond or a divalent linking group.
Rf represents an organic group.
x represents 0 or 1, y represents 1 or 2, z represents 1 or 2, and x + y + z = 3.
When x = z = 1, Ra and Rc may be bonded to each other to form a nitrogen-containing heterocycle.
When z = 1, Rf contains a fluorine atom or a silicon atom.
When z = 2, at least one of the two Rf contains a fluorine atom or a silicon atom, and the two Rc and the two Rf may be the same or different from each other. Two Rc's may be bonded to each other to form a ring.

  [5] The composition according to [1] or [2], wherein the second compound is an oligomer or a polymer compound.

  [6] The second compound includes a second repeating unit containing at least one of a fluorine atom and a silicon atom, and a third repeating unit having at least one of a basic group and a group whose basicity is increased by the action of an acid. [5] The composition according to [5].

[7] The first repeating unit is any one of [1] to [6] represented by at least one selected from the group consisting of the following general formulas (I-1) to (I-10): Composition.

Where
Each Ra independently represents a hydrogen atom, an alkyl group, or a group represented by —CH ₂ —O—Ra ₂ . Here, Ra2 represents a hydrogen atom, an alkyl group, or an acyl group.
R ₁ represents an (n + 1) valent organic group.
R ₂ independently represents a single bond or an (n + 1) -valent organic group when m ≧ 2.
OP each independently represents the above group which decomposes by the action of an acid to produce an alcoholic hydroxy group. When n ≧ 2 and / or m ≧ 2, two or more OPs may be bonded to each other to form a ring.
W represents a methylene group, an oxygen atom or a sulfur atom.
n and m represent an integer of 1 or more.
l represents an integer of 0 or more.
L ₁ represents a linking group represented by —COO—, —OCO—, —CONH—, —O—, —Ar—, —SO ₃ — or —SO ₂ NH—. Here, Ar represents a divalent aromatic ring group.
Each R independently represents a hydrogen atom or an alkyl group.
R ₀ represents a hydrogen atom or an organic group.
L ₃ represents a (m + 2) -valent linking group.
R ^L each independently represents an (n + 1) -valent linking group when m ≧ 2.
R ^S each independently represents a substituent when p ≧ 2. For p ≧ 2, plural structured R ^S may be bonded to each other to form a ring.
p represents an integer of 0 to 3.

[8] The group which is decomposed by the action of an acid to produce an alcoholic hydroxy group is represented by at least one selected from the group consisting of the following general formulas (II-1) to (II-9) [1 ] The composition in any one of-[7].

Where
R ₃ each independently represents a hydrogen atom or a monovalent organic group. Two R _{3 s} may be bonded to each other to form a ring.
R ₄ each independently represents a monovalent organic group. At least two R ₄ may be bonded to each other to form a ring. R ₃ and R ₄ may be bonded to each other to form a ring.
R ₅ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an alkynyl group. At least two R ₅ may be bonded to each other to form a ring. However, when one or two of the three R ₅ are hydrogen atoms, at least one of the remaining R ₅ represents an aryl group, an alkenyl group, or an alkynyl group.
R ₆ each independently represents a hydrogen atom or a monovalent organic group. R ₆ may be bonded to each other to form a ring.

[9] The composition according to any one of [1] to [8], wherein the first repeating unit is represented by the following general formula (III).

Where
R ₁ represents an (n + 1) valent organic group.
Ra represents a hydrogen atom, an alkyl group, or a group represented by —CH ₂ —O—Ra ₂ . Here, Ra2 represents a hydrogen atom, an alkyl group, or an acyl group.
R ₃ each independently represents a hydrogen atom or a monovalent organic group. R ₃ may be bonded to each other to form a ring.
R ₄ each independently represents a monovalent organic group when n ≧ 2. R ₄ may be bonded to each other to form a ring. R ₃ and R ₄ may be bonded to each other to form a ring.
n represents an integer of 1 or more.

[10] The composition according to [9], wherein R ₁ represents a non-aromatic hydrocarbon group.

[11] The composition according to [10], wherein R ₁ represents an alicyclic hydrocarbon group.

[12] The group that decomposes by the action of an acid to generate an alcoholic hydroxy group is represented by the general formula (II-1), and at least one of the R ₃ represents a monovalent organic group [8] to [11] The composition according to any one of [11].

  [13] The composition according to any one of [1] to [12], wherein the first repeating unit includes two or more of the groups that are decomposed by the action of an acid to generate an alcoholic hydroxy group.

  [14] The composition according to any one of [1] to [13], wherein the resin further includes a repeating unit having an alcoholic hydroxy group.

  [15] The composition according to any one of [1] to [14], wherein the resin further includes a repeating unit having a cyano group.

  [16] The composition according to any one of [1] to [15], wherein the resin further includes a repeating unit having a group that decomposes by the action of an acid to generate a carboxy group.

  [17] A resist pattern formed using the composition according to any one of [1] to [16].

  [18] (A) forming a film using the composition according to any one of [1] to [16], (B) exposing the film, and (C) the exposed film Forming a pattern.

  [19] The method according to [18], wherein the development is performed using a developer containing an organic solvent.

  [20] The method according to [19], wherein the organic solvent contained in the developer is any of ester, ketone, alcohol, amide, ether, and hydrocarbon.

  [21] The method according to [19] or [20], wherein the pattern formed by the development is a negative type.

  According to the present invention, an actinic ray-sensitive or radiation-sensitive resin composition excellent in roughness characteristics, focus margin, bridge defect performance, and post-exposure heating (PEB) temperature dependence of sensitivity, and the same are used. A pattern forming method can be provided.

Hereinafter, embodiments of the present invention will be described in detail.
Here, the groups and atomic groups that do not explicitly indicate substitution or non-substitution include both those that do not have a substituent and those that have a substituent. For example, an “alkyl group” that does not clearly indicate substitution or unsubstituted is not only an alkyl group that does not have a substituent (unsubstituted alkyl group) but also an alkyl group that has a substituent (substituted alkyl group) Is also included.

<Actinic ray-sensitive or radiation-sensitive resin composition>
First, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention will be described. This composition may be used for negative development or positive development. That is, this composition may be used for development using a developer containing an organic solvent, or may be used for development using an alkali developer. The composition according to the present invention is typically used for negative development, that is, development using a developer containing an organic solvent. That is, the composition according to the present invention is typically a negative resist composition.

The composition according to the present invention comprises (a) a resin whose solubility in a developer containing an organic solvent is reduced by the action of an acid (hereinafter also referred to as an acid-decomposable resin), and (b) irradiation with actinic rays or radiation. A compound that generates an acid (hereinafter also referred to as an acid generator), (c) a solvent, and (d) at least one of a fluorine atom and a silicon atom, has basicity or increases basicity by the action of an acid. And a compound to be included.
In addition, this composition comprises (e) a compound having basicity or increased basicity by the action of an acid, a compound other than (d); (f) a basicity that decreases in basicity upon irradiation with actinic rays or radiation. Or (a) a hydrophobic resin; (h) a surfactant; and (i) at least one of other additives. Hereinafter, each of these components will be described in order.

(A) Acid-decomposable resin The composition according to the present invention contains an acid-decomposable resin. The acid-decomposable resin includes a repeating unit (P) having a group that decomposes by the action of an acid to generate an alcoholic hydroxy group as an acid-decomposable group.

  In the case where at least part of the acid-decomposable group is a group that decomposes by the action of an acid to generate an alcoholic hydroxy group, for example, the acid-decomposable group decomposes by the action of an acid to form a carboxy group. It has been found that, for example, sensitivity, limit resolving power, roughness characteristics, exposure latitude (EL), post-exposure heating (PEB) temperature dependency, and focus margin (DOF) are improved as compared with the case where only the generated group is formed. ing. The reason for this is not always clear, but the present inventors speculate as follows. That is, the present inventors have improved the reactivity of the acid-decomposable resin as well as the acid-decomposability by using a group that decomposes by the action of an acid to generate an alcoholic hydroxy group as at least a part of the acid-decomposable group. This is considered to be because the polarity change of the resin due to the decomposition of the group becomes large and the dissolution contrast with respect to the developer containing the organic solvent is improved.

  In addition, when the present invention is a group in which at least a part of the acid-decomposable group is decomposed by the action of an acid to generate an alcoholic hydroxy group, the acid-decomposable group is decomposed by the action of an acid to form a carboxy group. It has been found that, for example, a decrease in film thickness during post-exposure heating (PEB) can be suppressed as compared with the case where only the generated groups are formed. The present inventors believe that this is because the change in the polarity of the resin before and after decomposition by the action of an acid is greater in the former case than in the latter case. This difference in the magnitude of the polarity change is particularly remarkable when the molecular weight of the protecting group that is eliminated by the action of an acid is small.

  The pKa of the alcoholic hydroxy group that can be generated by the above group being decomposed by the action of an acid is, for example, 12 or more, and typically 12 or more and 20 or less. If this pKa is excessively small, the stability of the composition containing the acid-decomposable resin is lowered, and the performance variation with time may increase. Here, “pKa” is a value calculated using “ACD / pKa DB” manufactured by Fujitsu Limited under an initial setting that is not customized.

  The repeating unit (P) preferably has two or more groups that decompose by the action of an acid to generate an alcoholic hydroxy group. If it carries out like this, the limit resolving power and roughness characteristic of the composition containing acid-decomposable resin can further be improved.

The repeating unit (P) is preferably represented by at least one selected from the group consisting of the following general formulas (I-1) to (I-10). The repeating unit is more preferably represented by at least one selected from the group consisting of the following general formulas (I-1) to (I-3), and is represented by the following general formula (I-1). More preferably.

Where
Each Ra independently represents a hydrogen atom, an alkyl group, or a group represented by —CH ₂ —O—Ra ₂ . Here, Ra2 represents a hydrogen atom, an alkyl group, or an acyl group.
R ₁ represents an (n + 1) valent organic group.
R ₂ independently represents a single bond or an (n + 1) -valent organic group when m ≧ 2.
OP each independently represents the above group which decomposes by the action of an acid to produce an alcoholic hydroxy group. When n ≧ 2 and / or m ≧ 2, two or more OPs may be bonded to each other to form a ring.
W represents a methylene group, an oxygen atom or a sulfur atom.
n and m represent an integer of 1 or more. In general formula (I-2), (I-3) or (I-8), n is 1 when R ₂ represents a single bond.
l represents an integer of 0 or more.
L ₁ represents a linking group represented by —COO—, —OCO—, —CONH—, —O—, —Ar—, —SO ₃ — or —SO ₂ NH—. Here, Ar represents a divalent aromatic ring group.
Each R independently represents a hydrogen atom or an alkyl group.
R ₀ represents a hydrogen atom or an organic group.
L ₃ represents a (m + 2) -valent linking group.
R ^L each independently represents an (n + 1) -valent linking group when m ≧ 2.
R ^S each independently represents a substituent when p ≧ 2. For p ≧ 2, plural structured R ^S may be bonded to each other to form a ring.
p represents an integer of 0 to 3.

Ra represents a hydrogen atom, an alkyl group, or a group represented by —CH ₂ —O—Ra ₂ . Ra is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom or a methyl group.

  W represents a methylene group, an oxygen atom or a sulfur atom. W is preferably a methylene group or an oxygen atom.

R ₁ represents an (n + 1) valent organic group. R ₁ is preferably a non-aromatic hydrocarbon group. In this case, R ₁ may be a chain hydrocarbon group or an alicyclic hydrocarbon group. R ₁ is more preferably an alicyclic hydrocarbon group.

R ₂ represents a single bond or an (n + 1) valent organic group. R ₂ is preferably a single bond or a non-aromatic hydrocarbon group. In this case, R ₂ may be a chain hydrocarbon group or an alicyclic hydrocarbon group.

When R ₁ and / or R ₂ is a chain hydrocarbon group, the chain hydrocarbon group may be linear or branched. The chain hydrocarbon group preferably has 1 to 8 carbon atoms. For example, when R ₁ and / or R ₂ is an alkylene group, R ₁ and / or R ₂ are methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group or sec- A butylene group is preferred.

When R ₁ and / or R ₂ is an alicyclic hydrocarbon group, the alicyclic hydrocarbon group may be monocyclic or polycyclic. This alicyclic hydrocarbon group has, for example, a monocyclo, bicyclo, tricyclo or tetracyclo structure. The carbon number of this alicyclic hydrocarbon group is usually 5 or more, preferably 6 to 30, and more preferably 7 to 25.

Examples of the alicyclic hydrocarbon group include those having the partial structures listed below. Each of these partial structures may have a substituent. In each of these partial structures, the methylene group (—CH ₂ —) includes an oxygen atom (—O—), a sulfur atom (—S—), a carbonyl group [—C (═O) —], a sulfonyl group [ -S (= O) _2- ], a sulfinyl group [-S (= O)-], or an imino group [-N (R)-] (R is a hydrogen atom or an alkyl group).

For example, when R ₁ and / or R ₂ is a cycloalkylene group, R ₁ and / or R ₂ may be an adamantylene group, a noradamantylene group, a decahydronaphthylene group, a tricyclodecanylene group, a tetracyclododeca group. Nylene group, norbornylene group, cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group, cyclodecanylene group, or cyclododecanylene group are preferable, and adamantylene group, norbornylene group, cyclohexylene group, cyclopentylene It is more preferably a len group, a tetracyclododecanylene group or a tricyclodecanylene group.

The non-aromatic hydrocarbon group of R ₁ and / or R ₂ may have a substituent. Examples of the substituent include an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxy group, an alkoxy group having 1 to 4 carbon atoms, a carboxy group, and an alkoxycarbonyl group having 2 to 6 carbon atoms. The above alkyl group, alkoxy group and alkoxycarbonyl group may further have a substituent. As this substituent, a hydroxy group, a halogen atom, and an alkoxy group are mentioned, for example.

L ₁ represents a linking group represented by —COO—, —OCO—, —CONH—, —O—, —Ar—, —SO ₃ — or —SO ₂ NH—. Here, Ar represents a divalent aromatic ring group. L ₁ is preferably a linking group represented by —COO—, —CONH— or —Ar—, and more preferably a linking group represented by —COO— or —CONH—.

  R represents a hydrogen atom or an alkyl group. The alkyl group may be linear or branched. Carbon number of this alkyl group becomes like this. Preferably it is 1-6, More preferably, it is 1-3. R is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

R ₀ represents a hydrogen atom or an organic group. Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, an alkynyl group, and an alkenyl group. R ₀ is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or a methyl group.

L ₃ represents a (m + 2) -valent linking group. That is, L ₃ represents a trivalent or higher linking group. Examples of such a linking group include corresponding groups in specific examples described later.

R ^L represents a (n + 1) -valent linking group. That is, R ^L represents a divalent or higher linking group. Examples of such a linking group include an alkylene group, a cycloalkylene group, and corresponding groups in the specific examples described below. R ^L may be bonded to each other or bonded to the following R ^S to form a ring structure.

R ^S represents a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an acyloxy group, an alkoxycarbonyl group, and a halogen atom.

  n is an integer of 1 or more. n is preferably an integer of 1 to 3, and more preferably 1 or 2. When n is 2 or more, it is possible to further improve the dissolution contrast with respect to a developer containing an organic solvent. Accordingly, in this way, the limit resolution and roughness characteristics can be further improved.

m is an integer of 1 or more. m is preferably an integer of 1 to 3, and more preferably 1 or 2.
l is an integer of 0 or more. l is preferably 0 or 1.
p is an integer of 0-3.

Specific examples of the repeating unit having a group that decomposes by the action of an acid to generate an alcoholic hydroxy group are shown below. In specific examples, Ra and OP have the same meanings as in general formulas (I-1) to (I-3). Further, when a plurality of OPs are bonded to each other to form a ring, the corresponding ring structure is represented as “OPO” for convenience.

The group that decomposes by the action of an acid to produce an alcoholic hydroxy group is preferably represented by at least one selected from the group consisting of the following general formulas (II-1) to (II-4).

Where
R ₃ each independently represents a hydrogen atom or a monovalent organic group. R ₃ may be bonded to each other to form a ring.
R ₄ each independently represents a monovalent organic group. R ₄ may be bonded to each other to form a ring. R ₃ and R ₄ may be bonded to each other to form a ring.
R ₅ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an alkynyl group. At least two R ₅ may be bonded to each other to form a ring. However, when one or two of the three R ₅ are hydrogen atoms, at least one of the remaining R ₅ represents an aryl group, an alkenyl group, or an alkynyl group.

The group that decomposes by the action of an acid to produce an alcoholic hydroxy group is also preferably represented by at least one selected from the group consisting of the following general formulas (II-5) to (II-9).

Where
R ₄ has the same meaning as in general formulas (II-1) to (II-3).
R ₆ each independently represents a hydrogen atom or a monovalent organic group. R ₆ may be bonded to each other to form a ring.
The group that decomposes by the action of an acid to produce an alcoholic hydroxy group is more preferably represented by at least one selected from the general formulas (II-1) to (II-3). More preferably, it is represented by 1) or (II-3), and particularly preferably represented by formula (II-1).

R ₃ represents a hydrogen atom or a monovalent organic group as described above. R ₃ is preferably a hydrogen atom, an alkyl group or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group.

The alkyl group for R ₃ may be linear or branched. The number of carbon atoms in the alkyl group of R ₃ is preferably 1 to 10, and more preferably 1 to 3. Examples of the alkyl group for R ₃ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.

The cycloalkyl group for R ₃ may be monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group represented by R ₃ is preferably 3 to 10, and more preferably 4 to 8. Examples of the cycloalkyl group represented by R ₃ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

In the general formula (II-1), at least one of R ₃ is preferably a monovalent organic group. When such a configuration is employed, particularly high sensitivity can be achieved.

R ₄ represents a monovalent organic group. R ₄ is preferably an alkyl group or a cycloalkyl group, and more preferably an alkyl group. These alkyl groups and cycloalkyl groups may have a substituent.

The alkyl group represented by R ₄ preferably has no substituent, or preferably has one or more aryl groups and / or one or more silyl groups as substituents. The carbon number of the unsubstituted alkyl group is preferably 1-20. It is preferable that carbon number of the alkyl group part in the alkyl group substituted by one or more aryl groups is 1-25. It is preferable that carbon number of the alkyl group part in the alkyl group substituted by the 1 or more silyl group is 1-30. Also, if the cycloalkyl group R ₄ does not have a substituent, the carbon number thereof is preferably from 3 to 20.

R ₅ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an alkynyl group. However, when one or two of the three R ₅ are hydrogen atoms, at least one of the remaining R ₅ represents an aryl group, an alkenyl group, or an alkynyl group. R ₅ is preferably a hydrogen atom or an alkyl group. The alkyl group may have a substituent or may not have a substituent. When the alkyl group does not have a substituent, the carbon number is preferably 1 to 6, and preferably 1 to 3.

R ₆ represents a hydrogen atom or a monovalent organic group as described above. R ₆ is preferably a hydrogen atom, an alkyl group or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group, and further preferably a hydrogen atom or an alkyl group having no substituent. R ₆ is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and having no substituent.

Examples of the alkyl group and cycloalkyl group of R ₄ , R _5, and R ₆ include the same as those described above for R ₃ .

Below, the specific example of the group which decomposes | disassembles by the effect | action of an acid and produces an alcoholic hydroxy group is shown.

As described above, the repeating unit (P) is particularly preferably represented by the general formula (I-1). Further, the group that decomposes by the action of an acid to produce an alcoholic hydroxy group is particularly preferably represented by the general formula (II-1). That is, the repeating unit (P) is particularly preferably represented by the following general formula (III).

_{Wherein, R 1, Ra, R 3} , R 4, and n are as defined above in the general formula (I-1) and (II-1).

As a preferable aspect of a repeating unit (P), what has the partial structure represented by the following general formula (D-1) is mentioned, for example.

Where
L _D1 represents a single bond or a divalent or higher valent linking group.
R _D each independently represents a hydrogen atom, an alkyl group, or a cycloalkyl group. At least two of the three R _D are bonded to each other, they may form a ring.
X _D1 represents a single bond or a linking group having 1 or more carbon atoms.
L _D1 , R _D and X _D1 may be bonded to each other to form a ring. Further, at least one of L _D1 , R _D and X _D1 may be bonded to a carbon atom constituting the main chain of the polymer to form a ring.
R _D1 each independently represents a hydrogen atom, an alkyl group, or a cycloalkyl group. Two R _D1 may be bonded to each other to form a ring.

Examples of the divalent or higher linking group represented by L _D1 include —COO—, —OCO—, —CONH—, —O—, —Ar—, —SO ₃ —, —SO ₂ NH—, and an alkylene group. , A cycloalkylene group, or a linking group represented by a combination of two or more thereof. Here, Ar represents a divalent aromatic ring group.

When L _D1 contains an alkylene group, the alkylene group may be linear or branched. The alkylene group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 carbon atom. Examples of such an alkylene group include a methylene group, an ethylene group, and a propylene group.

When L _D1 contains a cycloalkylene group, the cycloalkylene group preferably has 3 to 10 carbon atoms, and more preferably 5 to 7 carbon atoms. Examples of such a cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group.

  Each of these alkylene groups and cycloalkylene groups may have a substituent. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom; mercapto group; hydroxy group; alkoxy group of methoxy group, ethoxy group, isopropoxy group, t-butoxy group and benzyloxy group; Cycloalkyl groups such as propyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl; cyano group; nitro group; sulfonyl group; silyl group; ester group; acyl group; vinyl group;

L _D1 preferably contains —COO—, more preferably a linking group represented by a combination of —COO— and an alkylene group, and represented by —COO— (CH ₂ ) _n —. More preferably, it is a linking group. Here, n represents a natural number, preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1.

In addition, when L _D1 is a linking group represented by a combination of —COO— and an alkylene group, an embodiment in which this alkylene group and _RD are bonded to each other to form a ring is also preferable.

The alkyl group represented by _RD may be linear or branched. Carbon number of this alkyl group becomes like this. Preferably it is 1-6, More preferably, it is 1-3.

The cycloalkyl group represented by _RD may be monocyclic or polycyclic. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a norbornyl group, and an adamantyl group.
Ring at least two that can formed by bonding of the three R _D is preferably a 5- to 7-membered ring, more preferably a 6-membered ring.

The number of carbon atoms represented by X _D1 are as one or more linking groups, for example, alkylene group. This alkylene group may be linear or branched. The alkylene group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and particularly preferably 1 carbon atom. Examples of such an alkylene group include a methylene group, an ethylene group, and a propylene group.

The alkyl group represented by R _D1 may be linear or branched. Carbon number of this alkyl group becomes like this. Preferably it is 1-6, More preferably, it is 1-3.

The cycloalkyl group represented by R _D1 may be monocyclic or polycyclic. Examples of the cycloalkyl group include those described above as the cycloalkyl group represented by _RD .

The ring that can be formed by bonding two R _D1 to each other may be monocyclic or polycyclic, but may be monocyclic from the viewpoint of solubility in a solvent. More preferred. Moreover, this ring is preferably a 5- to 7-membered ring, and more preferably a 6-membered ring.

The repeating unit (P) represented by the general formula (D-1) typically has a configuration represented by the following general formula (D-2).

Where
Ra has the same meaning as that in formula (I-1). Ra is particularly preferably a methyl group.

L _D1 , R _D , X _D1 and R _D1 have the same meanings as those in General Formula (D-1).

Specific examples of the repeating unit (P) represented by the general formula (D-1) are given below.

