JP5799050B2 - Actinic ray-sensitive or radiation-sensitive resin composition, resist film using the same, pattern formation method, and electronic device manufacturing method - Google Patents

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a resist film using the same, a pattern formation method, an electronic device manufacturing method, and an electronic device. More specifically, the present invention relates to an ultra-microlithographic process applicable to a manufacturing process of a VLSI and a high-capacity microchip, a process for producing a mold for nanoimprinting, a manufacturing process of a high-density information recording medium, and other photofabrication. The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition suitably used in a process, a resist film using the same, a pattern formation method, an electronic device manufacturing method, and an electronic device.

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

In the development of such lithography technology, for example, various proposals have been made for photoacid generators used in photoresist compositions (see, for example, Patent Documents 1 and 2).
For example, Patent Document 1 describes a benzenesulfonic acid-based photoacid generator. Patent Document 2 describes a fluorinated alkylsulfonic acid photoacid generator having a bond cleaved by an acid. In particular, electron beam lithography is positioned as a next-generation or next-generation pattern forming technique, and a positive resist with high sensitivity and high resolution is desired. In particular, high sensitivity is an important issue for shortening the wafer processing time. However, in the positive resist for electron beams, there is a problem that resolution tends to be lowered when high sensitivity is sought.
Thus, high sensitivity, high resolution, and good pattern shape are in a trade-off relationship, and how to satisfy them simultaneously is important.

  Similarly, in lithography using X-rays or EUV light, it is important to simultaneously satisfy high sensitivity, high resolution, and a good pattern shape.

  However, in the positive image forming method, isolated lines and dot patterns can be formed satisfactorily. However, when an isolated space or a fine hole pattern is formed, the shape of the pattern tends to deteriorate.

In recent years, a pattern forming method using a developer (organic developer) containing an organic solvent is being developed. According to this method, it is supposed that a highly accurate fine pattern can be stably formed. For example, Patent Document 3 describes a photoacid generator having a group that is decomposed by the action of an acid from the viewpoint of resolving power of the dimensions before bridge.
However, the actual situation is that further improvement in performance is required for the exposure latitude (EL), pattern shape, and resolution of isolated space pattern formation in fine pattern formation with a narrow space width using a developer containing an organic solvent. is there.

JP 2005-97254 A JP 2007-196992 A JP 2012-27436 A

  An object of the present invention is to provide a fine isolated space pattern which is excellent in exposure latitude (EL) and pattern shape in the formation of a fine pattern having a narrow space width (for example, on the order of several tens of nm), and particularly difficult to form in alkali development. An actinic ray-sensitive or radiation-sensitive resin composition that can be formed with high resolution, a resist film using the same, a pattern formation method, an electronic device manufacturing method, and an electronic device.

That is, the present invention is as follows.
<1>
An actinic ray-sensitive or radiation-sensitive resin composition containing a compound represented by the following general formula (X).


In the above general formula,
Ar represents an (m + 1) -valent aromatic group, and Ar may further have a substituent other than the sulfonate anion and the m (PL) groups in the general formula (X). Good.
A ⁺ represents an organic cation.
m represents an integer of 1 or more.
L represents a single bond or a divalent linking group. When a plurality of L are present, the plurality of L may be the same or different.
P represents at least one group selected from the group consisting of groups represented by the following general formulas (I) to (IV). When a plurality of P are present, the plurality of P may be the same or different.
However, when P is a group represented by the following general formula (I), L is a single bond, an alkylene group, a cycloalkylene group, an arylene group, an ether bond, an ester bond, or a combination of two or more thereof. It is a divalent linking group.


In the general formula (I),
R ₁₁ represents a hydrogen atom or an alkyl group.
R ₁₂ represents a hydrogen atom, an ether bond or an alkyl group or cycloalkyl group which may contain a carbonyl group, an aryl group, or an aralkyl group.
R ₁₃ represents an alkyl group or a cycloalkyl group, an aryl group or an aralkyl group which may contain an ether bond.
R ₁₁ and R ₁₂ may be bonded to each other to form a ring.
R ₁₂ and R ₁₃ may be bonded to each other to form a ring.
* Represents a bond.
In the general formula (II),
R ₂₁ and R ₂₂ each independently represents an alkyl group or an aralkyl group.
R ₂₃ and R ₂₄ each independently represents an alkyl group or an aralkyl group.
R ₂₅ represents a hydrogen atom or an alkyl group.
At least two of R _{23 to} R ₂₅ may be bonded to each other to form a ring.
* Represents a bond.
In the general formula (III),
L ₂ represents a trivalent linking group.
R ₃₁ and R ₃₄ each independently represents a hydrogen atom or an alkyl group.
R ₃₂ and R ₃₅ each independently represents a hydrogen atom, an ether bond or an alkyl group, cycloalkyl group, aryl group or aralkyl group which may contain a carbonyl group.
R ₃₃ and R ₃₆ each independently represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group that may contain an ether bond.
R ₃₁ and R ₃₂ may be bonded to each other to form a ring.
R ₃₄ and R ₃₅ may be bonded to each other to form a ring.
R ₃₂ and R ₃₃ may be bonded to each other to form a ring.
R ₃₅ and R ₃₆ may be bonded to each other to form a ring.
* Represents a bond.
In the general formula (IV),
L ₃ represents a trivalent linking group.
R ₄₁ and R ₄₂ each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group. R ₄₁ and R ₄₂ may be bonded to each other to form a ring.
* Represents a bond.
<2>
When P in the general formula (X) is a group represented by the general formula (I) and the alkylene group, cycloalkylene group or arylene group for L has a substituent, the substituent is a halogen atom. , Halogen atom, alkyl group, cycloalkyl group, aryl group, amino group, amide group, ureido group, urethane group, hydroxyl group, carboxyl group, alkoxy group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group Or the actinic-ray-sensitive or radiation-sensitive resin composition as described in <1> which is a nitro group.
<3>
The actinic ray-sensitive or radiation-sensitive resin composition according to <1>, wherein L in the general formula (X) is a divalent linking group having a phenylene group.
<4>
The actinic ray-sensitive or radiation-sensitive resin composition according to <1>, wherein L in the general formula (X) is a single bond.
<5>
An actinic ray-sensitive or radiation-sensitive resin composition containing a compound represented by the following general formula (X).


In the above general formula,
Ar represents an (m + 1) -valent aromatic group, and Ar may further have a substituent other than the sulfonate anion and the m (PL) groups in the general formula (X). Good.
A ⁺ represents an organic cation.
m represents an integer of 1 or more.
L represents a single bond or a divalent linking group. When a plurality of L are present, the plurality of L may be the same or different.
P represents at least one group selected from the group consisting of groups represented by the following general formulas (I) to (IV). When a plurality of P are present, the plurality of P may be the same or different.


In the general formula (I),
R ₁₁ represents a hydrogen atom or an alkyl group.
R ₁₂ represents an alkyl group or a cycloalkyl group, an aryl group or an aralkyl group which may contain an ether bond or a carbonyl group.
R ₁₃ represents an alkyl group or a cycloalkyl group, an aryl group or an aralkyl group which may contain an ether bond.
R ₁₁ and R ₁₂ may be bonded to each other to form a ring.
R ₁₂ and R ₁₃ may be bonded to each other to form a ring.
* Represents a bond.
In the general formula (II),
R ₂₁ and R ₂₂ each independently represents an alkyl group or an aralkyl group.
R ₂₃ and R ₂₄ each independently represents an alkyl group or an aralkyl group.
R ₂₅ represents a hydrogen atom or an alkyl group.
At least two of R _{23 to} R ₂₅ may be bonded to each other to form a ring.
* Represents a bond.
In the general formula (III),
L ₂ represents a trivalent linking group.
R ₃₁ and R ₃₄ each independently represents a hydrogen atom or an alkyl group.
R ₃₂ and R ₃₅ each independently represents a hydrogen atom, an ether bond or an alkyl group, cycloalkyl group, aryl group or aralkyl group which may contain a carbonyl group.
R ₃₃ and R ₃₆ each independently represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group that may contain an ether bond.
R ₃₁ and R ₃₂ may be bonded to each other to form a ring.
R ₃₄ and R ₃₅ may be bonded to each other to form a ring.
R ₃₂ and R ₃₃ may be bonded to each other to form a ring.
R ₃₅ and R ₃₆ may be bonded to each other to form a ring.
* Represents a bond.
In the general formula (IV),
L ₃ represents a trivalent linking group.
R ₄₁ and R ₄₂ each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group. R ₄₁ and R ₄₂ may be bonded to each other to form a ring.
* Represents a bond.
<6>
The actinic ray-sensitive or radiation-sensitive resin composition according to <5>, wherein R ₁₂ is an alkyl group having 1 to 15 carbon atoms.
<7>
The actinic ray-sensitive or radiation-sensitive resin composition according to <5> or <6>, wherein R ₁₂ is a branched alkyl group having a tertiary carbon atom.
<8>
The actinic ray according to any one of <1> to <7>, wherein P is at least one group selected from the group consisting of groups represented by the general formulas (II) to (IV). Or radiation sensitive resin composition.
<9>
When P in the general formula (X) is a group represented by the general formula (I), L is a single bond or —L ₄ —COO— (L ₄ represents a single bond or a divalent linking group). Actinic ray-sensitive or radiation-sensitive resin composition according to <1> or <5>.
<10>
P in the general formula (X) is a group represented by the general formula (I) or (II), and in the general formula (I), L is —L ₄ —COO— (L ₄ is Represents a single bond or a divalent linking group), or an actinic ray-sensitive or radiation-sensitive resin composition according to <1> or <5>;
<11>
P in the general formula (X) is a group represented by the general formula (I), and L is —L ₄ —COO— (L ₄ represents a single bond or a divalent linking group). The actinic ray-sensitive or radiation-sensitive resin composition according to <10>.
<12>
Actinic ray-sensitive or radiation-sensitive according to <1> or <5>, wherein P in the general formula (X) is a group represented by the general formula (II), and L is a divalent linking group. Resin composition.
<13>
<1> or <5>, further comprising a resin containing a repeating unit having at least one group selected from the group consisting of the groups represented by formulas (I) to (IV). An actinic ray-sensitive or radiation-sensitive resin composition.
<14>
A resin containing a repeating unit having a group represented by the general formula (I) or a repeating unit having a group represented by the general formula (II), which can be decomposed by the action of an acid to generate a carboxyl group The actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1>, <5>, and <13>.
<15>
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <14>, which is exposed to extreme ultraviolet light or an electron beam.
<16>
A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <15>.
<17>
The pattern formation method which has the process of developing the resist film as described in <16>, and developing the said exposed film | membrane.
<18>
The pattern forming method according to <17>, wherein the exposure is performed with extreme ultraviolet rays or electron beams.
<19>
The pattern forming method according to <17> or <18>, wherein the development is performed using a developer containing an organic solvent.
<20>
<17>-<19> The manufacturing method of a semiconductor device containing the pattern formation method of any one of <19>.
Although this invention is invention which concerns on said <1>-<20>, below, other matters (for example, following [1]-[20]) are also described.
[1]
An actinic ray-sensitive or radiation-sensitive resin composition containing a compound represented by the following general formula (X).

In the above general formula,
Ar represents an (m + 1) -valent aromatic group, and the Ar further represents a substituent other than the sulfonate anion (SO ₃ ⁻ ) and the m (PL) groups in the general formula (X). You may have.
A ⁺ represents an organic cation.
m represents an integer of 1 or more.
L represents a single bond or a divalent linking group. When a plurality of L are present, the plurality of L may be the same or different.
P represents at least one group selected from the group consisting of groups represented by the following general formulas (I) to (IV). When a plurality of P are present, the plurality of P may be the same or different.

In the general formula (I),
R ₁₁ represents a hydrogen atom or an alkyl group.
R ₁₂ represents a hydrogen atom, an ether bond or an alkyl group or cycloalkyl group which may contain a carbonyl group, an aryl group, or an aralkyl group.
R ₁₃ represents an alkyl group or a cycloalkyl group, an aryl group or an aralkyl group which may contain an ether bond.
R ₁₁ and R ₁₂ may be bonded to each other to form a ring.
R ₁₂ and R ₁₃ may be bonded to each other to form a ring.
* Represents a bond.
In the general formula (II),
R ₂₁ and R ₂₂ each independently represents an alkyl group or an aralkyl group.
R ₂₃ and R ₂₄ each independently represents an alkyl group or an aralkyl group.
R ₂₅ represents a hydrogen atom or an alkyl group.
At least two of R _{23 to} R ₂₅ may be bonded to each other to form a ring.
* Represents a bond.
In the general formula (III),
L ₂ represents a trivalent linking group.
R ₃₁ and R ₃₄ each independently represents a hydrogen atom or an alkyl group.
R ₃₂ and R ₃₅ each independently represents a hydrogen atom, an ether bond or an alkyl group, cycloalkyl group, aryl group or aralkyl group which may contain a carbonyl group.
R ₃₃ and R ₃₆ each independently represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group that may contain an ether bond.
R ₃₁ and R ₃₂ may be bonded to each other to form a ring.
R ₃₄ and R ₃₅ may be bonded to each other to form a ring.
R ₃₂ and R ₃₃ may be bonded to each other to form a ring.
R ₃₅ and R ₃₆ may be bonded to each other to form a ring.
* Represents a bond.
In the general formula (IV),
L ₃ represents a trivalent linking group.
R ₄₁ and R ₄₂ each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group. R ₄₁ and R ₄₂ may be bonded to each other to form a ring.
* Represents a bond.
[2]
When P in the general formula (X) is a group represented by the general formula (I), L is a single bond or —L ₄ —COO— (L ₄ represents a single bond or a divalent linking group). Actinic ray-sensitive or radiation-sensitive resin composition according to [1].
[3]
P in the general formula (X) is a group represented by the general formula (I) or (II), and in the general formula (I), L is —L ₄ —COO— (L ₄ is Represents a single bond or a divalent linking group.), The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2].
[4]
P in the general formula (X) is a group represented by the general formula (I), and L is —L ₄ —COO— (L ₄ represents a single bond or a divalent linking group). The actinic ray-sensitive or radiation-sensitive resin composition according to [3].
[5]
The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein P in the general formula (X) is a group represented by the general formula (II), and L is a divalent linking group. .
[6]
Any one of [1] to [5], further comprising a resin containing a repeating unit having at least one group selected from the group consisting of the groups represented by the general formulas (I) to (IV). 2. The actinic ray-sensitive or radiation-sensitive resin composition according to item 1.
[7]
A resin containing a repeating unit having a group represented by the general formula (I) or a repeating unit having a group represented by the general formula (II), which can be decomposed by the action of an acid to generate a carboxyl group The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6].
[8]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], which is exposed to extreme ultraviolet light or an electron beam.
[9]
A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8].
[10]
[9] A pattern forming method comprising a step of exposing the resist film according to [9] and a step of developing the exposed film.
[11]
The pattern forming method according to [10], wherein the exposure is performed with extreme ultraviolet rays or an electron beam.
[12]
The pattern forming method according to [10] or [11], wherein the development is performed using a developer containing an organic solvent.
[13]
The manufacturing method of a semiconductor device containing the pattern formation method of any one of [10]-[12].
[14]
A semiconductor device manufactured by the method for manufacturing a semiconductor device according to [13].

The present invention preferably further has the following configuration.
[15]
The compound represented by the said general formula (X).
[16]
Any of the above [1] to [8], wherein Ar has a fluorine atom in addition to the sulfonate anion (SO ₃ ⁻ ) and m (PL) groups in the general formula (X). 2. The actinic ray-sensitive or radiation-sensitive resin composition according to item 1.
[17]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8] and [16] above, wherein the organic cation A ⁺ is a sulfonium cation or an iodonium cation.
[18]
In the above general formula (II), R ₂₁ and R ₂₂ are not bonded to each other to form a ring, and R _{23 to} R ₂₅ are not bonded to form a ring, [1] to [8] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [16] and [17].
[19]
Furthermore, the actinic ray-sensitive or radiation-sensitive resin composition according to any one of the above [1] to [8] and [16] to [18], which contains a basic compound.
[20]
Furthermore, the actinic ray-sensitive or radiation-sensitive resin composition according to any one of the above [1] to [8] and [16] to [19], which further contains a surfactant.

  According to the present invention, it is excellent in EL and pattern shape in forming a fine pattern with a narrow space width (for example, on the order of several tens of nm), and in particular, a fine isolated space pattern that is difficult to form in alkali development is formed with high resolution. An actinic ray-sensitive or radiation-sensitive resin composition that can be used, a resist film using the same, a pattern formation method, a method for manufacturing an electronic device, and an electronic device can be provided.

Hereinafter, embodiments of the present invention will be described in detail.
In addition, in the description of the group (atomic group) in this specification, the description which does not specify substitution or non-substitution is both the thing which does not have a substituent, and the thing which has a substituent. To be included. 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” or “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet (EUV) ray, an X-ray or an electron beam (EB). Yes. In the present invention, “light” means actinic rays or radiation.

  In addition, unless otherwise specified, “exposure” in the present invention is not only exposure with far-ultraviolet rays such as mercury lamps and excimer lasers, X-rays and EUV light, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a compound represented by the following general formula (X).

In the above general formula,
Ar represents an (m + 1) -valent aromatic group, and the Ar further represents a substituent other than the sulfonate anion (SO ₃ ⁻ ) and the m (PL) groups in the general formula (X). You may have.
A ⁺ represents an organic cation.
m represents an integer of 1 or more.
L represents a single bond or a divalent linking group. When a plurality of L are present, the plurality of L may be the same or different.
P represents at least one group selected from the group consisting of groups represented by the following general formulas (I) to (IV). When a plurality of P are present, the plurality of P may be the same or different.

In the general formula (I),
R ₁₁ represents a hydrogen atom or an alkyl group.
R ₁₂ represents a hydrogen atom, an ether bond or an alkyl group or cycloalkyl group which may contain a carbonyl group, an aryl group, or an aralkyl group.
R ₁₃ represents an alkyl group or a cycloalkyl group, an aryl group or an aralkyl group which may contain an ether bond.
R ₁₁ and R ₁₂ may be bonded to each other to form a ring.
R ₁₂ and R ₁₃ may be bonded to each other to form a ring.
* Represents a bond.
In the general formula (II),
R ₂₁ and R ₂₂ each independently represents an alkyl group or an aralkyl group.
R ₂₃ and R ₂₄ each independently represents an alkyl group or an aralkyl group.
R ₂₅ represents a hydrogen atom or an alkyl group.
At least two of R _{23 to} R ₂₅ may be bonded to each other to form a ring.
* Represents a bond.
In the general formula (III),
L ₂ represents a trivalent linking group.
R ₃₁ and R ₃₄ each independently represents a hydrogen atom or an alkyl group.
R ₃₂ and R ₃₅ each independently represents a hydrogen atom, an ether bond or an alkyl group, cycloalkyl group, aryl group or aralkyl group which may contain a carbonyl group.
R ₃₃ and R ₃₆ each independently represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group that may contain an ether bond.
R ₃₁ and R ₃₂ may be bonded to each other to form a ring.
R ₃₄ and R ₃₅ may be bonded to each other to form a ring.
R ₃₂ and R ₃₃ may be bonded to each other to form a ring.
R ₃₅ and R ₃₆ may be bonded to each other to form a ring.
* Represents a bond.
In the general formula (IV),
L ₃ represents a trivalent linking group.
R ₄₁ and R ₄₂ each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group. R ₄₁ and R ₄₂ may be bonded to each other to form a ring.
* Represents a bond.

  The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is excellent in EL and pattern shape in forming a fine pattern (for example, on the order of several tens of nm) with a narrow space width, and particularly difficult to form in alkali development. A pattern (for example, an isolated space pattern) can be formed with high resolution. The reason is not clear, but is estimated as follows.

All of the groups represented by the general formulas (I) to (IV) in the general formula (X) have a small activation energy (Ea) and a high reactivity of the decomposition reaction due to the action of an acid. Thereby, it is considered that the discrimination (contrast) of the progress degree of the decomposition reaction in the general formula (X) becomes clear between the exposed portion and the non-exposed portion in the resist film.
In particular, in the formation of a fine pattern, the content ratio of the photoacid generator in the resist film may be required in a relatively large amount. In such a case, the contrast of the degree of progress of the decomposition reaction in the general formula (X) can affect dissolution discrimination (hereinafter also referred to as dissolution contrast) of the resist film with respect to the developer.
As described above, by using the compound represented by the general formula (X), dissolution discrimination of the resist film containing the compound with respect to the developer is improved, and the EL and pattern shape are improved. It is estimated that a pattern (for example, an isolated space pattern) that is difficult to form in alkali development can be formed with high resolution.
In addition, when the compound represented by the general formula (X) has a (m + 1) -valent aromatic group Ar, a super strong acid such as a fluorinated alkyl sulfonic acid described in Patent Document 2 is used. In comparison, it is presumed that the effect of quenching the acid in the unexposed part works appropriately and improves the pattern shape.

The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may be used for negative development (development in which an exposed portion remains as a pattern and an unexposed portion is removed), or positive development (exposure). Development may be used in which a portion is removed and an unexposed portion remains as a pattern. That is, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is an actinic ray-sensitive or radiation-sensitive resin composition for organic solvent development used in development using a developer containing an organic solvent. Alternatively, it may be an actinic ray-sensitive or radiation-sensitive resin composition for alkali development used for development using an alkali developer. Here, the term “for organic solvent development” means an application provided for a step of developing using at least a developer containing an organic solvent, and the term “for alkali developing” means a step of developing using at least an alkali developer. This means the use for
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is typically a resist composition, particularly a negative resist composition (that is, a resist composition for developing an organic solvent). It is preferable because a high effect can be obtained. The composition according to the present invention is typically a chemically amplified resist composition.
Preferable actinic rays or radiation that can be exposed to the actinic ray-sensitive or radiation-sensitive resin composition of the present invention include, for example, KrF excimer laser, ArF excimer laser, electron beam, X-ray, and extreme ultraviolet (EUV light). It is done. The exposure is preferably performed with an electron beam, an X-ray or EUV light, and more preferably exposed with an EUV light or an electron beam from the viewpoint of forming a fine pattern.

