KR20110023773A - Active 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

ACTIVE RAY-SENSITIVE OR RADIATION-SENSITIVE RESIN COMPOSITION AND PATTERN FORMING METHOD USING THE SAME}

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 suitably used for the manufacturing process of ultra-LSI and high-capacity microchips, the process of making a mold for nanoimprinting, and the manufacturing process of a high density information recording medium, and the like. And a pattern forming method using the same. In more detail, this invention relates to the composition used suitably for the microfabrication of the semiconductor element using an electron beam or EUV light, and the pattern formation method using the same.

In addition, "active light" or "radiation" means here the light spectrum of a mercury lamp, the far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays, X rays, an electron beam, etc., for example. In addition, in this invention, "light" means actinic light or radiation.

In addition, unless otherwise indicated here, "exposure" means drawing by particle beams, such as an electron beam and an ion beam, as well as exposure by a mercury lamp, far ultraviolet rays, X-rays, and EUV light.

In microfabrication using a resist composition, formation of an ultrafine pattern is required in accordance with high integration of integrated circuits. Therefore, the tendency of shortening wavelength is seen also in exposure wavelength, For example, the development of the lithographic technique using an electron beam, X-ray, or EUV light instead of an excimer laser beam is progressing. In recent years, microfabrication using a resist composition has been used not only for the manufacture of integrated circuits but also for the production of imprint mold structures.

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

In addition, in electron beam (EB) lithography, it can be seen that by increasing the acceleration voltage of EB, the influence of electron scattering in the resist film, that is, forward scattering, is reduced. Therefore, in recent years, the acceleration voltage of EB tends to increase. However, when the acceleration voltage of EB is increased, the electron energy capture rate of a resist film may fall and a sensitivity may fall.

As one of the methods of solving these problems, use of resin which has a naphthalene frame | skeleton is examined (for example, refer patent document 1-3). By using resin which has a naphthalene skeleton, it becomes possible to improve dry etching resistance and a sensitivity, for example.

However, if the acceleration voltage of EB is increased, the influence of forward scattering, that is, back scattering, increases in the resist substrate instead of decreasing the influence of forward scattering. And when the isolation pattern with a large exposure area is formed, the influence of this backscattering is especially large. Therefore, if the acceleration voltage of EB is increased, for example, there is a possibility that the resolution of the isolation pattern is lowered.

Japanese Patent Publication No. 2008-169346 International Publication No. 2007-046453 Japanese Patent Publication No. 2008-50568

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

This invention is as follows, for example.

[1] An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin containing a repeating unit represented by the following General Formula (1).

Wherein 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 including a plurality of aromatic rings, and the plurality of aromatic rings are condensed to form a polycyclic structure or connected to each other through a single bond. Y represents a group which is released by the action of a hydrogen atom or an acid, and when n ₁ is 2 or more, a plurality of Y may be the same as or different from each other. n ₁ represents an integer of 1-5.

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

In formula, two or more R <^4> represents a monovalent substituent each independently. R ⁵ represents a hydrogen atom, an alkyl group, a cycloalkyl group, or A ¹ above. n ₂ is an integer from 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 one of the atoms constituting the plurality of aromatic rings.

[3] The actinic ray-sensitive or radiation-sensitive resin 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 resin according to any one of [1] to [3], wherein the resin further includes at least one of a repeating unit represented by the following general formula (3) and a repeating unit represented by the following general formula (4). Actinic ray-sensitive or radiation-sensitive resin composition.

In the formula, R ⁹ to R ¹⁴ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a cyano group. R ¹⁵ to R ¹⁷ each independently represent 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 group leaving by the action of a hydrogen atom or an acid. L ³ represents a single bond or a divalent linking group.

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

[6] A resist film formed by using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5].

[7] Pattern formation comprising forming a film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], exposing the film, and developing the exposed film Way.

[8] The pattern formation method according to [7], wherein the exposure is performed using electron beams, X-rays, or EUV light.

By this invention, it became possible to provide the actinic-ray-sensitive or radiation-sensitive resin composition excellent in the resolution of the isolation pattern, and the pattern formation method using the same.

Hereinafter, the present invention will be described in detail.

In addition, group and atom group which do not specify a substitution or unsubstitution here shall include both the thing which does not have a substituent, and the thing which has a substituent. For example, the "alkyl group" which does not specify a substituted or unsubstituted shall include not only the alkyl group (unsubstituted alkyl group) which does not have a substituent but the alkyl group (substituted alkyl group) which has a substituent.

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

[1] resins (P)

The composition by this invention contains resin (P). This resin (P) contains the repeating unit represented by following General formula (1).

Wherein 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 including a plurality of aromatic rings, and the plurality of aromatic rings are condensed to form a polycyclic structure or connected to each other through a single bond. Y represents a group which is released by the action of a hydrogen atom or an acid, and when n ₁ is 2 or more, a plurality of Y may be the same as or different from each other. n ₁ represents an integer of 1-5.

Each of R ¹ , R ² and R ³ is a hydrogen atom or a monovalent substituent as described above. As a monovalent substituent, For example, Alkyl group; Cycloalkyl group; Halogen atom; Substituent containing hetero atom, such as oxygen atom, sulfur atom, nitrogen atom, and silicon atom; And combinations thereof.

Carbon number of an alkyl group becomes like this. Preferably it is 20 or less, More preferably, it is 8 or less. As this alkyl group, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group are mentioned, for example. Especially, methyl group, ethyl group, propyl group, isopropyl group, and t-butyl group are especially preferable.