  The acid-decomposable resin may contain two or more types of repeating units (P) having a group that decomposes by the action of an acid to generate an alcoholic hydroxy group. Employing such a configuration makes it possible to finely adjust the reactivity and / or developability and facilitate optimization of various performances.

  The content of the repeating unit having a group that decomposes by the action of an acid to generate an alcoholic hydroxy group is preferably in the range of 10 mol% to 100 mol%, more preferably, based on all repeating units of the acid-decomposable resin. Is in the range of 30 mol% to 90 mol%, more preferably in the range of 50 mol% to 80 mol%.

  The acid-decomposable resin may further contain other repeating units in addition to the repeating unit (P). Examples of other repeating units include those described below.

(A) Repeating unit having a polar group The acid-decomposable resin preferably further contains a repeating unit (A) having a polar group. If it carries out like this, the sensitivity of the composition containing acid-decomposable resin can further be improved, for example.

  Examples of the “polar group” that the repeating unit (A) may contain include the following (1) to (4). In the following, “electronegativity” means a value by Pauling.

(1) A functional group including a structure in which an oxygen atom and an atom having an electronegativity difference of 1.1 or more are bonded by a single bond. Examples of such a polar group include a hydroxy group and the like. And a group containing a structure represented by O—H.

(2) Functional group including a structure in which a nitrogen atom and an atom having a difference in electronegativity of the nitrogen atom of 0.6 or more are bonded by a single bond. Examples of such a polar group include an amino group and the like. And a group containing a structure represented by N—H.

(3) Functional group including a structure in which two atoms having electronegativity different by 0.5 or more are bonded by a double bond or a triple bond. Examples of such a polar group include C≡N, C═O, N = And a group containing a structure represented by O, S═O or C═N.

(4) Functional group having an ionic moiety Examples of such a polar group include a group having a moiety represented by N ⁺ or S ⁺ .

  The “polar group” that the repeating unit (A) can contain includes, for example, (I) hydroxy group, (II) cyano group, (III) lactone group, (IV) carboxylic acid group or sulfonic acid group, (V) amide group , A group corresponding to a sulfonamide group or a derivative thereof, (VI) an ammonium group or a sulfonium group, and at least one selected from the group consisting of a combination of two or more thereof.

This polar group is particularly preferably an alcoholic hydroxy group, a cyano group, a lactone group, or a group containing a cyanolactone structure.
When the acid-decomposable resin further contains a repeating unit having an alcoholic hydroxy group, the exposure latitude (EL) of the composition containing the acid-decomposable resin can be further improved.
When the acid-decomposable resin further contains a repeating unit having a cyano group, the sensitivity of the composition containing the acid-decomposable resin can be further improved.
If the acid-decomposable resin further contains a repeating unit having a lactone group, the dissolution contrast with respect to the developer containing an organic solvent can be further improved. This also makes it possible to further improve the dry etching resistance, coating properties, and adhesion to the substrate of the composition containing the acid-decomposable resin.

  When the acid-decomposable resin further contains a repeating unit having a group containing a lactone structure having a cyano group, the dissolution contrast with respect to a developer containing an organic solvent can be further improved. This also makes it possible to further improve the sensitivity, dry etching resistance, applicability, and adhesion to the substrate of the composition containing the acid-decomposable resin. In addition, this makes it possible for a single repeating unit to have a function attributable to each of the cyano group and the lactone group, thereby further increasing the degree of freedom in designing the acid-decomposable resin.

Specific examples of structures that the “polar group” may contain are given below.

  Preferable repeating units (A) include, for example, those obtained by substituting “alcoholic hydroxy groups” in the above repeating units (P) with “groups that decompose by the action of an acid to produce alcoholic hydroxy groups”. .

Such a repeating unit (A) preferably has a structure in which “OP” is replaced with “OH” in each of the general formulas (I-1) to (I-10). That is, this repeating unit is preferably represented by at least one selected from the group consisting of the following general formulas (I-1H) to (I-10H). In particular, the repeating unit (A) is more preferably represented by at least one selected from the group consisting of the following general formulas (I-1H) to (I-3H). More preferably, it is represented by 1H).

In the formula, Ra, R ₁ , R ₂ , OP, W, n, m, l, L ₁ , R, R ₀ , L ₃ , R ^L , R ^S and p are represented by the general formulas (I-1) to ( It is synonymous with each in I-10).

  A repeating unit having a group capable of decomposing by the action of an acid to generate an alcoholic hydroxy group, and a repeating unit represented by at least one selected from the group consisting of the above general formulas (I-1H) to (I-10H) When the unit is used in combination, for example, by suppressing acid diffusion due to an alcoholic hydroxy group and increasing sensitivity due to a group that decomposes by the action of an acid to generate an alcoholic hydroxy group, without degrading other performances, The exposure latitude (EL) can be improved.

  In the above repeating unit (P), the content of the repeating unit (A) in which “the group that decomposes by the action of an acid to produce an alcoholic hydroxy group” is replaced with “alcoholic hydroxy group” is The total repeating unit is preferably 5 to 100 mol%, more preferably 10 to 90 mol%, still more preferably 20 to 80 mol%.

Specific examples of the repeating unit represented by any one of the general formulas (I-1H) to (I-10H) are shown below. In specific examples, Ra is as defined in general formulas (I-1H) to (I-10H).

  Other preferable repeating units (A) include, for example, repeating units having a hydroxy group or a cyano group. This improves the substrate adhesion and developer compatibility.

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

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

Examples of the repeating unit having a partial structure represented by general formulas (VIIa) to (VIId) 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 are in the general formula (VIIa) ~ (VIIc), same meanings as R ₂ c~R ₄ c.

  The content of the repeating unit having a hydroxy group or a cyano group is preferably from 5 to 70 mol%, more preferably from 5 to 60 mol%, still more preferably from 10 to 50 mol%, based on all repeating units in the acid-decomposable resin. .

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

  Other preferable repeating units (A) include, for example, repeating units having a lactone structure.

  The repeating unit having a lactone structure preferably has a 5- to 7-membered lactone structure, and other ring structures are condensed to form a bicyclo structure or a spiro structure on the 5- to 7-membered lactone structure. A ring is more preferable.

More specifically, a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-17) can be given. Preferred lactone structures include (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14) and (LC1-17). . By using specific lactone structures, line edge roughness and development defects can be further reduced.

Wherein, Rb ₂ represents a substituent, _{n 2} represents an integer of 0-4. n ₂ is preferably an integer of 0 to 2.
Preferred examples of Rb ₂ include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 1 to 8 carbon atoms, carboxy groups, and halogens. Examples include an atom, a hydroxy group, a cyano group, and an acid-decomposable group described later. Among these, an alkyl group having 1 to 4 carbon atoms, a cyano group, or an acid-decomposable group is particularly preferable. When n ₂ ≧ 2, the plurality of Rb ₂ may be the same as each other or different from each other. In addition, the plurality of Rb ₂ may be bonded to each other to form a ring.

Examples of the repeating unit having a lactone structure include a repeating unit represented by the following general formula (AII ′).

In general formula (AII ′),
Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. Preferable substituents that the alkyl group of Rb ₀ may have include a hydroxy 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.
be able to. 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.
V represents a group having a structure represented by any one of the general formulas (LC1-1) to (LC1-17).

Specific examples of the repeating unit having a lactone structure are listed below, but the present invention is not limited thereto.

Preferable examples of the repeating unit having a lactone structure include the following repeating units. By selecting an optimal lactone group, for example, the pattern profile and / or density dependence can be optimized.

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

The repeating unit having a lactone group may be a repeating unit represented by the following general formula (1).

In general formula (1),
A represents an ester bond or an amide bond.
R ₀ independently represents an alkylene group, a cycloalkylene group, or a combination thereof when n _S ≧ 2.
Z is independently an ether bond, an ester bond, an amide bond, or a urethane bond when n _S ≧ 2.

Or urea bond

Represents. In the formula, R represents, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
R ₈ represents a monovalent organic group having a lactone structure.
n _S represents an integer of 1 to 5. n _S is preferably 1.
R ₇ represents a hydrogen atom, an alkyl group or a halogen atom. This alkyl group may have a substituent. R ₇ preferably represents a hydrogen atom, a methyl group, a hydroxymethyl group or an acetoxymethyl group.

As described above, R ₀ represents an alkylene group, a cycloalkylene group, or a combination thereof.
The alkylene group as R ₀ may be linear or branched. The alkylene group preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms. Examples of such an alkylene group include a methylene group, an ethylene group, and a propylene group.

The cycloalkylene group as R ₀ preferably has 3 to 10 carbon atoms, and more preferably 5 to 7 carbon atoms. Examples of such a cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group.

  Each of these alkylene groups and cycloalkylene groups may have a substituent. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom; mercapto group; hydroxy group; alkoxy group of methoxy group, ethoxy group, isopropoxy group, t-butoxy group and benzyloxy group; Cycloalkyl groups such as propyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl; cyano group; nitro group; sulfonyl group; silyl group; ester group; acyl group; vinyl group;

  Z represents an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond as described above. Z is preferably an ether bond or an ester bond, and particularly preferably represents an ester bond.

R ₈ represents a monovalent organic group having a lactone structure as described above. This organic group has, for example, a lactone structure represented by any one of the above general formulas (LC1-1) to (LC1-17). Among these, the structure represented by general formula (LC1-4), (LC1-5) or (LC1-17) is more preferable, and the structure represented by general formula (LC1-4) is particularly preferable.

R ₈ preferably has an unsubstituted lactone structure or a lactone structure having a methyl group, a cyano group, or an alkoxycarbonyl group as a substituent. In particular, R ₈ is preferably a monovalent organic group having a lactone structure having a cyano group as a substituent (that is, a cyanolactone structure).

Specific examples of the repeating unit represented by the general formula (1) are shown below. In the following specific examples, R represents a hydrogen atom, an alkyl group or a halogen atom. This alkyl group may have a substituent. R preferably represents a hydrogen atom, a methyl group, a hydroxymethyl group or an acetoxymethyl group.

The repeating unit represented by the general formula (1) is preferably a repeating unit represented by the following general formula (2).

In general formula (2),
R ₇ , A, R ₀ , Z and n _S have the same _meaning as in general formula (1).
Rb independently represents an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, a cyano group, a hydroxy group, or an alkoxy group when m ≧ 2. When m ≧ 2, two or more Rb may be bonded to each other to form a ring.
X represents an alkylene group, an oxygen atom, or a sulfur atom.
m represents an integer of 0 to 5. m is preferably 0 or 1.

  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 cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups. Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, and a t-butoxycarbonyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, 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 halogen atom such as a fluorine atom. Rb is more preferably a methyl group, a cyano group or an alkoxycarbonyl group, and even more preferably a cyano group.

  When m ≧ 1, it is preferable that at least one Rb is substituted at the α-position or β-position of the carbonyl group of the lactone. In particular, Rb is preferably substituted at the α-position of the lactone carbonyl group.

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

Specific examples of the repeating unit represented by the general formula (2) are shown below. In the following specific examples, R represents a hydrogen atom, an alkyl group or a halogen atom. This alkyl group may have a substituent. R preferably represents a hydrogen atom, a methyl group, a hydroxymethyl group or an acetoxymethyl group.

In order to enhance the effect of the present invention, two or more lactone repeating units selected from general formula (1) can be used in combination. Of formulas (1) when used in combination, it is preferred that n _S to select a combination of two or more kinds of repeating units is 1.

  The content of the repeating unit having a lactone structure is preferably 10 to 80 mol%, more preferably 15 to 70 mol%, and more preferably 20 to 60 mol% with respect to all repeating units in the resin. Further preferred.

  Other preferable repeating units (A) include, for example, a carboxy group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, or an aliphatic alcohol group in which the α-position is substituted with an electron withdrawing group (for example, hexafluoro And those having an isopropanol group). This repeating unit (A) more preferably comprises a carboxy group.

  By containing the repeating unit having the above group, the resolution in the contact hole application is increased. Examples of such a repeating unit (A) include a repeating unit in which the above group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or the above main group of the resin through a linking group. Either a repeating unit to which a group is bonded, or a polymerization initiator or chain transfer agent having the above group is introduced at the end of the polymer chain during polymerization, and the linking group is a monocyclic or polycyclic cyclic carbonization. It may have a hydrogen structure. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

As for the content rate of the repeating unit (A) which has the said group, 0-20 mol% is preferable with respect to all the repeating units in an acid-decomposable resin, More preferably, it is 3-15 mol%, More preferably, it is 5-10 mol%. .
Although the specific example of the repeating unit which has the said group is shown below, this invention is not limited to this.
In specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

(B) A repeating unit having a group that decomposes by the action of an acid to generate a polar group other than an alcoholic hydroxy group. It is preferable that the repeating unit (B) provided with is further included. In particular, the acid-decomposable resin preferably further includes a repeating unit having a group that decomposes by the action of an acid to generate a carboxy group. In this case, the focus margin (DOF) of the composition containing the acid-decomposable resin can be further improved.

  The repeating unit (B) preferably has a structure in which a polar group is protected by a group that decomposes and leaves by the action of an acid. Examples of the polar group include a phenolic hydroxy group, a carboxy group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, an (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) methylene group, etc. It is done. Preferred polar groups include a carboxy group and a sulfonic acid group.

A preferable group as the acid-decomposable group is a group in which the hydrogen atom of these polar groups is substituted with a group capable of leaving with an acid.
Examples of the group leaving with an acid include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), -C (R ₀₁ ) (R ₀₂ ). ) (OR ₃₉ ) and the like.
In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

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

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

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

In general formula (AI),
Xa ₁ represents a hydrogen atom, a methyl group which may have a substituent, or a group represented by —CH ₂ —R ₉ . R ₉ represents a hydroxy group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and an acyl group, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. . Xa ₁ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.
T represents a single bond or a divalent linking group.
Rx _{1 to} Rx ₃ each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic).
At least two of Rx _{1 to} Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a —COO—Rt— group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group or a — (CH ₂ ) ₃ — group.
The alkyl group of Rx _{1 to} Rx ₃ is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group.

Examples of the cycloalkyl group represented by Rx _{1 to} Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. Groups are preferred.
Examples of the cycloalkyl group formed by combining at least two of Rx _{1 to} Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, A polycyclic cycloalkyl group such as an adamantyl group is preferred. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.
An embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are combined to form the above-described cycloalkyl group is preferred.

  Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxy group, an alkoxy group (1 to 4 carbon atoms), and a carboxy group. , Alkoxycarbonyl groups (having 2 to 6 carbon atoms) and the like, and those having 8 or less carbon atoms are preferable.

The acid-decomposable resin preferably has a repeating unit represented by the general formula (I) and / or a repeating unit represented by the general formula (II) as the repeating unit represented by the general formula (AI). .

In formulas (I) and (II),
R ₁ and R ₃ each independently represents a hydrogen atom, an optionally substituted methyl group or a group represented by —CH ₂ —R ₉ . R ₉ represents a monovalent organic group.
R ₂ , R ₄ , R ₅ and R ₆ each independently represents an alkyl group or a cycloalkyl group.
R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom.

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

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

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

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

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

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

As a repeating unit represented by general formula (I), the repeating unit represented by the following general formula (1-a) is mentioned, for example.

In formula, R < ₁ > and R < ₂ > are synonymous with each in general formula (I).

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

In formula (II-1),
R _{3 to} R ₅ have the same meaning as in general formula (II).
R ₁₀ represents a substituent containing a polar group. When a plurality of R ₁₀ are present, they may be the same as or different from each other. Examples of the substituent containing a polar group include a linear or branched alkyl group and a cycloalkyl group having a hydroxy group, a cyano group, an amino group, an alkylamide group or a sulfonamide group, and preferably a hydroxy group It is an alkyl group having As the branched alkyl group, an isopropyl group is particularly preferable.

  p represents an integer of 0 to 15. p is preferably 0 to 2, more preferably 0 or 1.

  The acid-decomposable resin is a resin containing at least one of the repeating unit represented by the general formula (I) and the repeating unit represented by the general formula (II) as the repeating unit represented by the general formula (AI). More preferably. In another embodiment, a resin containing at least two kinds of repeating units represented by the general formula (I) as the repeating unit represented by the general formula (AI) is more preferable.

When the resin of this invention has a repeating unit (B), 3-50 mol% is preferable with respect to all the repeating units in resin, 5-40 mol% is more preferable, and 7-30 mol is the total content. % Is more preferable.
In this case, the molar ratio of the repeating unit (B) to the repeating unit (P) is preferably 5:95 to 70:30, more preferably 7:93 to 50:50, 10 : 90-30: 70 is particularly preferable.

Specific examples of preferred repeating units (B) are shown below, but the present invention is not limited thereto.
In specific examples, Rx and Xa ₁ represent a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms. Z represents a substituent containing a polar group, and when there are a plurality of them, each is independent. p represents 0 or a positive integer.

In the case where the acid-decomposable resin contains a plurality of repeating units (B), preferred combinations include the following. In the following formula, each R independently represents a hydrogen atom or a methyl group.

(C) Repeating unit having an alicyclic hydrocarbon structure not having a polar group and not exhibiting acid decomposability Acid-decomposable resin has an alicyclic hydrocarbon structure having no polar group and has acid decomposability. It may further contain a repeating unit (C) not shown. Examples of the repeating unit (C) include a repeating unit represented by the general formula (IV).

In general formula (IV), 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, or a —CH ₂ —O—Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group or an acyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

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

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

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

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

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

As for the content rate of a repeating unit (C), 0-40 mol% is preferable with respect to all the repeating units in an acid-decomposable resin, More preferably, it is 1-20 mol%.
Specific examples of the repeating unit (C) are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

(D) Other repeating units In addition to the above repeating structural units, the acid-decomposable resin is composed of dry etching resistance, standard developer suitability, substrate adhesion, pattern profile, and actinic ray sensitive or radiation sensitive resin composition. Various repeating structural units can be included for the purpose of adjusting resolution, heat resistance, sensitivity, and the like, which are general necessary characteristics.

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

Thereby, performance required for the resin used in the composition of the present invention, in particular,
(1) Solubility in coating solvent, (2) Film formability (glass transition point), (3) Developability in organic solvent, (4) Film slippage (hydrophobic and polar group selection), (5) Unexposed part Can be finely adjusted such as adhesion to the substrate and (6) dry etching resistance.

  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 addition, in the acid-decomposable resin, the content molar ratio of each repeating structural unit is the dry etching resistance of the actinic ray-sensitive or radiation-sensitive resin composition, standard developer suitability, substrate adhesion, pattern profile, and the above It is appropriately set to adjust the resolving power, heat resistance, sensitivity, etc., which are general required performances of the composition.

When the composition according to the present invention is used for ArF exposure, the acid-decomposable resin preferably has no aromatic group from the viewpoint of transparency to ArF light. In particular, the acid-decomposable resin preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
Moreover, it is preferable that an acid-decomposable resin does not contain a fluorine atom and a silicon atom from a compatible viewpoint with the compound (d) mentioned later and hydrophobic resin (g).

  The acid-decomposable resin 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.

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

  Examples of the repeating unit having a preferred acid-decomposable group based on hydroxystyrene include, for example, t-butoxycarbonyloxystyrene, 1-alkoxyethoxystyrene, a repeating unit of (meth) acrylic acid tertiary alkyl ester, and the like. More preferred are repeating units of 2-alkyl-2-adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate.

  The acid-decomposable resin 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 heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, amides such as dimethylformamide and dimethylacetamide. Examples of the solvent include solvents that dissolve the composition of the present invention such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone described below. More preferably, the polymerization is performed using the same solvent as the solvent used in the 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 carboxy 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 acid-decomposable resin 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 the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, developability is deteriorated, and viscosity is increased, resulting in deterioration of film forming property. Can be prevented.

  The dispersity (molecular weight distribution) is usually 1 to 3, preferably 1 to 2.6, more preferably 1 to 2, and particularly preferably 1.4 to 2.0. The smaller the molecular weight distribution, the better the resolution and pattern shape, the smoother the side walls of the pattern, and the better the roughness.

In the present invention, the mixing ratio of the acid-decomposable resin in the entire composition is preferably 30 to 99% by mass, more preferably 60 to 95% by mass in the total solid content.
In addition, the resins of the present invention may be used alone or in combination. In addition, in the range which does not impair the effect of this invention, you may use together other resin other than the acid-decomposable resin mentioned above.

Specific examples of the acid-decomposable resin are shown below. Table 1 below shows the weight average molecular weight (Mw), the degree of dispersion (Mw / Mn), and the composition ratio of each repeating unit (corresponding in order from the left).

(B) Acid generator The composition based on this invention contains the acid generator. As an acid generator, photo-initiator of photocation polymerization, photo-initiator of photo-radical polymerization, photo-decoloring agent of dyes, photo-discoloring agent, or irradiation with actinic ray or radiation used for micro-resist etc. Known compounds that generate acids and mixtures thereof can be appropriately selected and used.

  Examples of the acid generator include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

  Further, a group that generates an acid upon irradiation with these actinic rays or radiation, or a compound in which a compound is introduced into the main chain or side chain of the polymer, such as US Pat. No. 3,849,137, German Patent No. No. 3914407, JP-A 63-26653, JP-A 55-164824, JP-A 62-69263, JP-A 63-146038, JP-A 63-163452, The compounds described in JP-A-62-153853 and JP-A-63-146029 can be used.

Furthermore, compounds capable of generating an acid by light described in US Pat. No. 3,779,778, European Patent 126,712, etc. can also be used.
Preferred examples of the acid generator include compounds represented by the following general formula (ZI), (ZII) or (ZIII).

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 a non-nucleophilic anion.

Examples of the non-nucleophilic anion as Z ⁻ include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.

  A non-nucleophilic anion is an anion that has an extremely low ability to cause a nucleophilic reaction, and is an anion that can suppress degradation over time due to an intramolecular nucleophilic reaction. This improves the temporal stability of the resist.

  Examples of the sulfonate anion include an aliphatic sulfonate anion, an aromatic sulfonate anion, and a camphor sulfonate anion.

  Examples of the carboxylate anion include an aliphatic carboxylate anion, an aromatic carboxylate anion, and an aralkylcarboxylate anion.

  The aliphatic moiety in the aliphatic sulfonate anion may be an alkyl group or a cycloalkyl group, preferably an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms such as methyl. Group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group , Tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, bornyl group and the like.

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

The alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group, and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion include, for example, a nitro group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), carboxy group , Hydroxy group, amino group, cyano group, alkoxy group (preferably having 1 to 15 carbon atoms), cycloalkyl group (preferably having 3 to 15 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), alkoxycarbonyl group (Preferably 2 to 7 carbon atoms), acyl group (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), alkylthio group (preferably 1 to 15 carbon atoms), alkylsulfonyl A group (preferably having a carbon number of 1 to 15), an alkyliminosulfonyl group (preferably having a carbon number of 2 to 15), Reeloxysulfonyl group (preferably having 6 to 20 carbon atoms), alkylaryloxysulfonyl group (preferably having 7 to 20 carbon atoms), cycloalkylaryloxysulfonyl group (preferably having 10 to 20 carbon atoms), alkyloxyalkyloxy group (Preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like. About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) can further be mentioned as a substituent.

As the aromatic sulfonate anion, an aryl sulfonate anion corresponding to the sulfonate represented by the following formula (BI) is also preferable.