[1] Compound represented by general formula (X) Hereinafter, the compound represented by general formula (X) will be described.
The (m + 1) -valent aromatic group Ar may have a substituent other than the sulfonate anion (SO ₃ ⁻ ) and the m (PL) groups in the general formula (X), An aromatic group having 3 to 35 carbon atoms is preferable, and an aromatic group having 6 to 35 carbon atoms is more preferable. The divalent aromatic group when m is 1 is, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, or a naphthylene group, a divalent diphenyl group, a divalent diphenyl ether group, or For example, a divalent aromatic group containing a heterocyclic ring such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole and the like can be mentioned as a preferred example. A naphthylene group is preferred.

Specific examples of the (m + 1) -valent aromatic group when m is an integer of 2 or more include (m-1) arbitrary hydrogen atoms removed from the above-described specific examples of the divalent aromatic ring group. The group formed can be preferably mentioned.
The (m + 1) -valent aromatic group may have a substituent other than the sulfonate anion (SO ₃ ⁻ ) and the m (PL) groups in the general formula (X). Examples of the group include a group having a halogen atom (particularly a fluorine atom), a halogen atom (fluorine atom, etc.), an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, and a hydroxyl group. Carboxyl group, alkoxy group, thioether group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group, nitro group and the like. From the viewpoint of improving the acid strength of the generated acid, a group having a fluorine atom (for example, A fluorine atom, an alkyl group, a cycloalkyl group, an aryl group, or the like) or a fluorine atom.
Further, as described later, from the viewpoint of controlling the diffusibility of the generated acid to improve the pattern shape, resolving power and EL, the substituent is preferably a bulky substituent, an alkyl group, a cycloalkyl group or More preferred is an aryl group.
m represents an integer of 1 or more, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and still more preferably 1.

L represents a single bond or a divalent linking group. When a plurality of L are present, the plurality of L may be the same or different.
The divalent linking group for L is preferably a divalent linking group having 30 or less carbon atoms, and may be an alkylene group (which may be linear or branched, and has 1 to 10 carbon atoms. An alkylene group is preferable, and an alkylene group having 1 to 3 carbon atoms is more preferable. For example, a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, an octylene group, etc.), a cycloalkylene group (for example, , Cyclopentylene group, cyclohexylene group, adamantylene group, etc.), arylene group (eg, phenylene group, tolylene group, naphthylene group, etc.), ether bond, thioether bond, carbonyl group, ester bond, sulfoxide bond, sulfone bond, Examples include a sulfonate bond and a divalent linking group formed by combining two or more of these. That.
L is a single bond, an alkylene group, a cycloalkylene group (preferably a cyclohexylene group or an adamantylene group), an arylene group (preferably a phenylene group), an ether bond, an ester bond, or a combination of two or more of these The divalent linking group is preferably a divalent linking group formed by combining at least one of an alkylene group having 1 to 6 carbon atoms, a cyclohexylene group or a phenylene group and at least one of an ether bond or an ester bond. More preferably, it is a group.
The alkylene group, cycloalkylene group, and arylene group for L may have a substituent. Specific examples and preferred examples of the substituent include a substituent that the (m + 1) -valent aromatic group Ar may have. Examples similar to the specific examples and preferred examples described above for.
Further, the alkylene group, cycloalkylene group, and arylene group for the (m + 1) -valent aromatic groups Ar and L are bulky from the viewpoint of controlling the diffusibility of the generated acid and improving the pattern shape, resolving power, and EL (for example, , Having 3 to 15 carbon atoms, an alkyl group, a cycloalkyl group, or an aryl group as a substituent. From the above viewpoint, the alkyl group as the substituent is more preferably a branched alkyl group having a secondary or tertiary carbon atom having 3 to 15 carbon atoms, and a secondary or having 3 to 10 carbon atoms. A branched alkyl group having a tertiary carbon atom is more preferable.

P in the general formula (X) represents at least one group selected from the group consisting of groups represented by the general formulas (I) to (IV). However, from the viewpoint of improving the dissolution contrast and improving the pattern shape, resolution and EL, when P in the general formula (X) is a group represented by the general formula (I), L is a single bond or it is preferable -L ₄ -COO- a is. Here, L ₄ represents a single bond or a divalent linking group, and is preferably a divalent linking group. Specific examples of the divalent linking group for L ₄ include those similar to the divalent linking group for L.
Similarly, from the viewpoint of improving dissolution contrast and improving pattern shape, resolution and EL, when P is a group represented by the general formula (II), adjacent L is a divalent linking group. It is preferable.
Among the groups consisting of the groups represented by the above general formulas (I) to (IV) for P, the compound has a high inhibitory effect on the organic developer, and the compound dissolves in the alkaline developer. From the viewpoint of generating a highly accelerating carboxylic acid group, it is a group represented by the general formula (I) or a group represented by the general formula (II) when L is -L ₄ -COO-. It is preferable.
In particular, from the viewpoint of generating a carboxylic acid group having high reactivity, high dissolution deterrence in the above-mentioned organic developer, and high dissolution promotion in an alkaline developer, the above-mentioned case where L is -L ₄ -COO-. A group represented by formula (I-1) is particularly preferable.

The group represented by the general formula (I) will be described.
The alkyl group for R ₁₁ in the general formula (I) may be linear or branched, and is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group or an ethyl group. Can be mentioned.
R ₁₁ is preferably a hydrogen atom.
R ₁₂ represents a hydrogen atom, an alkyl group or a cycloalkyl group, an aryl group, or an aralkyl group which may contain an ether bond (—O—) or a carbonyl group (—CO—).
The alkyl group as R ₁₂ may contain an ether bond or a carbonyl group, may be linear or branched, may have a substituent, and has 1 to 20 carbon atoms. An alkyl group is preferable, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, and an octyl group.
The cycloalkyl group as R ₁₂ may contain an ether bond or a carbonyl group, may have a substituent, and is preferably a cycloalkyl group having 3 to 15 carbon atoms, specifically May include a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like.
The aryl group as R ₁₂ may have a substituent, for example, preferably an aryl group having 6 to 15 carbon atoms, specifically, a phenyl group, a tolyl group, a naphthyl group, an anthryl group. Etc.
The aralkyl group as R ₁₂ may have a substituent, preferably an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylbutyl group, and the like. Can be mentioned.
R ₁₂ is preferably a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 11 carbon atoms. In view of the above, a branched alkyl group having a hydrogen atom or a tertiary carbon atom is preferred.

R ₁₃ represents an alkyl group or a cycloalkyl group, an aryl group or an aralkyl group which may contain an ether bond.
The alkyl group as R ₁₃ may contain an ether bond, may be linear or branched, may have a substituent, and is an alkyl group having 1 to 20 carbon atoms. It is preferable that it is a C1-C15 alkyl group, and it is more preferable.
The cycloalkyl group as R ₁₃ may contain an ether bond, and is preferably a cycloalkyl group having 3 to 15 carbon atoms.
Examples of the aryl group and aralkyl group as R ₁₃ include the same aryl groups and aralkyl groups as those described above as the aryl group and aralkyl group of R ₁₂ .
The ring that R ₁₁ and R ₁₂ may be bonded to each other may contain an ether bond or a carbonyl group, may have a substituent, and is preferably a 5- or 6-membered ring.
The ring that R ₁₂ and R ₁₃ may be bonded to each other may contain an ether bond or a carbonyl group, may have a substituent, and is preferably a 5- or 6-membered ring.
Specific examples and preferred examples of the substituents that each group and ring may have are the same as the specific examples and preferred examples described above for the substituents that the (m + 1) -valent aromatic group Ar may have. It is done.
In particular, the alkyl group, cycloalkyl group, aryl group, or aralkyl group that may contain an ether bond for R ₁₃ preferably has a fluorine atom as a substituent.

  Specific examples of the group represented by the general formula (I) are illustrated below, but the present invention is not limited thereto.

The group represented by the general formula (II) will be described.
R ₂₁ and R ₂₂ are preferably not bonded to each other or bonded to R _{23 to} R ₂₅ to form a ring from the viewpoint of preventing the decrease in the reactivity of the acid decomposition reaction.
The alkyl group as R _{21 to} R ₂₅ may have a substituent, and is preferably an alkyl group having 1 to 15 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, Examples include n-butyl group, sec-butyl group, t-butyl group, neopentyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group.
The alkyl group as R ₂₁ and R ₂₂ is more preferably an alkyl group having 1 to 4 carbon atoms, further preferably a methyl group or an ethyl group, and particularly preferably an ethyl group.
Examples of the aralkyl group as R _{21 to} R ₂₄ include the same aralkyl groups as those described above as the aralkyl group for R ₁₂ .
When R _{23 to} R ₂₅ do not form a ring, R ₂₅ is preferably a hydrogen atom or a methyl group.
The ring formed by bonding at least two of R _{23 to} R ₂₅ to each other may have a substituent, and may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkyl structure having 3 to 8 carbon atoms, and examples thereof include a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, and a cyclooctane structure. As the polycyclic type, a cycloalkyl structure having 6 to 20 carbon atoms is preferable, and examples thereof include an adamantane structure, a norbornane structure, a dicyclopentane structure, a tricyclodecane structure, and a tetracyclododecane structure. A part of carbon atoms in the cycloalkyl structure may be substituted with a hetero atom such as an oxygen atom.
Specific examples and preferred examples of the substituents that each group and ring may have are the same as the specific examples and preferred examples described above for the substituents that the (m + 1) -valent aromatic group Ar may have. It is done.
Specific examples of the group represented by the general formula (II) are illustrated below, but the present invention is not limited thereto.

The group represented by the general formula (III) will be described.
R ₃₁ and R ₃₄ are each independently synonymous with R ₁₁ in the formula (I), and specific examples and preferred examples are also the same.
R ₃₂ and R ₃₅ are each independently synonymous with R ₁₂ in the general formula (I), and specific examples and preferred examples are also the same.
R ₃₃ and R ₃₆ are each independently synonymous with R ₁₃ in formula (I), and specific examples and preferred examples are also the same.
Specific examples and preferred examples of the ring that R ₃₁ and R ₃₂ can be bonded to each other include, as preferred examples, specific examples and preferable examples of the ring that R ₁₁ and R ₁₂ in the above general formula (I) can be bonded to each other. The same thing is mentioned.
Specific examples and preferred examples of the ring that R ₃₄ and R ₃₅ can be bonded to each other include, as preferred examples, specific examples and preferable examples of the ring that R ₁₁ and R ₁₂ in the above general formula (I) can be bonded to each other. The same thing is mentioned.
Specific examples and preferred examples of the ring that R ₃₂ and R ₃₃ can be bonded to each other include, as preferred examples, specific examples and preferred examples of the ring that R ₁₂ and R ₁₃ in the general formula (I) can be bonded to each other. The same thing is mentioned.
Specific examples and preferred examples of the ring that R ₃₅ and R ₃₆ can be bonded to each other include, as preferred examples, specific examples and preferred examples of the ring that R ₁₂ and R ₁₃ in the above general formula (I) can be bonded to each other. The same thing is mentioned.
The trivalent linking group L ₂ may have a substituent, and includes an alkyl group, a cycloalkyl group, an aryl group, or a structure obtained by combining any two hydrogen atoms from a structure formed by combining them. It is done.
The alkyl group is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably an alkyl group having 3 to 10 carbon atoms, For example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, and an octyl group can be exemplified.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 15 carbon atoms, more preferably a cycloalkyl group having 3 to 10 carbon atoms, specifically, a cyclopentyl group or a cyclohexyl group. , Norbornyl group, adamantyl group and the like.
The aryl group is preferably an aryl group having 6 to 15 carbon atoms, and specific examples include a phenyl group, a tolyl group, a naphthyl group, and an anthryl group.
The trivalent linking group L ₂ is preferably an alkyl group, a cycloalkyl group, or a structure obtained by combining any two hydrogen atoms from a structure formed by combining them.
Specific examples and preferred examples of the substituents that each group and ring may have are the same as the specific examples and preferred examples described above for the substituents that the (m + 1) -valent aromatic group Ar may have. It is done.
Specific examples of the trivalent linking group L ₂ are illustrated below, but the present invention is not limited thereto.

  Specific examples of the group represented by the general formula (III) are illustrated below, but the present invention is not limited thereto.

The group represented by the general formula (IV) will be described.
The alkyl group for R ₄₁ and R ₄₂ may be linear or branched, may have a substituent, and is preferably an alkyl group having 1 to 20 carbon atoms, For example, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, and an octyl group can be exemplified.
The cycloalkyl group for R ₄₁ and R ₄₂ may contain an ether bond or a carbonyl group, may have a substituent, and is preferably a cycloalkyl group having 3 to 15 carbon atoms. Specific examples include a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like.
The ring that R ₄₁ and R ₄₂ may be bonded to each other may contain an ether bond or a carbonyl group, may have a substituent, and is preferably a 5- or 6-membered ring.
The trivalent linking group L ₃ has the same meaning as L ₂ in the general formula (III), and specific examples and preferred examples are also the same as L ₂ .
Specific examples and preferred examples of the substituents that each group and ring may have are the same as the specific examples and preferred examples described above for the substituents that the (m + 1) -valent aromatic group Ar may have. It is done.
Specific examples of particularly preferred examples of the trivalent linking group L ₃ are illustrated below, but the present invention is not limited thereto. * Represents a bond.

  Specific examples of the group represented by the general formula (IV) are illustrated below, but the present invention is not limited thereto.

Hereinafter, a sulfonate anion of the compound represented by the general formula ^(X) (SO 3 _-) are shown below Specific examples of the anion moiety with, the present invention is not limited thereto.

The organic cation A ⁺ in the general formula (X) will be described.
In the general formula (X), the organic cation A ⁺ is preferably a sulfonium cation or an iodonium cation.
In one embodiment of the present invention, A ⁺ is preferably a structure represented by the following general formula (ZA-1) or (ZA-2).

In General Formula (ZA-1), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group. The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.

Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure (including a condensed ring), and in addition to the sulfur atom in the formula, an oxygen atom, a sulfur atom, an ester bond, an amide It may contain a bond or a carbonyl group.

Examples of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include (ZA-1-1) and (ZA-1-) described below as preferred groups of the group represented by the general formula (ZA-1). 2) and a corresponding group in the group represented by (ZA-1-3). Particularly preferred are the corresponding groups in the groups represented by (ZA-1-1) and (ZA-1-3).

  First, the (ZA-1-1) group will be described.

The (ZA-1-1) group is a group having arylsulfonium as a cation, wherein at least one of R _{201 to} R ₂₀₃ in the general formula (ZA-1) is an aryl group.

All of R _{201 to} R ₂₀₃ may be an aryl group, or a part of R _{201 to} R ₂₀₃ may be an aryl group, and the rest may be an alkyl group or a monovalent aliphatic hydrocarbon ring group.

  For example, groups corresponding to triarylsulfonium, diarylalkylsulfonium, aryldialkylsulfonium, diarylcycloalkylsulfonium, aryldicycloalkylsulfonium can be exemplified.

  The aryl group in arylsulfonium is preferably a phenyl group or a naphthyl 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 structures such as pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.

  When arylsulfonium has two or more aryl groups, the two or more aryl groups may be the same or different.

  The alkyl group or monovalent aliphatic hydrocarbon ring group that arylsulfonium has as necessary is a linear or branched alkyl group having 1 to 15 carbon atoms and monovalent aliphatic carbonization having 3 to 15 carbon atoms. A hydrogen ring group is preferable, and examples thereof include a methyl group, 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. The monovalent aliphatic hydrocarbon ring group is preferably a cycloalkyl group.

The aryl group, alkyl group, and monovalent aliphatic hydrocarbon ring group represented by R _{201 to} R ₂₀₃ are an alkyl group (for example, having 1 to 15 carbon atoms) and a monovalent aliphatic hydrocarbon ring group (for example, having 3 to 15 carbon atoms). Preferably having a cycloalkyl group having 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms), an alkoxy group (for example having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group as substituents. May be. Preferred examples of the substituent include a linear or branched alkyl group having 1 to 12 carbon atoms, a monovalent aliphatic hydrocarbon ring group having 3 to 12 carbon atoms (preferably a cycloalkyl group having 3 to 12 carbon atoms), and 1 carbon atom. -12 linear, branched or cyclic alkoxy groups, more preferably 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 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.

  More preferable groups represented by (ZA-1-1) include structures represented by triarylsulfonium and the following general formulas (ZA-1-1A) and (ZA-1-1B).

In general formula (ZA-1-1A),
R ^{1a to} R ^13a each independently represents a hydrogen atom or a substituent, and at least one of R ^{1a to} R ^13a is preferably a substituent containing an alcoholic hydroxyl group.
Za is a single bond or a divalent linking group.
The alcoholic hydroxyl group in the present invention represents a hydroxyl group bonded to a carbon atom of a chain or cyclic alkyl group.

When R < ^1a > -R <^13a> is a substituent containing an alcoholic hydroxyl group, R < ^1a > -R <^13a> is represented by -W-Y. However, Y is a chain or cyclic alkyl group substituted with a hydroxyl group, and W is a single bond or a divalent linking group.

As the chain or cyclic alkyl group of Y, 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, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group etc. can be mentioned, preferably ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, It is a sec-butyl group, more preferably an ethyl group, a propyl group, or an isopropyl group. Y particularly preferably contains a —CH ₂ CH ₂ OH structure.

  W is preferably a single bond, or any hydrogen atom in an alkoxy group, acyloxy group, acylamino group, alkyl and arylsulfonylamino group, alkylthio group, alkylsulfonyl group, acyl group, alkoxycarbonyl group, and carbamoyl group is a single bond. It is a substituted divalent group, and more preferably a single bond or a divalent group in which any hydrogen atom in an acyloxy group, alkylsulfonyl group, acyl group or alkoxycarbonyl group is replaced with a single bond.

When R ^{1a to} R ^13a are a substituent containing an alcoholic hydroxyl group, the number of carbon atoms contained is preferably 2 to 10, more preferably 2 to 6, and particularly preferably 2 to 4. .
The substituent containing an alcoholic hydroxyl group as R ^{1a to} R ^13a may have two or more alcoholic hydroxyl groups. The number of alcoholic hydroxyl groups of the substituent containing an alcoholic hydroxyl group as R ^{1a to} R ^13a is 1 to 6, preferably 1 to 3, and more preferably 1.

The number of alcoholic hydroxyl groups contained in the cation represented by the general formula (ZA-1-1A) is preferably 1 to 10 in total for all of R ^{1a to} R ^13a , more preferably 1 to 6 And more preferably 1 to 3.

When R ^{1a to} R ^13a do not contain an alcoholic hydroxyl group, R ^{1a to} R ^13a are preferably a hydrogen atom or a halogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group (preferably a cycloalkyl group), an alkenyl group. Group (including cycloalkenyl group and bicycloalkenyl group), alkynyl group, aryl group, cyano group, carboxyl group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino Group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, alkylthio group, arylthio group, sulfamoyl group, alkyl and arylsulfonyl group, aryloxycarbonyl group, alkoxycarbo Group, a carbamoyl group, an imido group, a silyl group, a ureido group.

When R ^{1a to} R ^13a do not contain an alcoholic hydroxyl group, R ^{1a to} R ^13a are more preferably a hydrogen atom or a halogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group (preferably a cycloalkyl group), A cyano group, an alkoxy group, an acyloxy group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an alkyl and arylsulfonylamino group, an alkylthio group, a sulfamoyl group, an alkyl and arylsulfonyl group, an alkoxycarbonyl group, and a carbamoyl group.

Further, when R ^{1a to} R ^13a do not contain an alcoholic hydroxyl group, R ^{1a to} R ^13a are particularly preferably a hydrogen atom or an alkyl group, a monovalent aliphatic hydrocarbon ring group (preferably a cycloalkyl group), a halogen atom. An atom or an alkoxy group.

Further, two adjacent ones of R ^{1a to} R ^13a are combined to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring. These are further combined to form a polycyclic fused ring. For example, benzene ring, naphthalene ring, anthracene ring, phenanthrene 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, phenanthridine ring, acridi Ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring and a phenazine ring.) May also be formed.

In general formula (ZA-1-1A), at least one of R ^{1a to} R ^13a contains an alcoholic hydroxyl group, and preferably at least one of R ^{9a to} R ^13a contains an alcoholic hydroxyl group.

Za represents a single bond or a divalent linking group, and examples of the divalent linking group include an alkylene group, an arylene group, a carbonyl group, a sulfonyl group, a carbonyloxy group, a carbonylamino group, a sulfonylamide group, an ether group, A thioether group, an amino group, a disulfide group, an acyl group, an alkylsulfonyl group, —CH═CH—, —C≡C—, an aminocarbonylamino group, an aminosulfonylamino group, etc., and these groups have a substituent. May be. These substituents are the same as the substituents shown for R ^{1a to} R ^13a above. Za preferably has a single bond, an alkylene group, an arylene group, an ether group, a thioether group, an amino group, —CH═CH—, —C≡C—, an aminocarbonylamino group, an aminosulfonylamino group, or the like. A substituent, more preferably a single bond, an ether group or a thioether group, particularly preferably a single bond.

Next, general formula (ZA-1-1B) will be described.
In General Formula (ZA-1-1B), each R ₁₅ independently represents an alkyl group, a monovalent aliphatic hydrocarbon ring group (preferably a cycloalkyl group), or an aryl group. Two R ₁₅ may be bonded to each other to form a ring.
X ₂ is _{-CR 21 = CR 22 -, -} NR 23 -, - S -, - O- represents any. Here, R ₂₁ and R ₂₂ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group (preferably a cycloalkyl group), or an aryl group. R ₂₃ represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group (preferably a cycloalkyl group), an aryl group or an acyl group.
When there are a plurality of Rs, they each independently represent a substituent. As a substituent of R, the group corresponding to general formula (ZI-1)-(ZI-3) demonstrated below as a preferable aspect of general formula (ZA-1-1B) can be mentioned, for example.

n represents an integer of 0 to 3.
n1 represents an integer of 0 to 11.

The alkyl group in R ₁₅ and R _{21 to} R ₂₃ 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, It may have a nitrogen atom.

  In addition, as the alkyl group having a substituent, a group in which a monovalent aliphatic hydrocarbon ring group (preferably a cycloalkyl group) is substituted on a linear or branched alkyl group (for example, an adamantylmethyl group, an adamantylethyl group, cyclohexyl) Ethyl group, camphor residue, etc.).

