JP5264654B2 - Actinic ray-sensitive or radiation-sensitive resin composition and pattern forming method using the same - Google Patents

Abstract

PURPOSE: An active ray-sensitive or radiation-sensitive resin composition and a method for forming patterns using the same are provided to include a random type, a block type, a comb type, and a star type. CONSTITUTION: An active ray-sensitive or radiation-sensitive resin composition includes a resin which includes a repeating unit represented by general formula 1. In the formula 1, R1, R2, and R3 respectively represent a hydrogen atom or a monovalent substitution group, L1 represents an arylene group, and A1 represents a divalent connecting group. In the formula 1, X represents a structure unit including a plurality of aromatic rings, Y represents a hydrogen atom or a leaving group based on the action of acid.

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition and a pattern forming method using the same. In particular, the present invention is suitable for an ultra-microlithography process applicable to a manufacturing process of a VLSI and a high-capacity microchip, a mold making process for nanoimprinting, a manufacturing process of a high-density information recording medium, and other photofabrication processes. The present invention relates to a composition used, and a pattern forming method using the composition. More specifically, the present invention relates to a composition that can be suitably used for microfabrication of a semiconductor device using an electron beam or EUV light, and a pattern formation method using the composition.

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

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

  In microfabrication using a resist composition, it is required to form an ultrafine pattern as the integrated circuit is highly integrated. Therefore, there is a tendency for the exposure wavelength to be shortened, and for example, development of a lithography technique using an electron beam, X-rays or EUV light instead of excimer laser light is progressing. In recent years, fine processing using a resist composition has been used not only for the production of integrated circuits but also for the production of imprint mold structures.

  In order to form such an ultrafine pattern, it is necessary to reduce the thickness of the resist. However, when the resist is thinned, its dry etching resistance may decrease.

  In electron beam (EB) lithography, it is known that the influence of electron scattering in the resist film, that is, forward scattering is reduced by increasing the EB acceleration voltage. Therefore, in recent years, the acceleration voltage of EB has been increasing. However, when the acceleration voltage of EB is increased, the electron energy capture rate of the resist film is lowered, and the sensitivity may be lowered.

  As one method for solving these problems, use of a resin having a naphthalene skeleton has been studied (for example, see Patent Documents 1 to 3). By using a resin having a naphthalene skeleton, for example, dry etching resistance and sensitivity can be improved.

  However, when the acceleration voltage of EB is increased, the influence of forward scattering, that is, the influence of back scattering increases, instead of the influence of forward scattering being reduced. And when forming an isolated pattern with a large exposure area, the influence of this backscattering is especially large. Therefore, for example, when the acceleration voltage of EB is increased, the resolution of the isolated pattern may be reduced.

JP 2008-169346 A International Publication No. 2007-064553 JP 2008-50568 A

  An object of this invention is to provide the actinic-ray-sensitive or radiation-sensitive resin composition excellent in the resolution of an isolated pattern, and the pattern formation method using the same.

  For example, the present invention is as follows.

[1] An actinic ray-sensitive or radiation-sensitive resin composition provided with a resin containing a repeating unit represented by the following general formula (1).

In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent substituent. L ¹ represents an arylene group. A ¹ represents a divalent linking group. X represents a structural unit containing a plurality of aromatic rings, and the plurality of aromatic rings are condensed to form a polycyclic structure or are connected to each other through a single bond. Y represents a hydrogen atom or a group capable of leaving by the action of an acid. When n ₁ is 2 or more, the plurality of Y may be the same or different from each other. n ₁ represents an integer of 1 to 5.

[2] The composition according to [1], wherein X is a structural unit represented by any one of the following general formulas (X1) to (X6).

In the formula, when a plurality of R ⁴ are present, each independently represents a monovalent substituent. R ⁵ represents a hydrogen atom, an alkyl group, a cycloalkyl group, or A ¹ described above. n ₂ is an integer of 0 to 14. X ¹ represents CH or N, and two X ^{1 s} may be the same as or different from each other. The A ¹ , OY and R ⁴ may be bonded to any of the atoms constituting the plurality of aromatic rings.

[3] The composition according to [1] or [2], wherein Y is a hydrogen atom or a group represented by the following general formula (2).

In the formula, R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. M represents a single bond or a divalent linking group. Q represents an alkyl group, a cycloalkyl group, an alicyclic group which may contain a hetero atom, an aromatic ring group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group. . At least two of R ⁶ , R ⁷ , M and Q may be bonded to each other to form a ring.

[4] The composition according to any one of [1] to [3], wherein the resin further includes at least one of repeating units represented by the following general formulas (3) and (4).

In formula, R < ⁹ > -R < ¹⁴ > represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group each independently. R ^{15 to} R ¹⁷ each independently represents an alkyl group or a cycloalkyl group. At least two of R ^{15 to} R ¹⁷ may be bonded to each other to form a cycloalkyl group. L ² represents an arylene group. Z represents a hydrogen atom or a group capable of leaving by the action of an acid. L ³ represents a single bond or a divalent linking group.

  [5] The composition according to any one of [1] to [4], which is exposed to an electron beam, an X-ray or EUV light.

  [6] A pattern comprising forming a film using the composition according to any one of [1] to [5], exposing the film, and developing the exposed film Forming method.

  [7] The method according to [6], wherein the exposure is performed using an electron beam, an X-ray, or EUV light.

  According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition excellent in resolution of an isolated pattern and a pattern forming method using the same.

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

  The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is, for example, a positive composition, typically a positive resist composition. Hereinafter, the structure of this composition is demonstrated.

[1] Resin (P)
The composition according to the present invention contains a resin (P). This resin (P) contains a repeating unit represented by the following general formula (1).

In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a monovalent substituent. L ¹ represents an arylene group. A ¹ represents a divalent linking group. X represents a structural unit containing a plurality of aromatic rings, and the plurality of aromatic rings are condensed to form a polycyclic structure or are connected to each other through a single bond. Y represents a hydrogen atom or a group capable of leaving by the action of an acid. When n ₁ is 2 or more, the plurality of Y may be the same or different from each other. n ₁ represents an integer of 1 to 5.

Each of R ¹ , R ² and R ³ is a hydrogen atom or a monovalent substituent as described above. Examples of the monovalent substituent include an alkyl group; a cycloalkyl group; a halogen atom; a substituent containing a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom; and combinations thereof.

  The carbon number of the alkyl group is preferably 20 or less, more preferably 8 or less. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group. Among these, a methyl group, an ethyl group, a propyl group, an isopropyl group, and a t-butyl group are particularly preferable.

  The cycloalkyl group may be monocyclic or polycyclic. The cycloalkyl group preferably has 3 to 8 carbon atoms.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a chlorine atom, a bromine atom, and an iodine atom are more preferable, and a bromine atom is particularly preferable.

  Examples of the substituent containing a hetero atom include a hydroxyl group, an alkoxy group, a thiol group, a thioether group, and an amino group.

  The number of carbon atoms of the alkoxy group is preferably 20 or less, more preferably 8 or less. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, and an octyloxy group. Of these, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a t-butoxy group are particularly preferable. The thioether group is the same as the alkoxy group except that a sulfur atom is used instead of an oxygen atom.

  These groups may further have a substituent. Examples of the substituent that these groups may further have include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxy groups, carboxy groups, halogen atoms, alkoxy groups, and thioethers. Group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group and nitro group. The carbon number of this substituent is preferably 8 or less.

L ¹ represents an arylene group as described above. This arylene group may have a heterocycle. Further, this arylene group may further have a substituent.

  The number of carbon atoms of the arylene group is preferably 4-20, and more preferably 6-14. Examples of the arylene group include a phenylene group and a naphthylene group.

Examples of the substituent that the arylene group may further include, for example, a nitro group, a halogen atom such as a fluorine atom, a carboxy group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having a carbon number of 1 to 15), a cycloalkyl group (Preferably 3 to 15 carbon atoms), aryl group (preferably 6 to 14 carbon atoms), alkoxycarbonyl group (preferably 2 to 7 carbon atoms), acyl group (preferably 2 to 12 carbon atoms), and alkoxycarbonyl An oxy group (preferably having 2 to 7 carbon atoms) may be mentioned. A ¹ represents a divalent linking group as described above. Examples of the linking group include an alkylene group, a cycloalkylene group, —O—, —SO ₂ —, —CO—, —N (R) —, and combinations thereof. Here, R represents an aryl group, an alkyl group, or cycloalkyl. By interposing the A ¹ between L ¹ and X, it is possible to suppress a decrease in alkaline solubility of the resin.

  As an alkylene group, Preferably, C1-C12 things, such as a methylene group, ethylene group, a propylene group, a butylene group, a hexylene group, an octylene group, and a dodecanylene group, are mentioned.

  Preferred examples of the cycloalkylene group include those having 5 to 8 carbon atoms such as a cyclopentylene group and a cyclohexylene group.

  These alkylene groups and cycloalkylene groups may further have a substituent. Examples of the substituent include alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxy groups, carboxy groups, halogen atoms, alkoxy groups, thioether groups, acyl groups, and acyloxy groups. , Alkoxycarbonyl group, cyano group and nitro group.

The “minimum linking atom number” of A ¹ is preferably 1 to 50, more preferably 2 to 25, and particularly preferably 3 to 15. If this “minimum number of linked atoms” is excessively small, the structure of the side chain becomes rigid, and the solubility of the resin (P) in an alkaline developer may be significantly reduced. If this “minimum number of linking atoms” is excessively large, the glass transition temperature of the resin (P) is lowered, and the acid generated by exposure in the film is likely to diffuse, so that roughness characteristics, resolution, etc. are lowered. there is a possibility.

The “minimum number of connected atoms” of A ¹ is a number determined as follows. That is, first of all, let us consider a sequence of atoms connecting the atoms bonded to L ¹ and the atoms bonded to X among the atoms constituting A ¹ . Next, the number of atoms contained in each of these columns is obtained. Then, the smallest of these atoms, and "Minimum linking atoms" of A ^1.

For example, when A ¹ is a propylene group, the minimum number of linking atoms is 3. When A ¹ is —CH ₂ —O—CO—, the minimum number of linking atoms is 3. When A ¹ is a 2-methyl-butylene group, the minimum number of linking atoms is 4. When A ¹ is a cyclohexylene group, the minimum number of linking atoms is 4. When A ¹ is —O—CH ₂ CH ₂ CH ₂ —O—CO—, the minimum number of linked atoms is 6. When A ¹ is a linear alkylene group, the minimum number of connected atoms of A ¹ is equal to the number of carbon atoms.