In formula (BI),
Ar represents an aromatic ring and may further have a substituent in addition to the A group.
p represents an integer of 0 or more.
A represents a group having a hydrocarbon group having 3 or more carbon atoms.
When p is 2 or more, the plurality of A groups may be the same or different.
General formula (BI) will be described in more detail.
As the aromatic ring represented by Ar, an aromatic ring having 6 to 30 carbon atoms is preferable.
Specifically, benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acetaphthalene ring, phenanthrene ring, anthracene ring, naphthacene ring, pentacene ring, chrysene ring, Triphenylene ring, indene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine Ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthri Down ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring, phenazine ring, and the like, a benzene ring, a naphthalene ring, an anthracene ring are preferred, a benzene ring is more preferable.

  Examples of the substituent that the aromatic ring may have other than the A group include a group having a hydrocarbon group having 1 or more carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), hydroxyl group, A cyano group, a nitro group, a carboxyl group, etc. can be mentioned. Examples of the group having a hydrocarbon group having 1 or more carbon atoms include an alkoxy group such as a methoxy group, an ethoxy group, and a tert-butoxy group, an aryloxy group such as a phenoxy group and a p-tolyloxy group, a methylthioxy group, Alkylthioxy groups such as ethylthioxy group, tert-butylthioxy group, arylthioxy groups such as phenylthioxy group, p-tolylthioxy group, alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, acetoxy group, methyl Group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, dodecyl group, linear alkyl group such as 2-ethylhexyl group and branched alkyl group, alkenyl group such as vinyl group, propenyl group, hexenyl group, acetylene group , Propynyl group, hexynyl group, etc. Rukiniru group, aryl groups such as phenyl and tolyl groups, a benzoyl group, an acetyl group, and the like acyl groups such as tolyl group. Moreover, when it has two or more substituents, at least two substituents may be bonded to each other to form a ring.

Examples of the hydrocarbon group in the group having a hydrocarbon group having 3 or more carbon atoms represented by A include an acyclic hydrocarbon group and a cyclic aliphatic group.
As the A group, the carbon atom adjacent to Ar is preferably a tertiary or quaternary carbon atom.
Examples of the acyclic hydrocarbon group as the A group include isopropyl group, t-butyl group, t-pentyl group, neopentyl group, s-butyl group, isobutyl group, isohexyl group, 3,3-dimethylpentyl group, 2- An ethylhexyl group etc. are mentioned. The upper limit of the number of carbon atoms of the acyclic hydrocarbon group is preferably 12 or less, more preferably 10 or less.

  Cycloaliphatic groups as the A group include cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, cycloheptyl groups, cyclooctyl groups and other cycloalkyl groups, adamantyl groups, norbornyl groups, bornyl groups, camphenyl groups, decahydronaphthyl groups. , Tricyclodecanyl group, tetracyclodecanyl group, camphoroyl group, dicyclohexyl group, pinenyl group and the like, which may have a substituent. The upper limit of the carbon number of the cycloaliphatic group is preferably 15 or less, more preferably 12 or less.

When the acyclic hydrocarbon group or the cyclic aliphatic group has a substituent, examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a methoxy group, and an ethoxy group. Group, alkoxy group such as tert-butoxy group, aryloxy group such as phenoxy group, p-tolyloxy group, alkylthioxy group such as methylthioxy group, ethylthioxy group, tert-butylthioxy group, phenylthioxy group, p-tolyloxy group Arylthiooxy group such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, etc., acetoxy group, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, dodecyl group, 2- Linear alkyl groups such as ethylhexyl group, branched alkyl groups, A cyclic alkyl group such as a rohexyl group, an alkenyl group such as a vinyl group, a propenyl group and a hexenyl group, an alkynyl group such as an acetylene group, a propynyl group and a hexynyl group, an aryl group such as a phenyl group and a tolyl group, a hydroxy group, a carboxy group, Examples include a sulfonic acid group, a carbonyl group, and a cyano group.
Specific examples of the cyclic aliphatic group or acyclic hydrocarbon group as A include the following.

Among the above, the following structures are more preferable from the viewpoint of suppressing acid diffusion.

  p represents an integer of 0 or more, and the upper limit is not particularly limited as long as it is a chemically possible number. From the viewpoint of suppressing acid diffusion, p is usually 0 to 5, preferably 1 to 4, more preferably 2 to 3, and most preferably 3.

From the viewpoint of suppressing acid diffusion, the A group preferably has at least one ortho position (o position) of the sulfonic acid group substituted, and has a structure in which two ortho positions (o position) are substituted. Is more preferable.
In one embodiment, the acid generator is a compound that generates an acid represented by the following general formula (BII).

In the formula, A is the same as A in the general formula (BI), and two A may be the same or different. R _{1 to} R ₃ each independently represents a hydrogen atom, a group having a hydrocarbon group having 1 or more carbon atoms, a halogen atom, a hydroxyl group, a cyano group, or a nitro group. Specific examples of the hydrocarbon group having 1 or more carbon atoms include the same groups as those exemplified above.

Moreover, the anion which produces the acid represented with the following general formula (IA) as a preferable sulfonate anion can also be mentioned.

In the formula, each Xf 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 (IA) is demonstrated in 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, a 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 is preferable.

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. Among these, —COO—, —OCO—, —CO—, —O—, and —SO ₂ — are preferable, and —COO—, —OCO—, and —SO ₂ — 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. It is preferable from the viewpoint of improving MEEF (mask error enhancement factor) because diffusibility in the film can be suppressed.

  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, a pyridine ring, and a piperidine ring. Of these, a furan ring, a thiophene ring, a pyridine ring, and a piperidine ring are preferable. Further, the heterocyclic structure may be a ring structure having a lactone structure.

  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 thereof include an aryl group (preferably having 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonic acid ester group.

  Examples of the aliphatic moiety in the aliphatic carboxylate anion include the same alkyl group and cycloalkyl group as in the aliphatic sulfonate anion.

  Examples of the aromatic group in the aromatic carboxylate anion include the same aryl group as in the aromatic sulfonate anion.

  The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms, such as benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylbutyl group, and the like.

  The alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion include, for example, the same halogen atom and alkyl as in the aromatic sulfonate anion Group, cycloalkyl group, alkoxy group, alkylthio group and the like.

  Examples of the sulfonylimide anion include saccharin anion.

  The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl. Group, sec-butyl group, pentyl group, neopentyl group and the like. Examples of substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like. Alkyl groups substituted with fluorine atoms are preferred.

  Examples of other non-nucleophilic anions include fluorinated phosphorus, fluorinated boron, and fluorinated antimony.

Examples of the organic group represented by R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in the general formula (ZI) include, for example, a compound (ZI-1), (ZI-2), (ZI-3) or (ZI-4) described later. The corresponding groups can be mentioned.

The acid generator may be a compound having a plurality of structures represented by the general formula (ZI). For example, the general formula at least one of R ₂₀₁ to R ₂₀₃ of a compound represented by (ZI), the structures attached to at least one of R ₂₀₁ to R ₂₀₃ of another compound represented by formula (ZI) It may be a compound.

  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 R ₂₀₁
Some of to R ₂₀₃ is an aryl group and the remainder may be 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 pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, and the like. 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 hydroxy group, or a phenylthio group may be used as a substituent. 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. These are 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 hydroxy 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 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, a halogen atom or a phenylthio group.
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
R _x and R _y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

Any two or more of R _{1c to} R _5c , R _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. Examples of the group formed by combining any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.

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

The alkyl group as R _{1c to} R _7c may be either linear or branched, for example, an alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 12 carbon atoms ( Examples thereof include a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, and a linear or branched pentyl group. Examples of the cycloalkyl group include cyclohexane having 3 to 8 carbon atoms. An alkyl group (for example, a cyclopentyl group, a cyclohexyl group) can be mentioned.

The alkoxy group as R _{1c to} R _{5c may} be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms. (For example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), C3-C8 cyclic alkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group) ).

Preferably, any of R _{1c to} R _5c is a linear or branched alkyl group, a cycloalkyl group, or a linear, branched or cyclic alkoxy group, and more preferably the sum of the carbon number of R _{1c to} R _5c. Is 2-15. Thereby, solvent solubility improves more and generation | occurrence | production of a particle is suppressed at the time of a preservation | save.

The aryl group as R _6c and R _7c preferably has 5 to 15 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

When R _6c and R _7c are combined to form a ring, the group formed by combining R _6c and R _7c is preferably an alkylene group having 2 to 10 carbon atoms, such as ethylene group, propylene Group, butylene group, pentylene group, hexylene group and the like. The ring formed by combining R _6c and R _7c may have a hetero atom such as an oxygen atom in the ring.

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

Examples of the 2-oxoalkyl group and 2-oxocycloalkyl group include a group having> C═O at the 2-position of the alkyl group or cycloalkyl group as R _{1c to} R _7c .
Examples of the alkoxy group in the alkoxycarbonylalkyl group include the same alkoxy groups as in R _{1c to} R _5c , and examples of the alkyl group include an alkyl group having 1 to 12 carbon atoms, preferably 1 to 1 carbon atom. 5 straight chain (for example, methyl group and ethyl group).

  The allyl group is not particularly limited, but is preferably an allyl group which is unsubstituted or substituted with a monocyclic or polycyclic cycloalkyl group.

  Although there is no restriction | limiting in particular as a vinyl group, It is preferable that it is a vinyl group substituted by the unsubstituted or monocyclic or polycyclic cycloalkyl group.

As the ring structure that R _x and R _y may be bonded to each other, divalent R _x and R _y (for example, a methylene group, an ethylene group, a propylene group, and the like) are represented by the general formula (ZI-3). A 5-membered or 6-membered ring formed with a sulfur atom, particularly preferably a 5-membered ring (that is, a tetrahydrothiophene ring).

R _x and R _y are preferably an alkyl group or cycloalkyl group having 4 or more carbon atoms, more preferably 6 or more, and still more preferably 8 or more alkyl groups or cycloalkyl groups.

Specific examples of the cation moiety of compound (ZI-3) are shown below.

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 hydroxy group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton. These groups may have a substituent.
When there are a plurality of R _{14 s,} each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a monocyclic or polycyclic cycloalkyl skeleton. Represents a group having These groups may have a substituent.
R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R ₁₅ may be bonded to each other to form a ring. These groups may have a substituent.
l represents an integer of 0-2.
r represents an integer of 0 to 8.
Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same non-nucleophilic anion as Z ^{− in} formula (ZI).

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 represented by R ₁₃ , R ₁₄ and R ₁₅ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecanyl, cyclopentenyl, cyclohexenyl, cyclooctadienyl, norbornyl, tricyclo Examples include decanyl, tetracyclodecanyl, adamantyl and the like, and cyclopropyl, cyclopentyl, cyclohexyl and cyclooctyl are particularly preferable.

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 and R ₁₄ is linear or branched and preferably has 2 to 11 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, i- Propoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group, n-pentyloxycarbonyl group, neopentyloxycarbonyl group, n-hexyloxycarbonyl group, Examples include n-heptyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxycarbonyl group and the like. Of these alkoxycarbonyl groups, a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, and the like are preferable.

Examples of the group having a monocyclic or polycyclic cycloalkyl skeleton of R ₁₃ and R ₁₄ include a monocyclic or polycyclic cycloalkyloxy group and an alkoxy group having a monocyclic or polycyclic cycloalkyl group. Can be mentioned. These groups may further have a substituent.

The monocyclic or polycyclic cycloalkyloxy group for R ₁₃ and R ₁₄ preferably has a total carbon number of 7 or more, more preferably a total carbon number of 7 or more and 15 or less, It is preferable to have a cycloalkyl skeleton. The monocyclic cycloalkyloxy group having 7 or more carbon atoms is cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloptyloxy group, cyclooctyloxy group, cyclododecanyloxy group, etc. Optionally substituted with methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl, 2-ethylhexyl, isopropyl, sec-butyl, t -Alkyl group such as butyl group and iso-amyl group, hydroxy group, halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, amide group, sulfonamido group, methoxy group, ethoxy group, hydroxyethoxy group , Alkoxy groups such as propoxy group, hydroxypropoxy group, butoxy group, meth Monocyclic cycloalkyloxy having substituents such as alkoxycarbonyl groups such as xoxycarbonyl group, ethoxycarbonyl group, acyl groups such as formyl group, acetyl group and benzoyl group, acyloxy groups such as acetoxy group and butyryloxy group, and carboxy group And a group having a total carbon number of 7 or more in combination with an arbitrary substituent on the cycloalkyl group.

  Examples of the polycyclic cycloalkyloxy group having a total carbon number of 7 or more include a norbornyloxy group, a tricyclodecanyloxy group, a tetracyclodecanyloxy group, an adamantantyloxy group, and the like.

The alkoxy group having a monocyclic or polycyclic cycloalkyl skeleton of R ₁₃ and R ₁₄ preferably has a total carbon number of 7 or more, more preferably a total carbon number of 7 or more and 15 or less, An alkoxy group having a monocyclic cycloalkyl skeleton is preferable. The alkoxy group having a total of 7 or more carbon atoms and having a monocyclic cycloalkyl skeleton is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptoxy, octyloxy, dodecyloxy, 2-ethylhexyloxy, isopropoxy, A monocyclic cycloalkyl group that may have the above-mentioned substituents is substituted on an alkoxy group such as sec-butoxy, t-butoxy, iso-amyloxy, etc., and the total carbon number including the substituents is 7 or more Represents things. Examples include a cyclohexylmethoxy group, a cyclopentylethoxy group, a cyclohexylethoxy group, and the like, and a cyclohexylmethoxy group is preferable.

  Examples of the alkoxy group having a polycyclic cycloalkyl skeleton having 7 or more carbon atoms include norbornyl methoxy group, norbornyl ethoxy group, tricyclodecanyl methoxy group, tricyclodecanyl ethoxy group, tetracyclo A decanyl methoxy group, a tetracyclodecanyl ethoxy group, an adamantane methoxy group, an adamantane ethoxy group, etc. are mentioned, and a norbornyl methoxy group, a norbornyl ethoxy group, etc. are preferable.

The alkyl group of the alkyl group of R ^14, include the same specific examples as the alkyl group as R ₁₃ to R ₁₅ described above.

The alkylsulfonyl group and cycloalkylsulfonyl group 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 and cycloalkylsulfonyl 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.

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

  Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, cyclopentyloxy group, Examples thereof include a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms such as 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 methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t Examples thereof include linear, branched or cyclic alkoxycarbonyl groups having 2 to 21 carbon atoms such as butoxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl and the like.

  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 carbonyloxy group and cyclohexyloxycarbonyloxy.

The ring structure which two R ₁₅ may combine with each other is a 5-membered or 6-membered ring formed by two divalent R ₁₅ together with the sulfur atom in the general formula (ZI-4). Particularly preferred is a 5-membered ring (that is, a tetrahydrothiophene ring), which may be condensed with an aryl group or a cycloalkyl group. The divalent R ₁₅ may have a substituent. Examples of the substituent include a hydroxyl group, a carboxy group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, and the like. Groups and the like. R ₁₅ in the general formula (ZI-4) is preferably a methyl group, an ethyl group, a naphthyl group, a divalent group in which two R ^15s are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom.

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

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

Specific examples of the cation moiety of compound (ZI-4) are given below.

Next, the general formulas (ZII) and (ZIII) will be described.
In formula (ZII), (ZIII), R 204 ~R 207 each independently represents an aryl group, an alkyl group or a cycloalkyl group.

Phenyl group and a naphthyl group are preferred as the aryl group of R ₂₀₄ to R _207, more preferably a phenyl group. Aryl group R ₂₀₄ to R ₂₀₇ represents an oxygen atom, a nitrogen atom, may be an aryl group having a heterocyclic structure having a sulfur atom and the like. Examples of the aryl group having a heterocyclic structure include a pyrrole residue (a group formed by losing one hydrogen atom from pyrrole) and a furan residue (a group formed by losing one hydrogen atom from furan). Groups), thiophene residues (groups formed by the loss of one hydrogen atom from thiophene), indole residues (groups formed by the loss of one hydrogen atom from indole), benzofuran residues ( A group formed by losing one hydrogen atom from benzofuran), a benzothiophene residue (a group formed by losing one hydrogen atom from benzothiophene), and the like.

The alkyl group and cycloalkyl group in R _{204 to} R ₂₀₇ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, 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).

Aryl group, alkyl group of R ₂₀₄ to R _207, cycloalkyl groups may have a substituent. Aryl group, alkyl group of R ₂₀₄ to R _207, the cycloalkyl group substituent which may be possessed by, for example, 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, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxy group, and a phenylthio group.

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

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

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents an aryl group.

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

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

  Among the acid generators, compounds represented by the general formulas (ZI) to (ZIII) are more preferable.

  Further, the acid generator is preferably a compound that generates an acid having one sulfonic acid group or imide group, more preferably a compound that generates monovalent perfluoroalkanesulfonic acid, or a monovalent fluorine atom or fluorine atom. A compound that generates an aromatic sulfonic acid substituted with a group that contains a monovalent fluorine atom or an imido acid that is substituted with a group containing a fluorine atom, and even more preferably, a fluorinated compound It is a sulfonium salt of a substituted alkanesulfonic acid, a fluorine-substituted benzenesulfonic acid, a fluorine-substituted imide acid or a fluorine-substituted methide acid. The acid generator that can be used is particularly preferably a fluorinated substituted alkane sulfonic acid, a fluorinated substituted benzene sulfonic acid or a fluorinated substituted imido acid whose pKa of the generated acid is pKa = -1 or less, and the sensitivity is improved. .

  As the acid generator, a carboxylic acid onium salt may be used. When carboxylic acid onium salt is contained, transparency to light having a wavelength of 220 nm or less is ensured, sensitivity and resolution are further improved, and density dependency and exposure margin are further improved.

  As the carboxylic acid onium salt, an iodonium salt or a sulfonium salt is preferable. As the anion, for example, a linear or branched alkyl having 1 to 30 carbon atoms or a monocyclic or polycyclic cycloalkylcarboxylic acid anion is preferably used. In particular, a carboxylate anion in which some or all of the hydrogen atoms of these alkyl groups or cycloalkyl groups are substituted with fluorine atoms (hereinafter also referred to as fluorine-substituted carboxylate anions) is preferable. Note that an oxygen atom may be contained in the alkyl or cycloalkyl chain.

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

  When the composition according to the present invention contains a carboxylic acid onium salt, the content thereof is generally from 0.1 to 20% by mass, preferably from 0.8 to 20% by mass, based on the total solid content of the composition. It is 5-10 mass%, More preferably, it is 1-7 mass%.

  When the composition according to the present invention contains an acid generator, the acid that can be generated by the acid generator may or may not have a fluorine atom. For example, when the acid generator includes an anion, the anion may have a fluorine atom or may not have a fluorine atom.

  As described above, the composition according to the present invention contains a resin containing a repeating unit having a group that decomposes by the action of an acid to generate an alcoholic hydroxy group. Such a resin is a repeating unit having an acid-decomposable group, as compared with a resin containing only a repeating unit having a group that decomposes by the action of an acid to generate a carboxy group. The activation energy of is smaller. Therefore, even when an acid generator that generates an acid with relatively low acid strength, for example, an acid having no fluorine atom, is used, the effects of the present invention can be sufficiently obtained.

Among acid generators, particularly preferred examples are given below.

An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the acid generator is preferably 0.1 to 20% by mass, more preferably 0.5 to 17.5% by mass, still more preferably 1 to 15% by mass, based on the total solid content of the composition. is there.

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

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

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

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

  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. And 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, and 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 3-penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3 -Methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone and 3- And methylcycloheptanone.

  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.

  Examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.

  As the solvent, it is preferable to use a solvent having a boiling point of 130 ° C. or higher under normal temperature and pressure. Specifically, for example, cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), ethyl 3-ethoxypropionate, ethyl pyruvate, acetic acid-2 -Ethoxyethyl, 2- (2-ethoxyethoxy) ethyl acetate and propylene carbonate.

  These solvents may be used alone or in combination of two or more. In the latter case, it is preferable to use a mixed solvent of a solvent containing a hydroxy group and a solvent not containing a hydroxy group.

  Examples of the solvent containing a hydroxy group include alkylene glycol monoalkyl ether and alkyl lactate. Of these, propylene glycol monomethyl ether or ethyl lactate is more preferable.

  As the solvent not containing a hydroxy group, for example, alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, a monoketone compound which may contain a ring, cyclic lactone and alkyl acetate are preferable. Of these, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone or butyl acetate are more preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxypropionate or 2-heptanone is particularly preferred. .

  When a mixed solvent of a solvent containing a hydroxy group and a solvent not containing a hydroxy group is used, the mass ratio thereof is preferably 1/99 to 99/1, more preferably 10/90 to 90/10. And more preferably 20/80 to 60/40.

  When a mixed solvent containing 50% by mass or more of a solvent not containing a hydroxy group is used, particularly excellent coating uniformity can be achieved. The solvent is particularly preferably a mixed solvent of PGMEA and one or more other solvents.

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

(D) A compound containing at least one of a fluorine atom and a silicon atom and having basicity or increasing basicity by the action of an acid. Generally, a composition film formed using a composition containing an acid generator When the exposure is performed, the surface layer portion of the film is exposed to a higher degree than the inside thereof, the concentration of the generated acid is increased, and the reaction is more likely to proceed. Then, when development (particularly negative development) is performed on such an exposed film, there is a tendency that a cross section of the obtained pattern becomes a T-top shape or a bridge defect occurs. .

  However, the composition according to the present invention contains a compound containing at least one of a fluorine atom and a silicon atom and having basicity or increasing basicity by the action of an acid (hereinafter also referred to as compound (d)). ing.

  The compound (d) has at least one of a fluorine atom and a silicon atom, so that the surface free energy is lower than that in the case where it does not have these atoms, and it is unevenly distributed in the surface layer portion of the composition film. Cheap.

  Therefore, when a composition film containing such a compound (d) is exposed, a compound having basicity or a compound having increased basicity by the action of an acid is present in a high concentration in the surface layer portion of the film. Therefore, excess acid generated in the surface layer of the exposed portion can be captured. That is, the acid concentration distribution in the thickness direction of the exposed portion of the composition film can be made uniform. Thereby, the reaction of the composition film using the acid as a catalyst, for example, the insolubilization or the insolubilization reaction with respect to the developer containing the organic solvent can be performed more uniformly in the thickness direction of the film. Therefore, the problems such as the T-top shape and the bridge defect as described above can be suppressed.

  In addition, the present inventors use such a compound (d) in combination with the acid-decomposable resin containing the above-mentioned repeating unit (P), thereby providing roughness characteristics, focus margin, bridge defect performance, and It has been found that the post-exposure heating (PEB) temperature dependence of sensitivity can be further improved. The reason for this is not always clear, but the present inventors speculate as follows. That is, the acid-decomposable resin containing the repeating unit (P) described above has a large change in polarity due to acid decomposition, and is insoluble in a developer containing an organic solvent, and therefore requires a relatively small amount of deprotection. In such a system, the distribution of the portion of the composition film that is insoluble in the developer tends to be non-uniform. However, when the compound (d) is applied, the amount of base in the membrane can be reduced as compared with the surface of the membrane, so that the deprotection of the resin inside the latent pattern is promoted and the deprotection reaction can proceed uniformly. Therefore, the post-exposure heating (PEB) temperature dependence of roughness characteristics, focus margin, bridge defect performance, and sensitivity can be further improved.