The monovalent aliphatic hydrocarbon ring group in R ₁₅ and R _{21 to} R ₂₃ may have a substituent, preferably a cycloalkyl group, more preferably a cycloalkyl group having 3 to 20 carbon atoms. And may have an oxygen atom in the ring.

The aryl group in R ₁₅ and R _{21 to} R ₂₃ may have a substituent, and is preferably an aryl group having 6 to 14 carbon atoms.

The alkyl group in the acyl group for R ₂₃ is the same as the specific examples and preferred ranges of the alkyl group described above.

  Examples of the substituent that each of these groups may have include, for example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxy group, a carbonyl group, an alkyl group (preferably having a carbon number of 1 to 10), and a monovalent group. An aliphatic hydrocarbon ring group (preferably having 3 to 10 carbon atoms, more preferably a cycloalkyl group having 3 to 10 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxy group (preferably having a carbon number) 1-10), an aryloxy group (preferably having 6 to 14 carbon atoms), an acyl group (preferably having 2 to 20 carbon atoms), an acyloxy group (preferably having 2 to 10 carbon atoms), an alkoxycarbonyl group (preferably having a carbon number) 2-20), an aminoacyl group (preferably having 2 to 20 carbon atoms), an alkylthio group (preferably having 1 to 10 carbon atoms), an arylthio group (preferably having 6 to 14 carbon atoms), Etc., and the like. About the cyclic structure in an aryl group, a monovalent aliphatic hydrocarbon ring group, and the aminoacyl group, the substituent may further have an alkyl group (preferably having 1 to 20 carbon atoms).

The ring that may be formed by bonding two R ₁₅ to each other is a ring structure formed with —S ⁺ represented by the formula (ZA-1-1B), and is a 5-membered member containing one sulfur atom. A ring or a condensed ring containing the ring is preferred. In the case of a condensed ring, those containing one sulfur atom and 18 or less carbon atoms are preferred, and more preferred are ring structures represented by the following general formulas (IV-1) to (IV-3).
In the formula, * represents a bond. R represents an arbitrary substituent, and examples thereof include the same substituents that each group in R ₁₅ and R _{21 to} R ₂₃ may have. n represents an integer of 0 to 4. n ₂ represents an integer of 0 to 3.

  Among the cations represented by the general formula (ZA-1-1B), preferable cation structures include the following cation structures (ZI-1) to (ZI-3).

  The cation structure (ZI-1) is a structure represented by the following general formula (ZI-1).

In general formula (ZI-1),
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a monovalent aliphatic hydrocarbon ring group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton.

When there are a plurality of R _{14 s,} each independently represents an alkyl group, a monovalent aliphatic hydrocarbon ring group, an alkoxy group, an alkylsulfonyl group, a cycloalkylsulfonyl group, a hydroxyl group, or a monocyclic or polycyclic cycloalkyl skeleton. Represents a group having
R ₁₅ each independently represents an alkyl group, a monovalent aliphatic hydrocarbon ring group, or an aryl group. Two R ₁₅ may be bonded to each other to form a ring.
l represents an integer of 0-2.
r represents an integer of 0 to 8.

In the general formula (ZI-1), 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 more preferable.

The monovalent aliphatic hydrocarbon ring group represented by R ₁₃ , R ₁₄ and R ₁₅ may be monocyclic or polycyclic, preferably has 3 to 12 carbon atoms, and is preferably cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexane. Examples include butyl, cyclooctyl, cyclododecanyl, cyclopentenyl, cyclohexenyl, cyclooctadienyl, bicycloheptyl (norbornyl), adamantyl, and the like, and cyclopropyl, cyclopentyl, cyclohexyl, and cyclooctyl are more preferable. The monovalent aliphatic hydrocarbon ring group is preferably a cycloalkyl group.

The aryl group for R ₁₅ is preferably an aryl group having 6 to 14 carbon atoms, and more preferably a phenyl group or a naphthyl group.

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

The alkoxycarbonyl group for R ₁₃ is linear or branched and preferably has 2 to 11 carbon atoms, and examples thereof include those in which the alkyl group in R ₁₃ , R ₁₄ and R ₁₅ is substituted with a carbonyl group. Methoxycarbonyl group, ethoxycarbonyl group, 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, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxy Carbo It can be exemplified Le group. Of these alkoxycarbonyl groups, a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, and the like are more 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 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, and a monocyclic ring It is preferable to have a cycloalkyl skeleton. Monocyclic cycloalkyloxy group having 7 or more carbon atoms in total is cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy 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, iso-amyl group, hydroxyl 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 Monocyclic cycloalkyloxy having substituents such as alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, acyl groups such as formyl group, acetyl group, benzoyl group, acyloxy groups such as acetoxy group, 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 7 or more total carbon atoms include a norbornyloxy group, a tricyclodecanyloxy group, a tetracyclodecanyloxy group, an adamantyloxy 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 which may have the above-mentioned substituent is substituted on an alkoxy group such as sec-butoxy, t-butoxy, iso-amyloxy, etc., and the total carbon number including the substituent is 7 or more. Represents things. Examples thereof 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 adamantyl methoxy group, an adamantyl ethoxy group, etc. are mentioned, A norbornyl methoxy group, a norbornyl ethoxy group, etc. are preferable.

The alkylsulfonyl group and cycloalkylsulfonyl group of R ₁₄ are linear, branched, or cyclic, and preferably have 1 to 10 carbon atoms. For example, the alkyl group in R ₁₃ , R _14, and R ₁₅ is sulfonyl. Examples thereof include 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 and the like. 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 more preferable.
l is preferably 0 or 1, and more preferably 1.
As r, 0-2 are preferable.

Each group of R ₁₃ , R ₁₄ and R ₁₅ may further have a substituent, and examples of the substituent which may be included include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Alkyl groups such as hexyl group, heptyl group, octyl group, dodecyl group, 2-ethylhexyl group, isopropyl group, sec-butyl group, t-butyl group, iso-amyl group, monovalent aliphatic hydrocarbon ring group ( It may be monocyclic or polycyclic and preferably has 3 to 20 carbon atoms, more preferably 5 to 8 carbon atoms), hydroxyl group, halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, amide group , Sulfonamido group, alkoxy group, alkoxyalkyl group, alkoxycarbonyl group, alkoxycarbonyloxy group, formyl group, acetyl group, benzoyl group and other acyl groups, acetoxy Groups, acyloxy groups such as a butyryloxy group, and substituents such as a carboxy group.

  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 straight-chain, branched or cyclic alkoxycarbonyloxy groups having 2 to 21 carbon atoms such as carbonyloxy group and cyclohexyloxycarbonyloxy group.

As a ring structure that two R ₁₅ may be bonded to each other, a divalent group formed by bonding two R ₁₅ together with a sulfur atom in the general formula (ZI-1) A 5-membered ring or a 6-membered ring to be formed, particularly preferably a 5-membered ring (that is, a tetrahydrothiophene ring) is mentioned. You may do it. The divalent group may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxy group. Examples thereof include a carbonyl group and an alkoxycarbonyloxy group.

R ₁₅ in the general formula (ZI-1) includes a methyl group, an ethyl group, a naphthyl group, a divalent group in the case where two R ₁₅ are bonded to each other to form a tetrahydrothiophene ring structure with a sulfur atom, and the like. preferable.

R ₁₃ alkyl group, monovalent aliphatic hydrocarbon ring group, alkoxy group, or alkoxycarbonyl group, R ₁₄ alkyl group, monovalent aliphatic hydrocarbon ring group, alkoxy group, alkylsulfonyl group, cycloalkylsulfonyl The group may be substituted as described above, and the substituent is preferably a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, or a halogen atom (particularly a fluorine atom).
Below, the preferable specific example of the cation structure represented by general formula (ZI-1) is shown.

  The cation structure (ZI-2) is a structure represented by the following general formula (ZI-2).

In general formula (ZI-2),
X _I-2 represents an oxygen atom, a sulfur atom, or a —NRa ₁ — group, and Ra ₁ represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group, or an acyl group.

Ra ₂ and Ra ₃ each independently represents an alkyl group, a monovalent aliphatic hydrocarbon ring group, an alkenyl group or an aryl group. Ra ₂ and Ra ₃ may be bonded to each other to form a ring.

Ra ₄ is each independently in the presence of two or more groups, represents a monovalent group.
m represents an integer of 0 to 3.

The alkyl group of Ra _{1 to} Ra ₃ is preferably a linear or branched alkyl group having 1 to 20 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, sec- Butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl And an eicosyl group.

The monovalent aliphatic hydrocarbon ring group of Ra _{1 to} Ra ₃ is preferably a monovalent aliphatic hydrocarbon ring group having 3 to 20 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, or a cyclohexyl group. Group, cyclooctyl group, adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinanyl group, tricyclodecanyl group, tetracyclododecyl group and androstanyl group. The monovalent aliphatic hydrocarbon ring group is preferably a cycloalkyl group.

The aryl group of Ra _{1 to} Ra ₃ is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

The acyl group of Ra ₁ is preferably an acyl group having 2 to 20 carbon atoms, and examples thereof include a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a pivaloyl group, and a benzoyl group.

The alkenyl group of Ra ₂ and Ra ₃ is preferably an alkenyl group having 2 to 15 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.

The ring structure that Ra ₂ and Ra ₃ may be bonded to each other includes a 5- or 6-membered ring, particularly preferably a 5-membered ring (for example, tetrahydro) together with the sulfur atom in the general formula (ZI-2). A group that forms a thiophene ring), may contain an oxygen atom, and specifically, the same ring as that formed by bonding of R ₁₅ in the general formula (ZI-1) may be used. Can be mentioned.

Examples of the monovalent group for Ra ₄ include an alkyl group (preferably having 1 to 20 carbon atoms) and a monovalent aliphatic hydrocarbon ring group (preferably having 3 to 20 carbon atoms, more preferably 3 carbon atoms). -20 cycloalkyl group), aryl group (preferably 6-10 carbon atoms), alkoxy group (preferably 1-20 carbon atoms), acyl group (preferably 2-20 carbon atoms), acyloxy group (preferably carbon 2-20), fluorine atom, chlorine atom, bromine atom, iodine atom, hydroxyl group, carboxyl group, nitro group, cyano group, alkoxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, arylcarbonyl group, alkylcarbonyl group, alkenyl A carbonyl group etc. can be mentioned.
Ra ₁ is more preferably an alkyl group, and still more preferably an alkyl group having 1 to 4 carbon atoms.

Ra ₂ and Ra ₃ are more preferably connected to each other to form a 5- to 6-membered ring.
Each group in Ra _{1 to} Ra ₄ may further have a substituent, and examples of the further substituent that may be included include each group of R _{13 to} R ₁₅ in formula (ZI-1). The thing similar to the further substituent which you may have is mentioned.
Below, the preferable specific example of a cation structure (ZI-2) is shown.

  The cation structure (ZI-3) is a structure represented by the following general formula (ZI-3).

In general formula (ZI-3), R _{41 to} R ₄₃ each independently represents an alkyl group, an acetyl group, an alkoxy group, a carboxy group, a halogen atom, a hydroxyl group, or a hydroxyalkyl group.
Examples of the alkyl group and alkoxy group as R _{41 to} R ₄₃ include the same groups as R _{13 to} R ₁₅ in formula (ZI-1).
The hydroxyalkyl group is preferably a group in which one or more hydrogen atoms of the above alkyl group are substituted with a hydroxy group, and examples thereof include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and the like.
n1 is an integer of 0 to 3, preferably 1 or 2, and more preferably 1.
n2 is an integer of 0 to 3, preferably 0 or 1, and more preferably 0.
n3 is an integer of 0 to 2, preferably 0 or 1, and more preferably 1.
Each group in R _{41 to} R ₄₃ may further have a substituent, and examples of the further substituent that may be included include each group of R _{13 to} R ₁₅ in formula (ZI-1). The thing similar to the further substituent which you may have is mentioned.
The preferable specific example of a cation structure (ZI-3) is shown below.

  Of the cation structures represented by the general formulas (ZI-1) to (ZI-3), preferred structures are (ZI-1) and (ZI-2), and more preferred is (ZI-1). .

Next, (ZA-1-2) will be described.
(ZA-1-2) is a group in which R _{201 to} R ₂₀₃ in General Formula (ZA-1) 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 not containing an 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 monovalent aliphatic hydrocarbon ring group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, 2- An oxoaliphatic hydrocarbon ring group and an alkoxycarbonylmethyl group, particularly preferably a linear or branched 2-oxoaliphatic hydrocarbon ring group.

As the alkyl group and aliphatic hydrocarbon ring group of R _{201 to} R ₂₀₃ , a linear or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group) ), An aliphatic hydrocarbon ring group having 3 to 10 carbon atoms (for example, 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 aliphatic hydrocarbon ring group include a 2-oxoaliphatic hydrocarbon ring group. The aliphatic hydrocarbon ring group is preferably a cycloalkyl 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.

  Preferred examples of the 2-oxoaliphatic hydrocarbon ring group include a group having> C═O at the 2-position of the above aliphatic hydrocarbon ring group. The 2-oxoaliphatic hydrocarbon ring group is preferably a 2-oxocycloalkyl 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 (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

Next, (ZA-1-3) will be described.
(ZA-1-3) is a group represented by the following general formula and is a group having a phenacylsulfonium cation structure.

In the general formula (ZA-1-3), R _{1c to} R _5c each independently represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, an alkoxy group, a phenylthio group, or a halogen atom. Represent.
R _6c and R _7c each independently represent a hydrogen atom, an alkyl group or a monovalent aliphatic hydrocarbon ring group.

R _x and R _y each independently represents an alkyl group, a monovalent aliphatic hydrocarbon ring 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, 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.

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.

Further, the monovalent aliphatic hydrocarbon ring group as R _{1c to} R _7c may be monocyclic or polycyclic, for example, monovalent aliphatic carbonization having 3 to 8 carbon atoms. Examples thereof include a hydrogen ring group (for example, cyclopentyl group, cyclohexyl group). The monovalent aliphatic hydrocarbon ring group is preferably a cycloalkyl group.

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 monovalent aliphatic hydrocarbon ring group, or a linear, branched or cyclic alkoxy group, and more preferably R _{1c to} R 5 The sum of the carbon number of _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.

Examples of the alkyl group and monovalent aliphatic hydrocarbon ring group as R _x and R _y include the same alkyl group and monovalent aliphatic hydrocarbon ring group as in R _{1c to} R _7c , and 2- An oxoalkyl group, a 2-oxoaliphatic hydrocarbon ring group, and an alkoxycarbonylmethyl group are more preferable.

Examples of the 2-oxoalkyl group and 2-oxoaliphatic hydrocarbon ring group include a group having> C═O at the 2-position of the alkyl group and aliphatic hydrocarbon ring group as R _{1c to} R _7c .

As for the alkoxy group in the alkoxycarbonylmethyl group, the same alkoxy groups as in R _{1c to} R _5c can be exemplified.

R _x and R _y are preferably an alkyl group having 4 or more carbon atoms or a monovalent aliphatic hydrocarbon ring group, more preferably 6 or more, still more preferably 8 or more alkyl groups or a monovalent An aliphatic hydrocarbon ring 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 (ZA-1 -3) A 5-membered or 6-membered ring formed together with the sulfur atom in FIG.

Next, general formula (ZA-2) is demonstrated.
In General Formula (ZA-2), R ₂₀₄ and R ₂₀₅ each independently represents an aryl group, an alkyl group, or a monovalent aliphatic hydrocarbon ring group.

The aryl group for R ₂₀₄ and R ₂₀₅ is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group of R ₂₀₄ and R ₂₀₅ 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 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 a monovalent aliphatic hydrocarbon ring group in R ₂₀₄ and R _205, preferably a linear or branched alkyl group (e.g., methyl group having 1 to 10 carbon atoms, an ethyl group, a propyl group, a butyl group Pentyl group) and monovalent aliphatic hydrocarbon ring groups having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, norbornyl group). The monovalent aliphatic hydrocarbon ring group is preferably a cycloalkyl group.

Aryl groups R ₂₀₄ and R _205, an alkyl group, a monovalent aliphatic hydrocarbon ring group may have a substituent. Aryl groups R ₂₀₄ and R _205, an alkyl group, Examples of the monovalent aliphatic hydrocarbon ring group substituents which may be possessed by, for example, an alkyl group (for example, 1 to 15 carbon atoms), a monovalent aliphatic An aromatic hydrocarbon ring group (for example, a cycloalkyl group having 3 to 15 carbon atoms, preferably a cycloalkyl group having 3 to 15 carbon atoms), an aryl group (for example, 6 to 15 carbon atoms), an alkoxy group (for example, 1 to 15 carbon atoms), A halogen atom, a hydroxyl group, a phenylthio group, etc. can be mentioned.
The organic cation A ⁺ may be a cation present in the resin (P) described later.
More specifically, the resin represented by the general formula (X) has an organic cation A ⁺ that is decomposed by irradiation with actinic rays or radiation in the side chain (from the main chain through a single bond or a linking group). It may be. When the compound represented by the general formula (X) is a resin having an organic cation A ⁺ , examples of the repeating unit that the resin may have include the same repeating units as the repeating unit that the resin (P) may have. The preferred range of the average weight molecular weight and the degree of dispersion of the resin is the same as the preferred range of the average weight molecular weight and the degree of dispersion of the resin (P).
In this case, the compound represented by the general formula (X) is preferably a resin having a repeating unit having a structural site that decomposes upon irradiation with actinic rays or radiation to generate an organic cation A ⁺ in the side chain.
As content in the below-mentioned resin (P) of such a repeating unit, the range of 1-40 mol% is preferable with respect to all the repeating units of resin (P).

Specific examples of the organic cation A ⁺ are shown below, but the present invention is not limited thereto.

The compound represented by the general formula (X) in the present invention can be formed by combining the anion moiety having the sulfonate anion (SO ₃ ⁻ ) described above and the organic cation A ⁺ described above.
Specific examples c-1 to c-134 of the compound represented by the general formula (X) in the present invention are the anion portions Z-1 to Z-42 having the sulfonate anion (SO ₃ ⁻ ) described above in the following table, and Although illustrated as a combination with the organic cations A-1 to A-81 described above, the present invention is not limited to these.

The compound represented by the general formula (X) can be used alone or in combination of two or more.
The content of the compound represented by the general formula (X) is preferably 0.1 to 50% by mass, more preferably 0.5 to 45% by mass, based on the total solid content of the composition. More preferably, it is 1-40 mass%.
Further, when the compound represented by the general formula (X) is a resin having an organic cation A ⁺ that decomposes upon irradiation with actinic rays or radiation in the side chain (from the main chain via a single bond or a linking group), The sum of the organic cation A ⁺ part of the chain and the anion part represented by the following formula is preferably 0.1 to 50% by mass, more preferably 0.5, based on the total solid content of the composition. It is -45 mass%, More preferably, it is 1-40 mass%.

[2] (B ′) Combined Acid Generator The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a compound that generates an acid upon irradiation with actinic rays or radiation in addition to the compound (B) ( B ′) (hereinafter also referred to as “combination acid generator (B ′)”).
The combined acid generator (B ′) other than the compound (B) will be described below.
As the combined acid generator (B ′), an active photocatalyst polymerization photoinitiator, radical photopolymerization photoinitiator, dye photodecoloring agent, photochromic agent, or microresist is used. Known compounds that generate an acid upon irradiation with light or radiation and mixtures thereof can be appropriately selected and used.

Examples thereof include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.
Among the combined acid generators, preferred compounds are not particularly limited as long as they are known, but preferably include compounds represented by the following general formula (ZI ′), (ZII ′) or (ZIII ′). it can.

In the general formula (ZI ′), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.
Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R _{201 to} R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group).
Examples of the organic group represented by R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include a corresponding group in the compound (ZI′-1) described later.

In addition, the compound which has two or more structures represented by general formula (ZI ') may be sufficient. For example, at least one of R _{201 to} R ₂₀₃ of the compound represented by the general formula (ZI ′) is different from at least one of R _{201 to} R ₂₀₃ of the other compound represented by the general formula (ZI ′). It may be a compound having a structure bonded through a bond or a linking group.
Z ⁻ represents a non-nucleophilic anion (an anion having an extremely low ability to cause a nucleophilic reaction).
Examples of Z ⁻ include a sulfonate anion (an aliphatic sulfonate anion, an aromatic sulfonate anion, a camphor sulfonate anion, etc.), a carboxylate anion (an aliphatic carboxylate anion, an aromatic carboxylate anion, an aralkyl carboxylate anion). Etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.
The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number. 3-30 cycloalkyl groups are mentioned.
The aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group.
The alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. Specific examples thereof include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7), an alkylthio group (preferably 1 to 15 carbon atoms), an alkylsulfonyl group (preferably 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably 2 to 15 carbon atoms), an aryloxysulfonyl group (preferably carbon) Number 6-20), alkylaryloxysulfonyl group (preferably C7-20), cycloalkylary Examples thereof include an oxysulfonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like. . About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) can further be mentioned as a substituent.

The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.
Examples of the sulfonylimide anion include saccharin anion.
The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms.
Two alkyl groups in the bis (alkylsulfonyl) imide anion may be linked to each other to form an alkylene group (preferably having 2 to 4 carbon atoms), and may form a ring together with the imide group and the two sulfonyl groups.
The alkylene group formed by linking two alkyl groups in these alkyl groups and bis (alkylsulfonyl) imide anions may have a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group. Group, an alkyloxysulfonyl group, an aryloxysulfonyl group, a cycloalkylaryloxysulfonyl group, and the like, and a fluorine atom or an alkyl group substituted with a fluorine atom is preferable.

Examples of other Z ⁻ include fluorinated phosphorus (for example, PF ₆ ⁻ ), fluorinated boron (for example, BF ₄ ⁻ ), fluorinated antimony (for example, SbF ₆ ⁻ ), and the like.
Z ^- The aliphatic sulfonate anion in which at least α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a group having a fluorine atom or a fluorine atom, an alkyl group with a fluorine atom A substituted bis (alkylsulfonyl) imide anion and a tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom are preferred. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (more preferably 4 to 8 carbon atoms), a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, or perfluorooctane. A sulfonate anion, a pentafluorobenzenesulfonate anion, and a 3,5-bis (trifluoromethyl) benzenesulfonate anion.
From the viewpoint of acid strength, the pKa of the generated acid is preferably −1 or less in order to improve sensitivity.
As more preferred (ZI ′) component, there can be mentioned the compound (ZI′-1) described below.
The compound (ZI′-1) is an arylsulfonium compound in which at least one of R _{201 to} R _{203 in} the general formula (ZI ′) is an aryl group, that is, a compound having arylsulfonium as a cation.
Arylsulfonium _compound, all of R 201 _{to R 203} may be an aryl group _{or a} part of R 201 _{to R 203} is an aryl group, but the remainder is an alkyl group or a cycloalkyl _group, the R 201 _{to R 203} All are preferably aryl groups.