The cycloalkyl group may be monocyclic or polycyclic. Carbon number of this cycloalkyl group becomes like this. Preferably it is 3-8 pieces.

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

As a substituent containing a hetero atom, a hydroxyl group, an alkoxy group, a thiol group, a thioether group, and an amino group is mentioned, for example.

Carbon number of an alkoxy group becomes like this. Preferably it is 20 or less, More preferably, it is 8 or less. As this alkoxy group, a methoxy group, an ethoxy group, a propoxy group, isopropoxy group, n-butyloxy group, and octyloxy group are mentioned, for example. Especially, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and t-butoxy group are especially preferable. Moreover, the thing similar to an alkoxy group is mentioned also about a thioether group except using a sulfur atom instead of an oxygen atom.

These groups may further have a substituent. Substituents which these groups may have further include, for example, alkyl group, cycloalkyl group, aryl group, amino group, amide group, ureido group, urethane group, hydroxy group, carboxyl group, halogen atom, alkoxy group, thioether group, acyl group, acyl jade. A timing, an alkoxycarbonyl group, a cyano group, and a nitro group are mentioned. Moreover, carbon number of this substituent becomes like this. Preferably it is eight or less.

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

The arylene group preferably has 4 to 20 carbon atoms, more preferably 6 to 14 carbon atoms. As this arylene group, a phenylene group and a naphthylene group are mentioned, for example.

Examples of the substituent which the arylene group may have further include, for example, a halogen atom such as a nitro group and a fluorine atom, a carboxyl group, a hydroxy group, an amino group, a cyano group and an alkoxy group (preferably having 1 to 15 carbon atoms) and a cycloalkyl group (preferably Is 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 alkoxycar A carbonyloxy group (preferably C2-C7) is mentioned.

A ¹ represents a divalent linking group as described above. As the linking group, for example an alkylene group, a cycloalkylene group, -O-, -SO ₂ - may be mentioned, and a combination thereof -, -CO-, -N (R) . Here, R represents an aryl group, an alkyl group, or cycloalkyl. Interposed between the A ¹ L ¹ and X by it is possible to suppress a decrease in alkali solubility of the resin.

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

As a cycloalkylene group, Preferably, C5-C8 things, such as a cyclopentylene group and a cyclohexylene group, are mentioned.

These alkylene groups and cycloalkylene groups may further have a substituent. As this substituent, an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, an acyl group, an acyloxy group, an alkoxycarbonyl group, Cyano group and nitro group are mentioned.

It is preferable that "minimum connection atom number" of A <^1> is 1-50, It is more preferable that it is 2-25, It is especially preferable that it is 3-15. When this "minimum connection atom number" is too small, the structure of a side chain may become rigid, and the solubility of resin (P) in alkaline developing solution may fall remarkably. When the "minimum number of connection atoms" is excessively large, the glass transition temperature of the resin (P) decreases, and acid generated by exposure in the film tends to diffuse, which may reduce roughness characteristics, resolution, and the like.

Further, "connected to at least the number of atoms" of A ¹ is a number which is determined in the following manner. That is, first, the heat of the atom which connects the atom couple | bonded with L <^1> and the atom couple | bonded with X among the atoms which comprise A <^1> is considered. Next, the number of atoms contained in each of these columns is obtained. And the minimum of these atoms is called "minimum connection atom number" of A <^1> .

For example, when A <^1> is a propylene group, the minimum connection atom number is three. If A ¹ is -CH ₂ -O-CO-, the minimum number of linked atoms is three. When A ¹ is a 2-methyl-butylene group, the minimum number of linking atoms thereof is four. When A ¹ is a 1,4-cyclohexylene group, the minimum number of linking atoms thereof is four. When A ¹ is -O-CH ₂ CH ₂ CH ₂ -O-CO-, the minimum number of linked atoms is six. In addition, when A <^1> is a linear alkylene group, the minimum connection atom number of A <^1> is the same as the carbon number.

X represents the structural unit containing a some aromatic ring as mentioned above. These plural aromatic rings may be condensed to form a polycyclic structure, or may be connected to each other via a single bond. In addition, each of these aromatic rings may contain a hetero atom. By using the structural unit containing a plurality of aromatic rings as X, it is possible to achieve an improvement in sensitivity due to improvement in dry etching resistance and increase in secondary electron generation amount.

As an aromatic ring which X may contain, a benzene ring, a thiophene ring, a pyrrole ring, a furan ring, an imidazole ring, a pyridine ring, and a pyrazole ring are mentioned, for example.

As a polycyclic structure which a plurality of aromatic rings can be condensed and formed, a naphthalene ring, anthracene ring, a phenanthrene ring, a pyrene ring, a triphenylene ring, an indole ring, a benzimidazole ring, a carbazole ring, and a phenothiazine ring, for example Can be mentioned. Among these, indole ring, pyrene ring, phenanthrene ring, anthracene ring and naphthalene ring are more preferable, and an indole ring, anthracene ring and a naphthalene ring are especially preferable.

As a structure in which several aromatic rings were mutually connected through a single bond, a biphenyl structure, a terphenyl structure, and a viologen structure are mentioned, for example. Especially, a biphenyl structure and a terphenyl structure are especially preferable.