  X represents a structural unit containing a plurality of aromatic rings, as described above. The plurality of aromatic rings may be condensed to form a polycyclic structure, or may be connected to each other through a single bond. Each of these aromatic rings may contain a hetero atom. By using a structural unit containing a plurality of aromatic rings as X, it is possible to achieve an improvement in dry etching resistance and an improvement in sensitivity due to an increase in the amount of secondary electrons generated.

  Examples of the aromatic ring that X may include include a benzene ring, a thiophene ring, a pyrrole ring, a furan ring, an imidazole ring, a pyridine ring, and a pyrazole ring.

  Examples of the polycyclic structure that can be formed by condensing a plurality of aromatic rings include naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, triphenylene ring, indole ring, benzimidazole ring, carbazole ring, and phenothiazine ring. It is done. Among these, an indole ring, a pyrene ring, a phenanthrene ring, an anthracene ring and a naphthalene ring are more preferable, and an indole ring, an anthracene ring and a naphthalene ring are particularly preferable.

  Examples of the structure in which a plurality of aromatic rings are connected to each other through a single bond include a biphenyl structure, a terphenyl structure, and a viologen structure. Among these, a biphenyl structure and a terphenyl structure are particularly preferable.

  The number of aromatic rings contained in X is preferably 2-6, more preferably 2-4, and even more preferably 2 or 3. Here, the “number of aromatic rings” is the number of benzene rings or the corresponding monocyclic heteroaryl rings. For example, it is 2 for naphthalene, biphenyl and bipyridine residues and 3 for anthracene, carbazole and phenothiazine residues.

X is preferably a structural unit represented by any one of the following general formulas (X1) to (X6).

In the formula, when a plurality of R ⁴ are present, each independently represents a monovalent substituent. R ⁵ represents a hydrogen atom, an alkyl group, a cycloalkyl group, or A ¹ in the general formula (1). n ₂ is an integer of 0 to 14. X ¹ represents CH or N, and two X ^{1 s} may be the same as or different from each other. In X, A ¹ , OY and R ⁴ may be bonded to any of atoms constituting a plurality of aromatic rings.

R ⁴ is a monovalent substituent as described above. Examples of the monovalent substituent include the same ones as listed above for R ^{1 to} R ³ . Of these, halogen atoms such as fluorine atom and bromine atom, and alkyl groups are particularly preferred.

As described above, R ⁵ is a hydrogen atom, an alkyl group, a cycloalkyl group, or A ¹ in the general formula (1). Examples of the alkyl group and cycloalkyl group include the same groups as those enumerated above for R ^{1 to} R ³ .

n ₂ is an integer of 0 to ¹⁴ as described above. n ₂ is preferably 0-10, more preferably 0-8.

Specific examples of the structural unit represented by any one of the general formulas (X1) to (X6) are shown below, but the present invention is not limited to these.

Y is a hydrogen atom or a group capable of leaving by the action of an acid as described above. When n ₁ is 2 or more, the plurality of Y may be the same or different from each other.

Examples of the group capable of leaving by the action of an acid include groups represented by the following general formulas (5) to (7).

^Wherein, R 18 ^{to R 26} each independently represents an alkyl group, a cycloalkyl group or an aryl group. R ¹⁸ and R ¹⁹ may be bonded to each other to form a ring.
Examples of the alkyl group and cycloalkyl group include the same groups as those enumerated above for R ^{1 to} R ³ .

  The aryl group may contain a hetero atom. The aryl group preferably has 4 to 20 carbon atoms, more preferably 6 to 14 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group.

  The aryl group may further have a substituent. Examples of the substituent include a nitro group, a halogen atom such as a fluorine atom, a carboxy group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), a cycloalkyl group (preferably having 3 carbon atoms). To 15), 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), and an alkoxycarbonyloxy group (preferably carbon). Formula 2-7) is mentioned.

Specific examples of the group represented by any one of the general formulas (5) to (7) are shown below, but the present invention is not limited thereto. In the formula, “-” represents a linking group with an O atom, and a methyl group is distinguished as “Me-”.

When Y is a group capable of leaving by the action of an acid, this Y is preferably a group represented by the following general formula (2).

R ⁶ and R ⁷ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a combination thereof. M represents a single bond or a divalent linking group. Q represents an alkyl group, a cycloalkyl group, an alicyclic group which may contain a hetero atom, an aromatic ring group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group. .

In addition, at least two of R ⁶ , R ⁷ , M and Q may be bonded to each other to form a ring. This ring is preferably a 5-membered ring or a 6-membered ring.

The alkyl group as R ⁶ or R ⁷ is, for example, an alkyl group having 1 to 8 carbon atoms. Preferably, a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, hexyl group and octyl group are mentioned.

The cycloalkyl group as R ⁶ or R ⁷ is, for example, a cycloalkyl group having 3 to 15 carbon atoms. Preferably, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group are mentioned.

The aryl group as R ⁶ or R ⁷ is, for example, an aryl group having 6 to 15 carbon atoms. Preferably, a phenyl group, a tolyl group, a naphthyl group, and an anthryl group are mentioned.

The aralkyl group as R ⁶ and R ⁷ is, for example, an aralkyl group having 6 to 20 carbon atoms. Preferably, a benzyl group and a phenethyl group are mentioned.

The divalent linking group as M is, for example, an alkylene group (for example, methylene group, ethylene group, propylene group, butylene group, hexylene group or octylene group), cycloalkylene group (for example, cyclopentylene group or cyclohexylene group). ), an alkenylene group (e.g., an ethylene group, a propenylene group or a butenylene group), an arylene group (e.g., phenylene, tolylene or naphthylene group), - S -, - O -, - CO -, - SO 2 -, - N (R ₀ ) — or a combination thereof. Here, R ₀ is a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, Hexyl group and octyl group).

The alkyl group and cycloalkyl group as Q are the same as, for example, each group as R ⁶ and R ⁷ described above.

Examples of the alicyclic group and aromatic ring group as Q include the cycloalkyl group and aryl group as R ⁶ and R ⁷ described above. The carbon number is preferably 3-15.
Examples of the alicyclic group containing a hetero atom and the aromatic ring group containing a hetero atom include, for example, thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole. And pyrrolidone.

In the case where at least two of R ⁶ , R ⁷ , M and Q are bonded to each other to form a ring, for example, R ⁶ and R ⁷ are bonded to form a butylene group or a pentylene group to form a 5-membered ring or When a 6-membered ring is formed, and either M and Q and R ⁶ and R ⁷ are bonded to form a propylene group or butylene group, and a 5-membered or 6-membered ring containing an oxygen atom Is formed.

Each group represented by R ⁶ , R ⁷ , M and Q may further have a substituent. As the substituent, for example, the same ones as listed as the substituent which the above R ¹ to R ³ may have can be mentioned. The carbon number of this substituent is preferably 8 or less.

  The number of carbon atoms of the group represented by-(MQ) is preferably 1-30, and more preferably 5-20.

Although the specific example of group represented by General formula (2) below is shown, this invention is not limited to this. In the formula, “-” represents a linking group with an O atom, and a methyl group is distinguished as “Me-”.

When n ₁ is 2 or more, Y may be linked to two different oxygen atoms to form a ring. That is, Y may constitute a partial structure represented by “—O—Y—O—”. In this case, Y is preferably a group represented by the following general formula (2 ′).

In the formula, R ^{6 ′} and R ^{7 ′} each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. Preferred examples of these R ^{6 ′} and R ^{7 ′} are the same as the preferred examples of R ⁶ and R ⁷ .
As a ring that can be formed by linking two oxygen atoms different from Y, a 5-membered, 6-membered or 7-membered ring is preferable, and a 6-membered ring is particularly preferable.

Although the specific example of resin (P) is shown below, this invention is not limited to this.

  The resin (P) may contain only one type of repeating unit represented by the general formula (1), but more preferably contains a plurality of types of repeating units represented by the general formula (1).

The resin (P) may further contain a repeating unit represented by the following general formulas (3) and (4).

In formula, R < ⁹ > -R < ¹⁴ > represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group each independently. R ^{15 to} R ¹⁷ each independently represents an alkyl group or a cycloalkyl group. In addition, at least two of R ^{15 to} R ¹⁷ may be bonded to each other to form a cycloalkyl group.
L ² represents an arylene group. Z represents a hydrogen atom or a group capable of leaving by the action of an acid. L ³ represents a single bond or a divalent linking group.

The alkyl group and cycloalkyl group as R ^{9 to} R ¹⁴ are, for example, the same as those listed above for R ^{1 to} R ³ .
As the alkyl group for R ^{15 to} R ¹⁷ , a linear or branched group having 1 to 4 carbon atoms is preferable.
As the cycloalkyl group of R ^{15 to} R ¹⁷ , a monocyclic cycloalkyl group having 3 to 8 carbon atoms or a polycyclic cycloalkyl group having 7 to 20 carbon atoms is preferable.

The cycloalkyl group that can be formed by combining at least two of R ^{15 to} R ¹⁷ with each other is preferably a monocyclic cycloalkyl group having 3 to 8 carbon atoms or a polycyclic cycloalkyl group having 7 to 20 carbon atoms. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferable. An embodiment in which R ¹⁷ is a methyl group or an ethyl group, and R ¹⁵ and R ¹⁶ are bonded to form the above-described cycloalkyl group is more preferable.

Examples of L ² include the same groups as those listed above for L ¹ .
Examples of Z include the same groups as listed above for Y.

Examples of L ³ include an alkylene group, a cycloalkylene group, —O—, —SO ₂ —, —CO—, —N ( _RN ) —, and a plurality of combinations thereof. Here, _RN represents an aryl group, an alkyl group, or a cycloalkyl group.

The carbon number of the aryl group as R _N is preferably 4 to 20, more preferably from 6 to 14. Examples of the aryl group include a phenyl group and a naphthyl group.
The carbon number of the alkyl group as R _N is preferably 1-8. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an octyl group.
The carbon number of the cycloalkyl group as R _N is preferably 5-8. Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group.

Specific examples of the repeating unit represented by the general formula (3) are shown below, but are not limited thereto.

Specific examples of the repeating unit represented by the general formula (4) are shown below, but are not limited thereto.

  The content of the repeating unit represented by the general formula (1) in the resin (P) is preferably 3 to 100 mol%, more preferably 5 to 90 mol%, based on all repeating units. Preferably, it is more preferable to set it as 10-80 mol%.

The form of the resin (P) may be any of random type, block type, comb type, star type and the like.
The resin (P) described above can be synthesized, for example, by subjecting an unsaturated monomer corresponding to each repeating unit to radical, cation or anion polymerization. It is also possible to synthesize by polymerizing after using an unsaturated monomer corresponding to the precursor of each repeating unit.