  Examples of the arylsulfonium compound include a triarylsulfonium compound, a diarylalkylsulfonium compound, an aryldialkylsulfonium compound, a diarylcycloalkylsulfonium compound, and an aryldicycloalkylsulfonium compound, and a triarylsulfonium compound is preferable. .

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

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

The aryl group, alkyl group and cycloalkyl group of R _{201 to} R ₂₀₃ are an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms). , An alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be substituted. Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, more preferably carbon. 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 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, general formulas (ZII ′) and (ZIII ′) will be described.
In general formulas (ZII ′) and (ZIII ′),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.
The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ are the same as the aryl group described as the aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ in the aforementioned compound (ZI′-1). It is.
The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ may have a substituent. Also as this substituent, what the aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ in the above-mentioned compound (ZI′-1) may have may be mentioned.
Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} the general formula (ZI ′).
Examples of the acid generator (B ′) that can be used in combination with the acid generator in the present invention further include compounds represented by the following general formulas (ZIV ′), (ZV ′), and (ZVI ′).

In general formulas (ZIV ′) to (ZVI ′),
Ar ₃ and Ar ₄ each independently represents an aryl group.
R ₂₀₈ , R ₂₀₉ and R ₂₁₀ each independently represents an alkyl group, a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.
Specific examples of the aryl group represented by Ar ₃ , Ar ₄ , R ₂₀₈ , R ₂₀₉ and R ₂₁₀ are the same as the specific examples of the aryl group represented by R ₂₀₁ , R ₂₀₂ and R ₂₀₃ in the general formula (ZI′-1). Can be mentioned.
Specific examples of the alkyl group and the cycloalkyl group represented by R ₂₀₈ , R _209, and R ₂₁₀ include an alkyl group and a cycloalkyl group represented by R ₂₀₁ , R _202, and R ₂₀₃ in the general formula (ZI′-1), respectively. The thing similar to a specific example can be mentioned.
The alkylene group of A is alkylene having 1 to 12 carbon atoms (for example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, etc.), and the alkenylene group of A is 2 to 2 carbon atoms. 12 alkenylene groups (for example, ethenylene group, propenylene group, butenylene group, etc.), and as the arylene group for A, arylene groups having 6 to 10 carbon atoms (for example, phenylene group, tolylene group, naphthylene group, etc.) Can be mentioned.
Among the combined acid generators (B ′) that can be used in combination with the acid generator of the present invention, particularly preferred examples are given below.

The combined acid generator (B ′) can be synthesized by a known method, for example, according to the method described in JP-A No. 2007-161707.
The combined acid generator (B ′) can be used alone or in combination of two or more.
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may or may not contain the combined acid generator (B ′), but if included, the combined acid generator (B ′). The content in the composition is preferably 0.05 to 15% by mass, more preferably 0.1 to 10% by mass, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. Preferably it is 1-6 mass%.

[3] Resin (P)
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a resin (P). The resin (P) is preferably a resin whose solubility in the developer changes due to the action of an acid.
Resin (P) is a resin whose polarity is increased by the action of an acid and the solubility in a developer containing an organic solvent decreases when performing negative development using a developer containing an organic solvent, In addition, the resin (P) is a resin whose polarity is increased by the action of an acid and the solubility in the alkali developer is increased when positive development using an alkali developer is performed. In addition, the carboxyl group as a polar group functions as an alkali-soluble group when performing positive development using an alkali developer.
The resin (P) more preferably has an acid-decomposable repeating unit (hereinafter also simply referred to as a repeating unit (a)). The acid-decomposable repeating unit is, for example, a group (hereinafter referred to as “acid-decomposable group”) that is decomposed by the action of an acid on the main chain or side chain of the resin, or both of the main chain and side chain to generate a polar group. Also referred to as a repeating unit.
The definition of the polar group is the same as the definition explained in the section of the repeating unit having a polar group described later. Examples of the polar group generated by the decomposition of the acid-decomposable group include an alcoholic hydroxyl group, an amino group, and an acidic group. Etc.

The polar group generated by the decomposition of the acid-decomposable group is preferably an acidic group.
The acidic group is not particularly limited as long as it is a group that is insolubilized in a developer containing an organic solvent, but is preferably a phenolic hydroxyl group, a carboxylic acid group, a sulfonic acid group, a fluorinated alcohol group, a sulfonamide group, a sulfonyl group. Imido group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (Alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, more preferably carboxylic acid group, fluorinated alcohol group (preferably hexafluoroisopropanol), phenolic hydro Sill group, (used as a developer for conventional resist, a group dissociated in 2.38 mass% tetramethylammonium hydroxide aqueous solution) acidic group such as a sulfonic acid group include.

A preferable group as the acid-decomposable group is a group in which the hydrogen atom of these groups is substituted with a group capable of leaving with an acid.
As the acid eliminable group, there can be, for _{example, -C (R 36) (R} 37) (R 38), - C (R 36) (R 37) (OR 39), - C (R 01) (R 02 ) (OR ₃₉ ) and the like.
In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, a monovalent aromatic ring group, a group in which an alkylene group and a monovalent aromatic ring group are combined, 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 represent a hydrogen atom, an alkyl group, a cycloalkyl group, a monovalent aromatic ring group, a group in which an alkylene group and a monovalent aromatic ring group are combined, 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.

  As the acid-decomposable group that the resin (P) may have, from the viewpoint that the effects of the present invention can be achieved more reliably, the above-described general formula (I) to the compound represented by the general formula (X) described above are included. It is preferably at least one group selected from the group consisting of groups represented by (IV), and includes the following general formulas (I-1) and (I-2) and the above general formulas (II) to (IV) And more preferably at least one group selected from the group consisting of groups represented by:

In the general formulas (I-1) and (I-2),
R ₁₁ , R ₁₂ and R ₁₃ are each independently synonymous with R ₁₁ , R ₁₂ and R ₁₃ in formula (I), and specific examples and preferred examples are also the same.
R ₁₁ and R ₁₂ may be bonded to each other to form a ring.
R ₁₂ and R ₁₃ may be bonded to each other to form a ring.
Ar ′ represents a divalent aromatic group.
* Represents a bond.
Specific examples and preferred examples of the divalent aromatic group Ar ′ include those similar to the specific examples and preferred examples described above for the divalent aromatic group of Ar in the compound represented by the general formula (X). Can be mentioned.
The divalent aromatic group Ar ′ may further have a substituent.
Examples of the substituent that the divalent aromatic group Ar ′ may have include the specific examples described above for the substituent that the (m + 1) -valent aromatic group Ar in the compound represented by the general formula (X) may have The thing similar to a preferable example is mentioned.

  Moreover, resin (P) may contain the repeating unit represented by the following general formula (VI) as a repeating unit (a).

In general formula (VI),
R ₆₁ , R ₆₂ and R ₆₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. However, R ₆₂ may be bonded to Ar ₆ to form a ring, and R ₆₂ in this case represents a single bond or an alkylene group.
X ₆ represents a single bond, —COO—, or —CONR ₆₄ —. R ₆₄ represents a hydrogen atom or an alkyl group.
L ₆ represents a single bond or an alkylene group.
Ar ₆ represents an (n + 1) -valent aromatic ring group, and represents an (n + 2) -valent aromatic ring group when bonded to R ₆₂ to form a ring.
Y ₂ independently represents a hydrogen atom or a group capable of leaving by the action of an acid when n ≧ 2. However, at least one of Y ₂ represents a group capable of leaving by the action of an acid.
n represents an integer of 1 to 4.

General formula (VI) will be described in more detail.
As the alkyl group of R _{61 to} R ₆₃ in the general formula (VI), a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, which may preferably have a substituent, Examples thereof include alkyl groups having 20 or less carbon atoms such as hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group, and more preferable examples include alkyl groups having 8 or less carbon atoms.
As the alkyl group contained in the alkoxycarbonyl group, the same alkyl groups as those described above for R _{61 to} R ₆₃ are preferable.
The cycloalkyl group may be monocyclic or polycyclic, and is preferably a monocyclic type having 3 to 8 carbon atoms such as a cyclopropyl group, cyclopentyl group or cyclohexyl group which may have a substituent. A cycloalkyl group is mentioned.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is more preferable.

If R ₆₂ represents an alkylene group, the alkylene group, preferably a methylene group which may have a substituent group, an ethylene group, a propylene group, butylene group, hexylene group, 1 to 8 carbon atoms such as octylene Can be mentioned.
_-CONR 64 represented by X ₆ - _{(R 64} represents a hydrogen atom, an alkyl group) The alkyl group for _{R 64 in,} the same as the alkyl group of R 61 _{to R 63.}
X ₆ is preferably a single bond, —COO—, or —CONH—, and more preferably a single bond or —COO—.
The alkylene group for L ₆ is preferably an alkylene group having 1 to 8 carbon atoms, such as an optionally substituted methylene group, ethylene group, propylene group, butylene group, hexylene group or octylene group. The ring formed by combining R ₆₂ and L ₆ is particularly preferably a 5- or 6-membered ring.
Ar ₆ represents an (n + 1) -valent aromatic ring group. The divalent aromatic ring group when n is 1 may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, or a naphthylene group, or, for example, Preferred examples include divalent aromatic ring groups containing heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.

Specific examples of the (n + 1) -valent aromatic ring group in the case where n is an integer of 2 or more include (n-1) arbitrary hydrogen atoms excluded from the above-described specific examples of the divalent aromatic ring group. The group formed can be preferably mentioned.
The (n + 1) -valent aromatic ring group may further have a substituent.

Examples of the substituent that the alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n + 1) -valent aromatic ring group described above may have include an alkyl group, a cycloalkyl group, an aryl group, an amino group, and an amide group. , Ureido group, urethane group, hydroxyl group, carboxyl group, halogen atom, alkoxy group, thioether group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group, nitro group, etc. 8 or less is preferable.
n is preferably 1 or 2, and more preferably 1.
n Y ₂ each independently represents a hydrogen atom or a group capable of leaving by the action of an acid. However, at least one of n represents a group capable of leaving by the action of an acid.
Examples of the group Y ₂ leaving by the action of an acid include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (═O) —O—C (R ₃₆ ) (R ₃₇ ) (R _{38), - C (R 01} ) (R 02) (OR 39), - C (R 01) (R 02) -C (= O) -O-C (R 36) (R 37) (R 38) , —CH (R ₃₆ ) (Ar) and the like.
In the formula, R _{36 to} R ₃₉ each independently represent an alkyl group, a cycloalkyl group, a monovalent aromatic ring group, a group in which an alkylene group and a monovalent aromatic ring group are combined, 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 represent a hydrogen atom, an alkyl group, a cycloalkyl group, a monovalent aromatic ring group, a group in which an alkylene group and a monovalent aromatic ring group are combined, or an alkenyl group.

Ar represents a monovalent aromatic ring group.
The alkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl. Group, octyl group and the like.
The cycloalkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkyl group having 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. As the polycyclic type, a cycloalkyl group having 6 to 20 carbon atoms is preferable. Group, androstanyl group and the like. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

The monovalent aromatic ring group of R _{36 to} R ₃₉ , R ₀₁ , R ₀₂ and Ar is preferably a monovalent aromatic ring group having 6 to 10 carbon atoms, for example, an aryl such as a phenyl group, a naphthyl group or an anthryl group. And a divalent aromatic ring group containing a heterocyclic ring such as a group, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole.
The group in which the alkylene group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ and the monovalent aromatic ring group are combined is preferably an aralkyl group having 7 to 12 carbon atoms, such as benzyl group, phenethyl group, naphthylmethyl. Groups and the like.
The alkenyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.

The ring formed by combining R ₃₆ and R ₃₇ with each other may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkyl structure having 3 to 8 carbon atoms, and examples thereof include a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, and a cyclooctane structure. As the polycyclic type, a cycloalkyl structure having 6 to 20 carbon atoms is preferable, and examples thereof include an adamantane structure, a norbornane structure, a dicyclopentane structure, a tricyclodecane structure, and a tetracyclododecane structure. A part of carbon atoms in the cycloalkyl structure may be substituted with a hetero atom such as an oxygen atom.
Each of the groups as R _{36 to} R ₃₉ , R ₀₁ , R ₀₂ , and Ar may have a substituent, and the substituent is (m + 1) in the compound represented by the general formula (X). The same specific examples and preferred examples as those described above for the substituent that the valent aromatic group Ar may have may be mentioned.

  Specific examples of the repeating unit having an acid-decomposable group represented by the general formulas (I) to (IV) are shown below as preferred specific examples of the repeating unit (a), but the present invention is limited to this. It is not a thing.

  Specific examples of the repeating unit (a) are shown below as specific examples of the repeating unit having an acid-decomposable group represented by formula (I-2) or the repeating unit represented by formula (VI). However, the present invention is not limited to this.

The resin (P) preferably has at least one group selected from the group consisting of the groups represented by the general formulas (I) to (IV). In the general formulas (I) to (IV), It is more preferable to contain a repeating unit having at least one group selected from the group consisting of the groups represented, and is selected from the group consisting of groups represented by the above general formulas (I) and (II) It is more preferable to contain a repeating unit having at least one group, and the repeating unit having the group represented by the above general formula (I) which can be decomposed by the action of an acid to generate a carboxyl group or the above general formula ( It is particularly preferred to contain a repeating unit having a group represented by II).
As the repeating unit (a), a repeating unit represented by the following general formula (V) may be included.

In general formula (V),
R ₅₁ , R ₅₂ , and R ₅₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. R ₅₂ may be bonded to L ₅ to form a ring, and R ₅₂ in this case represents an alkylene group.
L ₅ represents a single bond or a divalent linking group, and in the case of forming a ring with R ₅₂ , represents a trivalent linking group.
R ₅₄ represents an alkyl group, and R ₅₅ and R ₅₆ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a monovalent aromatic ring group, or an aralkyl group. R ₅₅ and R ₅₆ may combine with each other to form a ring. _However, no and _{R 55} and _{R 56} are hydrogen atoms at the same time.

The general formula (V) will be described in more detail.
As the alkyl group, alkoxycarbonyl group, cycloalkyl group and halogen atom of R _{51 to} R ₅₃ in the general formula (V), the alkyl group, alkoxycarbonyl group and cycloalkyl group of R _{61 to} R ₆₃ in the general formula (VI) And a halogen atom, respectively, and the same applies to specific examples and preferred examples.

  Preferable substituents in the above groups are the substituents that the alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group and (n + 1) -valent aromatic ring group in the repeating unit represented by the general formula (VI) may have. The thing similar to the specific example mentioned above about the group and a preferable example is mentioned.

When R ₅₂ is an alkylene group and forms a ring with L ₅ , the alkylene group is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group. Groups. The ring formed by combining R ₅₂ and L ₅ is particularly preferably a 5- or 6-membered ring.

R ₅₁ and R ₅₃ in Formula (V) are more preferably a hydrogen atom, an alkyl group, or a halogen atom, and a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ), a hydroxymethyl group (—CH ₃ ). _2- OH), a chloromethyl group (—CH ₂ —Cl), and a fluorine atom (—F) are particularly preferable. R ₅₂ is more preferably a hydrogen atom, an alkyl group, a halogen atom, or an alkylene group (forming a ring with L ₅ ), a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF ₃ ), a hydroxymethyl group Particularly preferred are (—CH ₂ —OH), a chloromethyl group (—CH ₂ —Cl), a fluorine atom (—F), a methylene group (forms a ring with L ₅ ), and an ethylene group (forms a ring with L ₅ ). .

Examples of the divalent linking group represented by L _5, an alkylene group, a divalent aromatic ring _{group, -COO-L 1 -, -} O-L 1 -, a group formed by combining two or more of these Etc. Here, L ₁ represents an alkylene group, a cycloalkylene group, a divalent aromatic ring group, or a group in which an alkylene group and a divalent aromatic ring group are combined.
L ₅ is preferably a single bond, a group represented by —COO—L ₁ —, or a divalent aromatic ring group. L ₁ is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene or propylene group. As the divalent aromatic ring group, a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, and a 1,4-naphthylene group are preferable, and a 1,4-phenylene group is more preferable.
In the case of which L ₅ to form a ring with R _52, examples of the trivalent linking group represented by L _5, a specific example described above divalent linking group represented by L ₅ 1 single Preferable examples include groups formed by removing any hydrogen atom.
The alkyl group of R _{54 to} R ₅₆ is preferably an alkyl group having 1 to 20 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. Those of 1-4 are particularly preferred.
The cycloalkyl group represented by R ₅₅ and R _56, preferably one having 3 to 20 carbon atoms, cyclopentyl, may be of monocyclic and cyclohexyl group, norbornyl group, adamantyl group, Polycyclic ones such as a tetracyclodecanyl group and a tetracyclododecanyl group may be used.

The ring formed by combining R ₅₅ and R ₅₆ with each other preferably has 3 to 20 carbon atoms, and may be monocyclic such as a cyclopentyl group or a cyclohexyl group, or a norbornyl group. Polycyclic ones such as an adamantyl group, a tetracyclodecanyl group, and a tetracyclododecanyl group may be used. When R ₅₅ and R ₅₆ are bonded to each other to form a ring, R ₅₄ is preferably an alkyl group having 1 to 3 carbon atoms.
The monovalent aromatic ring group represented by R ₅₅ and R ₅₆ is preferably one having 6 to 20 carbon atoms, and may be monocyclic or polycyclic, and may have a substituent. For example, a phenyl group, 1-naphthyl group, 2-naphthyl group, 4-methylphenyl group, 4-methoxyphenyl group and the like can be mentioned.
When one of R ₅₅ and R ₅₆ is a hydrogen atom, the other is preferably a monovalent aromatic ring group.
The aralkyl group represented by R ₅₅ and R ₅₆ may be monocyclic or polycyclic and may have a substituent. Preferably it is C7-21, and a benzyl group, 1-naphthylmethyl group, etc. are mentioned.

As a method for synthesizing a monomer corresponding to the repeating unit represented by the general formula (V), a general method for synthesizing a polymerizable group-containing ester can be applied and is not particularly limited.
Specific examples of the repeating unit (a) represented by the general formula (V) 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 independently represent an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 19 carbon atoms. Z represents a substituent. p represents 0 or a positive integer, preferably 0 to 2, and more preferably 0 or 1. When a plurality of Z are present, they may be the same as or different from each other. Z is preferably a group consisting of only a hydrogen atom and a carbon atom from the viewpoint of increasing the dissolution contrast with respect to a developer containing an organic solvent before and after acid decomposition, for example, a linear or branched alkyl group, A cycloalkyl group is preferred.

  Moreover, resin (P) may contain the repeating unit represented by the following general formula (BZ) as a repeating unit (a).

In general formula (BZ), AR represents an aryl group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and AR may be bonded to each other to form a non-aromatic ring.
R ₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkyloxycarbonyl group.

As the aryl group of AR, those having 6 to 20 carbon atoms such as a phenyl group, a naphthyl group, an anthryl group, or a fluorene group are preferable.
When AR is a naphthyl group, anthryl group, or fluorene group, the bonding position between the carbon atom to which Rn is bonded and AR is not particularly limited. For example, when AR is a naphthyl group, this carbon atom may be bonded to the α-position of the naphthyl group or may be bonded to the β-position. Alternatively, when AR is an anthryl group, this carbon atom may be bonded to the 1-position, the 2-position, or the 9-position of the anthryl group.
Each of the aryl groups as AR may have one or more substituents. Specific examples of such substituents include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, octyl group and dodecyl group. A linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxy group containing these alkyl group parts, a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a cycloalkoxy group containing these cycloalkyl group parts, a hydroxyl group , Halogen atom, aryl group, cyano group, nitro group, acyl group, acyloxy group, acylamino group, sulfonylamino group, alkylthio group, arylthio group, aralkylthio group, thiophenecarbonyloxy group, thiophenemethylcarbonyloxy group, and pyrrolidone residue And heterocyclic residues such as groups. As this substituent, a linear or branched alkyl group having 1 to 5 carbon atoms and an alkoxy group containing the alkyl group portion are preferable, and a paramethyl group or a paramethoxy group is more preferable.

When the aryl group as AR has a plurality of substituents, at least two of the plurality of substituents may be bonded to each other to form a ring. The ring is preferably a 5- to 8-membered ring, and more preferably a 5- or 6-membered ring. Moreover, this ring may be a heterocycle containing a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom as a ring member.
Furthermore, this ring may have a substituent. As this substituent, the thing similar to what is mentioned later about the further substituent which Rn may have is mentioned.
Moreover, it is preferable that the repeating unit (a) represented by general formula (BZ) contains two or more aromatic rings from a viewpoint of roughness performance. The number of aromatic rings contained in this repeating unit is usually preferably 5 or less, and more preferably 3 or less.
In the repeating unit (a) represented by the general formula (BZ), from the viewpoint of roughness performance, AR preferably contains two or more aromatic rings, and AR is a naphthyl group or a biphenyl group. Is more preferable. The number of aromatic rings possessed by AR is usually preferably 5 or less, and more preferably 3 or less.

As described above, Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
The alkyl group of Rn may be a straight chain alkyl group or a branched chain alkyl group. The alkyl group is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an octyl group or a dodecyl group. A thing with 1-20 carbon atoms is mentioned. The alkyl group of Rn preferably has 1 to 5 carbon atoms, and more preferably has 1 to 3 carbon atoms.
Examples of the cycloalkyl group represented by Rn include those having 3 to 15 carbon atoms such as a cyclopentyl group and a cyclohexyl group.
As the aryl group of Rn, for example, those having 6 to 14 carbon atoms such as phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group and anthryl group are preferable.