The number of aromatic rings contained in X becomes like this. Preferably it is 2-6 pieces, More preferably, it is 2-4 pieces, More preferably, it is two or three pieces. In addition, "the number of aromatic rings" here is the number of a benzene ring or the monocyclic heteroaryl ring corresponding to it. For example, it is two of naphthalene residues, biphenyl residues and bipyridine residues, and three of anthracene residues, carbazole residues and phenothiazine residues.

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

In formula, two or more R <^4> represents a monovalent substituent each independently. R ⁵ represents a hydrogen atom, an alkyl group, a cycloalkyl group, or A ¹ in General Formula (1). n ₂ is an integer from 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 addition, in these X, A <^1> , OY and R <^4> may couple | bond with any of the atoms which comprise the some aromatic ring.

R ⁴ is a monovalent substituent as described above. As this monovalent substituent, the same thing as what was enumerated about R <^1> -R <^3> first is mentioned, for example. Among these, halogen atoms and alkyl groups such as fluorine and bromine atoms are particularly preferable.

R ⁵ is a hydrogen atom, an alkyl group, a cycloalkyl group, or A ¹ in General Formula (1) as described above. Examples of the alkyl group and the cycloalkyl group include those listed above for R ¹ to R ³ .

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

Although the specific example of the structural unit represented by either of general formula (X1)-(X6) below is shown, this invention is not limited to these.

Y is a group which is released by the action of a hydrogen atom or an acid as mentioned above. Furthermore, if n ₁ is 2 or more, plural Y are good gatahdo each other or different from each other.

As group leaving by the action of an acid, group represented by following General formula (5)-(7) is mentioned, for example.

In the formula, each of R ¹⁸ to R ²⁶ independently represents an alkyl group, a cycloalkyl group, or an aryl group. In addition, R ¹⁸ and R ¹⁹ may be bonded to each other to form a ring.

Examples of the alkyl group and the cycloalkyl group include those listed above for R ¹ to R ³ .

The aryl group may contain a hetero atom. Carbon number of this aryl group becomes like this. Preferably it is 4-20 pieces, More preferably, it is 6-14 pieces, Especially preferably, it is 6-12 pieces. As this aryl group, a phenyl group and a naphthyl group are mentioned, for example.

The aryl group may further have a substituent. Examples of the substituent include halogen atoms such as nitro group and fluorine atom, carboxyl group, hydroxy group, amino group, cyano group, alkoxy group (preferably 1 to 15 carbon atoms), cycloalkyl group (preferably 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), and an alkoxycarbonyloxy group (preferably Is C2-C7).

Although the specific example of group represented by either of General Formula (5)-(7) below is shown, this invention is not limited to this. In addition, in formula, "-" represents the coupling group with O atom, and a methyl group is described as "Me-", and is distinguished.

When Y is a group 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 represent 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. It is preferable that this ring is a 5- or 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, 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 C 3-15 cycloalkyl group. 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, a C6-C15 aryl group. Preferably, a phenyl group, tolyl group, naphthyl group, and anthryl group is 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 (e.g., methylene group, ethylene group, propylene group, butylene group, hexylene group or octylene group), a cycloalkylene group (e.g. cyclopentylene group or cyclo) Hexylene group), alkenylene group (for example, ethylene group, propenylene group or butenylene group), arylene group (for example, phenylene group, tolylene group 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 (e.g., an alkyl group having 1 to 8 carbon atoms, specifically, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, octyl group, etc.) .

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

As an alicyclic group and aromatic ring group as Q, the cycloalkyl group and aryl group as R <^6> and R <^7> mentioned above are mentioned, for example. The carbon number is preferably 3 to 15 pieces.

As an alicyclic group containing a hetero atom and an aromatic ring group containing a hetero atom, for example, thirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzo Imidazole, triazole, thiadiazole, thiazole and pyrrolidone.

When 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 a 6-membered ring. And a case in which any one of M and Q and any one of R ⁶ and R ⁷ combine to form a propylene group or a butylene group to form a five-membered ring or six-membered ring containing an oxygen atom.

Each group represented by R ⁶ , R ⁷ , M and Q may further have a substituent. As this substituent, the thing similar to what was listed as a substituent which said R <^1> -R <^3> may have is mentioned, for example. Moreover, carbon number of this substituent becomes like this. Preferably it is eight or less.

Carbon number of group represented by-(M-Q) becomes like this. Preferably it is 1-30, More preferably, it is 5-20.

Although the specific example of group represented by General formula (2) is shown below, this invention is not limited to this. In addition, in formula, "-" represents the coupling group with O atom, and a methyl group is described as "Me-", and is distinguished.

When n ₁ is 2 or more, Y may be connected to two other oxygen atoms to form a ring. That is, Y may comprise the partial structure represented by "-OYO-". 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 those of R ⁶ and R ⁷ .

As a ring which Y and two other oxygen atoms can connect and form, a 5-, 6-, or 7-membered ring is preferable, and a 6-membered ring is especially preferable.

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

Although resin (P) may include only one type of repeating unit represented by General formula (1), it is more preferable that it contains a plurality of types of repeating units represented by General formula (1).

Resin (P) may further contain the repeating unit represented by following General formula (3) and (4).

In the formula, R ⁹ to R ¹⁴ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a cyano group. R ¹⁵ to R ¹⁷ each independently represent an alkyl group or a cycloalkyl group. In addition, at least 2 of R <^15> -R <^17> may combine with each other, and may form the cycloalkyl group.