  Compound (d) is composed of “compound (d-1) containing at least one of fluorine atom and silicon atom and having basicity” and “compound containing at least one of fluorine atom and silicon atom and having basicity by the action of an acid. When the compound (d-2) is used, the more the basic substance is generated in the region where the acid concentration generated in the exposed area is higher. Therefore, the acid-base neutralization reaction is further promoted. Therefore, when the compound (d-2) is used, the acid concentration distribution in the thickness direction of the exposed portion of the composition film can be made more uniform than when the compound (d-1) is used. In this respect, the compound (d) is more preferably the compound (d-2).

The compound (d) is preferably a nitrogen-containing compound.
Here, when the compound (d) is a basic compound containing at least one of a fluorine atom and a silicon atom, in order for the compound (d) to have sufficient basicity, an electron with respect to the nitrogen atom It is preferable that an attractive functional group (a carbonyl group, a sulfonyl group, a cyano group, a halogen atom (especially a fluorine atom), etc.) is not directly connected, and all the atoms adjacent to the nitrogen atom are hydrogen atoms or carbon atoms. Is more preferable.

  In addition, when the compound (d) is a compound that contains at least one of a fluorine atom and a silicon atom and whose basicity is increased by the action of an acid, the compound that has increased basicity by the action of an acid has sufficient basicity. Therefore, electron-withdrawing functional groups (carbonyl group, sulfonyl group, cyano group, halogen atom (especially fluorine atom), etc.) are not directly connected to the nitrogen atom of the compound whose basicity has been increased by the action of acid. It is preferable that all the atoms adjacent to the nitrogen atom are hydrogen atoms or carbon atoms.

  In addition, in order for compound (d) to express the said effect | action reliably, it is preferable not to be accompanied by the unintended change of a chemical structure by irradiation of actinic light or a radiation. In other words, the compound (d) preferably has no photosensitivity (non-photosensitivity).

  Hereinafter, the compound (d) is divided into “compound (d-1) having at least one of fluorine atom and silicon atom and having basicity” and “compound containing at least one of fluorine atom and silicon atom, and a base by the action of an acid. This will be described separately with respect to the compound (d-2) whose property is increased.

[1] Compound (d-1) containing at least one of fluorine atom and silicon atom and having basicity
Compound (d-1) is not particularly limited as long as it contains at least one of a fluorine atom and a silicon atom and has basicity. For example, it has at least one of a fluorine atom and a silicon atom, and the following general formula The basic compound which has either of the structure shown by Formula (A)-(E) can be mentioned.

In general formula (A), R ²⁰¹ and R ²⁰² each independently represent a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), an aryl group (preferably Represents a C6-C20) or heteroaryl group.
In general formula (E), R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ each independently represents an alkyl group or a cycloalkyl group.

In the structure represented by the general formula (A), R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring.

  In the structures represented by the general formulas (B) to (D), two or more of a bond from a carbon atom and a bond from a nitrogen atom may be bonded to each other to form a ring.

In the structure represented by the general formula (E), two or more of R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , a bond from a carbon atom, and a bond from a nitrogen atom are bonded to each other, A ring may be formed.

In the general formula (A), the alkyl group of R ²⁰¹ and R ²⁰² is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, n -Butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n -Tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, i-propyl group, i-butyl group, sec-butyl group, t -A butyl group, t-dodecyl group, etc. can be mentioned.

The cycloalkyl group represented by R ²⁰¹ and R ²⁰² is preferably a cycloalkyl group having 3 to 20 carbon atoms, and examples thereof include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

Among the alkyl groups and cycloalkyl groups represented by R ²⁰¹ and R ^202, a linear alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 4 to 8 carbon atoms are preferable.

The aryl group of R ²⁰¹ and R ²⁰² is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group, a toluyl group, a benzyl group, a methylbenzyl group, a xylyl group, a mesityl group, a naphthyl group, and an anthryl group. It is done.

The heteroaryl group of R ²⁰¹ and R ²⁰² is a group containing one or more heteroatoms such as a sulfur atom, an oxygen atom, and a nitrogen atom in the aryl group as described above. For example, a pyridyl group, an imidazolyl group, a morpholinyl group , Piperidinyl group, pyrrolidinyl group and the like.

The alkyl group, cycloalkyl group, aryl group, and heteroaryl group of R ²⁰¹ and R ²⁰² may further have a substituent. Examples of such a substituent include a halogen atom, a hydroxyl group, an amino group, and a carboxyl group. Cyano group, nitro group, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, acyl group, arylcarbonyl group, alkoxyalkyl group, aryloxyalkyl group, alkylcarbonyloxy group, arylcarbonyloxy group, Examples thereof include an alkoxycarbonyl group, an aryloxycarbonyl group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group and the like.

Examples of the alkyl group as a substituent that R ²⁰¹ and R ²⁰² may further have include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a 2-methylpropyl group. And a linear or branched alkyl group having 1 to 12 carbon atoms such as 1-methylpropyl group and t-butyl group.

Examples of the cycloalkyl group as a substituent that R ²⁰¹ and R ²⁰² may further include a cycloalkyl group having 3 to 10 carbon atoms such as a cyclopentyl group and a cyclohexyl group.

Examples of the aryl group as a substituent that R ²⁰¹ and R ²⁰² may further include an aryl group having 6 to 15 carbon atoms such as a phenyl group and a naphthyl group.

Examples of the alkoxy group as a substituent that R ²⁰¹ and R ²⁰² may further have include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, and a 2-methylpropoxy group. , 1-methylpropoxy group, t-butoxy group, cyclopentyloxy group, cyclohexyloxy group and the like, such as a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms.

Examples of the aryloxy group as a substituent that R ²⁰¹ and R ²⁰² may further have include an aryloxy group having 6 to 10 carbon atoms such as a phenyloxy group and a naphthyloxy group. .

Examples of the acyl group as a substituent that R ²⁰¹ and R ²⁰² may further have include an acetyl group, a propionyl group, an n-butanoyl group, an i-butanoyl group, an n-heptanoyl group, and 2-methylbutanoyl. And a linear or branched acyl group having 2 to 12 carbon atoms such as a group, 1-methylbutanoyl group, t-heptanoyl group, and the like.

Examples of the arylcarbonyl group as a substituent that R ²⁰¹ and R ²⁰² may further have include an arylcarbonyl group having 6 to 10 carbon atoms such as a phenylcarbonyl group and a naphthylcarbonyl group. .

Examples of the alkoxyalkyl group as a substituent that R ²⁰¹ and R ²⁰² may further have include a methoxymethyl group, an ethoxymethyl group, a 1-methoxyethyl group, a 2-methoxyethyl group, and a 1-ethoxyethyl group. And a straight-chain, branched or cyclic alkoxyalkyl group having 2 to 21 carbon atoms such as 2-ethoxyethyl group.

Examples of the aryloxyalkyl group as a substituent that R ²⁰¹ and R ²⁰² may further have include a carbon number of 7 such as a phenyloxymethyl group, a phenyloxyethyl group, a naphthyloxymethyl group, a naphthyloxyethyl group, and the like. -12 aryloxyalkyl groups and the like can be mentioned.

Examples of the alkylcarbonyloxy group as a substituent that R ²⁰¹ and R ²⁰² may further have include a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an i-propylcarbonyloxy group, C2-C21 straight chain such as n-butylcarbonyloxy group, 2-methylpropylcarbonyloxy group, 1-methylpropylcarbonyloxy group, t-butylcarbonyloxy group, cyclopentylcarbonyloxy group, cyclohexylcarbonyloxy group , Branched, or cyclic alkylcarbonyloxy groups.

Examples of the arylcarbonyloxy group as a substituent that R ²⁰¹ and R ²⁰² may further have include an arylcarbonyloxy group having 7 to 11 carbon atoms such as a phenylcarbonyloxy group and a naphthylcarbonyloxy group. Can be mentioned.

Examples of the alkoxycarbonyl group as a substituent that R ²⁰¹ and R ²⁰² may further have include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, and an n-butoxycarbonyl group. A linear, branched or cyclic alkoxycarbonyl group having 2 to 21 carbon atoms such as 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl, etc. Etc.

Examples of the aryloxycarbonyl group as a substituent that R ²⁰¹ and R ²⁰² may further have include an aryloxycarbonyl group having 7 to 11 carbon atoms such as a phenyloxycarbonyl group and a naphthyloxycarbonyl group. Can be mentioned.

Examples of the alkoxycarbonyloxy group as a substituent that R ²⁰¹ and R ²⁰² may further have include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, an n-propoxycarbonyloxy group, an i-propoxycarbonyloxy group, List linear, branched or cyclic alkoxycarbonyloxy groups having 2 to 21 carbon atoms such as n-butoxycarbonyloxy group, t-butoxycarbonyloxy group, cyclopentyloxycarbonyloxy group, cyclohexyloxycarbonyloxy, etc. Can do.

Examples of the aryloxycarbonyloxy group as a substituent that R ²⁰¹ and R ²⁰² may further have include aryloxycarbonyl having 7 to 11 carbon atoms such as a phenyloxycarbonyloxy group and a naphthyloxycarbonyloxy group. An oxy group etc. can be mentioned.

As the compound (d-1) having the structure represented by the general formula (A),
(A1) A structure represented by the general formula (A) (wherein R ²⁰¹ and R ²⁰² do not include any of a fluorine atom and a silicon atom) and “fluorine positioned outside the structure represented by the general formula (A)” A compound having a group having at least one of an atom and a silicon atom;
(A2) The structure represented by the general formula (A) (provided that at least one of R ²⁰¹ and R ²⁰² is 1 in the alkyl group, cycloalkyl group, aryl group or heteroaryl group which may have a substituent) A compound having two or more hydrogen atoms replaced with a fluorine atom or a group having a silicon atom; and (A3) a structure represented by the general formula (A) (where R ²⁰¹ and R ^{201 At} least one of ²⁰² is substituted with one or more hydrogen atoms in the optionally substituted alkyl group, cycloalkyl group, aryl group or heteroaryl group with a group having a fluorine atom or a silicon atom. And a “group having at least one of a fluorine atom and a silicon atom” located outside the structure represented by the general formula (A) ;
Can be mentioned.

In the above (A1) and (A3), as the “group having at least one of a fluorine atom and a silicon atom” located outside the structure represented by the general formula (A), R ²⁰¹ and R ²⁰² further have Preferred examples of the above-described specific examples (excluding halogen atoms and hydroxyl groups) as preferred substituents include groups in which one or more hydrogen atoms are replaced with a group having a fluorine atom or a silicon atom. be able to.

Here, the group having a silicon atom is not particularly limited as long as it is a group containing at least one silicon atom, and examples thereof include a silyl group, a silyloxy group, and a group having a siloxane bond. Further, the group having a silicon atom is represented by an alkylsilyl structure or a cyclic siloxane structure (for example, general formulas (CS-1) to (CS-3) described later) that the resin (G) described later may have. Group). These groups may further have a substituent, and specific examples of such a substituent are the same as the specific examples of the substituent which R ²⁰¹ and R ²⁰² may further have.

  Specific examples of the group having a silicon atom include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, and a triisopropylsilyl group.

The compound (d-1) having a structure represented by the general formulas (B) to (D) includes a structure represented by the general formulas (B) to (D) and a group having at least one of a fluorine atom and a silicon atom. (For example, in the above specific examples (excluding a halogen atom and a hydroxyl group) listed as substituents that R ²⁰¹ and R ²⁰² may further have, one or more hydrogen atoms are fluorine atoms or silicon And a compound having a group substituted by a group having an atom).

  Here, specific examples of the group having a silicon atom are the same as those described above.

In General Formula (E), specific examples of the alkyl group and cycloalkyl group of R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ are the same as the specific examples of the alkyl group and cycloalkyl group of R ²⁰¹ and R ²⁰² , respectively. is there.

The alkyl group and cycloalkyl group of R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may further have a substituent, and specific examples of such a substituent are further included in R ²⁰¹ and R ^202. The same as the above specific examples of the substituents that may be present.

As the compound (d-1) having the structure represented by the general formula (E),
(E1) A structure represented by the general formula (E) (provided that R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ do not contain any of a fluorine atom and a silicon atom) and a general formula (E) A compound having “a group having at least one of a fluorine atom and a silicon atom” located outside the structure;
(E2) A structure represented by the general formula (E) (provided that at least one of R ²⁰³ , R ²⁰⁴ , R ^205, and R ²⁰⁶ is an alkyl group or cycloalkyl group that may have a substituent) A compound having the above-mentioned hydrogen atom replaced with a fluorine atom or a group having a silicon atom);
(E3) A structure represented by the general formula (E) (provided that at least one of R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ is one in an alkyl group or a cycloalkyl group which may have a substituent) The above hydrogen atom is a group formed by replacing a fluorine atom or a group having a silicon atom) and “at least one of a fluorine atom and a silicon atom located outside the structure represented by the general formula (E)” A compound having a “having group”;
Can be mentioned.

In the above (E1) and (E3), as the “group having at least one of a fluorine atom and a silicon atom” located outside the structure represented by the general formula (E), R ²⁰¹ and R ²⁰² further have Preferred examples of the above-described specific examples (excluding halogen atoms and hydroxyl groups) as preferred substituents include groups in which one or more hydrogen atoms are replaced with a group having a fluorine atom or a silicon atom. be able to.

  Here, specific examples of the group having a silicon atom are the same as those described above.

  In the structures represented by the general formulas (A) to (E), a bond from a carbon atom and / or a nitrogen atom is connected to another atom constituting the compound (d-1).

Further, as described above, in the structure represented by the general formula (A), R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring, and are represented by the general formulas (B) to (D). In the structure represented by formula (E), two or more of a bond from a carbon atom and a bond from a nitrogen atom may be bonded to each other to form a ring. , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , two or more of a bond from a carbon atom and a bond from a nitrogen atom may be bonded to each other to form a ring.

Examples of the ring include aromatic or non-aromatic nitrogen-containing heterocycles. As such a nitrogen-containing heterocyclic ring, a 3-10 membered ring can be mentioned, It is preferable that it is a 4-8 membered ring, and it is more preferable that it is a 5 or 6 membered ring. Such a ring may further have a substituent, and specific examples thereof are the same as the specific examples described above as substituents which R ²⁰¹ and R ²⁰² may further have.

In other words, as the compound (d-1), a compound having a nitrogen-containing heterocyclic ring and having this heterocyclic ring substituted with a fluorine atom or a group containing a fluorine atom or a silicon atom is also preferable. be able to. As the group containing a fluorine atom or a silicon atom, one or more hydrogen atoms in the above specific examples (excluding a halogen atom and a hydroxyl group) listed as substituents that R ²⁰¹ and R ²⁰² may further have Can be substituted with a fluorine atom or a group having a silicon atom.

  Preferable examples of the nitrogen-containing heterocycle include a pyrrole ring, a pyridine ring, and a pyrimidine ring.

When the compound (d-1) is a low-molecular compound (described in detail later), in the structures represented by the general formulas (A) to (E), the bond from the carbon atom and / or the nitrogen atom is Each of them is preferably bonded to a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group, and specific examples of these groups are the same as those described for R ²⁰¹ and R ²⁰² .

[2] Compound (d-2) containing at least one of fluorine atom and silicon atom and having increased basicity by the action of an acid
The compound (d-2) is not particularly limited as long as it contains at least one of a fluorine atom and a silicon atom and the basicity is increased by the action of an acid. For example, at least one of a fluorine atom and a silicon atom, and protection And compounds having a carbamate group having a group.

Such a protecting group constituting the carbamate group is preferably a group represented by the following general formula (P) (the group represented by the general formula (P) is a bond represented by the symbol *). It is bonded to the nitrogen atom at the site).

In general formula (P):
Rb ₁ , Rb ₂ and Rb ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Two of Rb _{1 to} Rb ₃ may be bonded to each other to form a ring. However, all of Rb _{1 to} Rb ₃ do not become hydrogen atoms at the same time.

Specific examples of the alkyl group, cycloalkyl group and aryl group of Rb ₁ , Rb ₂ and Rb ₃ are the alkyl group, cycloalkyl group and aryl group of R ²⁰¹ and R ^{202 in} the group represented by the general formula (A). This is the same as the above-described specific example.

Specific examples of aralkyl groups of Rb ₁ , Rb ₂ and Rb ₃ are preferably aralkyl groups having 6 to 12 carbon atoms, such as benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylbutyl group, etc. Can do.

Rb ₁ , Rb ₂ and Rb ₃ are preferably a linear or branched alkyl group, cycloalkyl group or aryl group. More preferably, it is a linear or branched alkyl group or cycloalkyl group.

The ring formed by combining two members out of Rb _{1 to} Rb ₃ is preferably a cycloalkyl group (monocyclic or polycyclic), and more specifically, a monocyclic cyclohexane such as a cyclopentyl group or a cyclohexyl group. A polycyclic cycloalkyl group such as an alkyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, adamantyl group and the like is preferable. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.

Rb ₁ , Rb ₂ and Rb ₃ may further have a substituent. Examples of such a substituent include a halogen atom (such as a fluorine atom), a hydroxyl group, a nitro group, a cyano group, a carboxy group, and a carbonyl group. Group, cycloalkyl group (preferably 3 to 10 carbon atoms), aryl group (preferably 6 to 14 carbon atoms), alkoxy group (preferably 1 to 10 carbon atoms), acyl group (preferably 2 to 20 carbon atoms) , An acyloxy group (preferably 2 to 10 carbon atoms), an alkoxycarbonyl group (preferably 2 to 20 carbon atoms), an aminoacyl group (preferably 2 to 10 carbon atoms), a group having a silicon atom (specific examples are compounds ( the same as described in d-1)). As for the cyclic structure in the aryl group, cycloalkyl group and the like, examples of the substituent further include an alkyl group (preferably having 1 to 10 carbon atoms). As for the aminoacyl group, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 10).

When _{two of} Rb ₁ , Rb ₂ and Rb ₃ are both hydrogen atoms, the remaining one is preferably an aryl group, and examples of the aryl group include a phenyl group and a naphthyl group. .

  The compound (d-2) can also be constituted by replacing at least one group connected to the nitrogen atom of the compound (d-1) with a group represented by the above general formula (P).

Although it does not specifically limit as a compound (d-2), As a particularly preferable form, the compound represented by the following general formula (1N) which has group represented by the said general formula (P) is mentioned. The compound represented by the following general formula (1N) has at least one of a fluorine atom and a silicon atom in a portion other than the group represented by the general formula (P) (protecting group constituting the carbamate group). Therefore, the compound (compound with increased basicity) obtained by the action of an acid on the compound represented by the general formula (1N) has at least one of a fluorine atom and a silicon atom. Thereby, also in the post-exposure heating (PEB) step, which will be described later, the compound having increased basicity exists in a desired position without diffusing in the internal direction of the composition film. Capture of excess acid generated in step 1) can be carried out more reliably, and the acid concentration distribution in the thickness direction of the exposed portion of the composition film can be made more uniform.

In general formula (1N),
Ra, Rb ₁ , Rb ₂ and Rb ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. At least two of Rb ₁ , Rb ₂ and Rb ₃ may be bonded to each other to form a ring. However, the case where all of Rb ₁ , Rb ₂ and Rb ₃ are simultaneously hydrogen atoms is excluded.

  Rc represents a single bond or a divalent linking group.

  Rf represents an organic group.

  x represents 0 or 1, y represents 1 or 2, z represents 1 or 2, and x + y + z = 3.

  When x = z = 1, Ra and Rc may be bonded to each other to form a nitrogen-containing heterocycle.

  When z = 1, Rf contains a fluorine atom or a silicon atom.

  When z = 2, at least one of the two Rf contains a fluorine atom or a silicon atom, and the two Rc and the two Rf may be the same or different from each other. Two Rc's may be bonded to each other to form a ring.

_Ra, alkyl groups as Rb 1, Rb ₂ and Rb _3, cycloalkyl group, specific examples of the aryl group or aralkyl group, the alkyl group of _Rb 1, Rb ₂ and Rb ₃ of the general formula (P), cycloalkyl This is the same as the specific examples of the group, aryl group or aralkyl group.

  Rc is preferably a divalent linking group having 2 to 12 carbon atoms (more preferably 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms), such as an alkylene group, a phenylene group, an ether group, Examples include an ester group, an amide group, and a group formed by combining two or more of these.

  The organic group as Rf is preferably an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group.

Specific examples of the alkyl group, cycloalkyl group, aryl group or heteroaryl group as Rf are the same as the specific examples of the cycloalkyl group, aryl group or heteroaryl group as R ²⁰¹ and R ^{202 in} the general formula (A). It is.

Ra, Rb ₁ , Rb ₂ , Rb ₃ , Rc and Rf may each further have a substituent, and specific examples of such a substituent include Rb ₁ , Rb of the above general formula (P). _This is the same as the specific examples of the substituent that ₂ and Rb ₃ may further have.

  When the organic group as Rf contains a fluorine atom or a silicon atom, Rf is preferably a group formed by replacing one or more hydrogen atoms in the organic group with a group having a fluorine atom or a silicon atom. Here, specific examples of the group having a silicon atom are the same as the specific examples of the group having a silicon atom described in the compound (d-1).

  As Rf when the organic group as Rf contains a fluorine atom or a silicon atom, for example, an alkyl group in which 30 to 100% of the number of hydrogen atoms are substituted with a fluorine atom is particularly preferable. And perfluoroalkyl groups such as a perfluoropropyl group and a perfluorobutyl group.

Examples of the nitrogen-containing heterocycle formed by combining Ra and Rc or Rc with each other include aromatic or non-aromatic nitrogen-containing heterocycles (preferably having 3 to 20 carbon atoms). Examples of such nitrogen-containing heterocycle include pyrrolidine, piperidine, morpholine, 1,4,5,6-tetrahydropyrimidine, 1,2,3,4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine. , Homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, 1H-1,2,3-triazole, 1,4,7-triazacyclononane, tetrazole, 7-azaindole, indazole, benz Imidazole, imidazo [1,2-a] pyridine, (1S, 4S)-(+)-2,5-diazabicyclo [2.2.1] heptane, 1,5,7-triazabicyclo [4.4. 0] deck-5-ene, indole, indoline, 1,2,3,4-tetrahydroquinoxaline, perhydroquinoline, Include a ring corresponding to the heterocyclic compounds such as 5,9-triazacyclododecane. These rings may further have one or more substituents, and specific examples of such substituents include Rb ₁ , Rb ₂ and Rb _{3 in the} general formula (P). Is the same as the specific examples of the substituent which may further have.

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

  The compound (d) may be a low molecular compound, an oligomer or a high molecular compound.

  Compared to the oligomer or polymer compound, the low molecular compound diffuses to some extent in the post-exposure heating (PEB) step, so that it is considered that the acid is captured more uniformly. For that reason, LWR can be more reliably reduced by using a low molecular weight compound as the compound (d).

  On the other hand, compared with a low molecular weight compound, an oligomer or a high molecular compound is less likely to diffuse in the internal direction of the composition film even in the post-exposure heating (PEB) step, so that an acid is easily generated in an excessive amount. It is considered that the acid can be reliably captured in the surface layer. Therefore, bridge defects can be more reliably reduced by using an oligomer or a polymer compound as the compound (d).

  When the compound (d) is a low molecular compound, its molecular weight is usually 1000 or less, preferably 150 to 500, more preferably 250 to 500.

Moreover, a compound (d-2) is compoundable by the method as described in Protective Groups in Organic Synthesis 4th edition etc. from an amine, for example. For example, the compound represented by the general formula (1) is preferably obtained by allowing a dicarbonate or haloformate to act on an amine as shown in the following scheme. In the formula, X represents a halogen atom. _{Ra, Rb 1, Rb 2,} Rb 3, Rc, Rf , respectively, the same meanings as _{Ra, Rb 1, Rb 2,} Rb 3, Rc, Rf in the general formula (1).