Each of the alkyl group, cycloalkyl group and aryl group as Rn may further have a substituent. Examples of the substituent include an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acyloxy group, an acylamino group, a sulfonylamino group, a dialkylamino group, an alkylthio group, an arylthio group, an aralkylthio group, and a thiophenecarbonyloxy group. , Thiophenemethylcarbonyloxy group, and heterocyclic residues such as pyrrolidone residues. Among these, an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acyloxy group, an acylamino group, and a sulfonylamino group are particularly preferable.
R ₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkyloxycarbonyl group as described above.
Examples of the alkyl group and cycloalkyl group for R ₁ include the same groups as those described above for Rn. Each of these alkyl groups and cycloalkyl groups may have a substituent. Examples of this substituent include the same as those described above for Rn.

When R ₁ is an alkyl group or a cycloalkyl group having a substituent, particularly preferable R ₁ includes, for example, a trifluoromethyl group, an alkyloxycarbonylmethyl group, an alkylcarbonyloxymethyl group, a hydroxymethyl group, and an alkoxymethyl group. Groups.
Examples of the halogen atom for R ₁ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom is particularly preferable.
The alkyl group moiety contained in the alkyloxycarbonyl group of R _1, for example, it is possible to adopt a configuration in which previously mentioned as the alkyl group of R _1.
Rn and AR are preferably bonded to each other to form a non-aromatic ring, and in particular, roughness performance can be further improved.

The non-aromatic ring that may be formed by bonding Rn and AR to each other is preferably a 5- to 8-membered ring, more preferably a 5- or 6-membered ring.
The non-aromatic ring may be an aliphatic ring or a heterocycle containing a hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom as a ring member.
The non-aromatic ring may have a substituent. As this substituent, the thing similar to having demonstrated previously about the further substituent which Rn may have is mentioned, for example.

  Specific examples of the repeating unit (a) represented by the general formula (BZ) are shown below, but are not limited thereto.

  In addition, the embodiment of the repeating unit having an acid-decomposable group different from the repeating unit exemplified above may be an embodiment of a repeating unit that decomposes by the action of an acid to generate an alcoholic hydroxyl group. In this case, it is preferably represented by any one of the following general formulas (I-1) to (I-10). The repeating unit is more preferably represented by any one of the following general formulas (I-1) to (I-3), and more preferably represented by the following general formula (I-1).

Where
Each Ra independently represents a hydrogen atom, an alkyl group or a group represented by —CH ₂ —O—Ra ₂ . Here, Ra ₂ 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 is a 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 preferable that they are 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 any one of the following general formulas (II-1) to (II-4).

Where
Rx ₃ each independently represents a hydrogen atom or a monovalent organic group. Rx ₃ may be bonded to each other to form a ring.
Rx ₄ each independently represents a monovalent organic group. Rx ₄ may be bonded to each other to form a ring. Rx ₃ and Rx ₄ may be bonded to each other to form a ring.
Rx 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 Rx ₅ may be bonded to each other to form a ring. However, when one or two of the three Rx ₅ are hydrogen atoms, at least one of the remaining Rx 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 any one of the following general formulas (II-5) to (II-9).

Where
Rx ₄ has the same meaning as in general formulas (II-1) to (II-3).
Rx ₆ each independently represents a hydrogen atom or a monovalent organic group. Rx 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 any one of the general formulas (II-1) to (II-3). More preferably, it is represented by II-3), and particularly preferably represented by formula (II-1).

Rx ₃ represents a hydrogen atom or a monovalent organic group as described above. Rx ₃ is preferably a hydrogen atom, an alkyl group or a cycloalkyl group, and more preferably a hydrogen atom or an alkyl group.
The alkyl group of Rx ₃ may be linear or branched. The carbon number of the alkyl group of rx ₃ is preferably 1-10. Examples of the alkyl group for Rx ₃ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
The cycloalkyl group represented by Rx ₃ may be monocyclic or polycyclic. The carbon number of the cycloalkyl group rx ₃ is preferably 3 to 10. Examples of the cycloalkyl group represented by Rx ₃ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

In general formula (II-1), at least one of Rx ₃ is preferably a monovalent organic group. When such a configuration is employed, particularly high sensitivity can be achieved.
Rx ₄ represents a monovalent organic group. Rx 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 of Rx ₄ preferably has no substituent, or 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 Rx ₄ does not have a substituent, the carbon number thereof is preferably from 3 to 20.
Rx 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 Rx ₅ are hydrogen atoms, at least one of the remaining Rx ₅ represents an aryl group, an alkenyl group, or an alkynyl group. Rx 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.
Rx ₆ represents a hydrogen atom or a monovalent organic group as described above. Rx ₆ is preferably a hydrogen atom, an alkyl group or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group, and still more preferably a hydrogen atom or an alkyl group having no substituent. Rx ₆ is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, 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 Rx ₄ , Rx _5, and Rx ₆ include the same as those described above for Rx 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.

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 the following specific examples, Xa ₁ represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH.

  One type of repeating unit having the acid-decomposable group may be used, or two or more types may be used in combination.

  The content of the repeating unit having an acid-decomposable group in the resin (P) (the total when there are a plurality of types) is 5 mol% or more and 90 mol% or less with respect to all the repeating units in the resin (P). It is preferably 5 mol% or more and 80 mol% or less, more preferably 10 mol% or more and 75 mol% or less.

  The resin (P) preferably has a non-acid-decomposable repeating unit (b) having a phenolic hydroxyl group, particularly when a pattern is formed by electron beam or extreme ultraviolet exposure. As the repeating unit (b) in this case, a structure represented by the following general formula (I) is more preferable.

Where
R ₄₁ , R ₄₂ and R ₄₃ each independently represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. However, R ₄₂ may form a ring with Ar _4, R ₄₂ in this case represents a single bond or an alkylene group.
X ₄ represents a single bond, —COO—, or —CONR ₆₄ —, and R ₆₄ represents a hydrogen atom or an alkyl group.
L ₄ represents a single bond or an alkylene group.
Ar ₄ represents an (n + 1) -valent aromatic ring group, and when bonded to R ₄₂ to form a ring, represents an (n + 2) -valent aromatic ring group.
n represents an integer of 1 to 4.

Specific examples of the alkyl group, cycloalkyl group, halogen atom, alkoxycarbonyl group of R ₄₁ , R ₄₂ , and R ₄₃ in formula (I), and the substituents that these groups may have include the above general formula (V). Are the same as the specific examples described for the groups represented by R ₅₁ , R ₅₂ , and R ₅₃ .
Ar ₄ represents an (n + 1) -valent aromatic ring group. The divalent aromatic ring group in the case where n is 1 may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, and an anthracenylene group, or Examples of preferred aromatic ring groups include heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.

Specific examples of the (n + 1) -valent aromatic ring group in the case where n is an integer of 2 or more include (n-1) arbitrary hydrogen atoms excluded from the above-described specific examples of the divalent aromatic ring group. The group formed can be preferably mentioned.
The (n + 1) -valent aromatic ring group may further have a substituent.

Examples of the substituent that the above-described alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n + 1) -valent aromatic ring group may have include the alkyl groups exemplified as R _{51 to} R ₅₃ in formula (V), Examples thereof include alkoxy groups such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group and butoxy group, and aryl groups such as phenyl group.
_-CONR 64 represented by X ₄ - _{(R 64} represents a hydrogen atom, an alkyl group) The alkyl group for _{R 64 in,} the same as the alkyl group of R 61 _{to R 63.}
X ₄ is preferably a single bond, —COO—, or —CONH—, and more preferably a single bond or —COO—.

The alkylene group for L ₄ is preferably an alkylene group having 1 to 8 carbon atoms, such as an optionally substituted methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group.
Ar ₄ is more preferably an aromatic ring group having 6 to 18 carbon atoms which may have a substituent, and particularly preferably a benzene ring group, a naphthalene ring group or a biphenylene ring group.
The repeating unit (b) preferably has a hydroxystyrene structure. That is, Ar ₄ is preferably a benzene ring group.

  Specific examples of the repeating unit (b) represented by the general formula (I) are shown below, but the present invention is not limited thereto. In the formula, a represents an integer of 1 or 2.

The resin (P) may contain two or more types of repeating units represented by the general formula (I).
The content of the non-acid-decomposable repeating unit (b) having a phenolic hydroxyl group in the resin (P) is preferably in the range of 5 to 90 mol% with respect to all repeating units of the resin (P), preferably 10 to 80 mol. % Is more preferable, and a range of 10 to 70 mol% is particularly preferable.

The resin (P) preferably further has the following repeating units as other repeating units.
(Repeating unit having a polar group)
The resin (P) may contain a repeating unit having a polar group different from the non-acid-decomposing repeating unit (b) having a phenolic hydroxyl group.
By including a repeating unit having a polar group, for example, the sensitivity of a composition containing a resin can be improved. The repeating unit having a polar group is preferably a non-acid-decomposable repeating unit (that is, having no acid-decomposable group).
Examples of the “polar group” that can be contained in the repeating unit having a polar group 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 ⁺ .
Specific examples of the partial structure that can be included in the “polar group” are given below.

  The “polar group” that the repeating unit having a polar group may include, for example, (I) hydroxy group, (II) cyano group, (III) lactone group, (IV) carboxylic acid group or sulfonic acid group, (V) amide It is preferably at least one selected from the group consisting of a group, a group corresponding to a sulfonamide group or a derivative thereof, (VI) an ammonium group or a sulfonium group, and a group formed by combining two or more thereof.

The polar group is selected from a hydroxyl group, a cyano group, a lactone group, a carboxylic acid group, a sulfonic acid group, an amide group, a sulfonamide group, an ammonium group, a sulfonium group, and a group formed by combining two or more thereof. Are preferable, and an alcoholic hydroxy group, a cyano group, a lactone group, or a group containing a cyanolactone structure is particularly preferable.
When the resin further contains a repeating unit having an alcoholic hydroxy group, the exposure latitude (EL) of the composition containing the resin can be further improved.
When the resin further contains a repeating unit having a cyano group, the sensitivity of the composition containing the resin can be further improved.
If the 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 resin-containing composition.
If the resin further contains a repeating unit having a group containing a lactone structure having a cyano 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 sensitivity, dry etching resistance, applicability, and adhesion to the substrate of the composition containing the 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 resin.

  When the polar group of the repeating unit having a polar group is an alcoholic hydroxy group, it is preferably represented by at least one selected from the group consisting of the following general formulas (I-1H) to (I-10H). . In particular, it is more preferably represented by at least one selected from the group consisting of the following general formulas (I-1H) to (I-3H), and may be represented by the following general formula (I-1H). Further preferred.

In the formula, Ra, R ₁ , R ₂ , 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 (I− It is synonymous with each of 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.
The content of the repeating unit having an alcoholic hydroxy group is preferably from 1 to 60 mol%, more preferably from 3 to 50 mol%, still more preferably from 5 to 40 mol%, based on all repeating units in the resin (P).
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).

  In the case where the polar group of the repeating unit having a polar group is an alcoholic hydroxy group or a cyano group, one embodiment of a preferable repeating unit is a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group Can be mentioned. At this time, it is preferable not to have an acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diamantyl group, or a norbornane group. As the alicyclic hydrocarbon structure substituted with a preferred hydroxyl group or cyano group, partial structures represented by the following general formulas (VIIa) to (VIIc) are preferable. This improves the substrate adhesion and developer compatibility.

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

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

In the general formulas (AIIa) to (AIIc),
R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

R ₂ c to R ₄ c are in the general formula (VIIa) ~ _(VIIc), same meanings as R 2 c~R ₄ c.

  The resin (P) may or may not contain a repeating unit having a hydroxyl group or a cyano group. However, when it is contained, the content of the repeating unit having a hydroxyl group or a cyano group is determined in the resin (P). The total repeating unit is preferably 1 to 60 mol%, more preferably 3 to 50 mol%, still more preferably 5 to 40 mol%.

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

The repeating unit having a polar group may be a repeating unit having a lactone structure as a polar group.
The repeating unit having a lactone structure is more preferably 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 optionally substituted alkyl group (preferably having 1 to 4 carbon atoms).
Preferable substituents that the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom for Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb ₀ is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic cycloalkyl structure, an ether bond, an ester bond, a carbonyl group, or a divalent linking group obtained by combining these. Ab is preferably a single bond or a divalent linking group represented by —Ab ₁ —CO ₂ —.
Ab ₁ is a linear or branched alkylene group, a monocyclic or polycyclic cycloalkylene group, and preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group.
V represents a group having a lactone structure.

  As the group having a lactone structure, any group having a lactone structure can be used, but a 5- to 7-membered ring lactone structure is preferable, and a bicyclo structure or a spiro structure is added to the 5- to 7-membered ring lactone structure. Those in which other ring structures are condensed in the form to be formed are preferred. It is more preferable to have a repeating unit having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). The lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-8), (LC1-13), and (LC1-14).

The lactone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a monovalent cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and an alkoxycarbonyl group having 2 to 8 carbon atoms. , Carboxyl group, halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferably, they are a C1-C4 alkyl group, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0-4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different, and a plurality of substituents (Rb ₂ ) may be bonded to form a ring. .

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

The resin (P) may or may not contain a repeating unit having a lactone structure, but when it contains a repeating unit having a lactone structure, the content of the repeating unit in the resin (P) is The range of 1 to 70 mol% is preferable with respect to the repeating unit, more preferably 3 to 65 mol%, and still more preferably 5 to 60 mol%.
Specific examples of the repeating unit having a lactone structure in the resin (P) are shown below, but the present invention is not limited thereto. In the formula, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  In addition, it is one of particularly preferable embodiments that the polar group that the repeating unit having a polar group may have is an acidic group. Preferred acidic groups include phenolic hydroxyl groups, carboxylic acid groups, sulfonic acid groups, fluorinated alcohol groups (eg hexafluoroisopropanol group), sulfonamide groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, Alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, A tris (alkylsulfonyl) methylene group is mentioned. Of these, the repeating unit (b) is more preferably a repeating unit having a carboxyl group. By containing the repeating unit having an acidic group, the resolution in the contact hole application is increased. The repeating unit having an acidic group includes a repeating unit in which an acidic group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or an acidic group in the main chain of the resin through a linking group. It is preferable to use a polymerization initiator or a chain transfer agent having a repeating unit bonded to each other, or an acidic group, at the time of polymerization and introduce it at the end of the polymer chain. Particularly preferred are repeating units of acrylic acid or methacrylic acid.

The acidic group that the repeating unit having a polar group may have may or may not contain an aromatic ring, but when it has an aromatic ring, it is preferably selected from acidic groups other than phenolic hydroxyl groups. When the repeating unit having a polar group has an acidic group, the content of the repeating unit having an acidic group is preferably 30 mol% or less, and 20 mol% or less, based on all repeating units in the resin (P). It is more preferable that When resin (P) contains the repeating unit which has an acidic group, content of the repeating unit which has an acidic group in resin (P) is 1 mol% or more normally.
Specific examples of the repeating unit having an acidic group are shown below, but the present invention is not limited thereto.
In specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  The resin (P) may further contain a repeating unit represented by the following general formula (4).

R ⁴¹ represents a hydrogen atom or a methyl group. L ⁴¹ represents a single bond or a divalent linking group. L ⁴² represents a divalent linking group. S represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain.

  Although the specific example of the repeating unit represented by General formula (4) below is shown, this invention is not limited to this.

  The content of the repeating unit represented by the general formula (4) in the resin (P) is preferably in the range of 1 to 40 mol%, and in the range of 2 to 30 mol% with respect to all the repeating units of the resin (P). Is more preferable, and the range of 5 to 25 mol% is particularly preferable.

(Repeating unit having a plurality of aromatic rings)
The resin (P) may have a repeating unit having a plurality of aromatic rings represented by the following general formula (c1).

In general formula (c1),
R ₃ represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group or a nitro group;
Y represents a single bond or a divalent linking group;
Z represents a single bond or a divalent linking group;
Ar represents an aromatic ring group;
p represents an integer of 1 or more.
The alkyl group as R ₃ may be either linear or branched, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl. Group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group and i-butyl group, and may further have a substituent. Preferred examples of the substituent include an alkoxy group, a hydroxyl group, a halogen atom, and a nitro group. Among them, examples of the alkyl group having a substituent include a CF ₃ group, an alkyloxycarbonylmethyl group, an alkylcarbonyloxymethyl group, and hydroxymethyl. Group, alkoxymethyl group and the like are preferable.

Examples of the halogen atom as R ₃ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.
Y represents a single bond or a divalent linking group, and examples of the divalent linking group include an ether group (oxygen atom), a thioether group (sulfur atom), an alkylene group, an arylene group, a carbonyl group, a sulfide group, Sulfone group, —COO—, —CONH—, —SO ₂ NH—, —CF ₂ —, —CF ₂ CF ₂ —, —OCF ₂ O—, —CF ₂ OCF ₂ —, —SS—, —CH ₂ SO ₂ CH ₂ —, —CH ₂ COCH ₂ —, —COCF ₂ CO—, —COCO—, —OCOO—, —OSO ₂ O—, amino group (nitrogen atom), acyl group, alkylsulfonyl group, —CH═CH And —C—C≡C—, an aminocarbonylamino group, an aminosulfonylamino group, or a combination thereof. Y preferably has 15 or less carbon atoms, more preferably 10 or less carbon atoms.

Y is preferably a single bond, —COO— group, —COS— group, —CONH— group, more preferably —COO— group, —CONH— group, and particularly preferably —COO— group.
Z represents a single bond or a divalent linking group, and examples of the divalent linking group include an ether group (oxygen atom), a thioether group (sulfur atom), an alkylene group, an arylene group, a carbonyl group, a sulfide group, Sulfone group, —COO—, —CONH—, —SO ₂ NH—, amino group (nitrogen atom), acyl group, alkylsulfonyl group, —CH═CH—, aminocarbonylamino group, aminosulfonylamino group, or these Group which consists of combination is mention | raise | lifted.
Z is preferably a single bond, an ether group, a carbonyl group, or —COO—, more preferably a single bond or an ether group, and particularly preferably a single bond.

Ar represents an aromatic ring group, specifically, phenyl group, naphthyl group, anthracenyl group, phenanthrenyl group, quinolinyl group, furanyl group, thiophenyl group, fluorenyl-9-one-yl group, anthraquinonyl group, phenanthralkyl. A nonyl group, a pyrrole group, etc. are mentioned, A phenyl group is preferable. These aromatic ring groups may further have a substituent. Preferred examples of the substituent include an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acyloxy group, an acylamino group, and a sulfonylamino group. Group, aryl group such as phenyl group, aryloxy group, arylcarbonyl group, heterocyclic residue, etc. Among them, phenyl group suppresses deterioration of exposure latitude and pattern shape caused by out-of-band light It is preferable from the viewpoint.
p is an integer of 1 or more, and is preferably an integer of 1 to 3.

  More preferred as a repeating unit having a plurality of aromatic rings is a repeating unit represented by the following formula (c2).

In general formula (c2), R ₃ represents a hydrogen atom or an alkyl group. The thing preferable as an alkyl group as R < ₃ > is the same as that of general formula (c1).

Here, regarding extreme ultraviolet (EUV light) exposure, leakage light (out-of-band light) generated in the ultraviolet region with a wavelength of 100 to 400 nm deteriorates surface roughness, resulting in bridges between patterns and disconnection of patterns. , Resolution and LWR performance tend to decrease.
However, the aromatic ring in the repeating unit having a plurality of aromatic rings functions as an internal filter capable of absorbing the out-of-band light. Therefore, from the viewpoint of high resolution and low LWR, the resin (P) preferably contains a repeating unit having a plurality of aromatic rings.
Here, it is preferable that the repeating unit having a plurality of aromatic rings does not have a phenolic hydroxyl group (a hydroxyl group bonded directly on the aromatic ring) from the viewpoint of obtaining high resolution.

  Specific examples of the repeating unit having a plurality of aromatic rings are shown below, but are not limited thereto.

  The resin (P) may or may not contain a repeating unit having a plurality of aromatic rings, but when it is contained, the content of the repeating unit having a plurality of aromatic rings is the same as that of the resin (P) all repeating units. On the other hand, it is preferable that it is the range of 1-30 mol%, More preferably, it is the range of 1-20 mol%, More preferably, it is the range of 1-15 mol%. The repeating unit having a plurality of aromatic rings contained in the resin (P) may contain a combination of two or more types.

  The resin (P) in the present invention may have a repeating unit other than the repeating unit as appropriate. As an example of such a repeating unit, a repeating unit that has an alicyclic hydrocarbon structure that does not have a polar group (for example, the acid group, hydroxyl group, or cyano group) and does not exhibit acid decomposability can be included. Thereby, the solubility of the resin can be appropriately adjusted during development using a developer containing an organic solvent. Examples of such a repeating unit 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 no polar group.
Ra represents a hydrogen atom, an alkyl group, or a —CH ₂ —O—Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group, or an acyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

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

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

Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5.2.1.0 ^2,6 ] decanyl group, and the like. More preferable examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.

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

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

The resin (P) has an alicyclic hydrocarbon structure having no polar group and may or may not contain a repeating unit that does not exhibit acid decomposability, but when it is contained, the content of this repeating unit is The amount is preferably 1 to 20 mol%, more preferably 5 to 15 mol%, based on all repeating units in the resin (P).
Specific examples of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  Further, the resin (P) may contain the following monomer components in view of the effects of improvement in Tg, improvement in dry edging resistance, the above-described internal filter of out-of-band light, and the like.

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

The form of the resin (P) of the present invention may be any of random type, block type, comb type, and star type.
The resin (P) can be synthesized, for example, by radical, cation, or anionic polymerization of an unsaturated monomer corresponding to each structure. It is also possible to obtain the desired resin by conducting a polymer reaction after polymerization using an unsaturated monomer corresponding to the precursor of each structure.
For example, as a general synthesis method, an unsaturated monomer and a polymerization initiator are dissolved in a solvent, and a batch polymerization method in which polymerization is performed by heating, a solution of an unsaturated monomer and a polymerization initiator in a heating solvent for 1 to 10 hours. The dropping polymerization method etc. which are dropped and added over are mentioned, and the dropping polymerization method is preferable.

Examples of the solvent used for the polymerization include a solvent that can be used in preparing the actinic ray-sensitive or radiation-sensitive resin composition described below, and more preferably the composition of the present invention. Polymerization is preferably carried out using the same solvent as used in the above. Thereby, generation | occurrence | production of the particle at the time of a preservation | save can be suppressed.
The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. If necessary, the polymerization may be performed in the presence of a chain transfer agent (for example, alkyl mercaptan).