L ² represents an arylene group. Z represents a group leaving by the action of a hydrogen atom or 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 the same as those listed for R ¹ to R ³ , for example.

As an alkyl group of R <^15> -R <^17> , a C1-C4 linear or branched thing is preferable.

As a cycloalkyl group of R <^15> -R <^17> , a C3-C8 monocyclic cycloalkyl group or a C7-C20 polycyclic cycloalkyl group is preferable.

As a cycloalkyl group which at least two of R <^15> -R <^17> couple | bonds and may form, C3-C8 monocyclic cycloalkyl group or C7-C20 polycyclic cycloalkyl group is preferable. Especially, a C5-C6 monocyclic cycloalkyl group is especially preferable. More preferably, R ¹⁷ is a methyl group or an ethyl group, and R ¹⁵ and R ¹⁶ are bonded to form the cycloalkyl group described above.

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

As Z, the group similar to what was enumerated about Y first, for example is mentioned.

Examples of L ³ include an alkylene group, a cycloalkylene group, an arylene group, -O-, -SO _2- , -CO-, -N (R _N )-and a plurality of combinations thereof. Here, R _N represents an aryl group, an alkyl group or a cycloalkyl group.

The number of carbon atoms of R _N as the aryl group is preferably 4 to 20 and, more preferably 6 to 14 atoms. As this aryl group, a phenyl group and a naphthyl group are mentioned, for example.

Of R _N as the alkyl group having a carbon number of preferably 1 to 8 atoms. As this alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and an octyl group are mentioned, for example.

Of R _N as a cycloalkyl group having a carbon number is preferably from 5 to 8 atoms. As this cycloalkyl group, a cyclopentyl group and a cyclohexyl group are mentioned, for example.

Although the specific example of the repeating unit represented by General formula (3) is given to the following, it is not limited to these.

Although the specific example of the repeating unit represented by General formula (4) is given to the following, it is not limited to these.

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 the total repeating units, 10 It is more preferable to set it as -80 mol%.

The form of the resin (P) may be any of random type, block type, comb type and star type.

Resin (P) mentioned above can be synthesize | combined, for example by radical, cation, or anionic polymerization of the unsaturated monomer corresponding to each repeating unit. Moreover, after superposing | polymerizing using the unsaturated monomer corresponded to the precursor of each repeating unit, it is also possible to synthesize | combine by performing a polymer reaction.

Although the molecular weight of this resin (P) is not specifically limited, It is preferable that the weight average molecular weight is the range of 1000-100000, It is more preferable that it is the range of 1500-70000, It is especially preferable that it is the range of 2000-50000. Here, the weight average molecular weight of resin shows the polystyrene conversion molecular weight measured by GPC (solvent: THF).

Moreover, dispersion degree (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 in a range not significantly impairing the dry etching resistance.

The content of the repeating unit derived from the other polymerizable monomer 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, addition polymerizable unsaturated selected from (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes and crotonic acid esters, and the like. Included are compounds with at least one bond. Others include maleic anhydride, maleimide, acrylonitrile, methacrylonitrile and maleylonitrile.

It is preferable to make content of resin (P) into 30-100 mass% on the basis of the total solid of a composition, It is more preferable to set it as 50-100 mass%, It is especially preferable to set it as 70-100 mass%.

As an example of resin (P), resin containing 1 or more types of repeating units chosen from the specific example of the repeating unit represented by General formula (1) is mentioned. In addition, as another example of resin (P), 1 or more types selected from the specific example of the repeating unit represented by General formula (1), and 1 type chosen from the specific example of the repeating unit represented by General formula (3) The resin containing the above repeating unit and 1 or more types of repeating units chosen from the specific example of the repeating unit represented by General formula (4) is mentioned.

Although the specific example of resin (P) is given to the following, 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, a compound for promoting dissolution in a developer, and a proton acceptor The compound etc. which have a functional group may further be included.

[2] basic compounds

The composition according to the present invention may further contain a basic compound. By containing a basic compound further, it becomes possible to further reduce the performance change with time from exposure to heating. In this way, it becomes possible to control the diffusibility of the acid generated by the exposure.

It is preferable that this basic compound is 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) a compound represented by the following General Formula (BS-1)

In general formula (BS-1),

R each independently represents a hydrogen atom or an organic group. Provided that 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 pieces, Preferably it is 1-12 pieces.

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

Although carbon number of the aryl group as R is not specifically limited, Usually, it is 6-20 pieces, Preferably it is 6-10 pieces. Specifically, a phenyl group, a naphthyl group, etc. are mentioned.

Although carbon number of the aralkyl group as R is not specifically limited, Usually, it is 7-20 pieces, Preferably it is 7-11 pieces. Specifically, a benzyl group etc. are mentioned.

The alkyl group, cycloalkyl group, aryl group and aralkyl group as R may have a hydrogen atom substituted by a substituent. As this substituent, 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, an alkyloxycarbonyl group, etc. are mentioned, for example.

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

Specific examples of the compound represented by 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-dibutyl aniline, N, N- dihexyl aniline, 2,6- diisopropyl aniline, and 2,4,6- tri (t-butyl) aniline are mentioned.

Moreover, as a preferable basic compound represented by general formula (BS-1), what is at least 1 R is the alkyl group substituted by the hydroxy group. Specifically, triethanolamine and N, N- dihydroxyethyl aniline are mentioned, for example.