Hereinafter, specific examples of the compounds (d-1) and (d-2), which are low molecular compounds, are listed below, but the present invention is not limited thereto.

  When the compound (d) is an oligomer or a polymer compound (hereinafter, this compound is also referred to as a resin (G)), at least one of a fluorine atom and a silicon atom may be contained in the main chain of the resin, It may be contained in the side chain.

  Since the resin (G) has a function similar to that of the hydrophobic resin described later, it is effective in reducing development defects.

  When the resin (G) contains a fluorine atom, the resin has an alkyl group containing a fluorine atom, a cycloalkyl group containing a fluorine atom, or an aryl containing a fluorine atom as a partial structure containing a fluorine atom. It is preferable to have a group.

  The alkyl group containing a fluorine atom is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. The alkyl group containing a fluorine atom may further have a substituent other than the fluorine atom.

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

  An aryl group containing a fluorine atom is an aryl group in which at least one hydrogen atom is substituted with a fluorine atom. Examples of the aryl group include a phenyl group and a naphthyl group. The aryl group containing a fluorine atom may further have a substituent other than the fluorine atom.

Preferable examples of the alkyl group containing a fluorine atom, the cycloalkyl group containing a fluorine atom, and the aryl group containing a fluorine atom include groups represented by the following general formulas (F2) to (F4).

In the general formulas (F2) to (F4), R _{57 to} R ₆₈ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group. However, at least one of R _{57 to} R ₆₁ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. At least one of R _{62 to} R ₆₄ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. At least one of R _{65 to} R ₆₈ represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. These alkyl groups preferably have 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 in which at least one hydrogen atom is substituted with a fluorine atom, and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. R ₆₂ and R ₆₃ may be bonded to each other to form a ring.

  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.

  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, Examples include 3,3-tetrafluorocyclobutyl group and perfluorocyclohexyl group. Among these, a hexafluoroisopropyl group, a heptafluoroisopropyl group, a hexafluoro (2-methyl) isopropyl group, an octafluoroisobutyl group, a nonafluoro-t-butyl group or a perfluoroisopentyl group is more preferable, and a hexafluoroisopropyl group or More preferred is a heptafluoroisopropyl group.

Examples of the group represented by the general formula (F4), for _{example, -C (CF 3) 2 OH} , -C (C 2 F 5) 2 OH, -C (CF 3) (CH 3) OH, and -CH (CF ₃ ) OH. Of these, -C _{(CF 3)} 2 OH is particularly preferred.

  Specific examples of the repeating unit containing a fluorine atom are shown below.

In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ . X ₂ represents -F or -CF _3.

  When the resin (G) contains a silicon atom, the resin preferably has an alkylsilyl structure or a cyclic siloxane structure as a partial structure containing a silicon atom. This allylsilyl structure is preferably a structure containing a trialkylsilyl group.

Preferable examples of the alkylsilyl structure and 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 or a cycloalkyl group. This alkyl group preferably has 1 to 20 carbon atoms. This cycloalkyl group preferably has 3 to 20 carbon atoms.

L < ₃ > -L < ₅ > represents a single bond or a bivalent coupling group. Examples of the divalent linking group include an alkylene group, a phenylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a urethane group, a urea group, or a combination thereof.

  n represents an integer of 1 to 5. n is preferably an integer of 2 to 4.

Below, the specific example of the repeating unit which has group represented by general formula (CS-1)-(CS-3) is given. In specific examples, X ₁ represents a hydrogen atom, —CH ₃ , —F or —CF ₃ .

As resin (G),
A resin (G-a) comprising a repeating unit having at least one of a fluorine atom and a silicon atom, and a repeating unit having at least one of a basic group and a group whose basicity is increased by the action of an acid; and a fluorine atom and Resin (Gb) including a repeating unit having at least one of silicon atoms and at least one of a basic group and a group whose basicity is increased by the action of an acid
Can be preferably mentioned.

  In the resin (G-a), typically, there are no electron-withdrawing fluorine atoms or bulky silicon atoms in the vicinity of the basic site. Therefore, basicity reduction and steric hindrance are small, and the generated acid is sufficiently quenched. Therefore, when the resin (G-a) is used, particularly excellent roughness characteristics can be achieved. In addition, since the surface uneven distribution and basicity can be changed separately, compound design is easy.

  On the other hand, in the resin (Gb), the content of fluorine atoms and silicon atoms can be increased. Therefore, this resin (Gb) has particularly good surface layer uneven distribution ability. Therefore, when the resin (Gb) is used, it is easy to suppress the pattern from having a T-top shape.

  Specific examples of the repeating unit having at least one of a fluorine atom and a silicon atom in the resin (G-a) include those listed above.

In the resin (G-a), the repeating unit having at least one of a basic group and a group whose basicity is increased by the action of an acid may be a repeating unit represented by the following general formula (BI). preferable.

In General Formula (BI), Xa represents a hydrogen atom, a methyl group which may have a substituent, or a group represented by —CH ₂ —R ₉ . R ₉ represents a hydroxyl group or a monovalent organic group, and examples of the monovalent organic group include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, preferably 3 or less carbon atoms. An alkyl group, more preferably a methyl group. Xa preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group, more preferably a hydrogen atom, a methyl group or a hydroxymethyl group.

  Ab represents a group having a basic group or a group having a group whose basicity is increased by the action of an acid.

  In Ab, the group having basicity and the group whose basicity increases by the action of an acid preferably both contain a nitrogen atom.

  The group having a basic group as Ab is preferably a group having any one of the structures represented by the general formulas (A) to (E), specifically, the general formulas (A) to (E) Basic compound (low molecular weight compound) having any of the structures shown (in this case, the basic compound may or may not have at least one of a fluorine atom and a silicon atom) And a monovalent group obtained by removing any one hydrogen from.

The group having a basic group as Ab is more preferably a group represented by the following formula (BI ′).

  In formula (BI ′), L represents a single bond or a divalent linking group, and Ac represents a structure represented by the above general formula (A) (a bond from a nitrogen atom in the above general formula (A)). Binds to L).

  Examples of the divalent linking group as L include an alkylene group, a cycloalkylene group, an ether group, a phenylene group, and a group formed by combining two or more of these, more preferably an alkylene group and a cyclo group. An alkylene group, more preferably an alkylene group. The total number of carbon atoms of the divalent linking group as L is preferably 0 to 10, more preferably 1 to 6, and still more preferably 2 or 3.

  The “group whose basicity is increased by the action of an acid” in the group having a group whose basicity is increased by the action of an acid as Ab is the “carbamate group having a protecting group” described in the above compound (d-2). Can be preferably mentioned.

The group having a group whose basicity is increased by the action of an acid as Ab is more preferably a group represented by the following formula (B-II).

In general formula (B-II),
Ra, Rb ₁ , Rb ₂ and Rb ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Two of Rb _{1 to} Rb ₃ may be bonded to each other to form a ring. However, all of Rb _{1 to} Rb ₃ do not become hydrogen atoms at the same time.
Rc represents a single bond or a divalent linking group.
x represents 0 or 1, y represents 1 or 2, and x + y = 2.
When x = 1, Ra and Rc may be bonded to each other to form a nitrogen-containing heterocycle.

In general formula (B-II), each group in Ra, Rb ₁ , Rb ₂ , Rb ₃ , Rc, a ring that two of Rb _{1 to} Rb ₃ may be bonded to each other, and Ra and Rc Specific examples of the nitrogen-containing heterocyclic ring that may be bonded to each other are the same as those described in the general formula (1).

In the resin (Gb), the repeating unit having at least one of a fluorine atom and a silicon atom and at least one of a basic group and a group whose basicity is increased by the action of an acid is represented by the general formula (B-1). A repeating unit represented by:
(I) Xa is a methyl group having at least one of a fluorine atom and a silicon atom (for example, a trifluoromethyl group),
(Ii) Ab has a basic group or a group whose basicity is increased by the action of an acid, and further has at least one of a fluorine atom and a silicon atom, and (iii) (i) and (ii) ) And
The repeating unit which satisfy | fills either of these can be mentioned.

  Regarding the above (ii), the group Ab having a basic group and further having at least one of a fluorine atom and a silicon atom may be any one of the structures represented by the general formulas (A) to (E) described above, for example. And a monovalent group formed by removing any one hydrogen from a basic compound (low molecular compound) having a hydrogen atom (however, the basic compound has at least one of a fluorine atom and a silicon atom). .

  In addition, regarding the above (ii), the group Ab having a group whose basicity is increased by the action of an acid and further having at least one of a fluorine atom and a silicon atom is represented by, for example, the general formula (1) described above. And monovalent groups formed by removing any one hydrogen from any one of Ra, Rc and Rf of the compound to be prepared.

Hereinafter, although the specific example of the repeating unit which has at least one of the basic group in resin (G) and the group which basicity increases by the effect | action of an acid is given, this invention is not limited to this. In specific examples, X represents a hydrogen atom, —CH ₃ , —CH ₂ OH, —F or —CF ₃ .

The resin (G) may further contain a repeating unit represented by the following general formula (III ′).

Rc ₃₁ represents a hydrogen atom, an alkyl group (which may be substituted with a fluorine atom or the like), a cyano group, or a —CH ₂ —O—Rac ₂ group. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group.

Rc ₃₁ is preferably a hydrogen atom, a methyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

Rc ₃₂ represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, or an aryl group. These groups may be substituted with a group containing a silicon atom, a fluorine atom or the like.

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

The alkyl group for R _c32 is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.
The cycloalkyl group preferably has 3 to 20 carbon atoms.
The alkenyl group preferably has 3 to 20 carbon atoms.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.
R _c32 is preferably an unsubstituted alkyl group or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.

L _c3 represents a single bond or a divalent linking group. Examples of the divalent linking group include an ester group, an alkylene group (preferably 1 to 5 carbon atoms), an oxy group, a phenylene group, an ester bond (a group represented by —COO—), or two of these. Examples include a group formed by combining the above, and a linking group having 1 to 12 carbon atoms in total is preferable.

The resin (G) may further contain a repeating unit represented by the following general formula (CII-AB).

In the formula (CII-AB),
R _c11 ′ and R _c12 ′ each independently represents a hydrogen atom, a cyano group, a halogen atom or an alkyl group. Zc ′ represents an atomic group necessary for forming an alicyclic structure together with two carbon atoms (C—C) to which R _c11 ′ and R _c12 ′ are bonded.
R _c32 is a substituent for the alicyclic structure, and the definition thereof is the same as R _c32 in the general formula (III ′).
p represents an integer of 0 to 3, and 0 or 1 is preferable.

Specific examples of the repeating unit represented by the general formula (III ′) or (CII-AB) are given below. In specific examples, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN.

Hereinafter, although the specific example of resin (G) is given below, this invention is not limited to this.

  When the resin (G) contains a fluorine atom, the fluorine atom content is preferably 5 to 80% by mass and preferably 10 to 80% by mass based on the molecular weight of the resin (G). More preferred. Moreover, it is preferable that it is 10-100 mass%, and, as for content of the repeating unit containing a fluorine atom on the basis of all the repeating units of resin (G), it is more preferable that it is 30-100 mass%.

  When the resin (G) contains a silicon atom, the content of the silicon atom is preferably 2 to 50% by mass, and 2 to 30% by mass based on the molecular weight of the resin (G). More preferred. Moreover, it is preferable that it is 10-100 mass%, and, as for content of the repeating unit containing a silicon atom on the basis of all the repeating units of resin (G), it is more preferable that it is 20-100 mass%.

  The content of “a repeating unit having at least one of a fluorine atom and a silicon atom” in the resin (G-a) is preferably 20 to 80 mol%, more preferably based on all repeating units constituting the resin (G). Is 25 to 70 mol%, particularly preferably 30 to 60 mol%.

  The content of “a repeating unit having at least one of a basic group and a group whose basicity is increased by the action of an acid” in the resin (G-a) is preferably with respect to all the repeating units constituting the resin (G). Is 20 to 80 mol%, more preferably 25 to 70 mol%, particularly preferably 30 to 60 mol%.

  The content of “a repeating unit having at least one of a fluorine atom and a silicon atom and at least one of a basic group and a group whose basicity is increased by the action of an acid” in the resin (Gb) is the resin (G) Is preferably 20 to 80 mol%, more preferably 25 to 70 mol%, and particularly preferably 30 to 60 mol%, based on all repeating units constituting the.

  The content of the repeating unit represented by the general formula (III ′) or (CII-AB) in the resin (G) is preferably 20 to 80 mol% with respect to all the repeating units constituting the resin (G). More preferably, it is 25-70 mol%, Most preferably, it is 30-60 mol%.

  The weight average molecular weight of the resin (G) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 100,000 as a polystyrene-converted value by the GPC method. 15,000.

  The degree of dispersion of the resin (G) is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 to 2. This makes it possible to achieve better resolution, pattern shape, and roughness characteristics.

  As the compound (d) (including the resin (G)), one type may be used alone, or two or more types may be used in combination.

  The content of the compound (d) (including the resin (G)) is preferably 0.01 to 10% by mass, and 0.05 to 8% by mass based on the total solid content in the composition. It is more preferable, and it is still more preferable that it is 0.1-5 mass%.

  As the compound (d) (including the resin (G)), a commercially available product may be used, or a compound synthesized according to a conventional method may be used. As a general synthesis method of the resin (G), for example, the same method as described above for the acid-decomposable resin can be given.

  As for resin (G), it is natural that there are few impurities, such as a metal, It is preferable that the residual amount of a monomer is 0-10 mass%, It is more preferable that it is 0-5 mass%, 0 More preferably, it is -1 mass%. As a result, the amount of foreign matter in the liquid can be reduced, and changes over time such as sensitivity can be reduced.

(E) A compound other than (d) that has basicity or increases basicity by the action of an acid. The composition according to the present invention comprises the above compound in order to reduce the change in performance over time from exposure to heating. Contains a compound other than (d) (having neither a fluorine atom nor a silicon atom), having basicity or increasing basicity by the action of an acid (hereinafter also referred to as compound (e)). May be.

Specific examples of the basic compound (basic compound) include basic compounds having structures represented by the following general formulas (A) to (E).

In general formulas (A) and (E),
R ²⁵⁰ , R ²⁵¹ and R ²⁵² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group.

R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ each independently represents an alkyl group or a cycloalkyl group.

In the structure represented by the general formula (A), R ²⁵¹ and R ²⁵² may be bonded to each other to form a ring.

  In the structures represented by the general formulas (B) to (D), two or more of a bond from a carbon atom and a bond from a nitrogen atom may be bonded to each other to form a ring.

In the structure represented by the general formula (E), two or more of R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ , R ²⁵⁶ , a bond from an elementary atom, and a bond from a nitrogen atom are bonded to each other, A ring may be formed.

In General Formula (A), specific examples of R ²⁵¹ and R ²⁵² are the same as the definitions and specific examples of R ²⁰¹ and R ^{202 in} the structure represented by General Formula (A) described in Compound (d-1). It is.

Specific examples of R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ^{256 in} the general formula (E) are R ²⁰³ , R ²⁰⁴ , and R ^{203 in} the structure represented by the general formula (A) described in the compound (d-1). This is the same as the specific examples of R ²⁰⁵ and R ²⁰⁶ .

  In the structures represented by the general formulas (A) to (E), specific examples of the ring that two or more of each group and each bond may form are as described for the compound (d-1) above. It is the same.

In addition, each group in the structures represented by the general formulas (A) to (E) and a ring that may be formed by bonding two or more of each group and each bond to each other further have a substituent. Specific examples of such substituents may be further included in R ²⁰¹ and R ²⁰² described in the structure represented by the general formula (A) of the compound (d-1). It is the same as the specific example of a good substituent.

Examples of the alkyl group having a substituent and the cycloalkyl group having a substituent as R ^{250 to} R ²⁵⁶ include an aminoalkyl group having 1 to 20 carbon atoms, an aminocycloalkyl group having 3 to 20 carbon atoms, and 1 to 20 carbon atoms. Or a hydroxycycloalkyl group having 3 to 20 carbon atoms is preferred.

  These may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain.

  Preferable basic compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, and piperidine, which may have a substituent. Further preferable compounds include an imidazole structure, a diazabicyclo structure, an onium hydroxide structure (particularly preferably, a tetraalkylammonium hydroxide such as tetrabutylammonium hydroxide), an onium carboxylate structure, a trialkylamine structure, an aniline structure, or a pyridine structure. A compound having a hydroxyl group and / or an ether bond, an aniline derivative having a hydroxyl group and / or an ether bond, and the like.

  Further, at least one nitrogen-containing compound selected from 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 can be exemplified. . Examples of these compounds include, but are not limited to, compounds (C1-1) to (C3-3) exemplified in [0066] of US Patent Application Publication No. 2007/02245539. It is not a thing.

Examples of the compound whose basicity is increased by the action of an acid include compounds represented by the following general formula (F). In addition, the compound represented by the following general formula (F) exhibits effective basicity in the system when a group capable of leaving by the action of an acid is eliminated.

  In the general formula (F), Ra independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When n = 2, the two Ras may be the same or different, and the two Ras are bonded to each other to form a divalent heterocyclic hydrocarbon group (preferably having 20 or less carbon atoms) or a derivative thereof. May be formed.

  Rb independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.

  At least two Rb's may combine to form an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group or a derivative thereof.

  n represents an integer of 0 to 2, m represents an integer of 1 to 3, and n + m = 3.

  In general formula (F), the alkyl group, cycloalkyl group, aryl group and aralkyl group represented by Ra and Rb are functional groups such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group and an oxo group, It may be substituted with an alkoxy group or a halogen atom (excluding a fluorine atom).

R alkyl group, cycloalkyl group, aryl group or aralkyl group (these alkyl group, cycloalkyl group, aryl group and aralkyl group are substituted with the above functional group, alkoxy group and halogen atom (excluding fluorine atom). As may be)
For example, a group derived from a linear or branched alkane such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, etc., a group derived from these alkanes, for example, A group substituted with one or more cycloalkyl groups such as a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group,
Groups derived from cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, adamantane, noradamantane, groups derived from these cycloalkanes, for example, methyl group, ethyl group, n-propyl group, a group substituted with one or more linear or branched alkyl groups such as i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group and the like,
Groups derived from aromatic compounds such as benzene, naphthalene, anthracene, etc., and groups derived from these aromatic compounds are, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2 A group substituted with one or more linear or branched alkyl groups such as -methylpropyl group, 1-methylpropyl group, t-butyl group, and the like;
Groups derived from heterocyclic compounds such as pyrrolidine, piperidine, morpholine, tetrahydrofuran, tetrahydropyran, indole, indoline, quinoline, perhydroquinoline, indazole, benzimidazole, and groups derived from these heterocyclic compounds are linear or branched A group substituted with one or more groups derived from an alkyl group or aromatic compound, a group derived from a linear or branched alkane, a group derived from a cycloalkane, a phenyl group, a naphthyl group A group substituted by one or more groups derived from an aromatic compound such as an anthryl group or the like, or the above substituent is a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, an oxo group And a group substituted with a functional group such as.

  Examples of the divalent heterocyclic hydrocarbon group (preferably having 1 to 20 carbon atoms) or a derivative thereof formed by bonding of Ra to each other include, for example, pyrrolidine, piperidine, morpholine, 1, 4, 5 , 6-tetrahydropyrimidine, 1,2,3,4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, 1H-1, 2,3-triazole, 1,4,7-triazacyclononane, tetrazole, 7-azaindole, indazole, benzimidazole, imidazo [1,2-a] pyridine, (1S, 4S)-(+)-2 , 5-diazabicyclo [2.2.1] heptane, 1,5,7-triazabicyclo [4.4.0] dec-5-ene Groups derived from heterocyclic compounds such as indole, indoline, 1,2,3,4-tetrahydroquinoxaline, perhydroquinoline, 1,5,9-triazacyclododecane, groups derived from these heterocyclic compounds A group derived from a linear or branched alkane, a group derived from a cycloalkane, a group derived from an aromatic compound, a group derived from a heterocyclic compound, a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group And a group substituted with one or more functional groups such as a morpholino group and an oxo group.

  Specifically shown in the present invention are particularly preferred examples: Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, Nt-butoxycarbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-2-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, ( S)-(−)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, (R)-(+)-1- (t-butoxycarbonyl) -2-pyrrolidinemethanol, Nt-butoxycarbonyl- 4-hydroxypiperidine, Nt-butoxycarbonylpyrrolidine, Nt-butoxy Rubonylmorpholine, Nt-butoxycarbonylpiperazine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt -Butoxycarbonyl-4,4'-diaminodiphenylmethane, N, N'-di-t-butoxycarbonylhexamethylenediamine, N, N, N'N'-tetra-t-butoxycarbonylhexamethylenediamine, N, N ' -Di-t-butoxycarbonyl-1,7-diaminoheptane, N, N'-di-t-butoxycarbonyl-1,8-diaminooctane, N, N'-di-t-butoxycarbonyl-1,9- Diaminononane, N, N′-di-t-butoxycarbonyl-1,10-diaminodecane, N, N′-di-t-butoxy Carbonyl-1,12-diaminododecane, N, N′-di-t-butoxycarbonyl-4,4′-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole Nt-butoxycarbonyl-2-phenylbenzimidazole and the like.

The compound represented by the general formula (F) may be a commercially available compound, or may be synthesized from a commercially available amine by the method described in Protective Groups in Organic Synthesis Fourth Edition. As the most general method, there is a method obtained by reacting a dicarbonate or haloformate with a commercially available amine. In the formula, X represents a halogen atom. R _a and R _b have the same meaning as in formula (F).

  The molecular weight of the compound (e) having basicity or increasing basicity by the action of an acid other than the compound (d) is preferably 250 to 2000, and more preferably 400 to 1000.

  These compounds (e) are used alone or in combination of two or more.

  When the compound (e) is contained, the content thereof is preferably 0.05 to 8.0% by mass, more preferably 0.05 to 5.0% by mass, based on the total solid content of the composition. %, Particularly preferably 0.05 to 4.0% by mass.

(F) Basic compound or ammonium salt compound whose basicity is decreased by irradiation with actinic light or radiation The composition according to the present invention is a basic compound or ammonium salt whose basicity is decreased by irradiation with active light or radiation. A compound (hereinafter also referred to as “compound (PA)”) may be contained. That is, the compound (PA) is accompanied by a change in chemical structure upon irradiation with actinic rays or radiation and has photosensitivity.

  The compound (PA) is preferably a compound (PA ′) having a basic functional group or an ammonium group and a group capable of generating an acidic functional group upon irradiation with actinic rays or radiation. That is, the compound (PA) is a basic compound having a basic functional group and a group capable of generating an acidic functional group upon irradiation with active light or radiation, or an acidic functional group upon irradiation with an ammonium group and active light or radiation. An ammonium salt compound having a group to be generated is preferable.

  The compound (PA) or (PA ′), which is generated by decomposing upon irradiation with actinic rays or radiation and has a reduced basicity, has the following general formula (PA-I), (PA-II) or (PA- Compounds represented by formula (III), and particularly from the viewpoint that the excellent effects of LWR and DOF can be achieved at a high level, in particular, compounds represented by formula (PA-II) or (PA-III) Is preferred.

First, the compound represented by the following general formula (PA-I) is demonstrated.