The reaction concentration is 5 to 70% by mass, preferably 10 to 50% by mass. The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, more preferably from 40 ° C to 100 ° C.
The reaction time is usually 1 to 48 hours, preferably 1 to 24 hours, more preferably 1 to 12 hours.
After completion of the reaction, the mixture is allowed to cool to room temperature and purified. Purification can be accomplished by a liquid-liquid extraction method that removes residual monomers and oligomer components by combining water and an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less. , Reprecipitation method that removes residual monomer by coagulating resin in poor solvent by dripping resin solution into poor solvent and purification in solid state such as washing filtered resin slurry with poor solvent A normal method such as a method can be applied. For example, the resin is precipitated as a solid by contacting a solvent (poor solvent) in which the resin is hardly soluble or insoluble in a volume amount of 10 times or less, preferably 10 to 5 times that of the reaction solution.

The solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent for the polymer, and may be a hydrocarbon, halogenated hydrocarbon, nitro, depending on the type of polymer. A compound, ether, ketone, ester, carbonate, alcohol, carboxylic acid, water, a mixed solvent containing these solvents, and the like can be appropriately selected for use. Among these, as a precipitation or reprecipitation solvent, a solvent containing at least an alcohol (particularly methanol) or water is preferable.
The amount of the precipitation or reprecipitation solvent used can be appropriately selected in consideration of efficiency, yield, and the like, but generally 100 to 10000 parts by mass, preferably 200 to 2000 parts by mass with respect to 100 parts by mass of the polymer solution, More preferably, it is 300-1000 mass parts.
The temperature for precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C., preferably around room temperature (for example, about 20 to 35 ° C.). The precipitation or reprecipitation operation can be performed by a known method such as a batch method or a continuous method using a conventional mixing vessel such as a stirring tank.
The precipitated or re-precipitated polymer is usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and dried before use. Filtration is performed using a solvent-resistant filter medium, preferably under pressure. Drying is performed at a temperature of about 30 to 100 ° C., preferably about 30 to 50 ° C. under normal pressure or reduced pressure (preferably under reduced pressure).

In addition, once the resin is precipitated and separated, it may be dissolved again in a solvent, and the resin may be brought into contact with a hardly soluble or insoluble solvent. That is, after completion of the radical polymerization reaction, a solvent in which the polymer is hardly soluble or insoluble is brought into contact, the resin is precipitated (step a), the resin is separated from the solution (step b), and dissolved again in the solvent. (Step c), and then contact the resin solution A with a solvent in which the resin is hardly soluble or insoluble in a volume amount less than 10 times that of the resin solution A (preferably 5 times or less volume). This may be a method including precipitating a resin solid (step d) and separating the precipitated resin (step e).
The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. As a polymerization initiator, a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization. As the radical initiator, an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable. Preferred examples of the initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is usually from 10 ° C to 150 ° C, preferably from 30 ° C to 120 ° C, more preferably from 60 ° C to 100 ° C.

  The molecular weight of the resin (P) according to the present invention is not particularly limited, but the weight average molecular weight is preferably in the range of 1000 to 100,000, more preferably in the range of 1500 to 60000, and in the range of 2000 to 30000. It is particularly preferred. By setting the weight average molecular weight in the range of 1000 to 100,000, it is possible to prevent heat resistance and dry etching resistance from being deteriorated, and also to prevent developability from being deteriorated and the film forming property from being deteriorated due to increased viscosity. be able to. Here, the weight average molecular weight of the resin indicates a molecular weight in terms of polystyrene measured by GPC (carrier: THF or N-methyl-2-pyrrolidone (NMP)).

  The dispersity (Mw / Mn) is preferably 1.00 to 5.00, more preferably 1.03 to 3.50, and still more preferably 1.05 to 2.50. The smaller the molecular weight distribution, the better the resolution and the resist shape, and the smoother the side wall of the resist pattern, the better the roughness.

  Resin (P) of this invention can be used individually by 1 type or in combination of 2 or more types. The content of the resin (P) is preferably 20 to 99 mass%, more preferably 30 to 89 mass%, based on the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. 40-79 mass% is especially preferable.

[4] Compound that decomposes by the action of an acid to generate an acid The actinic ray-sensitive or radiation-sensitive resin composition of the present invention further includes one or two compounds that decompose by the action of an acid to generate an acid. More than one species may be included. The acid generated from the compound that decomposes by the action of the acid to generate an acid is preferably a sulfonic acid, a methide acid, or an imido acid.

  Although the example of the compound which decomposes | disassembles by the effect | action of the acid which can be used for this invention and generate | occur | produces an acid is shown below, it is not limited to these.

The compound which decomposes | disassembles by the effect | action of the said acid and generate | occur | produces an acid can be used individually by 1 type or in combination of 2 or more types.
In addition, content of the compound which decomposes | disassembles by the effect | action of an acid and generate | occur | produces an acid may be 0.1-40 mass% on the basis of the total solid of the said actinic-ray-sensitive or radiation-sensitive resin composition. Preferably, it is 0.5-30 mass%, More preferably, it is 1.0-20 mass%.
[5] Resist solvent (coating solvent)
The solvent that can be used in preparing the composition is not particularly limited as long as it dissolves each component. For example, alkylene glycol monoalkyl ether carboxylate (propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy- 2-acetoxypropane)), alkylene glycol monoalkyl ether (propylene glycol monomethyl ether (PGME; 1-methoxy-2-propanol), etc.), lactic acid alkyl ester (ethyl lactate, methyl lactate, etc.), cyclic lactone (γ-butyrolactone) Etc., preferably 4 to 10 carbon atoms, chain or cyclic ketone (2-heptanone, cyclohexanone, etc., preferably 4 to 10 carbon atoms), alkylene carbonate (ethylene carbonate, propylene) Boneto etc.), alkyl acetate such as carboxylic acid alkyl (butyl acetate is preferred), and the like alkoxy alkyl acetates (ethyl ethoxypropionate). Other usable solvents include, for example, the solvents described in US Patent Application Publication No. 2008 / 0248425A1 after [0244].

  Of the above, alkylene glycol monoalkyl ether carboxylate and alkylene glycol monoalkyl ether are preferred.

These solvents may be used alone or in combination of two or more. When mixing 2 or more types, it is preferable to mix the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group. The mass ratio of the solvent having a hydroxyl group and the solvent having no hydroxyl group is from 1/99 to 99/1, preferably from 10/90 to 90/10, and more preferably from 20/80 to 60/40.
The solvent having a hydroxyl group is preferably an alkylene glycol monoalkyl ether, and the solvent having no hydroxyl group is preferably an alkylene glycol monoalkyl ether carboxylate.
[6] Basic compound The actinic ray-sensitive or radiation-sensitive composition according to the present invention may further contain a basic compound. The basic compound is preferably a compound having a stronger basicity than phenol. Moreover, this basic compound is preferably an organic basic compound, and more preferably a nitrogen-containing basic compound.

  Although the nitrogen-containing basic compound which can be used is not specifically limited, For example, the compound classified into the following (1)-(7) can be used.

  (1) Compound represented by general formula (BS-1)

In general formula (BS-1),
Each R independently represents a hydrogen atom or an organic group. However, at least one of the three Rs is an organic group. This organic group is a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an aryl group, or an aralkyl group.

Although carbon number of the alkyl group as R is not specifically limited, Usually, it is 1-20, Preferably it is 1-12.
Although carbon number of the cycloalkyl group as R is not specifically limited, Usually, it is 3-20, Preferably it is 5-15.

Although carbon number of the aryl group as R is not specifically limited, Usually, it is 6-20, Preferably it is 6-10. Specific examples include a phenyl group and a naphthyl group.
Although carbon number of the aralkyl group as R is not specifically limited, Usually, it is 7-20, Preferably it is 7-11. Specific examples include a benzyl group.

  In the alkyl group, cycloalkyl group, aryl group and aralkyl group as R, a hydrogen atom may be substituted with a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a hydroxy group, a carboxy group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, and an alkyloxycarbonyl group.

  In the compound represented by the general formula (BS-1), it is preferable that at least two of R are organic groups.

  Specific examples of the compound represented by the general formula (BS-1) include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexyl. Methylamine, tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N-dibutylaniline, N , N-dihexylaniline, 2,6-diisopropylaniline, and 2,4,6-tri (t-butyl) aniline.

  Moreover, as a preferable basic compound represented by the general formula (BS-1), a compound in which at least one R is an alkyl group substituted with a hydroxy group can be given. Specific examples include triethanolamine and N, N-dihydroxyethylaniline.

In addition, the alkyl group as R may have an oxygen atom in the alkyl chain. That is, an oxyalkylene chain may be formed. As the oxyalkylene chain, —CH ₂ CH ₂ O— is preferable. Specifically, for example, tris (methoxyethoxyethyl) amine and compounds exemplified in the 60th and subsequent lines of column 3 of US6040112 can be mentioned.

  As a basic compound represented by general formula (BS-1), the following are mentioned, for example.

(2) Compound having nitrogen-containing heterocyclic structure This nitrogen-containing heterocyclic ring may have aromaticity or may not have aromaticity. Moreover, you may have two or more nitrogen atoms. Furthermore, you may contain hetero atoms other than nitrogen. Specifically, for example, compounds having an imidazole structure (2-phenylbenzimidazole, 2,4,5-triphenylimidazole, etc.), compounds having a piperidine structure [N-hydroxyethylpiperidine and bis (1,2,2) , 6,6-pentamethyl-4-piperidyl) sebacate], compounds having a pyridine structure (such as 4-dimethylaminopyridine), and compounds having an antipyrine structure (such as antipyrine and hydroxyantipyrine).

  A compound having two or more ring structures is also preferably used. Specific examples include 1,5-diazabicyclo [4.3.0] non-5-ene and 1,8-diazabicyclo [5.4.0] -undec-7-ene.

(3) Amine compound having a phenoxy group An amine compound having a phenoxy group is a compound having a phenoxy group at the terminal opposite to the N atom of the alkyl group contained in the amine compound. The phenoxy group is, for example, a substituent such as an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxy group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. You may have.

This compound more preferably has at least one oxyalkylene chain between the phenoxy group and the nitrogen atom. The number of oxyalkylene chains in one molecule is preferably 3-9, more preferably 4-6. Among the oxyalkylene chains, —CH ₂ CH ₂ O— is particularly preferable.

  Specific examples include 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine, and paragraph [0066] of US2007 / 0224539A1. ] Compounds (C1-1) to (C3-3) exemplified in the above.

  The amine compound having a phenoxy group is prepared by reacting, for example, a primary or secondary amine having a phenoxy group with a haloalkyl ether, and adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. And then extracted with an organic solvent such as ethyl acetate and chloroform. In addition, the amine compound having a phenoxy group reacts by heating a primary or secondary amine and a haloalkyl ether having a phenoxy group at the terminal, and a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. It can also be obtained by adding an aqueous solution and then extracting with an organic solvent such as ethyl acetate and chloroform.

(4) Ammonium salt As the basic compound, an ammonium salt can also be used as appropriate. Examples of the anion of the ammonium salt include halides, sulfonates, borates, and phosphates. Of these, halides and sulfonates are particularly preferred.

As the halide, chloride, bromide and iodide are particularly preferable.
As the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is particularly preferable. Examples of the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates.

  The alkyl group contained in the alkyl sulfonate may have a substituent. Examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group, an acyl group, and an aryl group. Specific examples of the alkyl sulfonate include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate.

  Examples of the aryl group contained in the aryl sulfonate include a phenyl group, a naphthyl group, and an anthryl group. These aryl groups may have a substituent. As this substituent, a C1-C6 linear or branched alkyl group and a C3-C6 cycloalkyl group are preferable, for example. Examples of other substituents include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.

  The ammonium salt may be hydroxide or carboxylate. In this case, the ammonium salt is a tetraalkylammonium hydroxide having 1 to 8 carbon atoms (tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra- (n-butyl) ammonium hydroxide, etc.). It is particularly preferred.

  Preferred basic compounds include, for example, guanidine, aminopyridine, aminoalkylpyridine, aminopyrrolidine, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, piperazine, aminomorpholine and aminoalkylmorpholine. . These may further have a substituent.

  Preferred substituents include, for example, amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group And a cyano group.

  Particularly preferable basic compounds include, for example, guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2 -Phenylimidazole, 4,5-diphenylimidazole, 2,4,5-triphenylimidazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2- Diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethyl Pyridine, 4-aminoethylpyridine, 3-amino Pyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6 tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5 methylpyrazine, Examples include pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine and N- (2-aminoethyl) morpholine.

(5) A compound having a proton acceptor functional group and generating a compound which is decomposed by irradiation with actinic rays or radiation to decrease or disappear the proton acceptor property or change from proton acceptor property to acidity ( PA)
The composition according to the present invention has a proton acceptor functional group as a basic compound, and is decomposed by irradiation with actinic rays or radiation, resulting in a decrease, disappearance, or a proton acceptor property. It may further contain a compound (PA) that generates a compound that has been changed to acidic.
A compound (PA) having a proton acceptor functional group and generating a compound that is decomposed by irradiation with actinic rays or radiation to decrease, disappear, or change the proton acceptor property to acidic. As for the amount used thereof and the like, the description in paragraphs 0379 to 0425 of JP 2012-32762 A (corresponding to [0386] to [0435] of the corresponding US Patent Application Publication No. 2012/0003590) can be referred to. The contents are incorporated herein.

(6) Guanidine Compound The composition of the present invention may further contain a guanidine compound.
As the guanidine compound, description in paragraphs 0374 to 0378 of JP 2012-32762 A (corresponding to [0382] to [0385] of the corresponding US Patent Application Publication No. 2012/0003590) can be referred to, and the contents thereof are described in this application. Incorporated in the description.

(7) Low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid The composition of the present invention comprises a low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid (hereinafter referred to as “low molecular weight compound”). In this case, it is possible to contain “low molecular compound (D)” or “compound (D)”. The low molecular compound (D) preferably has basicity after the group capable of leaving by the action of an acid is eliminated.

  The group capable of leaving by the action of an acid is not particularly limited, but is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, and a carbamate group or a hemiaminal ether group. It is particularly preferred.

  The molecular weight of the low molecular weight compound (D) having a group capable of leaving by the action of an acid is preferably 100 to 1000, more preferably 100 to 700, and particularly preferably 100 to 500.

  As the compound (D), an amine derivative having a group capable of leaving by the action of an acid on the nitrogen atom is preferable.

  Compound (D) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group can be represented by the following general formula (d-1).

In general formula (d-1),
R ′ each independently represents a hydrogen atom, a linear or branched alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group. R ′ may be bonded to each other to form a ring.

R ′ is 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 specific structure of such a group is shown below.

  The compound (D) can also be constituted by arbitrarily combining the basic compound and the structure represented by the general formula (d-1).

  The compound (D) particularly preferably has a structure represented by the following general formula (A).

  The compound (D) may correspond to the basic compound as long as it is a low molecular compound having a group capable of leaving by the action of an acid.

  In the general formula (A), Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When n = 2, the two Ras may be the same or different, and the two Ras are bonded to each other 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, an aralkyl group, or an alkoxyalkyl group. However, in -C (Rb) (Rb) (Rb), when one or more Rb is a hydrogen atom, at least one of the remaining Rb is a cyclopropyl group, a 1-alkoxyalkyl group or an aryl group.

  At least two Rb may be bonded 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 (A), the alkyl group, cycloalkyl group, aryl group and aralkyl group represented by Ra and Rb are functional groups such as hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group and oxo group. , An alkoxy group and a halogen atom may be substituted. The same applies to the alkoxyalkyl group represented by Rb.

  The alkyl group, cycloalkyl group, aryl group, and aralkyl group of Ra and / or Rb (these alkyl group, cycloalkyl group, aryl group, and aralkyl group are substituted with the above functional group, alkoxy group, or halogen atom). Examples of the group may include the groups described in paragraph 0399 of JP 2012-27436 A.

  In addition, as the divalent heterocyclic hydrocarbon group (preferably having 1 to 20 carbon atoms) or a derivative thereof formed by bonding of Ra to each other, each described in paragraph 0400 of JP2012-27436A Group or a derivative thereof.

  A particularly preferred compound (D) in the present invention is specifically shown, but the present invention is not limited thereto.

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

  The composition of the present invention may or may not contain the low molecular compound (D), but when it is contained, the content of the compound (D) is the total solid of the composition combined with the basic compound described above. Based on the minutes, it is usually 0.001 to 20% by mass, preferably 0.001 to 10% by mass, and more preferably 0.01 to 5% by mass.

  When the composition of the present invention contains an acid generator, the ratio of the acid generator and the compound (D) used in the composition is: acid generator / [compound (D) + the following basic compound] (mole Ratio) = 2.5 to 300. In other words, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment. The acid generator / [compound (D) + basic compound] (molar ratio) is more preferably 5.0 to 200, and still more preferably 7.0 to 150.

  Other examples that can be used in the composition according to the present invention include compounds synthesized in Examples of JP-A No. 2002-363146, and compounds described in paragraph 0108 of JP-A No. 2007-298869. It is done.

  A photosensitive basic compound may be used as the basic compound. As the photosensitive basic compound, for example, JP-T-2003-524799 and J. Org. Photopolym. Sci & Tech. Vol. 8, P.I. 543-553 (1995) etc. can be used.

  The molecular weight of the basic compound is usually 100-1500, preferably 150-1300, and more preferably 200-1000.

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

  When the composition according to the present invention contains a basic compound, the content is preferably 0.01 to 8.0% by mass based on the total solid content of the composition, The content is more preferably 5.0% by mass, and particularly preferably 0.2 to 4.0% by mass.

  The molar ratio of the basic compound to the photoacid generator is preferably 0.01 to 10, more preferably 0.05 to 5, and still more preferably 0.1 to 3. If this molar ratio is excessively increased, sensitivity and / or resolution may be reduced. If this molar ratio is excessively small, there is a possibility that pattern thinning occurs between exposure and heating (post-bake). More preferably, it is 0.05-5, More preferably, it is 0.1-3. The photoacid generator at the molar ratio is based on the total amount of the repeating unit (B) of the resin and the photoacid generator that the resin may further contain.

[7] Hydrophobic resin (HR)
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may have a hydrophobic resin (HR) separately from the resin (P).
Since the hydrophobic resin (HR) is unevenly distributed on the film surface, the hydrophobic resin (HR) preferably contains a group having a fluorine atom, a group having a silicon atom, or a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on the side chain. Specific examples of the hydrophobic resin (HR) are shown below.

As the hydrophobic resin, those described in JP 2011-248019 A, JP 2010-175859 A, and JP 2012-032544 A can also be preferably used.
The weight average molecular weight of the hydrophobic resin (HR) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and even more preferably 2,000 to 20,000. is there.
Moreover, the hydrophobic resin (HR) may be used alone or in combination.
The content of the hydrophobic resin (HR) in the composition is preferably 0.01 to 20 mass%, more preferably 0.05 to 15 mass%, more preferably 0.1 to 0.1 mass% with respect to the total solid content in the composition. 10 mass% is still more preferable.
In addition, from the viewpoint of sensitivity, resolution, roughness, etc., the molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably 1 to 3, and still more preferably 1 to 2. is there.

[8] Surfactant The actinic ray-sensitive or radiation-sensitive composition according to the present invention may further contain a surfactant. As this surfactant, fluorine-based and / or silicon-based surfactants are particularly preferable.

  Examples of the fluorine-based and / or silicon-based surfactant include Megafac F176 and Megafac R08 manufactured by Dainippon Ink and Chemicals, PF656 and PF6320 manufactured by OMNOVA, and Troisol S manufactured by Troy Chemical Co., Ltd. -366, Fluorard FC430 manufactured by Sumitomo 3M Limited, and polysiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.

  Surfactants other than fluorine and / or silicon may be used. Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkyl aryl ethers.

  In addition, known surfactants can be used as appropriate. Examples of the surfactant that can be used include surfactants described in [0273] and after in US 2008 / 0248425A1.

One type of surfactant may be used alone, or two or more types may be used in combination.
When the composition according to the present invention further contains a surfactant, the amount used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 2, based on the total solid content of the composition. 1% by mass.
On the other hand, the surface unevenness of the hydrophobic resin is increased by setting the addition amount of the surfactant to 10 ppm or less with respect to the total amount of the actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent). The surface of the resist film can be made more hydrophobic, and the water followability during immersion exposure can be improved.

[9] Other additives In addition to the components described above, the composition of the present invention has a molecular weight of 3000 or less as described in carboxylic acid, carboxylic acid onium salt, Proceeding of SPIE, 2724, 355 (1996), etc. A blocking compound, a dye, a plasticizer, a photosensitizer, a light absorber, an antioxidant, and the like can be appropriately contained.
In particular, carboxylic acid is preferably used for improving the performance. As the carboxylic acid, aromatic carboxylic acids such as benzoic acid and naphthoic acid are preferable.
The content of the carboxylic acid is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and still more preferably 0.01 to 3% by mass in the total solid content concentration of the composition.

The actinic ray-sensitive or radiation-sensitive resin composition in the present invention is preferably used at a thickness of 10 to 250 nm, more preferably at a thickness of 20 to 200 nm, from the viewpoint of improving resolution. More preferably, it is preferably used at 30 to 100 nm. Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coating property and film forming property.
The solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition in the present invention is usually 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, and more preferably 2.0. It is -5.3 mass%. By setting the solid content concentration within the above range, it is possible to uniformly apply the resist solution on the substrate, and it is possible to form a resist pattern having excellent line width roughness. The reason for this is not clear, but perhaps the solid content concentration is 10% by mass or less, preferably 5.7% by mass or less, which suppresses aggregation of the material in the resist solution, particularly the photoacid generator. As a result, it is considered that a uniform resist film was formed.
The solid content concentration is a weight percentage of the weight of other resist components excluding the solvent with respect to the total weight of the actinic ray-sensitive or radiation-sensitive resin composition.

  In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the above components are dissolved in a predetermined organic solvent, preferably the mixed solvent, filtered, and then applied onto a predetermined support (substrate). Use. The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as in JP-A-2002-62667, circulation filtration may be performed, or filtration may be performed by connecting a plurality of types of filters in series or in parallel. The composition may be filtered multiple times. Furthermore, you may perform a deaeration process etc. with respect to a composition before and behind filter filtration.