  The molecular weight of the resin (P) 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 70000, and in the range of 2000 to 50000. Particularly preferred. Here, the weight average molecular weight of the resin indicates a molecular weight in terms of polystyrene measured by GPC (solvent: THF).

  Moreover, dispersity (Mw / Mn) becomes like this. Preferably it is 1.00-3.50, More preferably, it is 1.03-2.50, More preferably, it is 1.05-2.00.

  In order to further improve the performance of the resin (P), a repeating unit derived from another polymerizable monomer may be further contained within a range that does not significantly impair the dry etching resistance.

  The content of the repeating units derived from other polymerizable monomers in the resin (P) is generally 50 mol% or less, preferably 30 mol% or less, based on all repeating units. Other polymerizable monomers that can be used include, for example, additions selected from (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes and crotonic acid esters Compounds having at least one polymerizable unsaturated bond are included. Other examples include maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, and maleilonitrile.

  The content of the resin (P) is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, and 70 to 100% by mass based on the total solid content of the composition. Particularly preferred.

  Examples of the resin (P) include a resin containing one or more repeating units selected from the specific examples of the repeating unit represented by the general formula (1). Moreover, as another example of resin (P), 1 or more types of repeating units selected from the specific example of the repeating unit represented by General formula (1), and the repeating unit represented by General formula (3) And a resin containing one or more types of repeating units selected from the specific examples of the repeating unit represented by the general formula (4).

Although the specific example of resin (P) is given below, it is not limited to these.

<Other ingredients>
The composition according to the present invention comprises a basic compound, an acid-decomposable resin, a photoacid generator, an organic solvent, a surfactant, an acid-decomposable dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, and a developer. And a compound having a proton acceptor functional group may be further included.

[2] Basic compound The composition according to the present invention may further contain a basic compound. When a basic compound is further contained, it is possible to further reduce the change in performance over time from exposure to heating. This also makes it possible to control the diffusibility of the acid generated by exposure in the film.

  This basic compound is preferably a nitrogen-containing organic compound. Although the compound which can be used is not specifically limited, For example, the compound classified into the following (1)-(4) can be used.

(1) Compound represented by the following 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 carboxyl 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.

(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 carboxyl group, a carboxylate group, a sulfonate 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. ] (C1-1) to (C3-3) exemplified in the above.

(4) Ammonium salt Ammonium salts can also be used as appropriate. This ammonium salt is preferably a hydroxide or a carboxylate. More specifically, tetraalkylammonium hydroxide such as tetrabutylammonium hydroxide is preferable.

  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.

  Moreover, you may use a photosensitive basic compound as a basic compound. As the photosensitive basic compound, for example, JP 2003-524799 A 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 preferably 250 to 2000, and more preferably 400 to 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 further contains a basic compound, its content is usually 0.001 to 10% by mass, preferably 0.01 to 5%, based on the total solid content of the composition. Mass%.

  The molar ratio of the resin (P) to the basic compound is preferably 1.5 to 300. That is, 2.5 or more is preferable from the viewpoint of improving sensitivity and resolution, and 300 or less is preferable from the viewpoint of suppressing a reduction in resolution due to pattern thickening before post-exposure heat treatment. This molar ratio is more preferably 2.0 to 200, still more preferably 2.5 to 150.

[3] Acid-decomposable resin In addition to the resin (P), the composition according to the present invention further contains a resin that decomposes by the action of an acid to increase the dissolution rate with respect to alkaline water solubility, that is, an acid-decomposable resin. Also good.

  The acid-decomposable resin typically includes a group that decomposes by the action of an acid to generate an alkali-soluble group (hereinafter also referred to as an acid-decomposable group). This resin may have an acid-decomposable group in one of the main chain and the side chain, or in both of them. This resin preferably has an acid-decomposable group in the side chain.

  The acid-decomposable resin is, for example, disclosed in European Patent No. 254853, JP-A-2-25850, JP-A-3-223860 and JP-A-4-251259. It can be obtained by reacting a precursor of a group capable of leaving by reaction or copolymerizing an alkali-soluble resin monomer to which a group capable of leaving by the action of an acid is bonded with various monomers.

As the acid-decomposable group, a group in which a hydrogen atom of an alkali-soluble group such as a —COOH group and a —OH group is substituted with a group capable of leaving by the action of an acid is preferable.
Specific examples and preferred examples of the acid-decomposable group include those similar to “OY” in the resin (P).

The resin having an alkali-soluble group described above is not particularly limited, and examples thereof include resins containing a phenolic hydroxyl group and resins containing a repeating unit having a carboxyl group such as (meth) acrylic acid and norbornenecarboxylic acid. Can be mentioned.
The resin containing a phenolic hydroxyl group is preferably poly (o-hydroxystyrene), poly (m-hydroxystyrene), poly (p-hydroxystyrene), a copolymer thereof, or hydrogenated poly (hydroxystyrene). And having a hydroxystyrene structural unit such as a poly (hydroxystyrene) having a substituent represented by the following structure, a styrene-hydroxystyrene copolymer, an α-methylstyrene-hydroxystyrene copolymer, and a hydrogenated novolak resin. Resin.

  The alkali dissolution rate of these resins is preferably 170 kg / sec or more, more preferably 330 kg / sec or more as measured at 23 ° C. using 2.38 mass% tetramethylammonium hydroxide (TMAH). preferable.

  Examples of monomers that can be used as raw materials for these resins include alkylcarbonyloxystyrene (for example, t-butoxycarbonyloxystyrene), alkoxystyrene (for example, 1-alkoxyethoxystyrene or t-butoxystyrene), and (meta ) Acrylic acid tertiary alkyl ester (for example, t-butyl (meth) acrylate or 2-alkyl-2-adamantyl (meth) acrylate or dialkyl (1-adamantyl) methyl (meth) acrylate).

  When the composition according to the present invention is irradiated with KrF excimer laser light, electron beam, X-ray, or high energy light (for example, EUV) having a wavelength of 50 nm or less, the acid-decomposable resin is repeatedly provided with an aromatic group. Preferably it contains units. In particular, it is preferable that hydroxystyrene is contained as a repeating unit. Examples of such a resin include a copolymer of hydroxystyrene and a hydroxystyrene protected with a group capable of leaving by the action of an acid, or a copolymer of hydroxystyrene and a tertiary alkyl ester of (meth) acrylic acid. Coalescence is mentioned.

  As the acid-decomposable resin, a resin having a repeating unit represented by the general formula (3) or (4) is particularly preferable.

  The acid-decomposable resin may have a repeating unit derived from another polymerizable monomer. Examples of these other polymerizable monomers include those described above as other polymerizable monomers that can be contained in the resin (P). The content of repeating units derived from these other polymerizable monomers is generally 50 mol% or less, preferably 30 mol% or less, based on all repeating units.

  The content of the repeating unit having an alkali-soluble group such as a hydroxyl group, a carboxy group, and a sulfonic acid group is preferably 1 to 99 mol%, more preferably 3 to 95 mol% in all repeating units constituting the acid-decomposable resin. Particularly preferred is 5 to 90 mol%.

  The content of the repeating unit having an acid-decomposable group is preferably from 3 to 95 mol%, more preferably from 5 to 90 mol%, particularly preferably from 10 to 85 mol% in all repeating units constituting the acid-decomposable resin. It is.

The weight average molecular weight of the acid-decomposable resin is preferably 50,000 or less, more preferably 1,000 to 20,000, and particularly preferably 1, as a polystyrene converted value by GPC method (solvent: THF). 000 to 10,000.
The dispersity (Mw / Mn) of the acid-decomposable resin is preferably 1.0 to 3.0, more preferably 1.05 to 2.0, and still more preferably 1.1 to 1.7. is there.

  Two or more acid-decomposable resins may be used in combination.

Although the preferable specific example of an acid-decomposable resin is shown below, it is not limited to these.

  In addition, when the composition according to the present invention further contains a resin other than the resin (P), the content thereof is preferably 0.5 to 80% by mass based on the total solid content of the composition, More preferably, it is 5-50 mass%, More preferably, it is 10-30 mass%.

[4] Photoacid generator The photoacid generator is a compound that generates an acid upon irradiation with actinic rays or radiation. Examples of the photoacid generator include a photoinitiator for photocationic polymerization, a photoinitiator for radical photopolymerization, a photodecolorant for dyes, a photochromic agent, an actinic ray or radiation used for a microresist, etc. Known compounds that generate an acid upon irradiation and mixtures thereof can be appropriately selected and used. Examples of these include sulfonium salts, iodonium salts and bis (alkylsulfonyldiazomethanes).

Preferable examples of the photoacid generator include compounds represented by the following general formulas (ZI), (ZII) and (ZIII).

In the general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group. The carbon number of the organic group as R _201, R ₂₀₂ and R ₂₀₃ is, for example, 1 to 30, preferably 1 to 20.

Two of R _{201 to} R ₂₀₃ may be bonded to each other via a single bond or a linking group to form a ring. Examples of the linking group in this case include an ether bond, a thioether bond, an ester bond, an amide bond, a carbonyl group, a methylene group, and an ethylene group. Examples of the group formed by combining two of R _{201 to} R ₂₀₃ include alkylene groups such as a butylene group and a pentylene group.

Specific examples of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include corresponding groups in the compound (ZI-1), (ZI-2) or (ZI-3) described later.

X ⁻ represents a non-nucleophilic anion. Examples of X ⁻ include a sulfonate anion, a bis (alkylsulfonyl) amide anion, a tris (alkylsulfonyl) methide anion, BF ₄ ⁻ , PF ₆ ^—, and SbF ₆ ^— . X ⁻ is preferably an organic anion containing a carbon atom. As a preferable organic anion, the organic anion shown to following AN1-AN3 is mentioned, for example.

In the formula _AN1~AN3, Rc 1 ~Rc ₃ independently represents an organic group. Examples of the organic group include those having 1 to 30 carbon atoms, preferably an alkyl group, an aryl group, or a group in which a plurality of these groups are linked through a linking group. Examples of this linking group include a single bond, —O—, —CO ₂ —, —S—, —SO ₃ —, and —SO ₂ N (Rd ₁ ) —. Here, Rd ₁ represents a hydrogen atom or an alkyl group, and may form a ring with the bonded alkyl group or aryl group.