In general formula (PA-I),
A ₁ represents a single bond or a divalent linking group.
Q represents _-SO 3 H, or -CO ₂ H. Q corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.
X represents —SO ₂ — or —CO—.
n represents 0 or 1.
B represents a single bond, an oxygen atom or -N (Rx)-. Rx represents a hydrogen atom or a monovalent organic group.
R represents a monovalent organic group having a basic functional group or a monovalent organic group having an ammonium group.

The divalent linking group in A ₁ is preferably a divalent linking group having 2 to 12 carbon atoms, and examples thereof include an alkylene group and a phenylene group. More preferably, it is an alkylene group having at least one fluorine atom, and a preferable carbon number is 2 to 6, more preferably 2 to 4. The alkylene chain may have a linking group such as an oxygen atom or a sulfur atom. The alkylene group is particularly preferably an alkylene group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms, and more preferably, the carbon atom bonded to the Q site has a fluorine atom. Further, a perfluoroalkylene group is preferable, and a perfluoroethylene group, a perfluoropropylene group, and a perfluorobutylene group are more preferable.

  The monovalent organic group in Rx preferably has 4 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.

  The alkyl group in Rx may have a substituent and is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and an oxygen atom, a sulfur atom and / or a nitrogen atom in the alkyl chain. You may have.

  Examples of the alkyl group having a substituent include groups in which a linear or branched alkyl group is substituted with a cycloalkyl group (for example, an adamantylmethyl group, an adamantylethyl group, a cyclohexylethyl group, a camphor residue, etc.). .

  The cycloalkyl group in Rx may have a substituent, preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom in the ring.

  The aryl group in Rx may have a substituent, and is preferably an aryl group having 6 to 14 carbon atoms.

  The aralkyl group in Rx may have a substituent, and preferably an aralkyl group having 7 to 20 carbon atoms.

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

  Preferable partial structures of basic functional groups include, for example, the structures of crown ethers, primary to tertiary amines, and nitrogen-containing heterocycles (pyridine, imidazole, pyrazine, etc.).

  Preferable partial structures of the ammonium group include, for example, primary to tertiary ammonium, pyridinium, imidazolinium, and pyrazinium structures.

  In addition, as a basic functional group, the functional group which has a nitrogen atom is preferable, and the structure which has a 1-3 primary amino group, or a nitrogen-containing heterocyclic structure is more preferable. In these structures, it is preferable from the viewpoint of improving basicity that all atoms adjacent to the nitrogen atom contained in the structure are carbon atoms or hydrogen atoms. From the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, or a halogen atom) is not directly connected to the nitrogen atom.

  As the monovalent organic group in the monovalent organic group (group R) having such a structure, a preferable carbon number is 4 to 30, and an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, etc. Each group may have a substituent.

  The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group in the basic functional group or ammonium group in R are each represented by Rx. These are the same as the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group mentioned.

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

  When B is -N (Rx)-, R and Rx are preferably bonded to form a ring. By forming the ring structure, the stability is improved, and the storage stability of the composition using the ring structure is improved. The number of carbon atoms forming the ring is preferably 4 to 20, and may be monocyclic or polycyclic, and may contain an oxygen atom, a sulfur atom and / or a nitrogen atom in the ring.

  Examples of the monocyclic structure include a 4- to 8-membered ring containing a nitrogen atom. Examples of the polycyclic structure include a structure composed of a combination of two or three or more monocyclic structures. The monocyclic structure and polycyclic structure may have a substituent, for example, a halogen atom, a hydroxyl group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), Aryl group (preferably having 6 to 14 carbon atoms), alkoxy group (preferably having 1 to 10 carbon atoms), acyl group (preferably having 2 to 15 carbon atoms), acyloxy group (preferably having 2 to 15 carbon atoms), alkoxycarbonyl A group (preferably having 2 to 15 carbon atoms), an aminoacyl group (preferably having 2 to 20 carbon atoms) and the like are preferable. As for the cyclic structure in the aryl group, cycloalkyl group and the like, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 15). As for the aminoacyl group, examples of the substituent include 1 or 2 alkyl groups (preferably having 1 to 15 carbon atoms).

Among the compounds represented by the general formula (PA-I), a compound in which the Q site is a sulfonic acid (—SO ₃ H) can be synthesized by using a general sulfonamidation reaction. For example, a method in which one sulfonyl halide part of a bissulfonyl halide compound is selectively reacted with an amine compound to form a sulfonamide bond, and then the other sulfonyl halide part is hydrolyzed, or a cyclic sulfonic acid anhydride is used. It can be obtained by a method of ring-opening by reacting with an amine compound.

Next, the compound represented by general formula (PA-II) is demonstrated.

In general formula (PA-II),
Q ₁ and Q ₂ each independently represents a monovalent organic group. However, either Q ₁ or Q ₂ has a basic functional group. Q ₁ and Q ₂ may combine to form a ring, and the formed ring may have a basic functional group.
X ₁ and X ₂ each independently represent —CO— or —SO ₂ —.
Note that —NH— corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.

The monovalent organic group as Q ₁ and Q _{2 in} formula (PA-II) preferably has 1 to 40 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, An alkenyl group etc. can be mentioned.

The alkyl group in Q ₁ and Q ₂ may have a substituent, and is preferably a linear or branched alkyl group having 1 to 30 carbon atoms. In the alkyl chain, an oxygen atom, a sulfur atom, and / or Or you may have a nitrogen atom.

The cycloalkyl group in Q ₁ and Q ₂ may have a substituent, preferably a cycloalkyl group having 3 to 20 carbon atoms, and has an oxygen atom and / or a nitrogen atom in the ring. May be.

The aryl group in Q ₁ and Q ₂ may have a substituent, and is preferably an aryl group having 6 to 14 carbon atoms.

The aralkyl group in Q ₁ and Q ₂ may have a substituent, and preferably an aralkyl group having 7 to 20 carbon atoms.

The alkenyl group in Q ₁ and Q ₂ may have a substituent, and examples thereof include a group having a double bond at an arbitrary position of the alkyl group.

  Examples of the substituent that each of the above groups may have include the same groups as those exemplified above as the substituent that each of the groups in the above formula (PA-1) may have.

Preferable partial structures of the basic functional group possessed by at least one of Q ₁ and Q ₂ include the same partial structures as those described as the basic functional group possessed by R in the general formula (PA-I).

Q ₁ and Q ₂ are combined to form a ring, and the formed ring has a basic functional group. For example, the organic group of Q ₁ and Q ₂ is further an alkylene group, an oxy group, or an imino group. A structure bonded with a group or the like can be given.

In the general formula (PA-II), it is preferable that at least one of X ₁ and X ₂ is —SO ₂ —.

Next, the compound represented by general formula (PA-III) is demonstrated.

In general formula (PA-III),
Q ₁ and Q ₃ each independently represents a monovalent organic group. However, either one of Q ₁ and Q ₃ are a basic functional group. Q ₁ and Q ₃ may combine to form a ring, and the formed ring may have a basic functional group.
X ₁ , X ₂ and X ₃ each independently represent —CO— or —SO ₂ —.
A ₂ represents a divalent linking group.
B represents a single bond, an oxygen atom, or —N (Qx) —. Qx represents a hydrogen atom or a monovalent organic group.
B is, -N (Qx) - when, _{Q 3} and Qx and may be bonded to each other to form a ring.
m represents 0 or 1.
Note that —NH— corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.

Q ₁ has the same meaning as Q _{1 in} formula (PA-II).

Examples of the organic group of Q ₃ include the same organic groups as Q ₁ and Q ₂ in formula (PA-II).

The divalent linking group in A ₂ is preferably a divalent linking group having 1 to 8 carbon atoms, such as an alkylene group having 1 to 8 carbon atoms or a fluorine atom. Examples thereof include a phenylene group. More preferably, it is an alkylene group having a fluorine atom, preferably 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms. The alkylene chain may have a linking group such as an oxygen atom or a sulfur atom. The alkylene group is preferably an alkylene group in which 30 to 100% of the hydrogen atoms are substituted with fluorine atoms, more preferably a perfluoroalkylene group, and particularly preferably a C2 to C4 perfluoroalkylene group.

  The monovalent organic group in Qx is preferably an organic group having 4 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. As the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group, the same groups as those described above for Rx in the above formula (PA-I) can be mentioned.

In the general formula (PA-III), X ₁ , X ₂ , and X ₃ are preferably —SO ₂ —.

As the compound (PA), a sulfonium salt compound of the compound represented by the general formula (PA-I), (PA-II) or (PA-III), the general formula (PA-I), (PA-II) or The iodonium salt compound of the compound represented by (PA-III) is preferable, and the compound represented by the following general formula (PA1) or (PA2) is more preferable.

In general formula (PA1):
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group, and specifically, are the same as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ of the formula ZI in the acid generator.

X ⁻ represents a sulfonate anion or carboxylate anion from which a hydrogen atom of the —SO ₃ H site or —COOH site of the compound represented by the general formula (PA-I) is eliminated, or a general formula (PA-II) or ( PA-III) represents an anion in which a hydrogen atom is eliminated from the -NH- site of the compound represented by PA-III).

In the general formula (PA2),
R ₂₀₄ and R ₂₀₅ each independently represents an aryl group, an alkyl group or a cycloalkyl group, and specifically, are the same as R ₂₀₄ and R ₂₀₅ of the formula ZII in the acid generator.

X ⁻ represents a sulfonate anion or carboxylate anion from which a hydrogen atom of the —SO ₃ H site or —COOH site of the compound represented by the general formula (PA-I) is eliminated, or a general formula (PA-II) or ( PA-III) represents an anion in which a hydrogen atom is eliminated from the -NH- site of the compound represented by PA-III).

  The compound (PA) is decomposed by irradiation with actinic rays or radiation to generate, for example, a compound represented by the general formula (PA-I), (PA-II) or (PA-III).

  The compound represented by the general formula (PA-I) has a sulfonic acid group or a carboxylic acid group together with a basic functional group or an ammonium group, so that the basicity is reduced, disappeared, or basic compared to the compound (PA). It is a compound that has changed from acidic to acidic.

The compound represented by the general formula (PA-II) or (PA-III) has an organic sulfonylimino group or an organic carbonylimino group together with a basic functional group, so that the basicity is lower than that of the compound (PA). , Disappearance, or a compound changed from basic to acidic.

  In the present invention, the decrease in basicity upon irradiation with actinic rays or radiation means that the acceptor property to protons (acids generated by irradiation with actinic rays or radiation) of compound (PA) upon irradiation with actinic rays or radiation. Means lower. The acceptor property decreases when an equilibrium reaction occurs in which a non-covalent complex that is a proton adduct is formed from a compound having a basic functional group and a proton, or the counter cation of a compound having an ammonium group is exchanged for a proton. This means that when an equilibrium reaction occurs, the equilibrium constant at that chemical equilibrium decreases.

  Thus, the compound film (PA) whose basicity is reduced by irradiation with actinic rays or radiation is contained in the composition film, so that the acceptor property of the compound (PA) is sufficiently expressed in the unexposed area. Thus, an unintended reaction between the acid diffused from the exposed portion or the like and the acid-decomposable resin can be suppressed. Moreover, since the acceptor property of a compound (PA) falls in an exposure part, the intended reaction with an acid and an acid-decomposable resin occurs more reliably. It is presumed that a pattern excellent in roughness characteristics, focus margin (DOF) and pattern shape can be obtained by the contribution of such an action mechanism.

  In addition, basicity can be confirmed by measuring pH, and can also be confirmed by calculating a calculated value with commercially available software.

  Specific examples of the compound (PA) whose basicity is lowered by irradiation with actinic rays or radiation include those described in, for example, JP-A-2006-208781 and JP-A-2006-330098.

Hereinafter, although the specific example of the compound (PA) which generate | occur | produces the compound represented with general formula (PA-I) by irradiation of actinic light or a radiation is given, this invention is not limited to this.

  These compounds are synthesized from a compound represented by the general formula (PA-I) or a lithium, sodium or potassium salt thereof and a hydroxide, bromide or chloride of iodonium or sulfonium. Or a salt exchange method described in JP-A No. 2003-246786. Further, the synthesis method described in JP-A-7-333851 can also be applied.

Hereinafter, although the specific example of the compound (PA) which generate | occur | produces the compound represented by general formula (PA-II) or (PA-III) by irradiation of actinic light or a radiation is given, this invention is limited to this. is not.

These compounds can be easily synthesized by using a general sulfonic acid esterification reaction or sulfonamidation reaction. For example, one sulfonyl halide part of a bissulfonyl halide compound is selectively reacted with an amine, alcohol, or the like containing a partial structure represented by the general formula (PA-II) or (PA-III), After forming a sulfonate bond, the other sulfonyl halide moiety is hydrolyzed, or the cyclic sulfonic anhydride is opened with an amine or alcohol containing a partial structure represented by the general formula (PA-II) It can be obtained by a method. The amine or alcohol containing a partial structure represented by the general formula (PA-II) or (PA-III) is an amine or alcohol under basicity (R′O ₂ C) ₂ O or (R′SO _2). ) It can be synthesized by reacting with an anhydride such as ₂ O and an acid chloride compound such as R′O ₂ CCl or R′SO ₂ Cl (R ′ is a methyl group, an n-octyl group, a trifluoromethyl group, etc.) . In particular, it can be applied to the synthesis example of JP-A-2006-330098.

The molecular weight of the compound (PA) is preferably 500 to 1000.
Compound (PA) may be used alone or in combination of two or more. Moreover, you may use a compound (PA) together with the compound (e) mentioned above.
The content of the compound (PA) in the composition according to the present invention is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, based on the solid content of the composition.

(G) Hydrophobic resin The composition according to the present invention contains a hydrophobic resin (excluding the resin (G)) having at least one of a fluorine atom and a silicon atom, particularly when applied to immersion exposure. Also good. Thereby, when the hydrophobic resin is unevenly distributed in the film surface layer and the immersion medium is water, the static / dynamic contact angle of the resist film surface with respect to water can be improved, and the immersion water followability can be improved.

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

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

  In the case where the hydrophobic resin contains a fluorine atom, the resin has an alkyl group containing a fluorine atom, a cycloalkyl group containing a fluorine atom, or an aryl group containing a fluorine atom as a partial structure containing a fluorine atom. It is preferable to provide.

  The alkyl group containing a fluorine atom is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. The alkyl group containing a fluorine atom may further have a substituent other than the fluorine atom.

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

  An aryl group containing a fluorine atom is an aryl group in which at least one hydrogen atom is substituted with a fluorine atom. Examples of the aryl group include a phenyl group and a naphthyl group. The aryl group containing a fluorine atom may further have a substituent other than the fluorine atom.

  Preferred examples of the alkyl group containing a fluorine atom, the cycloalkyl group containing a fluorine atom, and the aryl group containing a fluorine atom are represented by the general formulas (F2) to (F4) described in the resin (G). Group.

  Specific examples of the repeating unit containing a fluorine atom are the same as those exemplified in the resin (G).

  When the hydrophobic resin contains a silicon atom, the resin preferably has an alkylsilyl structure or a cyclic siloxane structure as a partial structure containing a silicon atom. This allylsilyl structure is preferably a structure containing a trialkylsilyl group.

  Preferable examples of the alkylsilyl structure and the cyclic siloxane structure include groups represented by the general formulas (CS-1) to (CS-3) described in the resin (G).

  Specific examples of the repeating unit having a group represented by general formulas (CS-1) to (CS-3) are the same as those exemplified in the resin (G).

  The hydrophobic resin may further include at least one group selected from the group consisting of the following (x) to (z).

(X) an acid group;
(Y) a group having a lactone structure, an acid anhydride group, or an acid imide group;
(Z) Acid-decomposable group (x) As the acid group, for example, phenolic hydroxyl group, carboxylic acid group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl)
(Alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, A tris (alkylcarbonyl) methylene group and a tris (alkylsulfonyl) methylene group are mentioned. Preferred acid groups include fluorinated alcohol groups, sulfonimide groups, and bis (carbonyl) methylene groups. Preferred fluorinated alcohol groups include hexafluoroisopropanol groups.

  The repeating unit having an acid group is a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid and methacrylic acid. Alternatively, this repeating unit may be a repeating unit in which an acid group is bonded to the main chain of the resin via a linking group. Or this repeating unit may be introduce | transduced into the terminal of resin using the polymerization initiator or chain transfer agent which has an acid group at the time of superposition | polymerization.

  The content of the repeating unit having an acid group is preferably 1 to 50 mol%, more preferably 3 to 35 mol%, more preferably 5 to 20 mol, based on all repeating units in the hydrophobic resin. % Is more preferable.

Specific examples of the repeating unit having an acid group are shown below. In the formula, Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH.

  (Y) As the group having a lactone structure, the acid anhydride group, or the acid imide group, a group having a lactone structure is particularly preferable.

  The repeating unit containing these groups is a repeating unit in which this group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid ester and methacrylic acid ester. Alternatively, this repeating unit may be a repeating unit in which this group is bonded to the main chain of the resin via a linking group. Or this repeating unit may be introduce | transduced into the terminal of resin using the polymerization initiator or chain transfer agent which has this group at the time of superposition | polymerization.

  Examples of the repeating unit having a group having a lactone structure include those similar to the repeating unit having a lactone structure described above in the section of the acid-decomposable resin.

More preferably, the group having the lactone structure has a partial structure represented by the following general formula (KA-1). By having this structure, an improvement in the receding contact angle of the immersion liquid is expected.

In general formula (KA-1),
Z _ka1 each independently represents an alkyl group, a cycloalkyl group, an ether group, a hydroxy group, an amide group, an aryl group, a lactone ring group, or an electron-withdrawing group when nka is 2 or more. When nka is 2 or more, a plurality of Z _ka1 may be bonded to each other to form a ring. Examples of this ring include cycloalkyl rings and heterocyclic rings such as cyclic ether rings and lactone rings.

  nka represents an integer of 0 to 10. nka is preferably 0 to 8, more preferably 0 to 5, still more preferably 1 to 4, and particularly preferably 1 to 3.

  The structure represented by the general formula (KA-1) is a partial structure existing in the main chain, side chain, terminal, etc. of the resin, and is formed by removing at least one hydrogen atom contained in this structure. It exists as a substituent having a valence or higher.

Z _ka1 is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxy group or an electron withdrawing group, more preferably an alkyl group, a cycloalkyl group or an electron withdrawing group. The ether group is preferably an alkyl ether group or a cycloalkyl ether group.

The alkyl group of Z _ka1 may be linear or branched. This alkyl group may further have a substituent.

The alkyl group of Z _ka1 has 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group and t-butyl group. Is preferred.

The cycloalkyl group of Z _ka1 may be monocyclic or polycyclic. In the latter case, the cycloalkyl group may be bridged. That is, in this case, the cycloalkyl group may have a bridged structure. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

  The monocyclic cycloalkyl group preferably has 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

  Examples of the polycyclic cycloalkyl group include groups having a bicyclo, tricyclo, or tetracyclo structure having 5 or more carbon atoms. The polycyclic cycloalkyl group preferably has 6 to 20 carbon atoms. For example, an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group , Tetocyclododecyl group and androstanyl group.

  These structures may further have a substituent. Examples of the substituent include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxy group, and an alkoxycarbonyl group.

  The alkyl group as a substituent is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group, more preferably a methyl group, an ethyl group, a propyl group and an isopropyl group. .

  The alkoxy group as the substituent is preferably an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

  These alkyl groups and alkoxy groups as substituents may have further substituents. As this further substituent, a hydroxyl group, a halogen atom, and an alkoxy group (preferably C1-C4) are mentioned, for example.

Examples of the aryl group for Z _ka1 include a phenyl group and a naphthyl group.

Examples of the substituent that the alkyl group, cycloalkyl group, and aryl group of Z _ka1 may further include, for example, a hydroxyl group; a halogen atom; a nitro group; a cyano group; the above alkyl group; a methoxy group, an ethoxy group, a hydroxyethoxy group, Alkoxy groups such as propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group and t-butoxy group; alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; benzyl group, phenethyl group and cumyl group Aralkyloxy group; Aralkyloxy group; Acyl group such as formyl group, acetyl group, butyryl group, benzoyl group, cyanamyl group and valeryl group; Acyloxy group such as butyryloxy group; Alkenyl group; Vinyloxy group, propenyloxy group, allyloxy group And butenyl An alkenyloxy group such as an oxy group; the above aryl group; an aryloxy group such as a phenoxy group; and an aryloxycarbonyl group such as a benzoyloxy group.

Examples of the electron withdrawing group for Z _ka1 include a halogen atom, a cyano group, an oxy group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, a nitrile group, a nitro group, a sulfonyl group, a sulfinyl group, and —C (R _f1 ) (R _f2 ) —R _f3 , a halo (cyclo) alkyl group, a haloaryl group, and combinations thereof. The “halo (cyclo) alkyl group” means a (cyclo) alkyl group in which at least one hydrogen atom is substituted with a halogen atom.

Examples of the halogen atom for Z _ka1 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a fluorine atom is particularly preferable.

In the halo (cyclo) alkyl group represented by —C (R _f1 ) (R _f2 ) —R _f3 , R _f1 represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group, or a perhaloaryl group. R _f1 is more preferably a fluorine atom, a perfluoroalkyl group or a perfluorocycloalkyl group, and further preferably a fluorine atom or a trifluoromethyl group.

In the halo (cyclo) alkyl group represented by —C (R _f1 ) (R _f2 ) —R _f3 , R _f2 and R _f3 each independently represent a hydrogen atom, a halogen atom or an organic group. Examples of the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group. These groups may further have a substituent such as a halogen atom.

At least two of R _{f1 to} R _f3 may be bonded to each other to form a ring. Examples of the ring include a cycloalkyl ring, a halocycloalkyl ring, an aryl ring, and a haloaryl ring.

Examples of the alkyl group and haloalkyl group of R _{f1 to} R _f3 include an alkyl group described above for Z _ka1 and a group in which at least a part of hydrogen atoms of these alkyl groups is substituted with a halogen atom.

Examples of the halocycloalkyl group and haloaryl group include groups in which at least a part of the hydrogen atoms of the cycloalkyl group and aryl group described above for Z _ka1 are substituted with a halogen atom. More preferred examples of the halocycloalkyl group and haloaryl group include a fluorocycloalkyl group represented by -C _(n) F _(2n-2) H, a perfluoroaryl group, and the like. Here, although there is no restriction | limiting in particular in the range of carbon number n, it is preferable that n is an integer of 5-13, and it is especially preferable that n is 6.

More preferably, R _f2 is the same group as R _f1 , or is bonded to R _f3 to form a ring.

  The electron withdrawing group is particularly preferably a halogen atom, a halo (cyclo) alkyl group or a haloaryl group.

  In the electron withdrawing group, a part of the fluorine atom may be substituted with an electron withdrawing group other than the fluorine atom.

  When the electron withdrawing group is a divalent or higher valent group, the remaining bond is used for bonding with an arbitrary atom or substituent. In this case, said partial structure may be couple | bonded with the principal chain of hydrophobic resin through the further substituent.

Among those represented by the general formula (KA-1), those represented by the following general formula (KY-1) are more preferable.