[10] Pattern Forming Method The present invention relates to an actinic ray-sensitive or radiation-sensitive film (hereinafter also referred to as a resist film) formed using the above-described composition of the present invention.
Moreover, the pattern forming method of the present invention includes:
(A) a step of forming a film (resist film) with an actinic ray-sensitive or radiation-sensitive resin composition;
(A) a step of exposing the film, and (c) a step of developing using a developer,
At least.
The developer in the step (c) may be a developer containing an organic solvent or an alkali developer. However, since the effect of the present invention is more remarkably exhibited, the developer containing an organic solvent is developed. A liquid is preferred.
Specifically, the pattern forming method of the present invention includes:
(A) a step of forming a film (resist film) with an actinic ray-sensitive or radiation-sensitive resin composition;
It is preferable to include at least (i) a step of exposing the film, and (c) a step of developing the exposed film using a developer containing an organic solvent to form a negative pattern.
Further, the exposure in the step (ii) may be immersion exposure.
The pattern forming method of the present invention preferably comprises (i) a heating step after (b) the exposure step.
The pattern forming method of the present invention may further include (e) a step of developing using an alkali developer when the developer in the step (c) is a developer containing an organic solvent. On the other hand, when the developer in the step (c) is an alkali developer, (e) it may further include a step of developing using a developer containing an organic solvent.
The pattern formation method of this invention can have (b) exposure process in multiple times.
The pattern formation method of this invention can have (e) a heating process in multiple times.

  The resist film is formed from the actinic ray-sensitive or radiation-sensitive resin composition of the present invention described above, and more specifically, is preferably formed on a substrate. In the pattern forming method of the present invention, a step of forming a film of an actinic ray-sensitive or radiation-sensitive resin composition on a substrate, a step of exposing the film, and a developing step are generally known methods. Can be performed.

  This composition can be applied to, for example, a spinner and a substrate on a substrate (eg, silicon / silicon dioxide coating, silicon nitride and chromium-deposited quartz substrate) used for manufacturing precision integrated circuit elements and imprint molds. It is applied using a coater or the like. Thereafter, it can be dried to form an actinic ray-sensitive or radiation-sensitive film.

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

It is also preferable to include a preheating step (PB; Prebake) after the film formation and before the exposure step.
It is also preferable to include a post-exposure heating step (PEB; Post Exposure Bake) after the exposure step and before the development step.
The heating temperature is preferably 70 to 120 ° C., more preferably 80 to 110 ° C. for both PB and PEB.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds.
Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.
The reaction of the exposed part is promoted by baking, and the sensitivity and pattern profile are improved.
It is also preferable to include a heating step (Post Bake) after the rinsing step. The developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking.

Examples of actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, X-rays, and electron beams. As these actinic rays or radiation, for example, those having a wavelength of 250 nm or less, particularly 220 nm or less are more preferable. Examples of such actinic rays or radiation include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-rays, and electron beams. Examples of preferable actinic rays or radiation include KrF excimer laser, ArF excimer laser, electron beam, X-ray and EUV light. It is more preferably an electron beam, X-ray or EUV light, and further preferably an electron beam or EUV light.

  In the exposure step of the present invention, the immersion exposure method described in paragraphs 0421 to 0425 of JP2012-27436 can be applied.

The electrical resistance of the water used as the immersion liquid is preferably 18.3 MΩcm or more, the TOC (organic substance concentration) is preferably 20 ppb or less, and deaeration treatment is preferably performed.
Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive that increases the refractive index may be added to water, or heavy water (D ₂ O) may be used instead of water.

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

In order to prevent the film from directly contacting the immersion liquid between the film formed using the composition of the present invention and the immersion liquid, an immersion liquid hardly soluble film (hereinafter also referred to as “topcoat”). May be provided. Functions necessary for the top coat include suitability for application to the resist upper layer, transparency to radiation, particularly radiation having a wavelength of 193 nm, and poor immersion liquid solubility. It is preferable that the top coat is not mixed with the resist and can be uniformly applied to the upper layer of the resist.
From the viewpoint of transparency at 193 nm, the topcoat is preferably a polymer that does not contain aromatics.
Specific examples include hydrocarbon polymers, acrylic ester polymers, polymethacrylic acid, polyacrylic acid, polyvinyl ether, silicon-containing polymers, and fluorine-containing polymers. When impurities are eluted from the top coat into the immersion liquid, the optical lens is contaminated. Therefore, it is preferable that the residual monomer component of the polymer contained in the top coat is small.

When peeling the top coat, a developer may be used, or a separate release agent may be used. As the release agent, a solvent having low penetration into the film is preferable. In terms of being able to perform the peeling process simultaneously with the film development process, it is preferable that the peeling process can be performed with an alkaline developer. The top coat is preferably acidic from the viewpoint of peeling with an alkali developer, but may be neutral or alkaline from the viewpoint of non-intermixability with the film.
There is preferably no or small difference in refractive index between the top coat and the immersion liquid. In this case, the resolution can be improved. When the exposure light source is an ArF excimer laser (wavelength: 193 nm), it is preferable to use water as the immersion liquid. Therefore, the top coat for ArF immersion exposure is close to the refractive index of water (1.44). preferable. Moreover, it is preferable that a topcoat is a thin film from a viewpoint of transparency and a refractive index.

  The topcoat 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. Further, when the immersion liquid is an organic solvent, the topcoat may be water-soluble or water-insoluble.

  In the present invention, a substrate on which a film is formed is not particularly limited, and a substrate described in paragraph 0426 of JP 2012-27436 A can be used.

When the pattern forming method of the present invention includes a step of developing using an alkali developer, examples of the alkali developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia. Inorganic amines such as ethylamine, primary amines such as n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine, and triethanol Alkaline aqueous solutions such as alcohol amines such as amines, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and pihelidine can be used.
Furthermore, an appropriate amount of alcohol or surfactant may be added to the alkaline aqueous solution.
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.
In particular, an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide is desirable.

As a rinsing solution in the rinsing treatment performed after alkali development, pure water can be used, and an appropriate amount of a surfactant can be added.
In addition, after the developing process or the rinsing process, a process of removing the developing solution or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed.

When the pattern forming method of the present invention includes a step of developing using a developer containing an organic solvent, the developer in the step (hereinafter also referred to as an organic developer) includes a ketone solvent and an ester solvent. Polar solvents such as solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents can be used.
Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.
Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl 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, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, etc. Can be mentioned.
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, n-heptyl alcohol, alcohols such as n-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 monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butano It can be mentioned glycol ether solvents such as Le.
Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.
Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.
Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
A plurality of the above solvents may be mixed, or may be used by mixing with a solvent other than those described above or water.
However, in order to fully exhibit the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture.
That is, the amount of the organic solvent used in the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less, with respect to the total amount of the developer.
In particular, the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. .

The vapor pressure of the organic developer 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 organic developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, and the temperature uniformity in the wafer surface is improved. As a result, the dimensions in the wafer surface are uniform. Sexuality improves.
Specific examples having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 2-hexanone, diisobutyl ketone, Ketone solvents such as cyclohexanone, methylcyclohexanone, phenylacetone, methyl isobutyl ketone, butyl acetate, pentyl acetate, isopentyl 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, 3-methyl-3-methoxybutyl acetate, formate , Ester solvents such as propyl formate, ethyl lactate, butyl lactate, propyl lactate, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, alcohol solvents such as n-heptyl alcohol, n-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 monomethyl ether, triethylene glycol monoethyl ether, methoxyme Glycol ether solvents such as rubutanol, ether solvents such as tetrahydrofuran, amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, aromatic carbonization such as toluene and xylene Examples thereof include aliphatic hydrocarbon solvents such as hydrogen solvents, octane, and decane.
Specific examples having a vapor pressure of 2 kPa or less, which is a particularly preferable range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexanone, and methylcyclohexanone. , Ketone solvents such as phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3- Ester solvents such as methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate and propyl lactate, n-butyl alcohol, alcohol solvents such as ec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol and n-decanol; glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol And glycol ether solvents such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethylbutanol, N-methyl-2 Amide solvents of pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, Aromatic hydrocarbon solvents such as cyclohexylene, octane, aliphatic hydrocarbon solvents decane.

An appropriate amount of a surfactant can be added to the organic developer as required.
The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP 63-34540 A, JP 7-230165 A, JP 8-62834 A, JP 9-54432 A, JP 9-5988 A, US Pat. No. 5,405,720, etc. The surfactants described in US Pat. Nos. 5,360,692, 5,298,881, 5,296,330, 5,346,098, 5,576,143, 5,294,511, and 5,824,451 can be mentioned. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.
The amount of the surfactant used is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.
The organic developer may contain an appropriate amount of a basic compound as required. Examples of the basic compound include those described above in the section of [6] Basic compound.

As a developing method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc. can be applied.
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 it is 2 mL / sec / mm ² or less, More preferably, it is 1.5 mL / sec / mm ² or less, More preferably, it is 1 mL / sec / mm ² or less. There is no particular lower limit on the flow rate, but 0.2 mL / sec / mm ² or more is preferable in consideration of throughput.
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 by the developer to the resist film will decrease, and the resist film / 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 the method for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump or 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 substituting with another solvent after the process developed using the developing solution containing an organic solvent.

  After the step of developing with a developer containing an organic solvent, a step of washing with a rinse solution may be included. From the viewpoint of throughput (productivity), the amount of rinse solution used, etc. It is preferable not to include the step of using and washing.

The rinsing solution used in the rinsing step after the step of developing with a developer containing an organic solvent is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a general organic solvent can be used. . As the rinsing liquid, a rinsing liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents is used. It is preferable.
Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent are the same as those described in the developer containing an organic solvent.
More preferably, it contains at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, and amide solvents after the step of developing using a developer containing an organic solvent. A step of washing with a rinsing liquid is performed, more preferably, a step of washing with a rinsing liquid containing an alcohol solvent or an ester solvent is carried out, and particularly preferably, a rinsing liquid containing a monohydric alcohol is used. And, most preferably, the step of cleaning with a rinse solution containing a monohydric alcohol having 5 or more carbon atoms is performed.
Here, examples of the monohydric alcohol used in the rinsing step include linear, branched, and cyclic monohydric alcohols, and specifically, 1-butanol, 2-butanol, and 3-methyl-1-butanol. Tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2 -Octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used, and particularly preferable monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl- Use 2-pentanol, 1-pentanol, 3-methyl-1-butanol, etc. It can be.

  A plurality of these components may be mixed, or may be used by mixing with an organic solvent other than the above.

  The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

  The vapor pressure of the rinsing solution used after the step of developing with a developer containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less at 20 ° C. 12 kPa or more and 3 kPa or less are the most preferable. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface. Improves.

  An appropriate amount of a surfactant can be added to the rinse solution.

In the rinsing step, the wafer that has been developed using the developer containing the organic solvent is washed using the rinse solution containing the organic solvent. The cleaning method is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid on the substrate surface (spray method), and the like can be applied. Among them, a cleaning treatment is performed by a spin coating method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. The developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking. The heating step after the rinsing step is usually 40 to 160 ° C., preferably 70 to 95 ° C., and usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.
In the pattern formation method of the present invention, the step of developing using a developer containing an organic solvent (organic solvent developing step) and the step of developing using an aqueous alkali solution (alkali developing step) are also used. Also good. Thereby, a finer pattern can be formed.
In the present invention, a portion with low exposure intensity is removed by the organic solvent development step, but a portion with high exposure strength is also removed by further performing the alkali development step. In this way, by the multiple development process in which development is performed a plurality of times, a pattern can be formed without dissolving only the intermediate exposure intensity region, so that a finer pattern than usual can be formed (Japanese Patent Laid-Open No. 2008-292975 [0077]. ] And the same mechanism).
In the pattern forming method of the present invention, the order of the alkali development step and the organic solvent development step is not particularly limited, but it is more preferable to perform the alkali development before the organic solvent development step.

  In addition, you may produce the mold for imprint using the composition which concerns on this invention, For the details, for example, the patent 4109085 gazette, Unexamined-Japanese-Patent No. 2008-162101, and "the foundation and technique of nanoimprint" See “Development and Application Development-Nanoimprint Substrate Technology and Latest Technology Development-Editing: Yoshihiko Hirai (Frontier Publishing)”.

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

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

<Synthesis Example 1: Synthesis of Compound c-1>
The following synthesis scheme was performed.

  To 97 g of compound (c-1-1), 100 g of potassium carbonate, and 500 mL of acetone, 150 g of compound (c-1-2) was added dropwise at 25 ° C. over 1 hour. After adding 250 mL of ammonium chloride aqueous solution, acetone was distilled off with an evaporator, and the obtained aqueous phase was extracted with 300 mL of ethyl acetate three times. The obtained organic phases were combined and washed twice with 250 mL of water, and the obtained organic phase was evaporated with an evaporator to obtain 157 g of compound (c-1-3) (yield 86%).

  To 157 g of the compound (c-1-4), 29 g of tetrabutylammonium bromide, 500 mL of 1N aqueous sodium hydroxide solution and 500 mL of dichloroethane were added and cooled to 0 ° C. What diluted 157 g of compounds (c-1-3) with 150 g of ethyl acetate was dripped there over 1 hour. The aqueous phase was removed, and further washed with 150 mL of 1N aqueous sodium hydroxide solution three times, and the solvent of the organic phase was distilled off. To the distilled residue, 70 g of sodium iodide and 500 mL of acetonitrile were added, stirred, filtered, and washed with 300 mL of acetonitrile to find 227 g of compound (c-1-5) (yield 86% white solid) Obtained.

227 g of compound (c-1-5), 160 g of triphenylsulfonium bromide, and 500 mL of methanol were added and stirred. Methanol was distilled off with an evaporator, 250 mL of water was added, extraction was performed 4 times with 250 mL of chloroform, and the obtained organic phase was evaporated with an evaporator. As a result, 293 g of Compound (c-1) was obtained (yield 95% white). Solid) was obtained.
¹ H-NMR (400 MHz in CDCl ₃ ): (ppm) = 7.81-7.70 (m, 15H), 6.88 (s, 2H), 4.62 (s, 2H), 3.10 ( m, 2H), 2.31 (hep, 1H), 2.92-1.72 (m, 4H), 1.28 (d, 12H), 0.91-0.79 (m, 12H)
<Synthesis of Compounds c-2 to c-137>
Of the compounds c-2 to c-137, the following compounds used in the following examples were synthesized in the same manner as in Synthesis Example 1. The compounds used in the examples are shown below. However, c-132 will be described later.

<Synthesis Example 2: Synthesis of Resin P-2>
Under a nitrogen stream, 23 g of cyclohexanone was placed in a three-necked flask (solvent 1) and heated to 85 ° C. M-I-1 40% by mass cyclohexanone solution 6.5 g and M-II-1 10.8 g were dissolved in cyclohexanone 60 g. Furthermore, a solution in which 0.65 g of initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved was dropped into (solvent 1) over 4 hours. After completion of dropping, the reaction was further continued at 85 ° C. for 2 hours. The reaction solution was allowed to cool and then added dropwise to 1200 mL of hexane, and the precipitated powder was collected by filtration and dried to obtain 5.1 g of Resin P-2.

About the obtained resin P-2, the composition ratio (molar ratio) of the resin P-2 was calculated by ¹³ C-NMR measurement. In addition, by GPC (solvent: N-methylpyrrolidone (NMP)) measurement, the weight average molecular weight (Mw: polystyrene conversion), number average molecular weight (Mn: polystyrene conversion) and dispersity (Mw / Mn, below) of the resin P-2 (Also referred to as “PDI”). These results are shown in the chemical formula below.

<Synthesis of Resins (P-1), (P-3) to (P-11) and Compound c-132>
Resins (P-1), (P-3) to (P-11) and compound c-132 were synthesized in the same manner as in Synthesis Example 2, except that the polymerizable compound (monomer) to be used was appropriately changed.

  Hereinafter, the polymer structures, weight average molecular weight (Mw), and dispersity (Mw / Mn) (PDI) of resins (P-1) to (P-11) and compound c-132 are shown. Moreover, the composition ratio of each repeating unit of the following polymer structure was shown by molar ratio.

[Photoacid generator]
As the photoacid generator, the compounds (c-1), (c-7) to (c-12), (c-62), (c-82), (c-85) listed above as the compounds of the present invention. , (C-92), (c-93), (c-96), (c-103), (c-104), (c-115), (c-125) to (c-128), ( c-135) (however, (c-132) is as described above), compound PAG-1, 2 represented by the following formula is used, or for the comparative example, The represented compounds r-1 to r-3 were used.

[Basic compounds]
As the basic compound, any of the following compounds (N-1) to (N-10) was used.

  In addition, the said compound (N-7) corresponds to the compound (PA) mentioned above, and was synthesize | combined based on the description of [0354] of Unexamined-Japanese-Patent No. 2006-330098.

[Surfactant and solvent]
The following W-1 to W-3 were used as the surfactant.
W-1: Megafuck R08 (Dainippon Ink Chemical Co., Ltd .; fluorine and silicon)
W-2: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd .; silicon-based)
W-3: Troisol S-366 (manufactured by Troy Chemical Co .; fluorine type)

As the solvent, the following S1 to S4 were appropriately mixed and used.
S1: Propylene glycol monomethyl ether acetate (PGMEA; bp = 146 ° C.)
S2: Propylene glycol monomethyl ether (PGME; bp = 120 ° C.)
S3: Methyl lactate (bp = 145 ° C.)
S4: cyclohexanone (bp = 157 ° C.)
<Developer>
As the developer, the following was used.
SG-1: 2-nonanone SG-2: Methyl amyl ketone SG-3: Butyl acetate

<Rinse solution>
The following rinse solutions were used.
SR-1: 4-methyl-2-pentanol SR-2: 1-hexanol SR-3: methyl isobutyl carbinol

[Examples 1-1 to 1-21, Comparative Examples 1-1 to 1-3 (extreme ultraviolet (EUV) exposure)]
(1) Preparation and application of coating solution of actinic ray-sensitive or radiation-sensitive resin composition Using a membrane filter having a pore size of 0.05 μm, a coating solution composition having a solid content concentration of 1.5% by mass having the composition shown in the table below is used. Microfiltration was performed to obtain an actinic ray-sensitive or radiation-sensitive resin composition (resist composition) solution.
This actinic ray-sensitive or radiation-sensitive resin composition solution is applied onto a 6-inch Si wafer that has been previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark8 manufactured by Tokyo Electron, and heated at 100 ° C. for 60 seconds. It dried on the plate and obtained the resist film with a film thickness of 50 nm.

(2) EUV exposure and development The wafer coated with the resist film obtained in the above (1) is subjected to an EUV exposure apparatus (Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0, manufactured by Exitech) .36) and pattern exposure was performed using an exposure mask (line / space = 1/1). After irradiation, after heating at 110 ° C. for 60 seconds on a hot plate, paddle the organic developer listed in the table below for 30 seconds, rinse with the rinse solution listed in the table below, and then rotate at 4000 rpm After rotating the wafer for 30 seconds at the number of rotations, baking was performed at 90 ° C. for 60 seconds to obtain a 1: 1 line and space pattern resist pattern having a line width of 50 nm.

(3) Evaluation of resist pattern Using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.), the resist pattern obtained was isolated space resolving power, exposure latitude (EL), and pattern shape by the following method. evaluated. The results are shown in the table below.

(3-1) Isolated space resolution (EUV)
Irradiation energy when resolving a 1: 1 line and space pattern with a line width of 50 nm was defined as sensitivity (Eop).
The critical resolving power (minimum space width at which lines and spaces were separated and resolved) of the isolated pattern (line: space = 5: 1) at the irradiation dose showing the above sensitivity was obtained. This value was defined as “isolated space resolution (nm)”.

(3-2) EL evaluation (EUV exposure)
The exposure amount that reproduces a line-and-space pattern (line: space = 1: 1) with a line width of 50 nm is the optimum exposure amount, and the exposure amount width that allows a pattern size of 50 nm ± 20% when the exposure amount is changed. This value was divided by the optimum exposure amount and displayed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.

(3-3) Pattern shape evaluation (EUV exposure)
A 1: 1 line and space pattern having a line width of 50 nm was observed using a scanning electron microscope (S4800, manufactured by Hitachi, Ltd.), and the ratio of the length L1 at the bottom of the resist pattern to the length L2 at the top (L2 / L1). ) It can be said that the closer the L2 / L1 is to 1, the better the shape.

As is clear from the results shown in the above table, Comparative Examples 1-1 to 1-3, in which the photoacid generator is not a compound represented by the general formula (X), have a small pattern formation EL and a pattern to be formed. It turns out that the shape of is also inferior. It can also be seen that the isolated space was not resolved.
On the other hand, Examples 1-1 to 1-21 using the compound represented by the general formula (X) all have large EL, the pattern shape is also known to be rectangular or rectangular, and the resolution in an isolated space is excellent. I understand that

[Examples 2-1 to 2-19, Comparative Examples 2-1 to 2-3 (electron beam (EB) exposure)]
(1) Preparation and application of coating liquid of actinic ray-sensitive or radiation-sensitive resin composition A coating liquid composition having a solid content concentration of 2.5% by mass having the composition shown in the table below is applied with a membrane filter having a pore size of 0.1 μm. Microfiltration was performed to obtain an actinic ray-sensitive or radiation-sensitive resin composition (resist composition) solution.
This actinic ray-sensitive or radiation-sensitive resin composition solution is applied onto a 6-inch Si wafer that has been previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark8 manufactured by Tokyo Electron, and heated at 100 ° C. for 60 seconds. It dried on the plate and obtained the resist film with a film thickness of 50 nm.

(2) EB exposure and development The wafer coated with the resist film obtained in (1) above was subjected to pattern irradiation using an electron beam drawing apparatus (HL750 manufactured by Hitachi, Ltd., acceleration voltage 50 KeV). . At this time, drawing was performed so that a 1: 1 line and space was formed. After the electron beam drawing, after heating at 110 ° C. for 60 seconds on a hot plate, paddle the organic developer shown in the table below and develop for 30 seconds, and rinse using the rinse solution shown in the table below. Thereafter, the wafer was rotated at a rotation speed of 4000 rpm for 30 seconds and then heated at 90 ° C. for 60 seconds to obtain a 1: 1 line and space pattern resist pattern having a line width of 100 nm.

(3) Evaluation of resist pattern Using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.), the resist pattern obtained was isolated space resolution, exposure latitude (EL), and pattern shape by the following method. evaluated. The results are shown in the table below.