In addition, the alkyl group as R may have an oxygen atom in the alkyl chain. That is, the oxyalkylene chain may be formed. As the oxyalkylene chain, -CH ₂ CH ₂ O- is preferable. Specifically, for example, tris (methoxyethoxyethyl) amine and the compound exemplified after line 60 of column 3 of the US 6040112 specification can be mentioned.

(2) a compound having a nitrogen-containing heterocyclic structure

This nitrogen-containing heterocycle may have aromaticity and does not need to have aromaticity. It may also have a plurality of nitrogen atoms. It may also contain heteroatoms other than nitrogen. Specifically, for example, a compound having an imidazole structure (2-phenylbenzoimidazole, 2,4,5-triphenylimidazole, etc.), a compound having a piperidine structure [N-hydroxyethylpiperi Dine and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and the like], compounds having a pyridine structure (such as 4-dimethylaminopyridine), and compounds having an antipyrine structure (antipyrine And hydroxyantipyrine and the like).

Moreover, the compound which has 2 or more of ring structure is also used suitably. Specifically, 1, 5- diazabicyclo [4.3.0] nona-5-ene and 1,8- diazabicyclo [5.4.0]-undeca-7-ene are mentioned, for example.

(3) an amine compound having a phenoxy group

The amine compound which has a phenoxy group is a compound which has a phenoxy group in the terminal opposite to the N atom of the alkyl group which an amine compound contains. Phenoxy groups include substituents such as alkyl groups, alkoxy groups, halogen atoms, cyano groups, nitro groups, carboxyl groups, carboxylic acid ester groups, sulfonic acid ester groups, aryl groups, aralkyl groups, acyloxy groups and aryloxy groups, for example. You may have it.

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 to 9, more preferably 4 to 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 paragraphs of the specification of US 2007/0224539 A1. The compound (C1-1)-(C3-3) illustrated by [0066] can be mentioned.

(4) ammonium salt

Ammonium salt can also be used suitably. This ammonium salt is preferably hydroxide or carboxylate. More specifically, tetraalkylammonium hydroxides, such as tetrabutylammonium hydroxide, are preferable.

In addition, the compound synthesize | combined by the Example of Unexamined-Japanese-Patent No. 2002-363146, the compound of Paragraph 0108 of Unexamined-Japanese-Patent No. 2007-298569, etc. are mentioned as usable for the composition by this invention.

Moreover, you may use the photosensitive basic compound as a basic compound. As a photosensitive basic compound, the compound of Unexamined-Japanese-Patent No. 2003-524799, J. Photopolym. Sci & Tech. Vol. 8, p. 543-553 (1995) etc. can be used, for example.

It is preferable that it is 250-2000, and, as for the molecular weight of a basic compound, it is more preferable that it is 400-1000.

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

When the composition by this invention contains the basic compound further, the content is made into 0.001-10 mass% normally on the basis of the total solid of a composition, Preferably it is 0.01-5 mass%.

It is preferable that molar ratio with respect to the basic compound of resin (P) is 1.5-300. That is, 2.5 or more are preferable from a viewpoint of improving a sensitivity and a resolution, and 300 or less are preferable from a viewpoint of suppressing the fall of the resolution by pattern thickening before post-exposure heat processing. This molar ratio becomes like this. More preferably, it is 2.0-200, More preferably, it is 2.5-150.

[3] acid-decomposable resins

In addition to the resin (P), the composition according to the present invention may further include a resin that is decomposed by the action of an acid and the dissolution rate for alkali water solubility increases, that is, an acid decomposable resin.

Acid-decomposable resins typically have a group (hereinafter also referred to as an acid-decomposable group) that decomposes under the action of an acid to form an alkali-soluble group. This resin may be provided with an acid-decomposable group in one of a main chain and a side chain, and may be provided in both of these. It is preferable that this resin is equipped with the acid-decomposable group in the side chain.

The acid-decomposable resin is disclosed in, for example, European Patent No. 254853, Japanese Patent Application Laid-Open No. 2-25850, Japanese Patent No. 3-223860, Japanese Patent No. 4-251259 and the like. It is obtained by reacting the precursor of leaving group or copolymerizing an alkali-soluble resin monomer to which the leaving group is bound by the action of an acid with various monomers.

As the acid-decomposable group, a group in which a hydrogen atom of an alkali-soluble group such as -COOH group and -OH group is removed by a group leaving by the action of an acid is preferable.

Specific examples and preferred examples of the acid-decomposable group include the same ones as "OY" in the resin (P).

Although it does not specifically limit as resin which has an alkali-soluble group mentioned above, For example, resin containing phenolic hydroxyl group and resin containing repeating unit which has carboxyl groups, such as (meth) acrylic acid and norbornenecarboxylic acid, is mentioned. have.

The resin containing a phenolic hydroxy group is preferably poly (o-hydroxystyrene), poly (m-hydroxystyrene), poly (p-hydroxystyrene) and copolymers thereof, and hydrogenated poly (hydroxystyrene). And hydroxystyrene structural units such as poly (hydroxystyrene) having a substituent represented by the following structure, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, and hydrogenated novolak resin Resin can be mentioned.

It is preferable that it is 170 Pa / sec or more, and, as for the alkali dissolution rate of these resin, measured at 23 degreeC using 2.38 mass% tetramethylammonium hydroxide (TMAH), it is more preferable that it is 330 Pa / sec or more.