In formula (KY-1),
R _{ky6 to} R _ky10 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, carbonyl group, carbonyloxy group, oxycarbonyl group, ether group, hydroxy group, cyano group, amide group, or aryl. Represents a group. At least two _members out of R _{ky6 to} R _ky10 may be bonded to each other to form a ring.
R _ky5 represents an electron-withdrawing group. Examples of the electron withdrawing group include the same groups as Z _ka1 in the general formula (KA-1). This electron withdrawing group is preferably a halogen atom, a halo (cyclo) alkyl group represented by —C (R _f1 ) (R _f2 ) —R _f3 , or a haloaryl group.
nkb represents 0 or 1.
R _kb1 and R _kb2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an electron withdrawing group. Specific examples of these atomic groups include the same groups as Z _ka1 in formula (KA-1).

The structure represented by the general formula (KY-1) is more preferably a structure represented by the following general formula (KY-1-1).

In the formula (KY-1-1), each of Z _ka1 and nka has the same meaning as that in the general formula (KA-1). Each of Rky ₅ , R _kb1 , R _kb2 and nkb is synonymous with that in the general formula (KY-1).

L _ky represents an alkylene group, an oxygen atom, or a sulfur atom. Examples of the alkylene group for L _ky include a methylene group and an ethylene group. L _ky is preferably an oxygen atom or a methylene group, and more preferably a methylene group.

  Rs independently represents an alkylene group or a cycloalkylene group. When ns is 2 or more, the plurality of Rs may be the same or different from each other.

  Ls represents a single bond, an ether bond, an ester bond, an amide bond, a ureylene bond or a urea bond, and when there are a plurality of Ls, they may be the same or different.

  ns is the number of repeating linking groups represented by-(Rs-Ls)-and represents an integer of 0 to 5.

Although the preferable specific example of the repeating unit which has a structure represented by general formula (KA-1) is shown below, it is not limited to this. Ra represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

  The content of the repeating unit having a group having a lactone structure, an acid anhydride group, or an acid imide group is preferably 1 to 40 mol% based on all repeating units in the hydrophobic resin, and 3 to 30 It is more preferable that it is mol%, and it is still more preferable that it is 5-15 mol%.

  Examples of the (z) acid-decomposable group include the same groups as described above in the section of (a) acid-decomposable resin.

  The content of the repeating unit having an acid-decomposable group is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, based on all repeating units in the hydrophobic resin, and more preferably 20 to 20 mol%. More preferably, it is 60 mol%.

  The hydrophobic resin may contain a repeating unit represented by the general formula (III ′) or (CII-AB) described in the resin (G).

  Specific examples of the repeating unit represented by the general formula (III ') or (CII-AB) are the same as those exemplified for the resin (G).

  When the hydrophobic resin (G) contains a repeating unit represented by the general formula (III ′) or (CII-AB), the amount of the repeating unit is based on the total repeating units constituting the hydrophobic resin (G). The content is preferably 1 to 100 mol%, more preferably 5 to 95 mol%, and still more preferably 20 to 80 mol%.

Specific examples of the hydrophobic resin are given below. Table 2 below shows the molar ratio of repeating units in each resin (corresponding to each repeating unit in order from the left), weight average molecular weight, and dispersity (Mw / Mn).

  When the hydrophobic resin contains a fluorine atom, the fluorine atom content is preferably 5 to 80% by mass, more preferably 10 to 80% by mass based on the molecular weight of the hydrophobic resin. . In addition, the content of the repeating unit containing a fluorine atom is preferably 10 to 100% by mass, more preferably 30 to 100% by mass, based on all repeating units of the hydrophobic resin.

  When the hydrophobic resin contains silicon atoms, the silicon atom content is preferably 2 to 50% by mass, more preferably 2 to 30% by mass, based on the molecular weight of the hydrophobic resin. . In addition, the content of the repeating unit containing a silicon atom is preferably 10 to 100% by mass, more preferably 20 to 100% by mass, based on all repeating units of the hydrophobic resin.

  The weight average molecular weight of hydrophobic resin becomes like this. Preferably it is 1,000-100,000, More preferably, it is 1,000-50,000, More preferably, it is 2,000-15,000.

  The degree of dispersion of the hydrophobic resin is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 to 2. This makes it possible to achieve better resolution, pattern shape, and roughness characteristics.

  One type of hydrophobic resin may be used alone, or two or more types may be used in combination.

  The content of the hydrophobic resin is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass, based on the total solid content in the composition, More preferably, it is 5 mass%.

  As the hydrophobic resin, commercially available products may be used, or those synthesized according to a conventional method may be used. As a general method for synthesizing this resin, for example, the same method as described above for the acid-decomposable resin can be cited.

  It is natural that the hydrophobic resin has few impurities such as metals, and the residual amount of the monomer and oligomer components is preferably 0 to 10% by mass, and more preferably 0 to 5% by mass. More preferably, it is 0 to 1% by mass. As a result, the amount of foreign matter in the liquid can be reduced, and changes over time such as sensitivity can be reduced.

The film formed from the composition according to the present invention is filled with a liquid (immersion medium) having a refractive index higher than that of air between the film and the lens when irradiated with actinic rays or radiation. You may go. Thereby, resolution can be improved. As the immersion medium to be used, any liquid can be used as long as it has a higher refractive index than air, but pure water is preferred.
The immersion liquid used for the immersion exposure will be described below.

The immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has the smallest possible temperature coefficient of refractive index so as to minimize distortion of the optical image projected onto the composition film. When the light source is an ArF excimer laser (wavelength; 193 nm), it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above-described viewpoints.
Further, a medium having a refractive index of 1.5 or more can be used in that the refractive index can be further improved. This medium may be an aqueous solution or an organic solvent.

  When water is used as the immersion liquid, the surface tension of the water is reduced and the surface activity is increased, so that the composition film on the wafer is not dissolved and the influence on the optical coating on the lower surface of the lens element is ignored. A possible additive (liquid) may be added in a small proportion. The additive is preferably an aliphatic alcohol having a refractive index substantially equal to that of water, and specifically includes methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. By adding an alcohol having a refractive index substantially equal to that of water, even if the alcohol component in water evaporates and the content concentration changes, an advantage that the change in the refractive index of the entire liquid can be extremely small can be obtained. On the other hand, when an opaque substance or an impurity having a refractive index significantly different from that of water is mixed with 193 nm light, the optical image projected on the composition film is distorted. preferable. Further, pure water filtered through an ion exchange filter or the like may be used.

The electrical resistance of 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.
Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive for increasing the refractive index may be added to water, or heavy water (D ₂ O) may be used instead of water.

  An immersion liquid poorly soluble film (hereinafter also referred to as “topcoat”) may be provided between the film of the composition of the present invention and the immersion liquid so that the film does not directly contact the immersion liquid. Good. The functions required for the top coat are suitability for application to the upper layer of the composition film, transparency to radiation, particularly 193 nm, and poor immersion liquid solubility. It is preferable that the top coat is not mixed with the composition and can be uniformly applied to the upper layer of the composition film.

  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 above-mentioned hydrophobic resin (G) is also suitable as a top coat. From the viewpoint of contaminating the optical lens when impurities are eluted from the top coat into the immersion liquid, it is preferable that the residual monomer component of the polymer contained in the top coat is small.

  When peeling the top coat, a developer may be used, or a separate release agent may be used. As the release agent, a solvent having low penetration into the film is preferable. From the viewpoint that the peeling step can be performed at the same time as the film development processing step, it is preferable that the peeling step can be performed with a developer containing an organic solvent.

  The resolution is improved when there is no difference in refractive index between the top coat and the immersion liquid. In the case of using water as the immersion liquid in an ArF excimer laser (wavelength: 193 nm), the top coat for ArF immersion exposure is preferably close to the refractive index of the immersion liquid. From the viewpoint of making the refractive index close to the immersion liquid, it is preferable to have fluorine atoms in the topcoat. A thin film is more preferable from the viewpoint of transparency and refractive index.

  The top coat is preferably not mixed with the membrane and further not mixed with the immersion liquid. From this point of view, when the immersion liquid is water, the solvent used for the top coat is preferably a water-insoluble medium that is hardly soluble in the solvent used for the composition of the present invention. Furthermore, when the immersion liquid is an organic solvent, the topcoat may be water-soluble or water-insoluble.

(H) Surfactant The composition according to the present invention may further contain a surfactant. By containing a surfactant, when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less, is used, it is possible to form a pattern with less adhesion and development defects with good sensitivity and resolution. Become.

As the surfactant, it is particularly preferable to use a fluorine-based and / or silicon-based surfactant.
Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in [0276] of US Patent Application Publication No. 2008/0248425. Also, F-top EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Florard FC430, 431 or 4430 (manufactured by Sumitomo 3M Co., Ltd.); Megafac F171, F173, F176, F189, F113, F110, F177, F120 or R08 (Dainippon Ink Chemical Co., Ltd.); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (Asahi Glass Co., Ltd.); Troisol S-366 (Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by Toa Gosei Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.); F-top EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 or F601 (manufactured by Gemco); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA); or FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (manufactured by Neos) May be used. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

  In addition to known surfactants as described above, the surfactant is a fluoroaliphatic compound produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method). You may synthesize. Specifically, a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as a surfactant. This fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-90991.

  The polymer having a fluoroaliphatic group is preferably a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate or methacrylate and / or (poly (oxyalkylene)) methacrylate. Even if it distributes, block copolymerization may be sufficient.

  Examples of the poly (oxyalkylene) group include a poly (oxyethylene) group, a poly (oxypropylene) group, and a poly (oxybutylene) group. In addition, units having different chain length alkylene in the same chain, such as poly (block connection body of oxyethylene, oxypropylene, and oxyethylene) and poly (block connection body of oxyethylene and oxypropylene) Also good.

  Further, a copolymer of a monomer having a fluoroaliphatic group and (poly (oxyalkylene)) acrylate or methacrylate has a monomer having two or more different fluoroaliphatic groups and two or more different (poly (oxyalkylene). )) It may be a ternary or higher copolymer obtained by copolymerizing acrylate or methacrylate simultaneously.

For example, Megafac F178, F-470, F-473, F-475, F-476 and F-472 (Dainippon Ink Chemical Co., Ltd.) are mentioned as commercially available surfactants. Further, a copolymer of an acrylate or methacrylate having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate or methacrylate, an acrylate or methacrylate having a C ₆ F ₁₃ group and (poly (oxyethylene)) acrylate or methacrylate And a copolymer of (poly (oxypropylene)) acrylate or methacrylate, a copolymer of an acrylate or methacrylate having a C ₈ F ₁₇ group and (poly (oxyalkylene)) acrylate or methacrylate, and C ₈ F ₁₇ And a copolymer of an acrylate or methacrylate having a group and (poly (oxyethylene)) acrylate or methacrylate and (poly (oxypropylene)) acrylate or methacrylate. That.

  Further, surfactants other than fluorine-based and / or silicon-based surfactants described in [0280] of US Patent Application Publication No. 2008/0248425 may be used.

One of these surfactants may be used alone, or two or more thereof may be used in combination.
When the composition according to the present invention contains a surfactant, the content is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, based on the total solid content of the composition. More preferably, it is 0.0005-1 mass%.

(I) Other additives The composition according to the present invention comprises a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (for example, a molecular weight of 1000 The following phenol compounds or alicyclic or aliphatic compounds containing a carboxy group) may further be included.

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

  As this dissolution inhibiting compound, since it does not decrease the transmittance for light having a wavelength of 220 nm or less, acid decomposition such as a cholic acid derivative containing an acid-decomposable group described in Proceeding of SPIE, 2724, 355 (1996) An alicyclic or aliphatic compound containing a functional group is preferred. Examples of the acid-decomposable group and the alicyclic structure include the same ones as described above.

  When the resist composition according to the present invention is exposed with a KrF excimer laser or irradiated with an electron beam, the dissolution inhibiting compound includes a structure in which the phenolic hydroxy group of the phenol compound is substituted with an acid-decomposable group. The compound is preferred. As a phenol compound, what contains 1-9 phenol frame | skeleton is preferable, and what contains 2-6 pieces is still more preferable.

  When the composition according to the present invention contains a dissolution inhibiting compound, the content thereof is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, based on the total solid content of the composition. is there.

Specific examples of the dissolution inhibiting compound are given below.

  The phenol compound having a molecular weight of 1000 or less can be obtained by referring to, for example, the methods described in JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294, etc. It can be easily synthesized.

  Examples of alicyclic or aliphatic compounds containing a carboxy group include carboxylic acid derivatives containing steroid structures such as cholic acid, deoxycholic acid and lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, And cyclohexanedicarboxylic acid.

<Pattern formation method>
The pattern forming method according to the present invention includes (A) forming a film using the resist composition described above, (B) exposing the film, and (C) developing the exposed film. Including that. The developing step (C) is typically performed using a developer containing an organic solvent. Moreover, the pattern formed by the development using the developer containing the organic solvent is typically a negative type. This method may further include (D) rinsing the developed film with a rinse solution.

  It is also preferable to include a preheating (PB) step after the film formation and before the exposure step. It is also preferable to include a post exposure bake (PEB) step after the exposure step and before the development step.

The heating temperature is preferably 40 to 130 ° C., more preferably 50 to 120 ° C., and still more preferably 60 to 110 ° C. for both the PB process and the PEB process. In particular, when the PEB process is performed at a low temperature of 60 to 90 ° C., the exposure latitude (EL) and the resolution can be remarkably improved.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds.

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

There is no limitation on the wavelength of the light source used for exposure of the, for example, KrF excimer laser wavelength (248 nm), ArF excimer laser wavelength (193 nm), and, _{F 2} excimer laser wavelength (157 nm) and the like.

Liquid immersion exposure may be performed on the film formed using the composition according to the present invention. Thereby, the resolution can be further improved. As the immersion medium to be used, any liquid can be used as long as it has a higher refractive index than air, but pure water is preferred.
In this case, the above-described hydrophobic resin may be added to the composition in advance, or after forming a film, an immersion liquid hardly soluble film (hereinafter also referred to as “topcoat”) may be provided thereon. Good. The performance required for the top coat and how to use it are described in Chapter 7 of CM Publishing “Immersion Lithography Processes and Materials”.

  From the viewpoint of transparency to a laser having a wavelength of 193 nm, the top coat is preferably a polymer that does not contain abundant aromatics. For example, hydrocarbon polymer, acrylate polymer, polymethacrylic acid, polyacrylic acid, polyvinyl ether, silicon And a fluorine-containing polymer. The hydrophobic resin described above is also suitable as a top coat. Commercially available top coat materials can also be used as appropriate.

  When the topcoat is peeled after exposure, a developer may be used, or a separate release agent may be used. As the release agent, a solvent having low penetration into the film is preferable. From the viewpoint that the peeling step can be performed simultaneously with the development processing step of the film, it is preferable that the peeling step can be performed with a developer.

In the present invention, the substrate on which the film is formed is not particularly limited. As the substrate, a substrate generally used in a semiconductor manufacturing process such as an IC, a manufacturing process of a circuit board such as a liquid crystal and a thermal head, and other photofabrication lithography processes can be used. Examples of such a substrate, e.g., silicon, SiN, and SiO ₂ or the like of the inorganic substrate, as well, include coating inorganic substrates such as SOG. Further, if necessary, an organic antireflection film may be formed between the film and the substrate.

  Examples of the developer containing an organic solvent include polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents, and developers containing hydrocarbon solvents. .

  Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, and methyl ethyl ketone. , Methyl isobutyl ketone, methyl amyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.

  Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, n-pentyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate. , Diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate , Butyl lactate, propyl lactate, methyl propionate, methyl 3-methoxypropionate (MMP), ethyl propionate, 3-ethoxypropionate Examples include ethyl onate (EEP) and propyl propionate. In particular, alkyl acetates such as methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate and amyl acetate or propionate alkyl esters such as methyl propionate, ethyl propionate and propyl propionate are preferred.

  Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2- Alcohols such as pentanol, n-heptyl alcohol, n-octyl alcohol and n-decanol; glycols such as ethylene glycol, diethylene glycol and triethylene glycol; and ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, Propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl Glycol ethers such as ether and methoxymethyl butanol.

  Examples of the ether solvent include dioxane and tetrahydrofuran in addition to the above glycol ether.

  Examples of amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, and 1,3-dimethyl-2-imidazolidinone. Can be mentioned.

  Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene, xylene and anisole, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.

  Two or more of the above solvents may be mixed and used. Moreover, you may mix and use with solvent and / or water other than the above within the range which can exhibit sufficient performance. However, the water content of the entire developer is preferably less than 10% by mass, and more preferably the developer does not substantially contain moisture. That is, this developer is preferably a developer substantially consisting of only an organic solvent. Even in this case, the developer may contain a surfactant described later. In this case, the developer may contain unavoidable impurities derived from the atmosphere.

  The amount of the organic solvent used in the developer is preferably 80% by mass or more and 100% by mass or less, more preferably 90% by mass or more and 100% by mass or less, and 95% by mass with respect to the total amount of the developer. More preferably, it is 100 mass% or less.

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

  The vapor pressure of the developer containing the organic solvent is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the developing solution to 5 kPa or less, evaporation of the developing solution on the substrate or in the developing cup is suppressed, and temperature uniformity in the wafer surface is improved. As a result, dimensional uniformity in the wafer surface. Will improve.

  Specific examples of the developer having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone and Ketone solvents such as methyl isobutyl ketone; butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3- Such as methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate and propyl lactate Ter solvent: n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n- Alcohol solvents such as octyl alcohol and n-decanol; glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol; ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol Glycos such as monomethyl ether, triethylene glycol monoethyl ether and methoxymethylbutanol Ether solvents; ether solvents such as tetrahydrofuran; amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylformamide; aromatic hydrocarbon solvents such as toluene and xylene; In addition, aliphatic hydrocarbon solvents such as octane and decane are listed.

  Specific examples of the developer having a vapor pressure of 2 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, and phenylacetone. Ketone solvents of: butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, Ester solvents such as 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate and propyl lactate; n-butyl alcohol, sec-butyl Alcohol solvents such as alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol and n-decanol; ethylene glycol, diethylene glycol and triethylene glycol Glycol solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether and methoxymethyl butanol; N -Methyl-2-pyrrolidone, N, N-dimethylacetamide and N, N-dimethylform Bromide amide solvents; aromatic hydrocarbon solvents such as xylene; and include aliphatic hydrocarbon solvents such as octane and decane.

An appropriate amount of a surfactant can be added to the developer as necessary.
Although there is no restriction | limiting in particular in this surfactant, For example, an ionic or nonionic fluorine type and / or silicon type surfactant can be used. Examples of these fluorine and / or silicon surfactants are, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950. JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, Mention may be made of the surfactants described in the specifications of US Pat. it can. This surfactant is preferably nonionic. As the nonionic surfactant, it is more preferable to use a fluorine-based surfactant or a silicon-based surfactant.

  In addition, the usage-amount of surfactant is 0.001-5 mass% normally with respect to the whole quantity of a developing solution, Preferably it is 0.005-2 mass%, More preferably, it is 0.01-0. 0.5% by mass.

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

When the various development methods described above include a step of discharging the developer from the developing nozzle of the developing device toward the resist film, the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is , Preferably 2 mL / sec / mm ² or less, more preferably 1.5 mL / sec / mm ² or less, and even more preferably 1 mL / sec / mm ² or less. There is no particular lower limit on the flow rate, but considering the throughput, it is preferably 0.2 mL / sec / mm ² or more.
By setting the discharge pressure of the discharged developer to be in the above range, pattern defects derived from the resist residue after development can be remarkably reduced.

The details of this mechanism are not clear, but perhaps by setting the discharge pressure within the above range, the pressure applied to the resist film by the developer is reduced, and the resist film and / or resist pattern may be inadvertently cut or collapsed. This is considered to be suppressed.
The developer discharge pressure (mL / sec / mm ² ) is a value at the developing nozzle outlet in the developing device.

Examples of a method for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump and the like, and a method of changing the pressure by adjusting the pressure by supply from a pressurized tank.
Moreover, you may implement the process of stopping image development, after the process of developing, substituting with another solvent.

  The pattern forming method according to the present invention preferably includes a rinsing step (a step of cleaning the film using a rinsing liquid containing an organic solvent) after the developing step.

  The rinsing liquid used in the rinsing step is not particularly limited as long as it does not dissolve the pattern after development, and a solution containing a general organic solvent can be used.

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

The rinsing liquid preferably contains a monohydric alcohol, and more preferably contains a monohydric alcohol having 5 or more carbon atoms.
These monohydric alcohols may be linear, branched, or cyclic. Examples of these monohydric alcohols include 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, and 4-methyl-2- Examples include pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, and 4-octanol. Examples of the monohydric alcohol having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, and 3-methyl-1-butanol.

  Each of the above components may be used as a mixture of two or more, or may be used as a mixture with an organic solvent other than the above.

  The water content of the rinsing liquid is preferably less than 10% by mass, preferably less than 5% by mass, and more preferably less than 3% by mass. That is, the amount of the organic solvent used in the rinse liquid is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less, based on the total amount of the rinse liquid. It is particularly preferable that the content is not less than 100% by mass. By setting the water content of the rinse liquid to less than 10% by mass, even better development characteristics can be achieved.

The vapor pressure of the rinse liquid is preferably 0.05 kPa to 5 kPa at 20 ° C., more preferably 0.1 kPa to 5 kPa, and more preferably 0.12 kPa to 3 kPa. Is more preferable. By setting the vapor pressure of the rinsing liquid to 0.05 kPa or more and 5 kPa or less, temperature uniformity in the wafer surface is improved, and swelling due to penetration of the rinsing liquid is suppressed, and dimensional uniformity in the wafer surface is achieved. It improves.
An appropriate amount of a surfactant may be added to the rinse solution.

  In the rinsing step, the developed wafer is cleaned using the above rinsing liquid. The method of the cleaning process is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), and immersing the substrate in a bath filled with the rinse liquid for a certain period of time. Examples thereof include a method (dip method) and a method (spray method) in which a rinse liquid is sprayed onto the substrate surface. Among these, it is preferable to remove the rinse liquid from the substrate by performing a cleaning process by a spin coating method and then rotating the substrate at a rotational speed of 2000 rpm to 4000 rpm.

  The pattern formation method according to the present invention may include a development step (positive pattern formation step) using an alkaline developer in addition to a development step using a developer containing an organic solvent. There is no particular limitation on the order of the development step using an alkali developer and the development step using a developer containing an organic solvent, but development using an alkali developer was performed using a developer containing an organic solvent. More preferably, it is performed before development. Moreover, it is preferable to accompany a heating process before each image development process.

  The type of alkali developer is not particularly limited, but an aqueous solution of tetramethylammonium hydroxide is usually used. An appropriate amount of alcohol and / or surfactant may be added to the alkaline developer.

  The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass. The pH of the alkali developer is usually from 10.0 to 15.0. As the alkali developer, it is particularly preferable to use a 2.38% by mass aqueous solution of tetramethylammonium hydroxide.

  When rinsing is performed after development using an alkaline developer, pure water is typically used as the rinse. An appropriate amount of a surfactant may be added to the rinse solution.

<Acid-decomposable resin and hydrophobic resin>
[Synthesis Example 1: Synthesis of Resin (P-1)]
Under a nitrogen stream, 40 g of a 6/4 (mass ratio) mixed solvent of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether was placed in a three-necked flask and heated to 80 ° C. (solvent 1). Monomers corresponding to the following repeating units were dissolved in a mixed solvent of 6/4 (mass ratio) of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether at a molar ratio of 40/60, respectively, and a 22 mass% monomer solution (400 g ) Was prepared. Furthermore, 8 mol% of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the monomer, and a dissolved solution was added dropwise to the solvent 1 over 6 hours. After completion of dropping, the reaction was further continued at 80 ° C. for 2 hours. The reaction solution was allowed to cool and then poured into 3600 ml of hexane / 400 ml of ethyl acetate, and the precipitated powder was collected by filtration and dried to obtain 74 g of Resin (P-1). The obtained resin (P-1) had a weight average molecular weight of 11,000 and a dispersity (Mw / Mn) of 1.6.