The organic group of Rc _{1 to} Rc ₃ may be an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, or a phenyl group substituted with a fluorine atom or a fluoroalkyl group. By containing a fluorine atom or a fluoroalkyl group, it becomes possible to increase the acidity of the acid generated by light irradiation. Thereby, the sensitivity of the actinic ray-sensitive or radiation-sensitive resin composition can be improved. Rc _{1 to} Rc ₃ may be bonded to other alkyl groups and aryl groups to form a ring.

Further, as preferred X ⁻ , a sulfonate anion represented by the following general formula (SA1) or (SA2) can be mentioned.

In formula (SA1),
Ar represents an aryl group and may further have a substituent other than a-(D-B) group.
n represents an integer of 1 or more. n is preferably 1 to 4, more preferably 2 to 3, and most preferably 3.
D represents a single bond or a divalent linking group. The divalent linking group is an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonic acid ester group, or an ester group.
B represents a hydrocarbon group.

In formula (SA2),
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.

R ₁ and R ₂ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or a group selected from an alkyl group substituted with at least one fluorine atom, and R ₁ and R ₂ when there are a plurality of R ₁ and R ₂ Each may be the same as or different from each other.
L represents a single bond or a divalent linking group, and when there are a plurality of L, they may be the same as or different from each other.
E represents a group having a cyclic structure.
x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

First, the sulfonate anion represented by the formula (SA1) will be described in detail.
In formula (SA1), Ar is preferably an aromatic ring having 6 to 30 carbon atoms. Specifically, Ar represents, for example, a benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acetaphthalene ring, phenanthrene ring, anthracene ring, naphthacene ring, chrysene Ring, triphenylene ring, fluorene 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, acridine ring, phenanthroline ring, Antoren ring, a chromene ring, a xanthene ring, a phenoxathiin ring, a phenothiazine ring or a phenazine ring. Of these, a benzene ring, a naphthalene ring or an anthracene ring is preferable, and a benzene ring is more preferable, from the viewpoint of achieving both roughness improvement and high sensitivity.

  When Ar further has a substituent other than a-(D-B) group, examples of this substituent include the following. That is, as this substituent, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group Alkylthioxy groups such as methylthioxy, ethylthioxy and tert-butylthioxy groups; arylthioxy groups such as phenylthioxy and p-tolylthioxy groups; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl and phenoxycarbonyl Acetoxy group; straight chain alkyl group such as methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, dodecyl group and 2-ethylhexyl group; branched alkyl group; vinyl group, propenyl group and hexenyl group, etc. Alkenyl group; ace Hydroxy group; a carboxy group; an aryl group such as a phenyl group and tolyl group; an alkynyl group such as propynyl group and hexynyl group; alkylene group and sulfonic acid group. Of these, straight chain alkyl groups and branched alkyl groups are preferred from the viewpoint of improving roughness.

  In formula (SA1), D is preferably a single bond, or an ether group or an ester group. More preferably, D is a single bond.

  In formula (SA1), B is, for example, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a cycloalkyl group. B is preferably an alkyl group or a cycloalkyl group. The alkyl group, alkenyl group, alkynyl group, aryl group or cycloalkyl group as B may have a substituent.

  The alkyl group as B is preferably a branched alkyl group. Examples of this branched alkyl group include isopropyl group, tert-butyl group, tert-pentyl group, neopentyl group, sec-butyl group, isobutyl group, isohexyl group, 3,3-dimethylpentyl group and 2-ethylhexyl group. It is done.

  The cycloalkyl group as B may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. Examples of the monocyclic cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic cycloalkyl group include adamantyl group, norbornyl group, bornyl group, camphenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camphoroyl group, dicyclohexyl group and pinenyl group. Can be mentioned.

  When the alkyl group, alkenyl group, alkynyl group, aryl group or cycloalkyl group as B has a substituent, examples of the substituent include the following. That is, as this substituent, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group Alkylthioxy groups such as methylthioxy, ethylthioxy and tert-butylthioxy groups; arylthioxy groups such as phenylthioxy and p-tolylthioxy groups; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl and phenoxycarbonyl Acetoxy group; straight chain alkyl group such as methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, dodecyl group and 2-ethylhexyl group; branched alkyl group; cycloalkyl group such as cyclohexyl group; vinyl group , Propenyl group Alkenyl groups such as fine hexenyl group; acetylene group; hydroxy group; a carboxy group; a sulfonic group; an aryl group such as a phenyl group and tolyl group; an alkynyl group such as propynyl group and hexynyl group and a carbonyl group, and the like. Among these, a straight chain alkyl group and a branched alkyl group are preferable from the viewpoint of achieving both improvement in roughness and high sensitivity.

Next, the sulfonate anion represented by the formula (SA2) will be described in detail.
In formula (SA2), Xf is a fluorine atom or an alkyl group substituted with at least one fluorine atom. As this alkyl group, a C1-C10 thing is preferable and a C1-C4 thing is more preferable. The alkyl group substituted with a fluorine atom is preferably a perfluoroalkyl group.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specifically, Xf is preferably a fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F _{17, CH 2 CF 3, CH} 2 CH 2 CF 3, CH 2 C 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH 2 C 4 F ₉ or CH ₂ CH ₂ C ₄ F ₉ . Among these, a fluorine atom or CF ₃ is preferable, and a fluorine atom is most preferable.

In formula (SA2), each of R ₁ and R ₂ is a group selected from a hydrogen atom, a fluorine atom, an alkyl group, and an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. The alkyl group which may be substituted with a fluorine atom is preferably an alkyl group having 1 to 4 carbon atoms. Moreover, as an alkyl group substituted by the fluorine atom, a C1-C4 perfluoroalkyl group is especially preferable. Specifically, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , CH _{2 CH 2 CF 3, CH 2 C} 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH 2 C 4 F 9 and _CH 2 _CH 2 _{C 4} F ₉ is mentioned, and among them, CF ₃ is preferable.

In the formula (SA2), x is preferably 1 to 8, and more preferably 1 to 4. y is preferably 0 to 4, and more preferably 0. z is preferably from 0 to 8, and more preferably from 0 to 4.
In formula (SA2), L represents a single bond or a divalent linking group. Examples of the divalent linking group include —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group, a cycloalkylene group, and an alkenylene group. It is done. Among these, —COO—, —OCO—, —CO—, —O—, —S—, —SO— or —SO ₂ — is preferable, and —COO—, —OCO— or —SO ₂ — is more preferable.

  In formula (SA2), E represents a group having a ring structure. Examples of E include a cyclic aliphatic group, an aryl group, and a group having a heterocyclic structure.

  The cycloaliphatic group as E may have a monocyclic structure or a polycyclic structure. As the cyclic aliphatic group having a monocyclic structure, monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group are preferable. The cycloaliphatic group having a polycyclic structure is preferably a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group. In particular, when a cycloaliphatic group having a bulky structure of 6-membered ring or more is adopted as E, diffusibility in the film in the PEB (post-exposure heating) step is suppressed, and the resolution and EL (exposure latitude) are further improved. It becomes possible to improve.

The aryl group as E is, for example, a benzene ring, naphthalene ring, phenanthrene ring or anthracene ring.
The group having a heterocyclic structure as E may have aromaticity or may not have aromaticity. The heteroatom contained in this group is preferably a nitrogen atom or an oxygen atom. Specific examples of the heterocyclic structure include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, a pyridine ring, a piperidine ring, and a morpholine ring. Among these, a furan ring, a thiophene ring, a pyridine ring, a piperidine ring, and a morpholine ring are preferable.

  E may have a substituent. Examples of the substituent include an alkyl group (which may be linear, branched or cyclic, preferably 1 to 12 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), a hydroxy group, an alkoxy group. Groups, ester groups, amide groups, urethane groups, ureido groups, thioether groups, sulfonamide groups and sulfonic acid ester groups. Among these substituents, a branched alkyl group, a cyclic alkyl group, and an aryl group are particularly preferable. By having these substituents, diffusion of the generated acid can be suppressed, and improvement in resolution and exposure latitude can be expected.

As the photoacid generator, a compound having a plurality of structures represented by the general formula (ZI) may be used. For example, the general formula at least one of R ₂₀₁ to R ₂₀₃ of a compound represented by (ZI), at least one coupling structure of R ₂₀₁ to R ₂₀₃ of another compound represented by formula (ZI) It may be a compound.

  More preferred (ZI) components include compounds (ZI-1) to (ZI-4) described below.

In the compound (ZI-1), at least one of R _{201 to} R _{203 in} the general formula (ZI) is an aryl group. That is, the compound (ZI-1) is an arylsulfonium compound, that is, a compound having arylsulfonium as a cation.

The compound (ZI-1), all of R ₂₀₁ to R ₂₀₃ is may be an aryl group or a part of R ₂₀₁ to R ₂₀₃ is an aryl group, except they may be an alkyl group. In addition, when compound (ZI-1) includes a plurality of aryl groups, these aryl groups may be the same as or different from each other.

  Examples of the compound (ZI-1) include triarylsulfonium compounds, diarylalkylsulfonium compounds, and aryldialkylsulfonium compounds.

  As the aryl group in the compound (ZI-1), a phenyl group, a naphthyl group, or a heteroaryl group such as an indole residue and a pyrrole residue is preferable, and a phenyl group, a naphthyl group, or an indole residue is particularly preferable.

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

  These aryl groups and alkyl groups may have a substituent. Examples of the substituent include an alkyl group (preferably 1 to 15 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), an alkoxy group (preferably 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and phenylthio. Groups.

Preferable substituents include linear, branched or cyclic alkyl groups having 1 to 12 carbon atoms and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms. Particularly preferred substituents include alkyl groups having 1 to 6 carbon atoms and alkoxy groups having 1 to 6 carbon atoms. The substituent may be substituted to any one of the three R ₂₀₁ to R _203, or may be substituted on all three. When R _{201 to} R ₂₀₃ are a phenyl group, the substituent is preferably substituted at the p-position of the aryl group.

Also preferred is an embodiment in which one or two of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ are an aryl group which may have a substituent, and the remaining group is a linear, branched or cyclic alkyl group. . Specific examples of this structure include the structures described in paragraphs 0141 to 0153 of JP-A-2004-210670.

At this time, as the aryl group, specifically, the same as the aryl group of R _201, R ₂₀₂ and R _203, a phenyl group or a naphthyl group is preferable. The aryl group preferably has any one of a hydroxyl group, an alkoxy group, and an alkyl group as a substituent. More preferably, it is a C1-C12 alkoxy group as a substituent, More preferably, it is a C1-C6 alkoxy group.

  The linear, branched or cyclic alkyl group as the remaining group is preferably an alkyl group having 1 to 6 carbon atoms. These groups may further have a substituent. In addition, when two of the remaining groups are present, these two may be bonded to each other to form a ring structure.