As a monomer employable as a raw material of these resins, for example, alkylcarbonyloxystyrene (for example, t-butoxycarbonyloxystyrene), alkoxy styrene (for example, 1-alkoxyethoxystyrene or t-part) Methoxystyrene), and (meth) acrylic acid tertiary alkylesters (eg, t-butyl (meth) acrylate or 2-alkyl-2-adamantyl (meth) acrylate or dialkyl (1-adamantyl) ) (Methyl) (meth) acrylate).

When irradiating the composition according to the present invention with KrF excimer laser light, electron beam, X-ray or high energy ray (e.g. EUV) having a wavelength of 50 nm or less, the acid-decomposable resin preferably contains a repeating unit having an aromatic group. Do. In particular, it is preferable that hydroxystyrene is included as a repeating unit. As such resin, the copolymer of hydroxy styrene protected by the group which detach | desorbs by the action of hydroxy styrene and an acid, or the copolymer of hydroxy styrene and a (meth) acrylic-acid tertiary alkyl ester is mentioned, for example.

As acid-decomposable resin, resin which has a repeating unit represented by the said General formula (3) or (4) is especially preferable.

The acid-decomposable resin may have a repeating unit derived from another polymerizable monomer. As another polymerizable monomer, what was demonstrated as another polymerizable monomer which resin (P) may contain, for example is mentioned first. Moreover, content of the repeating unit derived from these other polymerizable monomers is generally 50 mol% or less based on all repeating units, Preferably it is 30 mol% or less.

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

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

The weight average molecular weight of the acid-decomposable resin is preferably polystyrene equivalent by GPC method (solvent: THF), preferably 50,000 or less, more preferably 1,000 to 20,000, and particularly preferably 1,000 to 10,000.

Preferably dispersion degree (Mw / Mn) of acid-decomposable resin is 1.0-3.0, More preferably, it is 1.05-2.0, More preferably, it is 1.1-1.7.

In addition, you may use acid-decomposable resin in combination of 2 or more types.

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

Moreover, when the composition by this invention contains resin other than resin (P) further, the content is 0.5-80 mass% based on the total solid of a composition, More preferably, it is 5-50 It is mass%, More preferably, it is 10-30 mass%.

[4] photoacid generators

Photoacid generators are compounds that generate acids by irradiation with actinic light or radiation. As a photo-acid generator, the well-known compound which generate | occur | produces an acid by irradiation of the actinic light or radiation used for the photoinitiator of photocationic polymerization, the photoinitiator of radical photopolymerization, the photochromic agent of pigment | dye, photochromic agent, microresist, etc., for example , And mixtures thereof can be appropriately selected and used. Examples thereof include sulfonium salts, iodonium salts and bis (alkylsulfonyldiazomethanes).

As a preferable example of a photoacid generator, the compound represented by the following general formula (ZI), (ZII), and (ZIII) is mentioned.

In General Formula (ZI), R ₂₀₁ , R _202, and R ₂₀₃ each independently represent an organic group. _{Carbon number} of the organic group as R <_201> , R <_202> and R <_203> is 1-30 pieces, for example, Preferably it is 1-20 pieces.

Two of R ₂₀₁ to R ₂₀₃ may be bonded to each other through a single bond or a linking group to form a ring. As a coupling group in this case, an ether bond, a thioether bond, an ester bond, an amide bond, a carbonyl group, a methylene group, and an ethylene group are mentioned, for example. Examples of the group formed by bonding of two of R ₂₀₁ to R ₂₀₃ include alkylene groups such as a butylene group and a pentylene group.

As a specific example of R <_201> , R <_202> and R <_203> , the corresponding group in compound (ZI-1), (ZI-2), or (ZI-3) mentioned later is mentioned.

X ⁻ represents a non-nucleophilic anion. Examples of X ⁻ include sulfonic acid anions, bis (alkylsulfonyl) amide anions, tris (alkylsulfonyl) methed anions, 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.

Expression of the AN3 AN1 ~, ₁ ~ Rc Rc ₃ represents an organic group independently. As this organic group, a C1-C30 thing is mentioned, for example, Preferably it is an alkyl group, an aryl group, or group in which several of these were connected via the coupling group. Furthermore, the linking group as, for example, a single bond, -O-, -CO ₂ - there may be mentioned -, -S-, -SO ₃ - and -SO ₂ N (Rd _1). Here, Rd ₁ may represent a hydrogen atom or an alkyl group, and may form a ring with the alkyl group or aryl group couple | bonded.

The organic group of Rc ₁ to Rc ₃ may be an alkyl group substituted in one 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 raise the acidity of the acid generated by light irradiation. Thereby, the sensitivity of actinic-ray-sensitive or radiation-sensitive resin composition can be improved. Rc ₁ to Rc ₃ may be bonded to another alkyl group, aryl group, or the like to form a ring.

Moreover, the sulfonic acid anion represented by following General formula (SA1) or (SA2) is mentioned as preferable X <^-> .

In formula (SA1),

Ar represents an aryl group and may further have substituents other than-(D-B) group.

n represents an integer of 1 or more. n becomes like this. Preferably it is 1-4, More preferably, it is 2-3, Most preferably, it is 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.

(SA2)

(SA2)

In formula (SA2),

Each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.

R ₁ and R ₂ each independently represent a group selected from a hydrogen atom, a fluorine atom, an alkyl group, and an alkyl group substituted with at least one fluorine atom, and in the case where a plurality of R ₁ and R ₂ are present, each of R ₁ and R ₂ may be the same as or different from each other; good.