[Synthesis Example 2: Synthesis of hydrophobic resin (6b)]
First, compound (4) was synthesized according to the following scheme.

  The said compound (1) was synthesize | combined by the method as described in international publication 07/037213 pamphlet.

  150.00 g of water was added to 35.00 g of compound (1), and 27.30 g of sodium hydroxide was further added. The mixture was stirred for 9 hours under heating and reflux conditions. Hydrochloric acid was added to make it acidic, and the mixture was extracted with ethyl acetate. The organic layers were combined and concentrated to obtain 36.90 g of compound (2) (yield 93%).

¹ H-NMR (400 MHz / (CD ₃ ) ₂ CO): δ (ppm) = 1.56-1.59 (1H), 1.68-1.72 (1H), 2.13-2.15 ( 1H), 2.13-2.47 (2H), 3.49-3.51 (1H), 3.68 (1H), 4.45-4.46 (1H).

200 ml of CHCl ₃ was added to 20.00 g of compound (2), and 50.90 g of 1,1,1,3,3,3-hexafluoroisopropyl alcohol and 30.00 g of 4-dimethylaminopyridine were further added and stirred. To the solution, 22.00 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added and stirred for 3 hours. The reaction solution was added to 500 ml of 1N HCl to stop the reaction. The organic layer was further washed with 1N HCl, then with water, and the organic layer was concentrated to obtain 30.00 g of Compound (3) (yield 85%).

¹ H-NMR (400 MHz / (CD ₃ ) ₂ CO): δ (ppm) = 1.62 (1H), 1.91-1.95 (1H), 2.21-2.24 (1H), 2 .45-2.53 (2H), 3.61-3.63 (1H), 3.76 (1H), 4.32-4.58 (1H), 6.46-6.53 (1H)
While adding 300.00 g of toluene to 15.00 g of compound (3), further adding 3.70 g of methacrylic acid and 4.20 g of p-toluenesulfonic acid monohydrate, and removing the produced water by azeotropic distillation, 15 hours Refluxed. The reaction solution was concentrated, and the concentrate was purified by column chromatography to obtain 11.70 g of Compound (4) (yield 65%).

¹ H-NMR (400 MHz / (CD ₃ ) ₂ CO): δ (ppm) = 1.76-1.79 (1H), 1.93 (3H), 2.16-2.22 (2H), 2 57-2.61 (1H), 2.76-2.81 (1H), 3.73-3.74 (1H), 4.73 (1H), 4.84-4.86 (1H), 5.69-5.70 (1H), 6.12 (1H), 6.50-6.56 (1H).

  Next, the monomer corresponding to each repeating unit of the following resin (6b) was charged at a ratio (molar ratio) of 90/10 and dissolved in PGMEA to prepare 450 g of a solution having a solid content concentration of 15% by mass. 1 mol% of Wako Pure Chemical Co., Ltd. polymerization initiator V-601 was added to this solution, and this was added dropwise to 50 g of PGMEA heated to 100 ° C. in a nitrogen atmosphere over 6 hours. The reaction liquid was stirred for 2 hours after completion | finish of dripping. After completion of the reaction, the reaction solution was cooled to room temperature, crystallized in 5 L of methanol, and the precipitated white powder was collected by filtration to recover the target resin (6b).

The polymer composition ratio determined from NMR was 90/10. Moreover, the weight average molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 12000, and dispersion degree was 1.5.

  Resins (P-2) to (P-14) and hydrophobicity in the same manner as in Synthesis Example 1 except that the monomers corresponding to the respective repeating units were used so as to have a desired composition ratio (molar ratio). Resins (1b) to (5b) were synthesized.

The structures of the resins (P-1) to (P-14) and the hydrophobic resins (1b) to (6b) are shown below. Table 3 shows the composition ratio (molar ratio), weight average molecular weight, and dispersity of these resins.

<Acid generator>
The following compounds (PAG-1) to (PAG-12) were prepared as acid generators.

<Compounds (d), (e) and (PA)>
The following compounds (B-7) to (B-18) were prepared as the compound (d). Among these, the compounds (B-12) to (B-18) correspond to the resin (G).
The following compounds (B-1) to (B-6) were prepared as the compound (e).
The following compound (B-19) was prepared as the compound (PA).

[Synthesis Example 3: Synthesis of Compound (B-10)]
To 2.3 g of 1- (tert-butoxycarbonyl) isonipecotic acid, 50 ml of tetrahydrofuran (THF) was added, and 3.4 g of 1,1,1,3,3,3-hexafluoroisopropyl alcohol, 4-dimethylaminopyridine 1 0.7 g was added and stirred. To the solution, 3.5 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added and stirred for 3 hours. The reaction solution was added to 30 ml of 1N HCl to stop the reaction. The organic layer was further washed with 1N HCl, then with water, and the organic layer was concentrated to obtain 3.2 g of Compound (B-10) (yield 83%).

¹ H-NMR (400 MHz / (CD ₃ ) ₂ CO): δ (ppm) = 1.45 (9H), 1.6-1.75 (2H), 1.90-2.00 (2H), 2.70 (1H), 2.85-3.00 (2H), 3.95-4.10 (2H), 5.75 (1H).

[Synthesis Example 4: Synthesis of Compound (B-12)]
Monomers corresponding to the above repeating units were respectively charged in a ratio (molar ratio) of 39/49/10/2 and dissolved in PGMEA to prepare 450 g of a solution having a solid content concentration of 15% by mass. 1 mol% of Wako Pure Chemical Co., Ltd. polymerization initiator V-601 was added to this solution, and this was added dropwise to 50 g of PGMEA heated to 100 ° C. in a nitrogen atmosphere over 6 hours. The reaction liquid was stirred for 2 hours after completion | finish of dripping. After completion of the reaction, the reaction solution was cooled to room temperature, crystallized in 5 L of methanol, and the precipitated white powder was collected by filtration to recover the target compound (B-12).
The polymer composition ratio determined from NMR was 39/49/10/2. Moreover, the weight average molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 4300, and dispersion degree was 1.5.

  Other compounds (B-1) to (B-9), (B-11) and (B-13) to (B-19) were synthesized in the same manner as described in Synthesis Examples 3 and 4. did.

Table 4 below shows the composition ratio (molar ratio), weight average molecular weight, and dispersity of the compounds (B-12) to (B-18).

<Surfactant>
As the surfactant, the following were used.
W-1: MegaFuck F176 (Dainippon Ink Chemical Co., Ltd.) (Fluorine)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd.) (fluorine and silicon)
W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) (silicon-based).

  W-4: PF-6320 (made by OMNOVA) (fluorine type).

<Solvent>
The following were used as the solvent.

A1: Propylene glycol monomethyl ether acetate (PGMEA)
A2: γ-butyrolactone A3: Cyclohexanone B1: Propylene glycol monomethyl ether (PGME)
B2: Ethyl lactate B3: 2-Heptanone B4: Propylene carbonate C1: Diisopentyl ether.

<Preparation of resist and topcoat composition>
The components shown in Table 5 below were dissolved in the solvent shown in the same table to give a total solid content concentration of 3.5% by mass, and each was filtered through a polyethylene filter having a pore size of 0.03 μm to obtain a resist composition Ar-1. -Ar-28 and topcoat composition t-1 were prepared.

  A resist pattern was formed by the following method using the prepared resist composition.

<Example 1 (exposure → bake → development → rinse: abbreviation EBDR)>
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on the silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 86 nm. A resist composition Ar-1 was applied thereon, and baked at 100 ° C. for 60 seconds to form a resist film having a thickness of 100 nm.

  An ArF excimer laser scanner (PAS5500 / 1100, NA0.75, Dipole, outer sigma 0.89, inner sigma 0.65) manufactured by ASML was used for the obtained wafer, and an exposure mask (line / space = 1/1). ) Was used to perform pattern exposure. Then, after heating at 100 ° C. for 60 seconds, the developer described in Table 6 below was paddled for 30 seconds to develop, padded with a rinse solution listed in the same table for 30 seconds, rinsed at 4000 rpm. The wafer was rotated for 30 seconds and baked at 90 ° C. for 60 seconds to obtain a 100 nm (1: 1) line-and-space resist pattern.

<Examples 2, 3, 5, 10, 11, 14, 15, 18-23, and 26>
A line and space resist pattern of 100 nm (1: 1) was obtained in the same manner as in Example 1 except that the resists and conditions described in Tables 5 and 6 were employed.

<Example 6 (immersion exposure → bake → development → rinse: abbreviation iE-B-D-R)>
An organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied onto the silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 95 nm. A resist composition Ar-6 was applied thereon, and baked at 100 ° C. for 60 seconds to form a resist film having a thickness of 100 nm.

  Using an ArF excimer laser immersion scanner (XTML1700i, NA1.20, C-Quad, outer sigma 0.981, inner sigma 0.895, XY deflection) manufactured by ASML on the obtained wafer / Space = 1/1), pattern exposure was performed. At this time, ultrapure water was used as the immersion liquid. Then, after heating at 100 ° C. for 60 seconds, the developer described in Table 6 below was paddled for 30 seconds to develop, padded with a rinse solution listed in the same table for 30 seconds, rinsed at 4000 rpm. The wafer was rotated for 30 seconds and baked at 90 ° C. for 60 seconds to obtain a 100 nm (1: 1) line-and-space resist pattern.

<Examples 7 to 9, 12, 24, and 25>
A line and space resist pattern of 100 nm (1: 1) was obtained in the same manner as in Example 6 except that the resists and conditions described in Tables 5 and 6 were employed.

<Example 13 (exposure → bake → development: abbreviation E-BD)>
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on the silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 86 nm. A resist composition Ar-13 was applied thereon, and baked at 100 ° C. for 60 seconds to form a resist film having a thickness of 100 nm.

  An ArF excimer laser scanner (PAS5500 / 1100, NA0.75, Dipole, outer sigma 0.89, inner sigma 0.65) manufactured by ASML was used for the obtained wafer, and an exposure mask (line / space = 1/1). ) Was used to perform pattern exposure. Then, after heating at 100 ° C. for 60 seconds, the developer shown in Table 6 below is paddled for 30 seconds to develop, and the wafer is rotated at 4000 rpm for 30 seconds and baked at 90 ° C. for 60 seconds. A 100 nm (1: 1) line and space resist pattern was obtained.

<Example 16 (exposure → bake → development → rotation rinse: abbreviation E-BD-R2)>
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on the silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 86 nm. A resist composition Ar-16 was applied thereon and baked at 100 ° C. for 60 seconds to form a resist film having a thickness of 100 nm.

  An ArF excimer laser scanner (PAS5500 / 1100, NA0.75, Dipole, outer sigma 0.89, inner sigma 0.65) manufactured by ASML was used for the obtained wafer, and an exposure mask (line / space = 1/1). ) Was used to perform pattern exposure. Then, after heating at 100 ° C. for 60 seconds, the developer described in Table 6 below is paddled for 30 seconds for development, and the rinse liquid described in the same table is flowed on the wafer while rotating the wafer at 500 rpm. After rinsing for 30 seconds, the wafer was rotated at 4000 rpm for 30 seconds and baked at 90 ° C. for 60 seconds to obtain a 100 nm (1: 1) line-and-space resist pattern.

<Example 17 (exposure → bake → rotary development → rinse: abbreviation EB-D2-R)>
An organic antireflection film ARC29A (Nissan Chemical Co., Ltd.) was applied on the silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 86 nm. A resist composition Ar-17 was applied thereon, and baked at 100 ° C. for 60 seconds to form a resist film having a thickness of 100 nm.

  An ArF excimer laser scanner (PAS5500 / 1100, NA0.75, Dipole, outer sigma 0.89, inner sigma 0.65) manufactured by ASML was used for the obtained wafer, and an exposure mask (line / space = 1/1). ) Was used to perform pattern exposure. Then, after heating at 100 ° C. for 60 seconds, the developer shown in Table 6 below is flowed onto the wafer for 30 seconds while rotating the wafer at a rotation speed of 500 rpm, and paddled for 30 seconds with the rinse solution shown in the same table. After rinsing, the wafer was rotated at 4000 rpm for 30 seconds and baked at 90 ° C. for 60 seconds to obtain a 100 nm (1: 1) line-and-space resist pattern.

<Example 4 (immersion exposure → bake → development → rinse: abbreviation tiE-B-D-R)>
An organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied onto the silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 95 nm. A resist composition Ar-4 was applied thereon and baked at 100 ° C. for 60 seconds to form a resist film having a thickness of 100 nm. Furthermore, the topcoat composition t-1 was applied thereon, and baked at 100 ° C. for 60 seconds to form a topcoat film having a thickness of 100 nm.

  The obtained wafer was exposed using an ArF excimer laser immersion scanner (manufactured by ASML, XT1700i, NA 1.20, C-Quad, outer sigma 0.981, inner sigma 0.895, XY deflection). Pattern exposure was performed via space = 1/1). At this time, ultrapure water was used as the immersion liquid. Then, after heating at 100 ° C. for 60 seconds, the developer described in Table 6 below was paddled for 30 seconds to develop, padded with a rinse solution listed in the same table for 30 seconds, rinsed at 4000 rpm. The wafer was rotated for 30 seconds and baked at 90 ° C. for 60 seconds to obtain a 100 nm (1: 1) line-and-space resist pattern.

<Example 27 (Inorganic antireflection film substrate->exposure->bake->development-> rinse: abbreviation I-E-B-D-R)>
A 100 nm (1: 1) line-and-space resist pattern was obtained in the same manner as in Example 2 except that a SiON substrate was used as the substrate having an inorganic antireflection film.

  In Table 6, “PB” represents heating before exposure, and “PEB” represents heating after exposure. In each column of “PB”, “top coat bake”, and “PEB”, “XCYs” means that heating was performed at X ° C. for Y seconds. A1 and B1 in each column of “developer” and “rinse” represent the above-described solvents.

<Evaluation method>
[Sensitivity (Eopt)]
The obtained resist pattern was observed using a length-measuring scanning electron microscope (SEM, Ltd., Hitachi, Ltd. S-9380II). The exposure amount at which the line width of the pattern obtained by measuring the average value becomes the desired line width (100 nm (1: 1) line and space) was defined as the resist sensitivity.

[Line width roughness (LWR)]
A 100 nm (1: 1) line-and-space resist pattern was observed using a length-measuring scanning electron microscope (SEM, Hitachi, Ltd., S-9380II), and the range of the space pattern in the longitudinal direction of 2 μm was equally spaced. The 50 dotted line width was measured, and 3σ (nm) was calculated from the standard deviation. A smaller value indicates better performance.

[Defocus margin (DOF)]
When the exposure amount and focus for forming a 100 nm (1: 1) line-and-space resist pattern are set to the optimum exposure amount and the optimum focus, respectively, and the focus is changed (defocused) while keeping the exposure amount at the optimum exposure amount. In addition, the width of the focus allowing the pattern size to be 100 nm ± 10% was obtained. The larger the value, the smaller the performance change due to the focus change, and the better the defocus margin (DOF).

[Bridge defect (pattern shape)]
A 100 nm (1: 1) line-and-space resist pattern at the optimum exposure and optimum focus was observed using a length-measuring scanning electron microscope (SEM, Hitachi, Ltd. S-9380II). The level where no bridging defects were found was marked as “Good”, the level where no bridging defects were seen but slightly T-top shape was marked as △ (Fair), and the level where bridging defects were seen as x (Insufficient). .

Table 7 below summarizes the evaluation results for each example.

  From the results shown in Table 7, it was found that the compositions according to the examples were excellent in roughness characteristics, focus margin, and bridge defect performance.

<Examples 28 and 29>
A 100 nm (1: 1) line-and-space resist pattern was obtained in the same manner as in Example 1 except that the resists and conditions listed in Table 8 below were employed.

<Evaluation method>
[Dependence of sensitivity on PEB temperature]
For Examples 28 and 29, the sensitivity Eopt was measured in the same manner as described above. The results are shown in Table 9 below.

  From the results shown in Table 9, it was found that the composition according to the example has small PEB temperature dependency of sensitivity.

<Acid-decomposable resin>
The following resins (P-15) to (P-24) were synthesized in the same manner as described for the resin (P-1).

Table 10 below summarizes the composition ratio (molar ratio), weight average molecular weight, and dispersity of these resins (P-15) to (P-24).

<Preparation of resist composition>
Using these resins, resist compositions shown in Table 11 below were prepared in the same manner as described above.

Using these resist compositions, a resist pattern was formed under the conditions shown in Table 12 below. In Table 12, items such as “process abbreviation” have the same meanings as described above for Table 6.

The evaluation results corresponding to these examples are summarized in Table 13 below. The evaluation method and the like are the same as described above.

  From the results shown in Table 13, it was found that the compositions according to the examples were excellent in roughness characteristics, focus margin, and bridge defect performance.

The PEB temperature dependency was evaluated in the same manner as described above except that the resists and conditions described in Table 14 below were employed. The results are shown in Table 15 below.

  From the results shown in Table 15, it was found that the composition according to the example has small PEB temperature dependency of sensitivity.

Claims (21)

A resin containing a first repeating unit having a group capable of decomposing by the action of an acid to generate an alcoholic hydroxy group and having reduced solubility in a developer containing an organic solvent by the action of an acid;
A first compound that generates an acid upon irradiation with actinic rays or radiation;
Solvent,
An actinic ray-sensitive or radiation-sensitive resin composition containing a second compound containing at least one of a fluorine atom and a silicon atom and having basicity or increasing basicity by the action of an acid.   The composition according to claim 1, wherein the second compound is a nitrogen-containing compound.   The composition according to claim 1, wherein the second compound is a low molecular compound. The composition according to any one of claims 1 to 3, wherein the second compound is represented by the following general formula (1N).

In general formula (1N),
Ra, Rb ₁ , Rb ₂ and Rb ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. At least two of Rb ₁ , Rb ₂ and Rb ₃ may be bonded to each other to form a ring. However, the case where all of Rb ₁ , Rb ₂ and Rb ₃ are simultaneously hydrogen atoms is excluded.
Rc represents a single bond or a divalent linking group.
Rf represents an organic group.
x represents 0 or 1, y represents 1 or 2, z represents 1 or 2, and x + y + z = 3.
When x = z = 1, Ra and Rc may be bonded to each other to form a nitrogen-containing heterocycle.
When z = 1, Rf contains a fluorine atom or a silicon atom.
When z = 2, at least one of the two Rf contains a fluorine atom or a silicon atom, and the two Rc and the two Rf may be the same or different from each other. Two Rc's may be bonded to each other to form a ring.   The composition according to claim 1, wherein the second compound is an oligomer or a polymer compound.   The second compound includes a second repeating unit containing at least one of a fluorine atom and a silicon atom, and a third repeating unit having at least one of a basic group and a group whose basicity is increased by the action of an acid. The composition according to claim 5. The composition according to any one of claims 1 to 6, wherein the first repeating unit is represented by at least one selected from the group consisting of the following general formulas (I-1) to (I-10). .

Where
Each Ra independently represents a hydrogen atom, an alkyl group, or a group represented by —CH ₂ —O—Ra ₂ . Here, Ra2 represents a hydrogen atom, an alkyl group, or an acyl group.
R ₁ represents an (n + 1) valent organic group.
R ₂ independently represents a single bond or an (n + 1) -valent organic group when m ≧ 2.
OP each independently represents the above group which decomposes by the action of an acid to produce an alcoholic hydroxy group. When n ≧ 2 and / or m ≧ 2, two or more OPs may be bonded to each other to form a ring.
W represents a methylene group, an oxygen atom or a sulfur atom.
n and m represent an integer of 1 or more.
l represents an integer of 0 or more.
L ₁ represents a linking group represented by —COO—, —OCO—, —CONH—, —O—, —Ar—, —SO ₃ — or —SO ₂ NH—. Here, Ar represents a divalent aromatic ring group.
Each R independently represents a hydrogen atom or an alkyl group.
R ₀ represents a hydrogen atom or an organic group.
L ₃ represents a (m + 2) -valent linking group.
R ^L each independently represents an (n + 1) -valent linking group when m ≧ 2.
R ^S each independently represents a substituent when p ≧ 2. For p ≧ 2, plural structured R ^S may be bonded to each other to form a ring.
p represents an integer of 0 to 3. The group which is decomposed by the action of an acid to produce an alcoholic hydroxy group is represented by at least one selected from the group consisting of the following general formulas (II-1) to (II-9). The composition according to any one of the above.

Where
R ₃ each independently represents a hydrogen atom or a monovalent organic group. Two R _{3 s} may be bonded to each other to form a ring.
R ₄ each independently represents a monovalent organic group. At least two R ₄ may be bonded to each other to form a ring. R ₃ and R ₄ may be bonded to each other to form a ring.
R ₅ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an alkynyl group. At least two R ₅ may be bonded to each other to form a ring. However, when one or two of the three R ₅ are hydrogen atoms, at least one of the remaining R ₅ represents an aryl group, an alkenyl group, or an alkynyl group.
R ₆ each independently represents a hydrogen atom or a monovalent organic group. R ₆ may be bonded to each other to form a ring. The composition according to any one of claims 1 to 8, wherein the first repeating unit is represented by the following general formula (III).

Where
R ₁ represents an (n + 1) valent organic group.
Ra represents a hydrogen atom, an alkyl group, or a group represented by —CH ₂ —O—Ra ₂ . Here, Ra2 represents a hydrogen atom, an alkyl group, or an acyl group.
R ₃ each independently represents a hydrogen atom or a monovalent organic group. R ₃ may be bonded to each other to form a ring.
R ₄ each independently represents a monovalent organic group when n ≧ 2. R ₄ may be bonded to each other to form a ring. R ₃ and R ₄ may be bonded to each other to form a ring.
n represents an integer of 1 or more. The composition according to claim 9, wherein R ₁ represents a non-aromatic hydrocarbon group. The composition according to claim 10, wherein R ₁ represents an alicyclic hydrocarbon group. 12. The group according to claim 8, wherein the group that decomposes by the action of an acid to produce an alcoholic hydroxy group is represented by the general formula (II-1), and at least one of the R ₃ represents a monovalent organic group. The composition according to claim 1.   The composition according to any one of claims 1 to 12, wherein the first repeating unit includes two or more of the groups that are decomposed by the action of an acid to generate an alcoholic hydroxy group.   The composition according to claim 1, wherein the resin further contains a repeating unit having an alcoholic hydroxy group.   The composition according to claim 1, wherein the resin further includes a repeating unit having a cyano group.   The composition according to any one of claims 1 to 15, wherein the resin further includes a repeating unit having a group that decomposes by the action of an acid to generate a carboxy group.   A resist pattern formed using the composition according to claim 1. (A) forming a film using the composition according to any one of claims 1 to 16,
(B) exposing the film;
(C) A pattern forming method including developing the exposed film.   The method according to claim 18, wherein the development is performed using a developer containing an organic solvent.   The method according to claim 19, wherein the organic solvent contained in the developer is any of ester, ketone, alcohol, amide, ether, and hydrocarbon.   21. The method according to claim 19 or 20, wherein the pattern formed by the development is a negative type.