Compound (ZI-1) is, for example, a compound represented by the following general formula (ZI-1A).

In general formula (ZI-1A),
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy group or an alkoxycarbonyl group.
When a plurality of R ₁₄ are present, each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group or a cycloalkylsulfonyl group.

R ₁₅ each independently represents an alkyl group or a cycloalkyl group. Two R ₁₅ may be bonded to each other to form a ring structure.
l represents an integer of 0-2.
r represents an integer of 0 to 8.
X ⁻ represents a non-nucleophilic anion, and examples thereof include the same as X ⁻ in the general formula (ZI).

The alkyl group for R ₁₃ , R ₁₄ or R ₁₅ may be a linear alkyl group or a branched alkyl group. The alkyl group is preferably one having 1 to 10 carbon atoms, for example, methyl group, 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-octyl group, 2-ethylhexyl group, n-nonyl group and n-decyl group. Of these, a methyl group, an ethyl group, an n-butyl group, and a t-butyl group are particularly preferable.

Examples of the cycloalkyl group represented by R ₁₃ , R ₁₄ or R ₁₅ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecanyl, cyclobenenyl, cyclohexenyl and cyclooctadienyl groups. Can be mentioned. Of these, cyclopropyl, cyclopentyl, cyclohexyl and cyclooctyl groups are particularly preferred.

Examples of the alkyl group moiety of the alkoxy group of R ₁₃ or R ₁₄ include those enumerated above as the alkyl group of R ₁₃ , R ₁₄ or R ₁₅ . As the alkoxy group, a methoxy group, an ethoxy group, an n-propoxy group, and an n-butoxy group are particularly preferable.

The cycloalkyl moiety of the cycloalkyl group of R _13, for example, those previously listed as the cycloalkyl group of _{R 13, R 14} or _{R 15.} As this cycloalkyloxy group, a cyclopentyloxy group and a cyclohexyloxy group are particularly preferable.

The alkoxy group moiety of the alkoxycarbonyl group R _13, for example, those previously listed as alkoxy groups R ₁₃ or R _14. As the alkoxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, and an n-butoxycarbonyl group are particularly preferable.

The alkyl group moiety of the alkylsulfonyl group R _14, for example, those previously listed as alkyl group _{R 13, R 14} or _{R 15. Further,} the cycloalkyl group moiety cycloalkylsulfonyl group _{R 14,} for example, those previously listed as the cycloalkyl group of _{R 13, R 14} or _{R 15.} As these alkylsulfonyl groups or cycloalkylsulfonyl groups, a methanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, an n-butanesulfonyl group, a cyclopentanesulfonyl group, and a cyclohexanesulfonyl group are particularly preferable.

  l is preferably 0 or 1, more preferably 1. r is preferably 0-2.

Each group of R ₁₃ , R ₁₄ and R ₁₅ may further have a substituent. Examples of this substituent include halogen atoms such as fluorine atoms, hydroxy groups, carboxy groups, cyano groups, nitro groups, alkoxy groups, cycloalkyloxy groups, alkoxyalkyl groups, cycloalkyloxyalkyl groups, alkoxycarbonyl groups, cyclocarbonyls, Examples include an alkyloxycarbonyl group, an alkoxycarbonyloxy group, and a cycloalkyloxycarbonyloxy group.

The alkoxy group may be linear or branched. Examples of the alkoxy group include carbon number 1 such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, and t-butoxy group. -20.
Examples of the cycloalkyloxy group include those having 3 to 20 carbon atoms such as a cyclopentyloxy group and a cyclohexyloxy group.

The alkoxyalkyl group may be linear or branched. Examples of the alkoxyalkyl group include those 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. Can be mentioned.
Examples of the cycloalkyloxyalkyl group include those having 4 to 21 carbon atoms such as a cyclopentyloxyethyl group, a cyclopentyloxypentyl group, a cyclohexyloxyethyl group, and a cyclohexyloxypentyl group.

The alkoxycarbonyl group may be linear or branched. 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 and t. -A C2-C21 thing, such as a butoxycarbonyl group, is mentioned.
Examples of the cycloalkyloxycarbonyl group include those having 4 to 21 carbon atoms such as a cyclopentyloxycarbonyl group and cyclohexyloxycarbonyl.

The alkoxycarbonyloxy group may be linear or branched. Examples of the alkoxycarbonyloxy group include carbon such as methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i-propoxycarbonyloxy group, n-butoxycarbonyloxy group and t-butoxycarbonyloxy group. The thing of number 2-21 is mentioned.
Examples of the cycloalkyloxycarbonyloxy group include those having 4 to 21 carbon atoms such as a cyclopentyloxycarbonyloxy group and a cyclohexyloxycarbonyloxy group.

The ring structure that can be formed by bonding two R ₁₅ to each other includes a 5-membered ring or a 6-membered ring, particularly preferably a 5-membered ring (that is, a tetrahydrothiophene ring) together with the S atom in the general formula (ZI-1A). ) Is preferred.
This ring structure may further have a substituent. Examples of the substituent include a hydroxy group, a carboxy group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group.

As R ₁₅ , a methyl group, an ethyl group, and a divalent group in which two R ₁₅ are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom are particularly preferable.

Alkyl groups R _13, cycloalkyl group, alkoxy group and alkoxycarbonyl group, alkyl group of R _14, cycloalkyl group, alkoxy group, alkylsulfonyl group and cycloalkylsulfonyl group may further have a substituent . As this substituent, a hydroxy group, an alkoxy group, an alkoxycarbonyl group, and a halogen atom (particularly a fluorine atom) are preferable.

Below, the preferable specific example of the cation in the compound represented by general formula (ZI-1A) is shown.

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

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

The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ is a 1 to 30 carbon atoms for example, preferably 1 to 20.

R _{201 to} R ₂₀₃ are preferably each independently an alkyl group, a 2-oxoalkyl group, an alkoxycarbonylmethyl group, an allyl group, or a vinyl group. A linear, branched or cyclic 2-oxoalkyl group or an alkoxycarbonylmethyl group is more preferable, and a linear or branched 2-oxoalkyl group is particularly preferable.

The alkyl group as R ₂₀₁ to R ₂₀₃ may be linear, branched and or cyclic, preferred examples include linear or branched alkyl group (e.g., methyl group having 1 to 10 carbon atoms, An ethyl group, a propyl group, a butyl group or a pentyl group) and a cycloalkyl group having 3 to 10 carbon atoms (a cyclopentyl group, a cyclohexyl group or a norbornyl group).

2-oxoalkyl group as R ₂₀₁ to R ₂₀₃ may be linear, it may be either branched or cyclic, preferably, includes a group having> C = O at the 2-position of the above alkyl group.

Preferred examples of the alkoxy group in the alkoxycarbonylmethyl group as R ₂₀₁ to R ₂₀₃ is an alkoxy group having 1 to 5 carbon atoms (a methoxy group, an ethoxy group, a propoxy group, a butoxy group, pentoxy group).

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

Two of R ₂₀₁ to R ₂₀₃ is bonded to each other, they may form a ring structure. This ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond and / or a carbonyl group in the ring. The two of the group formed by bonding of the R ₂₀₁ to R _203, for example, an alkylene group (e.g., butylene or pentylene group).

Next, the compound (ZI-3) will be described.
The compound (ZI-3) is a compound represented by the following general formula (ZI-3), and is a compound having a phenacylsulfonium salt structure.

In the formula, R _{1c to} R _5c each independently represent a hydrogen atom, an alkyl group, an alkoxy group, or a halogen atom. As for carbon number of an alkyl group and an alkoxy group, 1-6 are preferable.
R _6c and R _7c represent a hydrogen atom or an alkyl group. As for carbon number of an alkyl group, 1-6 are preferable.
R _x and R _y each independently represents an alkyl group, a 2-oxoalkyl group, an alkoxycarbonylmethyl group, an allyl group, or a vinyl group. As for carbon number of these atomic groups, 1-6 are preferable.

Any two or more of R _{1c to} R _7c may be bonded to each other to form a ring structure. Further, R _x and R _y may be bonded to form a ring structure. These ring structures may contain an oxygen atom, a sulfur atom, an ester bond and / or an amide bond.
X in the general formula (ZI-3) ^- is, X in formula (ZI) ^- is synonymous.

  Specific examples of the compound (ZI-3) are described in the compounds exemplified in paragraphs 0047 and 0048 of JP-A No. 2004-233661 or paragraphs 0040 to 0046 of JP-A No. 2003-35948. Compounds.

Subsequently, the compound (ZI-4) will be described.
The compound (ZI-4) is a compound having a cation represented by the following general formula (ZI-4). This compound (ZI-4) is effective in suppressing outgassing.

In general formula (ZI-4),
R ^{1 to} R ¹³ each independently represents a hydrogen atom or a substituent. At least one of R ^{1 to} R ¹³ is preferably a substituent containing an alcoholic hydroxyl group. Here, “alcoholic hydroxyl group” means a hydroxyl group bonded to a carbon atom of an alkyl group.
Z is a single bond or a divalent linking group.

When R ^{1 to} R ¹³ are substituents containing an alcoholic hydroxyl group, R ^{1 to} R ¹³ are preferably groups represented by — (W—Y). Here, Y is an alkyl group substituted with a hydroxyl group, and W is a single bond or a divalent linking group.

Preferable examples of the alkyl group represented by Y include an ethyl group, a propyl group, and an isopropyl group. Y particularly preferably includes a structure represented by —CH ₂ CH ₂ OH.

  The divalent linking group represented by W is not particularly limited, but preferably a single bond, an alkoxy group, an acyloxy group, an acylamino group, an alkyl and arylsulfonylamino group, an alkylthio group, an alkylsulfonyl group, an acyl group, A divalent group in which an arbitrary hydrogen atom in an alkoxycarbonyl group or a carbamoyl group is replaced by a single bond, and more preferably an arbitrary hydrogen atom in a single bond, an acyloxy group, an alkylsulfonyl group, an acyl group or an alkoxycarbonyl group. It is a divalent group replaced by a single bond.

When R ^{1 to} R ¹³ are substituents 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 ^{1 to} R ¹³ may have two or more alcoholic hydroxyl groups. The number of the alcoholic hydroxyl group which the substituent containing the alcoholic hydroxyl group as R < ¹ > -R < ¹³ > has is 1-6, Preferably it is 1-3, More preferably, it is 1.

The number of alcoholic hydroxyl groups possessed by the compound represented by the general formula (ZI-4) is 1 to 10, preferably 1 to 6, more preferably 1 to 3 in total for R ^{1 to} R ^13. is there.