(3-1) Isolated space resolution (EB)
The irradiation energy when resolving a 1: 1 line and space pattern with a line width of 100 nm was defined as sensitivity (Eop).
The critical resolving power (minimum space width at which the line and space were separated and resolved) of the isolated pattern (line: space = 100: 1) at the irradiation amount showing the above sensitivity was obtained. This value was defined as “isolated space resolution (nm)”.

(3-2) EL evaluation (EB exposure)
The exposure amount that reproduces a line-and-space pattern (line: space = 1: 1) with a line width of 100 nm is the optimum exposure amount, and the exposure amount width that allows the pattern size to be 100 nm ± 20% when the exposure amount is changed. This value was divided by the optimum exposure amount and displayed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.

(3-3) Pattern shape evaluation (EB exposure)
A 1: 1 line and space pattern with a line width of 100 nm was observed using a scanning electron microscope (S4800, manufactured by Hitachi, Ltd.), and the ratio of the lowermost length L1 of the resist pattern to the uppermost length L2 (L2 / L1). ) It can be said that the closer the L2 / L1 is to 1, the better the shape.

As is clear from the results shown in the above table, Comparative Example 2-1 in which the photoacid generator is not a compound represented by the general formula (X) has a small pattern formation EL and a poor pattern shape. Also, it can be seen that the isolated space is inferior in resolution although it is resolved. It can be seen that Comparative Examples 2-2 and 2-3 in which the photoacid generator is not a compound represented by the general formula (X) have a small pattern formation EL and a poor pattern shape. Moreover, it turns out that it did not resolve in an isolated space.
On the other hand, Examples 2-1 to 2-19 using the compound represented by the general formula (X) all have large EL, the pattern shape is also known to be rectangular or rectangular, and the resolution in an isolated space is excellent. I understand that

[Examples 3-1 to 3-5, Comparative example 3-1 (ArF exposure)]
(1) Preparation of coating liquid of actinic ray-sensitive or radiation-sensitive resin composition A coating liquid composition having a composition shown in the following table and having a solid content concentration of 3.8% by mass is finely filtered with a membrane filter having a pore size of 0.03 μm. Then, an actinic ray-sensitive or radiation-sensitive resin composition (resist composition) solution was prepared.

(2) Exposure conditions: ArF immersion exposure An organic antireflection film ARC29A (manufactured by Nissan Chemical Industries, Ltd.) is applied onto a 12-inch silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a film thickness of 75 nm. Formed. The actinic ray-sensitive or radiation-sensitive resin composition prepared thereon was applied and baked at 130 ° C. for 60 seconds to form a resist film having a thickness of 120 nm. An ArF excimer laser scanner (XT1700i, NA 1.20, C-Quad, outer sigma 0.981, inner sigma 0.895, XY deflection manufactured by ASML) was used for exposure through a mask. Ultra pure water was used as the immersion liquid. Then, after heating at 100 ° C. for 60 seconds, the film was developed with an organic solvent-based developer described in the following table for 30 seconds, and rinsed with a rinse solution described in the following table for 30 seconds while rotating the wafer at a rotation speed of 1000 rpm. Thereafter, spin drying was performed to obtain a 1: 1 line and space resist pattern having a line width of 80 nm.

(3) Evaluation of resist pattern Using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.), the obtained resist pattern was evaluated for isolated space resolution, EL, and pattern shape by the following methods. The results are shown in the table below.

(3-1) Isolated space resolution (ArF)
The irradiation energy when resolving a 1: 1 line and space pattern with a line width of 80 nm was defined as sensitivity (Eop).
The critical resolving power (minimum space width at which lines and spaces are separated and resolved) of the isolated pattern (line: space = 10: 1) at the irradiation dose showing the above sensitivity was obtained. This value was defined as “isolated space resolution (nm)”.

(3-2) EL evaluation (ArF exposure)
The exposure amount that reproduces a line and space pattern (line: space = 1: 1) with a line width of 80 nm is the optimum exposure amount, and the exposure amount width that allows the pattern size to be 80 nm ± 20% when the exposure amount is changed. This value was divided by the optimum exposure amount and displayed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.

(3-3) Pattern shape evaluation (ArF exposure)
A 1: 1 line and space pattern with a line width of 80 nm was observed using a scanning electron microscope (S4800, manufactured by Hitachi, Ltd.), and the ratio of the lowermost length L1 to the uppermost length L2 (L2 / L1). ) It can be said that the closer the L2 / L1 is to 1, the better the shape.

As is clear from the results shown in the above table, Comparative Example 3-1, in which the photoacid generator is not a compound represented by the general formula (X), has a small pattern formation EL and a poor pattern shape. I understand that. It can also be seen that the isolated space was not resolved.
On the other hand, all of Examples 3-1 to 3-5 using the compound represented by the general formula (X) have large EL, the pattern shape is also known to be rectangular or rectangular, and the resolution in an isolated space is excellent. I understand that

[Examples 4-1 to 4-18, Comparative Examples 4-1 to 4-3 (EUV (extreme ultraviolet) exposure)]
(1) Coating solution preparation and coating of actinic ray-sensitive or radiation-sensitive resin composition The components shown in the following table are dissolved in a solvent, and a solution with a solid content concentration of 4% by mass is prepared for each, and this is 0.10 μm. An actinic ray-sensitive or radiation-sensitive resin composition (resist composition) was prepared by filtration through a polytetrafluoroethylene filter having a pore size of 5 μm. The actinic ray-sensitive or radiation-sensitive resin composition was evaluated by the following method, and the results are shown in the following table.
About each component in the following table, ratio when using two or more is a mass ratio.

(2) EUV exposure and development The prepared actinic ray-sensitive or radiation-sensitive resin composition is uniformly applied on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, and is heated at 120 ° C. for 90 seconds. Heat drying was performed on a hot plate to form an actinic ray-sensitive or radiation-sensitive film (resist film) having a thickness of 100 nm. The wafer coated with the resist film is exposed to an EUV exposure apparatus (Microexposure Tool, manufactured by Exitech, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36) using an exposure mask (line / space = 1 / Pattern exposure was performed using 1). Immediately after exposure, it was heated on a hot plate at 110 ° C. for 90 seconds. Further, development was performed at 23 ° C. for 60 seconds using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass, rinsed with pure water for 30 seconds, and then spin-dried to obtain a resist pattern.

(3) Evaluation of resist pattern Using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.), the obtained resist pattern was evaluated for isolated space resolving power, EL, and pattern shape by the following methods. The results are shown in the table below.

(3-1) Isolated space resolution (EUV)
Irradiation energy when resolving a 1: 1 line and space pattern with a line width of 50 nm was defined as sensitivity (Eop).
The critical resolving power (minimum space width at which lines and spaces were separated and resolved) of the isolated pattern (line: space = 5: 1) at the irradiation dose showing the above sensitivity was obtained. This value was defined as “isolated space resolution (nm)”.

(3-2) EL evaluation (EUV exposure)
The exposure amount that reproduces a line-and-space pattern (line: space = 1: 1) with a line width of 50 nm is the optimum exposure amount, and the exposure amount width that allows a pattern size of 50 nm ± 20% when the exposure amount is changed. This value was divided by the optimum exposure amount and displayed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.

(3-3) Pattern shape evaluation (EUV exposure)
A 1: 1 line and space pattern having a line width of 50 nm was observed using a scanning electron microscope (S4800, manufactured by Hitachi, Ltd.), and the ratio of the length L1 at the bottom of the resist pattern to the length L2 at the top (L2 / L1). ) It can be said that the closer the L2 / L1 is to 1, the better the shape.

As is clear from the results shown in the above table, Comparative Example 4-1, in which the photoacid generator is not a compound represented by the general formula (X), has a small pattern formation EL and a poor pattern shape. Also, it can be seen that the isolated space is inferior in resolution although it is resolved. It can be seen that Comparative Examples 4-2 and 4-3, in which the photoacid generator is not a compound represented by the general formula (X), have a small pattern formation EL and a poor pattern shape. Moreover, it turns out that it did not resolve in an isolated space.
On the other hand, Examples 4-1 to 4-18 using the compound represented by the general formula (X) all have large EL, the pattern shape is also known to be rectangular or rectangular, and the resolution in an isolated space is excellent. I understand that

[Examples 5-1 to 5-9, Comparative examples 5-1 to 5-3 (electron beam (EB) exposure)]
(1) Coating solution preparation and coating of actinic ray-sensitive or radiation-sensitive resin composition The components shown in the following table are dissolved in a solvent, and a solution with a solid content concentration of 4% by mass is prepared for each, and this is 0.10 μm. An actinic ray-sensitive or radiation-sensitive resin composition (resist composition) was prepared by filtration through a polytetrafluoroethylene filter having a pore size of 5 μm. The actinic ray-sensitive or radiation-sensitive resin composition was evaluated by the following method, and the results are shown in the following table.
About each component in the following table, ratio when using two or more is a mass ratio.

(2) EB exposure and development The prepared actinic ray-sensitive or radiation-sensitive resin composition is uniformly applied on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater, and is heated at 120 ° C. for 90 seconds. Heat drying was performed on a hot plate to form an actinic ray-sensitive or radiation-sensitive film (resist film) having a thickness of 100 nm. This actinic ray-sensitive or radiation-sensitive film was irradiated with an electron beam using an electron beam irradiation apparatus (HL750 manufactured by Hitachi, Ltd., acceleration voltage 50 keV). Immediately after irradiation, it was heated on a hot plate at 110 ° C. for 90 seconds. Further, development was performed at 23 ° C. for 60 seconds using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass, rinsed with pure water for 30 seconds, and then spin-dried to obtain a resist pattern.

(3) Evaluation of resist pattern Using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.), the obtained resist pattern was evaluated for isolated space resolving power, EL, and pattern shape by the following methods. The results are shown in the table below.

(3-1) Isolated space resolution (EB)
The irradiation energy when resolving a 1: 1 line and space pattern with a line width of 100 nm was defined as sensitivity (Eop).
The critical resolving power (minimum space width at which the line and space were separated and resolved) of the isolated pattern (line: space = 100: 1) at the irradiation amount showing the above sensitivity was obtained. This value was defined as “isolated space resolution (nm)”.

(3-2) EL evaluation (EB exposure)
The exposure amount that reproduces a line-and-space pattern (line: space = 1: 1) with a line width of 100 nm is the optimum exposure amount, and the exposure amount width that allows the pattern size to be 100 nm ± 20% when the exposure amount is changed. This value was divided by the optimum exposure amount and displayed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.

(3-3) Pattern shape evaluation (EB exposure)
A 1: 1 line and space pattern with a line width of 100 nm was observed using a scanning electron microscope (S4800, manufactured by Hitachi, Ltd.), and the ratio of the lowermost length L1 of the resist pattern to the uppermost length L2 (L2 / L1). ) It can be said that the closer the L2 / L1 is to 1, the better the shape.

As is clear from the results shown in the above table, Comparative Example 5-1, in which the photoacid generator is not a compound represented by the general formula (X), has a small pattern formation EL and a poor pattern shape. Also, it can be seen that the isolated space is inferior in resolution although it is resolved. It can be seen that Comparative Examples 5-2 and 5-2, in which the photoacid generator is not a compound represented by the general formula (X), have a small pattern formation EL and an inferior pattern shape. Moreover, it turns out that it did not resolve in an isolated space.
On the other hand, Examples 5-1 to 5-9 using the compound represented by the general formula (X) all have large EL, the pattern shape is also known to be rectangular or rectangular, and the resolution in an isolated space is also excellent. I understand that

[Examples 6-1 to 6-5, Comparative Example 6-1 (ArF exposure)]
(1) Preparation of coating liquid of actinic ray-sensitive or radiation-sensitive resin composition A coating liquid composition having a composition shown in the following table and having a solid content concentration of 3.8% by mass is finely filtered with a membrane filter having a pore size of 0.03 μm. Then, an actinic ray-sensitive or radiation-sensitive resin composition (resist composition) solution was prepared.

(2) Exposure conditions: ArF immersion exposure An organic antireflection film ARC29A (manufactured by Nissan Chemical Industries, Ltd.) is applied onto a 12-inch silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a film thickness of 75 nm. Formed. The actinic ray-sensitive or radiation-sensitive resin composition prepared thereon was applied and baked at 130 ° C. for 60 seconds to form a resist film having a thickness of 120 nm. This was exposed through a mask using an ArF excimer laser scanner (manufactured by ASML; XT1700i, NA 1.20, C-Quad, outer sigma 0.981, inner sigma 0.895, XY deflection). Ultra pure water was used as the immersion liquid. Thereafter, the mixture was heated at 100 ° C. for 60 seconds, developed with an aqueous tetramethylammonium hydroxide solution (2.38 mass%) for 30 seconds, rinsed with pure water, and spin-dried to obtain a resist pattern.

(3) Evaluation of resist pattern Using a scanning electron microscope (S-9220, manufactured by Hitachi, Ltd.), the obtained resist pattern was evaluated for isolated space resolving power, EL, and pattern shape by the following methods. The results are shown in the table below.

(3-1) Isolated space resolution (ArF)
The irradiation energy when resolving a 1: 1 line and space pattern with a line width of 80 nm was defined as sensitivity (Eop).
The critical resolving power (minimum space width at which lines and spaces are separated and resolved) of the isolated pattern (line: space = 10: 1) at the irradiation dose showing the above sensitivity was obtained. This value was defined as “isolated space resolution (nm)”.

(3-2) EL evaluation (ArF exposure)
The exposure amount that reproduces a line and space pattern (line: space = 1: 1) with a line width of 80 nm is the optimum exposure amount, and the exposure amount width that allows the pattern size to be 80 nm ± 20% when the exposure amount is changed. This value was divided by the optimum exposure amount and displayed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure latitude.

(3-3) Pattern shape evaluation (ArF exposure)
A 1: 1 line and space pattern with a line width of 80 nm was observed using a scanning electron microscope (S4800, manufactured by Hitachi, Ltd.), and the ratio of the lowermost length L1 to the uppermost length L2 (L2 / L1). ) It can be said that the closer the L2 / L1 is to 1, the better the shape.

As is apparent from the results shown in the above table, Comparative Example 6-1 in which the photoacid generator is not a compound represented by the general formula (X) has a small pattern formation EL and an inferior pattern shape. I understand that. It can also be seen that the isolated space was not resolved.
On the other hand, Examples 6-1 to 6-5 using the compound represented by the general formula (X) all have large EL, the pattern shape is also known to be rectangular or rectangular, and the resolution in an isolated space is excellent. I understand that

Claims (20)

An actinic ray-sensitive or radiation-sensitive resin composition containing a compound represented by the following general formula (X).


In the above general formula,
Ar represents an (m + 1) -valent aromatic group, and Ar may further have a substituent other than the sulfonate anion and the m (PL) groups in the general formula (X). Good.
A ⁺ represents an organic cation.
m represents an integer of 1 or more.
L represents a single bond or a divalent linking group. When a plurality of L are present, the plurality of L may be the same or different.
P represents at least one group selected from the group consisting of groups represented by the following general formulas (I) to (IV). When a plurality of P are present, the plurality of P may be the same or different.
However, when P is a group represented by the following general formula (I), L is a single bond, an alkylene group, a cycloalkylene group, an arylene group, an ether bond, an ester bond, or a combination of two or more thereof. It is a divalent linking group.


In the general formula (I),
R ₁₁ represents a hydrogen atom or an alkyl group.
R ₁₂ represents a hydrogen atom, an ether bond or an alkyl group or cycloalkyl group which may contain a carbonyl group, an aryl group, or an aralkyl group.
R ₁₃ represents an alkyl group or a cycloalkyl group, an aryl group or an aralkyl group which may contain an ether bond.
R ₁₁ and R ₁₂ may be bonded to each other to form a ring.
R ₁₂ and R ₁₃ may be bonded to each other to form a ring.
* Represents a bond.
In the general formula (II),
R ₂₁ and R ₂₂ each independently represents an alkyl group or an aralkyl group.
R ₂₃ and R ₂₄ each independently represents an alkyl group or an aralkyl group.
R ₂₅ represents a hydrogen atom or an alkyl group.
At least two of R _{23 to} R ₂₅ may be bonded to each other to form a ring.
* Represents a bond.
In the general formula (III),
L ₂ represents a trivalent linking group.
R ₃₁ and R ₃₄ each independently represents a hydrogen atom or an alkyl group.
R ₃₂ and R ₃₅ each independently represents a hydrogen atom, an ether bond or an alkyl group, cycloalkyl group, aryl group or aralkyl group which may contain a carbonyl group.
R ₃₃ and R ₃₆ each independently represents an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group that may contain an ether bond.
R ₃₁ and R ₃₂ may be bonded to each other to form a ring.
R ₃₄ and R ₃₅ may be bonded to each other to form a ring.
R ₃₂ and R ₃₃ may be bonded to each other to form a ring.
R ₃₅ and R ₃₆ may be bonded to each other to form a ring.
* Represents a bond.
In the general formula (IV),
L ₃ represents a trivalent linking group.
R ₄₁ and R ₄₂ each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group. R ₄₁ and R ₄₂ may be bonded to each other to form a ring.
* Represents a bond. When P in the general formula (X) is a group represented by the general formula (I) and the alkylene group, cycloalkylene group or arylene group for L has a substituent, the substituent is a halogen atom. , Halogen atom, alkyl group, cycloalkyl group, aryl group, amino group, amide group, ureido group, urethane group, hydroxyl group, carboxyl group, alkoxy group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group Or the actinic-ray-sensitive or radiation-sensitive resin composition of Claim 1 which is a nitro group. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein L in the general formula (X) is a divalent linking group having a phenylene group. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein L in the general formula (X) is a single bond.   An actinic ray-sensitive or radiation-sensitive resin composition containing a compound represented by the following general formula (X).


  In the above general formula,
  Ar represents an (m + 1) -valent aromatic group, and Ar may further have a substituent other than the sulfonate anion and the m (PL) groups in the general formula (X). Good.
  A ⁺ Represents an organic cation.
  m represents an integer of 1 or more.
  L represents a single bond or a divalent linking group. When a plurality of L are present, the plurality of L may be the same or different.
  P represents at least one group selected from the group consisting of groups represented by the following general formulas (I) to (IV). When a plurality of P are present, the plurality of P may be the same or different.


  In the general formula (I),
  R ₁₁ Represents a hydrogen atom or an alkyl group.
  R ₁₂ Represents an alkyl group or a cycloalkyl group, an aryl group, or an aralkyl group which may contain an ether bond or a carbonyl group.
  R ₁₃ Represents an alkyl group or a cycloalkyl group, an aryl group or an aralkyl group which may contain an ether bond.
  R ₁₁ And R ₁₂ May be bonded to each other to form a ring.
  R ₁₂ And R ₁₃ May be bonded to each other to form a ring.
  * Represents a bond.
  In the general formula (II),
  R ₂₁ And R ₂₂ Each independently represents an alkyl group or an aralkyl group.
  R ₂₃ And R ₂₄ Each independently represents an alkyl group or an aralkyl group.
  R ₂₅ Represents a hydrogen atom or an alkyl group.
  R ₂₃ ~ R ₂₅ At least two of them may be bonded to each other to form a ring.
  * Represents a bond.
  In the general formula (III),
  L ₂ Represents a trivalent linking group.
  R ₃₁ And R ₃₄ Each independently represents a hydrogen atom or an alkyl group.
  R ₃₂ And R ₃₅ Each independently represents a hydrogen atom, an ether bond or an alkyl group, cycloalkyl group, aryl group or aralkyl group which may contain a carbonyl group.
  R ₃₃ And R ₃₆ Each independently represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group which may contain an ether bond.
  R ₃₁ And R ₃₂ May be bonded to each other to form a ring.
  R ₃₄ And R ₃₅ May be bonded to each other to form a ring.
  R ₃₂ And R ₃₃ May be bonded to each other to form a ring.
  R ₃₅ And R ₃₆ May be bonded to each other to form a ring.
  * Represents a bond.
  In the general formula (IV),
  L ₃ Represents a trivalent linking group.
  R ₄₁ And R ₄₂ Each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group. R ₄₁ And R ₄₂ May be bonded to each other to form a ring.
  * Represents a bond. R ₁₂ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 5, wherein is an alkyl group having 1 to 15 carbon atoms. R ₁₂ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 5 or 6, wherein is a branched alkyl group having a tertiary carbon atom. The actinic ray-sensitive property according to any one of claims 1 to 7, wherein P is at least one group selected from the group consisting of groups represented by the general formulas (II) to (IV). Radiation sensitive resin composition. When P in the general formula (X) is a group represented by the general formula (I), L is a single bond or —L ₄ —COO— (L ₄ represents a single bond or a divalent linking group). The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 5 ; P in the general formula (X) is a group represented by the general formula (I) or (II), and in the general formula (I), L is —L ₄ —COO— (L ₄ is Represents a single bond or a divalent linking group), and the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 5 ; P in the general formula (X) is a group represented by the general formula (I), and L is —L ₄ —COO— (L ₄ represents a single bond or a divalent linking group). The actinic ray-sensitive or radiation-sensitive resin composition according to claim 10 . The actinic ray-sensitive or radiation-sensitive resin according to claim 1 or 5 , wherein P in the general formula (X) is a group represented by the general formula (II), and L is a divalent linking group. Composition. The activity sensitivity according to claim 1 or 5 , further comprising a resin containing a repeating unit having at least one group selected from the group consisting of groups represented by the general formulas (I) to (IV). A light-sensitive or radiation-sensitive resin composition. A resin containing a repeating unit having a group represented by the general formula (I) or a repeating unit having a group represented by the general formula (II), which can be decomposed by the action of an acid to generate a carboxyl group The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 , which is contained. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 14 , which is exposed to extreme ultraviolet rays or an electron beam. The resist film formed using the actinic-ray-sensitive or radiation-sensitive resin composition of any one of Claims 1-15 . A pattern forming method comprising a step of exposing the resist film according to claim 16 and a step of developing the exposed film. The pattern forming method according to claim 17 , wherein the exposure is performed using extreme ultraviolet rays or an electron beam. The development, the pattern forming method according to claim 1 7 or 1 8 carried out using a developer containing an organic solvent. Including a pattern forming method according to any one of claims 1 7-1 9, a method of manufacturing a semiconductor device.