L represents a single bond or a divalent linking group, and when there are a plurality of L's, they may be the same as or different from each other.

E represents a group having a cyclic structure.

x represents the integer of 1-20, y represents the integer of 0-10, z represents the integer of 0-10.

First, the sulfonic acid anion represented by formula (SA1) will be described in detail.

In formula (SA1), Ar is preferably an aromatic ring having 6 to 30 carbon atoms. Specifically, Ar is a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptylene ring, an indencene ring, a perylene ring, a pentacene ring, an acenaphthalene ring, a phenanthrene ring, anthracene ring, a 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, indole Lidine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carba Sol ring, phenanthridine ring, acridine ring, phenanthroline ring, thianthrene ring, chromen ring, xanthene ring, phenoxatiin ring, phenothiazine ring or phenazine ring. Especially, a benzene ring, a naphthalene ring, or an anthracene ring is preferable from a viewpoint of both roughness improvement and high sensitivity, and a benzene ring is more preferable.

When Ar has further substituents other than-(D-B) group, the following are mentioned as this substituent, for example. That is, as this substituent, Halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; Alkoxy groups such as methoxy, ethoxy and tert-butoxy groups; Aryloxy groups such as phenoxy group and p-tolyloxy group; Alkyl thioxy groups such as methyl thioxy group, ethyl thioxy group and tert-butyl thioxy group; Aryl thioxy groups, such as a phenyl thioxy group and p-tolyl thioxy group; Alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; Acetoxy group; Linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, dodecyl group and 2-ethylhexyl group; Branched alkyl groups; Alkenyl groups such as vinyl group, propenyl group and hexenyl group; Acetylene group; Alkynyl groups such as propynyl and hexynyl; Aryl groups such as phenyl group and tolyl group; Hydroxyl group; Carboxyl groups; And sulfonic acid groups. Especially, a linear alkyl group and a branched alkyl group are preferable from a viewpoint of roughness improvement.

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 an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a cycloalkyl group, for example. 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. As this branched alkyl group, for example, isopropyl group, tert-butyl group, tert-pentyl group, neopentyl group, sec-butyl group, isobutyl group, isohexyl group, 3,3-dimethylpentyl group and 2-ethyl Hexyl group is mentioned.

The cycloalkyl group as B may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. As a monocyclic cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group is mentioned, for example. As a polycyclic cycloalkyl group, for example, an adamantyl group, norbornyl group, bornyl group, campenyl group, decahydronaphthyl group, tricyclodecanyl group, tetracyclodecanyl group, camphoroyl group, dicyclohexyl group, and pineinyl group Can be mentioned.

When the alkyl group, alkenyl group, alkynyl group, aryl group or cycloalkyl group as B has a substituent, the following are mentioned as this substituent, for example. That is, as this substituent, Halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; Alkoxy groups such as methoxy, ethoxy and tert-butoxy groups; Aryloxy groups such as phenoxy group and p-tolyloxy group; Alkyl thioxy groups such as methyl thioxy group, ethyl thioxy group and tert-butyl thioxy group; Aryl thioxy groups, such as a phenyl thioxy group and p-tolyl thioxy group; Alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; Acetoxy group; Linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, dodecyl group and 2-ethylhexyl group; Branched alkyl groups; Cycloalkyl groups such as cyclohexyl group; Alkenyl groups such as vinyl group, propenyl group and hexenyl group; Acetylene group; Alkynyl groups such as propynyl and hexynyl; Aryl groups such as phenyl group and tolyl group; Hydroxyl group; Carboxyl groups; Sulfonic acid groups; And a carbonyl group. Especially, a linear alkyl group and a branched alkyl group are preferable from a viewpoint of coexistence of roughness improvement and high sensitivity.

Next, the sulfonic acid anion represented by 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. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. In addition, 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 C4F ₉ . Among these, a fluorine atom or CF ₃ are preferred, and most preferably a fluorine atom.

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. As an alkyl group which may be substituted by this fluorine atom, a C1-C4 thing is preferable. 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 And CF ₃ is particularly preferable.

In formula (SA2), 1-8 are preferable and, as for x, 1-4 are more preferable. 0-4 are preferable and, as for y, 0 is more preferable. 0-8 are preferable and, as for z, 0-4 are more preferable.

In formula (SA2), L represents a single bond or a divalent linking group. As the divalent linking group, e.g., -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO 2 - may be mentioned, an alkylene group, a cycloalkylene group and the alkenylene group . Among them, -COO-, -OCO-, -CO-, -O-, -S-, -SO- or -SO ₂ -are preferred, and -COO-, -OCO- or -SO ₂ -are more preferred. Do.

In formula (SA2), E represents a group having a ring structure. As E, group which has a cyclic aliphatic group, an aryl group, and a heterocyclic structure is mentioned, for example.

The cyclic aliphatic group as E may have a monocyclic structure or may have a polycyclic structure. As a cyclic aliphatic group which has a monocyclic structure, monocyclic cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group, are preferable. As a cyclic aliphatic group which has a polycyclic structure, polycyclic cycloalkyl groups, such as a norbornyl group, a tricyclo decanyl group, a tetracyclo decanyl group, a tetracyclo dodecanyl group, and an adamantyl group, are preferable. In particular, when E is used as a cyclic aliphatic group having a bulk structure of six or more members, the diffusibility in the film in the PEB (post-exposure heating) step is suppressed, and the resolution and EL (exposure latitude) can be further improved.