When R ^{1 to} R ¹³ do not contain an alcoholic hydroxyl group, examples of the substituent as R ^{1 to} R ¹³ include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, and an aryl group. , Heterocyclic group, cyano group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group ( Anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, Elementary ring thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group Phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group [—B (OH) ₂ ], phosphato group [—OPO (OH) ₂ ] , Sulfato groups (—OSO ₃ H), and other known substituents.

When R ^{1 to} R ¹³ do not contain an alcoholic hydroxyl group, R ^{1 to} R ¹³ are preferably a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an 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, alkoxycarbonyl group, carbamoyl group, imide group, silyl group or ureido group.

When R ^{1 to} R ¹³ do not contain an alcoholic hydroxyl group, R ^{1 to} R ¹³ are more preferably a hydrogen atom, a halogen atom, an alkyl group, 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 or a carbamoyl group.

When R ^{1 to} R ¹³ do not contain an alcoholic hydroxyl group, R ^{1 to} R ¹³ are particularly preferably a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or an alkoxy group.

Two adjacent ones of R ^{1 to} R ¹³ may be bonded to each other to form a ring. This ring includes aromatic and non-aromatic hydrocarbon rings and heterocycles. These rings may be further combined to form a condensed ring.

The compound (ZI-4) preferably has a structure in which at least one of R ^{1 to} R ¹³ contains an alcoholic hydroxyl group, and more preferably at least one of R ^{9 to} R ¹³ is alcoholic. It has a structure containing a hydroxyl group.

  Z represents a single bond or a divalent linking group as described above. 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, Examples thereof include an alkylsulfonyl group, -CH = CH-, an aminocarbonylamino group, and an aminosulfonylamino group.

This divalent linking group may have a substituent. As these substituents, for example, those similar to those listed above for R ^{1 to} R ¹³ can be mentioned.

  Z is preferably a single bond, an alkylene group, an arylene group, an ether group, a thioether group, an amino group, a bond having no electron withdrawing property such as —CH═CH—, an aminocarbonylamino group, and an aminosulfonylamino group, or A group, more preferably a single bond, an ether group or a thioether group, and particularly preferably a single bond.

  Hereinafter, general formulas (ZII) and (ZIII) will be described.

In formula (ZII) and (ZIII), R ₂₀₄ ~R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group. These aryl group, alkyl group and cycloalkyl group may have a substituent.

Preferable examples of the aryl group as R _{204 to} R ₂₀₇ include the same groups as those enumerated above for R _{201 to} R ₂₀₃ in the compound (ZI-1).
Preferable examples of the alkyl group and cycloalkyl group as R _{204 to} R ₂₀₇ include the linear, branched or cycloalkyl groups listed above for R _{201 to} R ₂₀₃ in compound (ZI-2).

In addition, X < ^- > in general formula (ZII) and (ZIII) is synonymous with X < ^- > in general formula (ZI).

Other preferred examples of the photoacid generator include compounds represented by the following general formula (ZIV), (ZV) or (ZVI).

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents a substituted or unsubstituted aryl group.
R ₂₀₈ represents an alkyl group, a cycloalkyl group, or an aryl group independently in the general formulas (ZV) and (ZVI). These alkyl group, cycloalkyl group and aryl group may be substituted or unsubstituted.
These groups are preferably substituted with a fluorine atom. In this way, it is possible to increase the strength of the acid generated by the photoacid generator.

R ₂₀₉ and R ₂₁₀ each independently represents an alkyl group, a cycloalkyl group, an aryl group, or an electron-withdrawing group. These alkyl group, cycloalkyl group, aryl group and electron-withdrawing group may be substituted or unsubstituted.
Preferable R ₂₀₉ includes a substituted or unsubstituted aryl group.
Preferable R ₂₁₀ includes an electron withdrawing group. Preferred examples of the electron withdrawing group include a cyano group and a fluoroalkyl group.

  A represents an alkylene group, an alkenylene group or an arylene group. These alkylene group, alkenylene group and arylene group may have a substituent.

A compound having a plurality of structures represented by the general formula (ZVI) is also preferable as the photoacid generator. Such compounds, for example, binding to _{R 209} or _{R 210} of the compound represented by the general formula (ZVI), and the _{R 209} or _{R 210} of another compound represented by the general formula (ZVI) together And a compound having the above structure.

  As the photoacid generator, compounds represented by general formulas (ZI) to (ZIII) are more preferable, compounds represented by general formula (ZI) are more preferable, and compounds (ZI-1) to (ZI-3) are more preferable. Is particularly preferred.

Specific examples of the photoacid generator are shown below, but the scope of the present invention is not limited thereto.

  In addition, a photo-acid generator may be used individually by 1 type, and may be used in combination of 2 or more type. When two or more types are used in combination, it is preferable to combine two types of compounds that generate two types of organic acids that differ in the total number of atoms excluding hydrogen atoms by two or more.

  When the composition according to the present invention further contains a photoacid generator, the content thereof is preferably 0.1 to 40% by mass, more preferably 0. 0% by mass, based on the total solid content of the composition. It is 5-30 mass%, More preferably, it is 1-20 mass%.

[5] 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 (such as propylene glycol monomethyl ether acetate), alkylene Glycol monoalkyl ether (such as propylene glycol monomethyl ether), alkyl lactate ester (such as ethyl lactate and methyl lactate), cyclic lactone (such as γ-butyrolactone, preferably 4 to 10 carbon atoms), chain or cyclic ketone (2- Heptanone, cyclohexanone, etc., preferably 4-10 carbon atoms, alkylene carbonate (ethylene carbonate, propylene carbonate, etc.), alkyl carboxylate (preferably alkyl acetate such as butyl acetate), and alkane Like alkoxy alkyl acetates (ethyl ethoxypropionate). Other usable solvents include, for example, the solvents described in US2008 / 0248425A1 [0244] and thereafter.

  Of the above solvents, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, and ethyl lactate are particularly preferred.

  These solvents may be used alone or in combination of two or more. When using 2 or more types mixed, it is preferable to mix the solvent containing a hydroxyl group and the solvent which does not contain a hydroxyl group. The mass ratio of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is usually from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 60. / 40.

  The solvent containing a hydroxyl group is preferably an alkylene glycol monoalkyl ether or an alkyl lactate ester, and the solvent not containing a hydroxyl group is preferably an alkylene glycol monoalkyl ether carboxylate. It is particularly preferable to use a solvent in which 50% by mass or more of the solvent is propylene glycol monomethyl ether.

  The amount of the solvent used is determined so that the total solid concentration of the composition is preferably 2.0 to 4.0% by weight, more preferably 2.0 to 3.0% by weight.

[6] Surfactant The 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 surfactant include Megafac F176 and Megafac R08 manufactured by Dainippon Ink & Chemicals, Inc., PF656 and PF6320 manufactured by OMNOVA, Troisol S-366 manufactured by Troy Chemical Co., Ltd., Sumitomo 3M ( For example, Fluorad FC430 manufactured by Co., Ltd. and polysiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd. may be mentioned.

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

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

Surfactant may be used independently and may use 2 or more types together.
When the composition according to the present invention further contains a surfactant, the content thereof is preferably 0.0001 to 2% by mass, more preferably 0.001 based on the total solid content of the composition. ˜1% by mass.

[7] Dissolution-inhibiting compound The composition according to the present invention is a dissolution-inhibiting compound having a molecular weight of 3000 or less (hereinafter also referred to as “dissolution-inhibiting compound”), which decomposes by the action of an acid to increase the solubility in an alkaline developer. May further be included.

  This dissolution inhibiting compound contains an acid-decomposable group such as a cholic acid derivative containing an acid-decomposable group described in Proceeding of SPIE, 2724,355 (1996) so as not to lower the permeability of 220 nm or less. Preferred are alicyclic or aliphatic compounds. Examples of the acid-decomposable group include the same groups as those described above for “OY” of the resin (P).

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

  The molecular weight of the dissolution inhibiting compound is 3000 or less, preferably 300 to 3000, and more preferably 500 to 2500.

  The addition amount of the dissolution inhibiting compound is preferably 0 to 20% by mass, more preferably 0.5 to 10% by mass, based on the total solid content of the composition.

Specific examples of the dissolution inhibiting compound are shown below, but the present invention is not limited thereto.

[8] Other Additives The composition according to the present invention comprises, if necessary, a dye, a plasticizer, a photosensitizer, a light absorber, and a compound that promotes dissolution in a developer (hereinafter referred to as a dissolution promoting compound). Or the like) can be further contained. Moreover, the compound provided with the proton acceptor functional group described in Unexamined-Japanese-Patent No. 2006-208781 and 2007-286574 grade | etc., Can also be used suitably.

  The dissolution promoting compound is a low molecular compound having a molecular weight of 1,000 or less and having two or more phenolic OH groups or one or more carboxy groups. In addition, when it has a carboxy group, it is preferable that a dissolution promoting compound is an alicyclic or an aliphatic compound.

  The addition amount of these dissolution promoting compounds is preferably 0 to 50% by mass, more preferably 5 to 30% by mass, based on the mass of the resin (P). From the viewpoint of suppressing development residue and preventing pattern deformation during development, the amount added is preferably 50% by mass or less.

  The above-mentioned dissolution promoting compound can be easily synthesized with reference to the methods described in, for example, JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210 and European Patent 219294. can do.

[9] Pattern Forming Method The composition according to the present invention is typically used as follows. That is, the composition according to the present invention is typically applied on a support such as a substrate to form a film. The thickness of this film is preferably 0.02 to 0.1 μm. As a method of coating on the substrate, spin coating is preferable, and the rotation speed is preferably 1000 to 3000 rpm.

  For example, the composition can be applied to a substrate (eg, silicon / silicon dioxide coating, silicon nitride and chromium-deposited quartz substrate, etc.) used in the manufacture of precision integrated circuit elements, etc., by appropriate application such as a spinner and a coater It is applied by the method. Thereafter, this is dried to obtain an actinic ray-sensitive or radiation-sensitive film (hereinafter also referred to as a photosensitive film). In addition, a known antireflection film can be applied in advance.

  Next, the photosensitive film is irradiated with actinic rays or radiation, and preferably baked (usually 80 to 150 ° C., more preferably 90 to 130 ° C.), followed by development. Thereby, a good pattern can be obtained. Then, using this pattern as a mask, etching processing, ion implantation, and the like are performed as appropriate to create a semiconductor microcircuit, an imprint mold structure, and the like.

  For details of the process for producing an imprint mold using the composition of the present invention, see, for example, Japanese Patent No. 4109085, Japanese Patent Application Laid-Open No. 2008-162101, and “Nanoimprint Basics and Technology Development / Application development-Nanoimprint substrate technology and latest technological development-Editing: Yoshihiko Hirai (Frontier Publishing) " For a method for manufacturing a mold structure particularly suitable for manufacturing an information recording medium, see, for example, Japanese Patent No. 4109085 and Japanese Patent Application Laid-Open No. 2008-162101.

  In the development process, an alkaline developer is usually used. As a developing method, a known method such as paddle formation, dipping and dynamic dispensing is appropriately used. Various alkaline aqueous solutions can be used as the alkaline developer, but usually an aqueous tetramethylammonium hydroxide aqueous solution is used. An appropriate amount of alcohol and / or surfactant may be added to the alkaline developer.

  The 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.

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

〔resin〕
First, monomers (M-1) to (M-9) shown below were synthesized. Moreover, the monomer (R-1) was prepared.

<Synthesis Example 1: Synthesis of Monomer (M-1)>
15 parts by mass of 6-hydroxy-2-naphthoic acid was dissolved in 80 parts by mass of methanol. A solution prepared by dissolving 3.35 parts by mass of lithium hydroxide monohydrate in 48 parts by mass of methanol was added dropwise to the resulting solution, and the mixture was stirred at room temperature for 1 hour. Thereafter, methanol was removed under reduced pressure to obtain a reaction product.
This reaction product was redissolved in 55 parts by mass of dimethyl sulfoxide. Next, 12.2 parts by mass of chloromethylstyrene (CMS-14, manufactured by Seimi Chemical Co., Ltd.) was added thereto, and the mixture was stirred at 80 ° C. for 4 hours. Subsequently, ethyl acetate and a saturated aqueous ammonium chloride solution were added thereto, followed by extraction and washing. The organic layer was concentrated and then purified using column chromatography to obtain 17.1 parts by mass of monomer (M-1).

¹ H NMR (DMSO-d ⁶ ): δ 10.22 (s, 1H), 8.53 (s, 1H), 8.00 (d, J = 8.4 Hz, 1H), 7.90 (d, J = 8.7 Hz, 1H), 7.77 (d, J = 8.7 Hz, 1H), 7.54-7.47 (m, 4H), 7.19-7.15 (m, 2H), 6.76 (dd, J = 17.6, 10.5 Hz, 1H), 5.86 (d, J = 17.6 Hz, 1H), 5.38 (s, 2H), 5.29 (d, J = 10.5 Hz, 1H).

<Synthesis Example 2: Synthesis of Monomer (M-2)>
10 parts by mass of the monomer (M-1) and 5 parts by mass of 2-cyclohexylethyl vinyl ether were dissolved in 50 parts by mass of propylene glycol monomethyl ether acetate (PGMEA). Subsequently, 0.015 mass part camphorsulfonic acid was added to this solution, and it stirred over 30 minutes at room temperature. 0.1 parts by mass of triethylamine was added to the reaction solution, and the solvent was distilled off under reduced pressure, followed by purification using column chromatography. This obtained 12.6 mass parts monomer (M-2).

¹ H NMR (DMSO-d ⁶ ): δ 8.60 (s, 1H), 8.08 (d, J = 9.0 Hz, 1H), 7.97 (d, J = 8.7 Hz, 1H), 7.90 (d, J = 8.7 Hz , 1H), 7.54-7.48 (m, 5H), 7.30 (d, J = 9.0 Hz, 1H), 6.76 (dd, J = 18.0, 11.1 Hz, 1H), 5.86 (d, J = 18.0 Hz, 1H) , 5.71 (q, J = 5.4 Hz, 1H), 5.39 (s, 2H), 5.28 (d, J = 11.1 Hz, 1H), 3.71-3.44 (m, 2H), 1.72-0.66 (m, 16H).

<Synthesis Example 3: Synthesis of Monomer (M-3)>
15 In the same manner as in Synthesis Example 1, except that 16.3 parts by mass of 3,5-dihydroxy-2-naphthoic acid was used instead of 15 parts by mass of 6-hydroxy-2-naphthoic acid. .2 parts by mass of monomer (M-3) was synthesized.

<Synthesis Example 4: Synthesis of Monomer (M-4)>
10.1 mass in the same manner as in Synthesis Example 2 except that 2.4 mass parts of 3,5-dihydroxy-2-naphthoic acid was used instead of 5 mass parts of 2-cyclohexylethyl vinyl ether. Part of the monomer (M-4) was synthesized.

<Synthesis Example 5: Synthesis of Monomer (M-5)>
First, 6-vinyl-2-naphthol (m-5a) was synthesized as follows. That is, 24 parts by mass of methyltriphenylphosphonium bromide and 130 parts by mass of toluene were added to 7.6 parts by mass of tert-butoxy potassium and 90 parts by mass of tetrahydrofuran, followed by stirring at room temperature for 2 hours. To this reaction solution, 5.0 parts by mass of 6-hydroxy-2-naphthaldehyde was added, and the mixture was further stirred at room temperature for 4 hours. The reaction product was extracted and washed with ethyl acetate and saturated aqueous ammonium chloride solution, and purified by column chromatography using hexane / ethyl acetate. As a result, 2.6 parts by mass of 6-vinyl-2-naphthol (m-5a) was obtained.
Next, the monomer (M-5) was synthesized according to the following reaction scheme.

  Specifically, 5 parts by mass of (m-5a) and 6.12 parts by mass of 3-bromo-1-propanol were first dissolved in 45 parts by mass of N-methylpyrrolidone. Subsequently, 8.12 mass parts potassium carbonate was added to this, and it stirred at 80 degreeC over 7 hours. The reaction product was extracted and washed with ethyl acetate and saturated aqueous ammonium chloride solution, and purified by column chromatography using hexane / ethyl acetate. As a result, 5.73 parts by mass of the compound (m-5b) was obtained.

  5 parts by mass of (m-5b) and 4.59 parts by mass of para-toluenesulfonyl chloride were dissolved in 50 parts by mass of pyridine and stirred at room temperature for 5 hours. The reaction product was extracted and washed with ethyl acetate and saturated aqueous ammonium chloride solution, and purified by column chromatography using hexane / ethyl acetate. As a result, 7.15 parts by mass of the compound (m-5c) was obtained.

4.81 parts by mass of 4- (4-hydroxyphenyl) benzoic acid was dissolved in 60 parts by mass of methanol. To this solution, a solution prepared by dissolving 0.94 parts by mass of lithium hydroxide monohydrate in 20 parts by mass of methanol was added dropwise and stirred at room temperature for 1 hour. Thereafter, methanol was removed under reduced pressure to obtain a reaction product.
This reaction product was redissolved in 50 parts by mass of N-methylpyrrolidone. Subsequently, 7.15 mass parts (m-5c) was added to this, and it stirred at 80 degreeC over 8 hours. Subsequently, ethyl acetate and a saturated aqueous ammonium chloride solution were added thereto, followed by extraction and washing. The organic layer was concentrated and then purified using column chromatography to obtain 5.1 parts by mass of a monomer (M-5).

<Synthesis Example 6: Synthesis of Monomer (M-6)>
5 parts by mass of the monomer (M-1) and 0.4 parts by mass of 4-dimethylaminopyridine were dissolved in 80 parts by mass of acetonitrile. To the resulting solution, 4.3 parts by mass of di-tert-butyl dicarbonate was added and stirred at room temperature for 2 hours. Subsequently, chloroform and dilute hydrochloric acid aqueous solution were added thereto, and extraction and washing were performed. The organic layer was concentrated to obtain 6.0 parts by mass of a monomer (M-6).

<Synthesis Example 7: Synthesis of Monomer (M-7)>
Monomer (M-7) was synthesized according to the following synthesis scheme.

  Specifically, 400 parts by mass of acetonitrile was added to 5 parts by mass of 4-hydroxyindole, 5.64 parts by mass of succinic anhydride, and 38 parts by mass of triethylamine, and the mixture was refluxed for 16 hours. After the solvent was distilled off, column chromatography purification was performed using hexane / ethyl acetate. As a result, 2.71 parts by mass of the compound (m-7a) was obtained.

  4 parts by mass of (m-7a) was dissolved in 100 parts by mass of methanol. A solution obtained by dissolving 0.72 parts by mass of lithium hydroxide monohydrate in 20 parts by mass of methanol was added dropwise to the obtained solution, and the mixture was stirred for 1 hour. After concentrating the reaction product, it was redissolved in 100 parts by mass of N-methylpyrrolidone. 2.75 parts by mass of chloromethylstyrene (CMS-14, manufactured by Seimi Chemical Co., Ltd.) was added and stirred at 80 ° C. for 8 hours. Subsequently, ethyl acetate and a saturated aqueous ammonium chloride solution were added thereto, followed by extraction and washing. The organic layer was concentrated and then purified using column chromatography to obtain 4.25 parts by mass of the compound (m-7b).

  5 parts by mass of (m-7b) and 2.97 parts by mass of 2- (vinyloxy) ethyl phenylcarbamate were dissolved in 100 parts by mass of propylene glycol monomethyl ether acetate (PGMEA). Next, 0.004 part by mass of camphor sulfonic acid was added to the obtained solution, and the mixture was stirred at room temperature for 2 hours. 0.1 parts by mass of triethylamine was added to the reaction solution, and the solvent was distilled off under reduced pressure, followed by purification using column chromatography. This obtained 6.53 mass parts monomer (M-7).

<Synthesis Example 8: Synthesis of Monomer (M-8)>
Monomer (M-8) was synthesized according to the following synthesis scheme.

  Specifically, 2.52 parts by mass of sodium hydride (oiliness, 60%) was added to 5.56 parts by mass of diethylene glycol and 80 parts by mass of THF, and the mixture was stirred at room temperature for 1 hour. Subsequently, 5 parts by mass of chloromethylstyrene (CMS-14, manufactured by Seimi Chemical Co., Ltd.) was added and stirred at room temperature for 3 hours. After concentrating the reaction solution, ethyl acetate and a saturated aqueous ammonium chloride solution were added, followed by extraction and washing. The organic layer was concentrated and then purified using column chromatography to obtain 3.93 parts by mass of the compound (m-8a).

  4 parts by mass of (m-8a) and 3.77 parts by mass of para-toluenesulfonyl chloride were dissolved in 50 parts by mass of pyridine and stirred at room temperature for 5 hours. The reaction product was extracted and washed with ethyl acetate and saturated aqueous ammonium chloride solution, and purified by column chromatography using hexane / ethyl acetate. As a result, 5.42 parts by mass of the compound (m-8b) was obtained.

Next, 17.58 parts by mass of a compound was obtained in the same manner as in Synthesis Example 1 except that 30.12 parts by mass of (m-8b) was used instead of 12.2 parts by mass of chloromethylstyrene. (M-8c) was obtained.
Then, 15.27 parts by weight of monomer was the same as in Synthesis Example 2 except that 12.89 parts by weight of (m-8c) was used instead of 10 parts by weight of monomer (M-1). (M-8) was obtained.

<Synthesis Example 9: Synthesis of Monomer (M-9)>
10 parts by mass of (m-5a) and 4.24 parts by mass of ethyl vinyl ether were dissolved in 50 parts by mass of propylene glycol monomethyl ether acetate (PGMEA). Subsequently, 0.015 mass part camphorsulfonic acid was added to the obtained solution, and it stirred at room temperature for 1 hour. 0.1 parts by mass of triethylamine was added to the reaction solution, and the solvent was distilled off under reduced pressure, followed by purification using column chromatography. This obtained 12.1 mass parts monomer (M-9).

Next, a resin was synthesized using these monomers.
<Synthesis Example 9: Synthesis of Resin (P-1)>
A resin (P-1) represented by the following formula was synthesized as follows.

  That is, first, 3.86 parts by mass of 1-methoxy-2-propanol was heated to 75 ° C. under a nitrogen stream. While stirring this liquid, 7.00 parts by mass of 4-hydroxystyrene (hereinafter also referred to as “HOST”), 2.64 parts by mass of monomer (M-2), 15.42 parts by mass of 1- A mixed solution of methoxy-2-propanol and 0.74 parts by mass of dimethyl 2,2′-azobisisobutyrate [V-601; manufactured by Wako Pure Chemical Industries, Ltd.] was added dropwise over 4 hours. After completion of dropping, the mixture was further stirred at 75 ° C. for 2 hours. The reaction solution was allowed to cool and then reprecipitated using a large amount of hexane / ethyl acetate. Then, 3.95 mass parts resin (P-1) was obtained by performing vacuum drying.

¹ H-NMR measurement was performed on the obtained resin (P-1). Thereby, the composition ratio (molar ratio) of the resin (P-1) was calculated. Moreover, by GPC (solvent: THF) measurement, the weight average molecular weight (Mw: polystyrene conversion), number average molecular weight (Mn: polystyrene conversion) and dispersity (Mw / Mn, hereinafter referred to as “PDI”) of the resin (P-1). Calculated). These results are shown in the above chemical formula and in Table 1 below.

<Synthesis Example 10: Synthesis of Resins (P-2) to (P-8)>
Resins (P-2) to (P-8) were synthesized in the same manner as in Synthesis Example 9. The structural unit used, its charge (parts by mass), the polymerization concentration (reaction solution concentration: mass%), and the charge of the polymerization initiator (parts by mass), and the composition ratio (molar ratio) of the obtained resin, The weight average molecular weight and dispersity (PDI) are shown in Table 1 below.

Hereinafter, the structure, the composition ratio, the weight average molecular weight, and the degree of dispersion of each of the resins (P-1) to (P-8) are shown.

[Photoacid generator]
As the photoacid generator, a compound represented by the following formula was used.

<Synthesis Example 11: PAG-1>
(Synthesis of tricyclohexylbenzene)
6.83 g of aluminum chloride was added to 20.0 g of benzene, the mixture was cooled and stirred at 3 ° C., and 40.4 g of cyclohexyl chloride was slowly added dropwise. After dropping, the mixture was stirred at room temperature for 5 hours and poured into ice water. The organic layer was extracted with ethyl acetate, and the obtained organic layer was distilled off under reduced pressure at 40 ° C. Furthermore, after depressurizingly distilling at 170 degreeC, it cooled to room temperature, thrown in 50 ml of acetone, and recrystallized. The precipitated crystals were collected by filtration to obtain 14 g of tricyclohexylbenzene.

(Synthesis of sodium tricyclohexylbenzenesulfonate)
30 g of tricyclohexylbenzene was dissolved in 50 ml of methylene chloride, cooled and stirred at 3 ° C., and 15.2 g of chlorosulfonic acid was slowly added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 5 hours. After adding 10 g of ice, 40 g of 50% aqueous sodium hydroxide solution was added. Further, 20 g of ethanol was added, and the mixture was stirred at 50 ° C. for 1 hour. The insoluble matter was removed by filtration, and the residue was distilled off under reduced pressure at 40 ° C. The precipitated crystals were collected by filtration and washed with hexane to obtain 30 g of sodium 1,3,5-tricyclohexylbenzenesulfonate.

(Synthesis of PAG-1)
4.0 g of triphenylsulfonium bromide was dissolved in 20 ml of methanol, and 5.0 g of sodium 1,3,5-tricyclohexylbenzenesulfonate dissolved in 20 ml of methanol was added. After stirring at room temperature for 2 hours, 50 ml of ion-exchanged water was added and extracted with chloroform. The obtained organic layer was washed with water and then distilled off under reduced pressure at 40 ° C., and the obtained crystal was recrystallized from a methanol / ethyl acetate solvent. This obtained 5.0g of compounds PAG-1.

¹ H-NMR (400 MHz, CDCl ₃ ) δ = 7.85 (d, 6H), 7.68 (t, 3H), 7.59 (t, 6H), 6.97 (s, 2H), 4.36-4.27 (m, 2H), 2.48 -2.38 (m, 1H), 1.97-1.16 (m, 30H).

[Basic compounds]
As the basic compound, a compound represented by the following formula was used.

[Surfactant and solvent]
As the surfactant, the following were used.

W-1: MegaFuck F176 (Dainippon Ink Chemical Co., Ltd .; fluorine-based)
W-2: Megafuck R08 (Dainippon Ink Chemical Co., Ltd .; fluorine and silicon)
The following were used as the solvent.

S1: Propylene glycol monomethyl ether acetate (PGMEA)
S2: Propylene glycol monomethyl ether (PGME)
[Examples 1 to 11 and Comparative Example 1]
Each component shown in Table 2 below was dissolved in the solvent shown in Table 2. This was filtered using a polytetrafluoroethylene filter having a pore size of 0.1 μm. Thereby, a positive resist solution having a total solid content concentration shown in Table 2 was prepared. In addition, the density | concentration of each component shown in Table 2 is mass concentration on the basis of the mass of total solid.

<Resist evaluation>
The prepared positive resist solution was uniformly applied on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater. Subsequently, it was heated and dried at 130 ° C. for 90 seconds using a hot plate. As a result, a resist film having a thickness of 100 nm was formed.

  The resist 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 120 ° C. for 90 seconds. Thereafter, 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 dried. Thereby, a line and space pattern (line: space = 1: 1) and an isolated line pattern (line: space = 1:> 100) were formed, respectively. Hereinafter, the line and space pattern may be abbreviated as L & S, and the isolated line pattern may be abbreviated as IL.

〔sensitivity〕
The cross-sectional shape of each pattern obtained was observed using a scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.). For both the L & S pattern and the IL pattern, the minimum irradiation energy when resolving a line having a line width of 100 nm was defined as sensitivity (μC / cm ² ).

[Resolution]
The resolving power (nm) was defined as the limiting resolving power (minimum line width at which lines and spaces were separated and resolved) at the irradiation amount showing the above sensitivity.

[Residual film rate (plasma etching resistance)]
A positive resist film having a thickness of 100 nm was formed on a wafer subjected to hexamethyldisilazane treatment. Plasma etching was performed on this film at 23 ° C. for 30 seconds using a mixed gas of CF ₄ (10 mL / min), O ₂ (20 mL / min), and Ar (1000 mL / min). Thereafter, the film thickness of the resist film after plasma etching was measured. Then, the film thickness after etching was divided by the film thickness before etching and multiplied by 100 to obtain a residual film ratio (%). In addition, plasma etching tolerance is so favorable that the remaining film rate is large.

  As shown in Table 2, the compositions according to Examples 1 to 11 were more excellent in sensitivity and resolution when forming an IL pattern than the composition according to Comparative Example 1. Moreover, the composition which concerns on Examples 1-11 was excellent also in the resolution at the time of forming plasma etching tolerance and an L & S pattern.

Claims (7)

An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin containing a repeating unit represented by the following general formula (1).

Where
R ¹ , R ² and R ³ each independently represents a hydrogen atom or a monovalent substituent.
L ¹ represents an arylene group.
A ¹ represents a divalent linking group.
X represents a structural unit containing a plurality of aromatic rings, and the plurality of aromatic rings are condensed to form a polycyclic structure or are connected to each other through a single bond.
Y represents a hydrogen atom or a group capable of leaving by the action of an acid. When n ₁ is 2 or more, the plurality of Y may be the same or different from each other.
n ₁ represents an integer of 1 to 5. The composition according to claim 1, wherein X is a structural unit represented by any one of the following general formulas (X1) to (X6).

Where
When a plurality of R ⁴ are present, each independently represents a monovalent substituent.
R ⁵ represents a hydrogen atom, an alkyl group, a cycloalkyl group, or A ¹ described above.
n ₂ is an integer of 0 to 14.
X ¹ represents CH or N, and two X ^{1 s} may be the same as or different from each other.
The A ¹ , OY and R ⁴ may be bonded to any of the atoms constituting the plurality of aromatic rings. The composition according to claim 1 or 2, wherein Y is a hydrogen atom or a group represented by the following general formula (2).

Where
R ⁶ and R ⁷ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group.
M represents a single bond or a divalent linking group.
Q represents an alkyl group, a cycloalkyl group, an alicyclic group which may contain a hetero atom, an aromatic ring group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group. .
At least two of R ⁶ , R ⁷ , M and Q may be bonded to each other to form a ring. The composition according to any one of claims 1 to 3, wherein the resin further contains at least one of repeating units represented by the following general formulas (3) and (4).

In formula, R < ⁹ > -R < ¹⁴ > represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group each independently.
R ^{15 to} R ¹⁷ each independently represents an alkyl group or a cycloalkyl group. At least two of R ^{15 to} R ¹⁷ may be bonded to each other to form a cycloalkyl group.
L ² represents an arylene group.
Z represents a hydrogen atom or a group capable of leaving by the action of an acid.
L ³ represents a single bond or a divalent linking group.   The composition according to any one of claims 1 to 4, which is exposed to an electron beam, an X-ray or EUV light. Forming a film using the composition according to any one of claims 1 to 5,
Exposing the film;
Developing a pattern of the exposed film.   The method according to claim 6, wherein the exposure is performed using an electron beam, an X-ray, or EUV light.