The aryl group as E is a benzene ring, a naphthalene ring, a phenanthrene ring, or an anthracene ring, for example.

The group which has a heterocyclic structure as E may have aromaticity, and does not need to have aromaticity. As a hetero atom contained in this group, a nitrogen atom or an oxygen atom is preferable. As a specific example of a heterocyclic structure, a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, a pyridine ring, a piperidine ring, a morpholine ring, etc. are mentioned. Especially, a furan ring, a thiophene ring, a pyridine ring, a piperidine ring, and a morpholine ring are preferable.

E may have a substituent. As this substituent, an alkyl group (linear, branched, cyclic may be sufficient, for example, C1-C12 is preferable), an aryl group (C6-C14 is preferable), a hydroxyl group, an alkoxy group, ester group, for example. , Amide group, urethane group, ureido group, thioether group, sulfonamide group and sulfonic acid ester group. Especially among these substituents, a branched alkyl group, a cyclic alkyl group, and an aryl group are preferable. Diffusion of the acid generated by having these substituents is suppressed, and improvement of resolution and exposure latitude can be expected.

As a photo-acid generator, you may use the compound which has two or more structures represented by general formula (ZI). For example, the compound represented by formula (ZI) R _{201 ~} R ₂₀₃ of at least one is the general formula (ZI) a compound having a structure that combines and one at least one of R _{201 ~} R ₂₀₃ of another compound represented by the It may be.

As a more preferable (ZI) component, the compound (ZI-1)-(ZI-4) demonstrated below is mentioned.

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

All of R _{201 to} R ₂₀₃ may be an aryl group, or a part of R _{201 to} R ₂₀₃ may be an aryl group, and the compound (ZI-1) may be an alkyl group other than these. In addition, when compound (ZI-1) contains several aryl groups, these aryl groups may mutually be same or different.

As a compound (ZI-1), a triarylsulfonium compound, a diarylalkylsulfonium compound, and an aryldialkylsulfonium compound are mentioned, for example.

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

As an alkyl group which compound (ZI-1) has as needed, a C1-C15 linear, branched or cycloalkyl group is preferable, For example, a methyl group, an ethyl group, a propyl group, n-butyl group, a sec-butyl group , t-butyl group, cyclopropyl group, cyclobutyl group and 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 hydroxy group and A phenylthio group is mentioned.

As a preferable substituent, a C1-C12 linear, branched or cyclic alkyl group, and a C1-C12 linear, branched or cyclic alkoxy group are mentioned. Especially preferable substituents are a C1-C6 alkyl group and a C1-C6 alkoxy group. The substituent may be substituted with any one of three R _{201 to} R ₂₀₃ , or may be substituted with all three. In the case where R _{201 to} R ₂₀₃ are phenyl groups, the substituent is preferably substituted at the p-position of the aryl group.

In addition, one or two of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may be an aryl group which may have a substituent, and a form in which the remaining groups are linear, branched or cyclic alkyl groups is also preferable. As a specific example of this structure, Paragraph 0141 of Unexamined-Japanese-Patent No. 2004-210670-the structure of 0153 can be mentioned.

At this time, specifically as said aryl group, it is the same as the aryl group as R <_201> , R <_202> and R <_203> , and a phenyl group or a naphthyl group is preferable. Moreover, it is preferable that an aryl group has either a hydroxyl group, an alkoxy group, or an alkyl group as a substituent. As a substituent, More preferably, it is a C1-C12 alkoxy group, 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 said remaining groups exist, these two may combine with each other and may form the ring structure.

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

In general formula (ZI-1A),

R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxy group, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy group or an alkoxycarbonyl group.

When two or more R <_14> exists, they represent an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group, or a cycloalkylsulfonyl group each independently.

R ₁₅ each independently represents an alkyl group or a cycloalkyl group. Two R _{15 's} may be bonded to each other to form a ring structure.

l represents the integer of 0-2.

r represents the integer of 0-8.

X <^-> represents a non-nucleophilic anion, For example, the same thing as X <^-> in general formula (ZI) is mentioned.

The alkyl group of R ₁₃ , R ₁₄ or R ₁₅ may be a straight chain alkyl group or a branched chain alkyl group. As this alkyl group, a C1-C10 thing is preferable, For example, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group , n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group and n-decyl group. Among these, a methyl group, an ethyl group, n-butyl group, and t-butyl group are especially preferable.

As R _13, a cycloalkyl group of R ₁₄ or R _15, for example the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo FIG decanyl, cyclopentenyl, cyclohexenyl and cyclooctadiene D. And a silyl group. Among these, cyclopropyl, cyclopentyl, cyclohexyl and cyclooctyl groups are particularly preferred.

As an alkyl group part of the alkoxy group of R <_13> or R <_14> , what was listed as an alkyl group of R <_13> , R <_14> or R <_15> is mentioned, for example first. As this alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, and n-butoxy group are especially preferable.

As the cycloalkyl group of R ₁₃ portion of the cycloalkyloxy groups may be, for example, the first listed as the cycloalkyl group of R _13, R ₁₄ or R _15. As this cycloalkyloxy group, a cyclopentyloxy group and a cyclohexyl oxy group are especially preferable.

As the alkoxy group of R ₁₃ parts of the alkoxycarbonyl group includes, for example, the first listed as the alkoxy group of R ₁₃ or R _14. As this alkoxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, and n-butoxycarbonyl group are especially preferable.

As the alkyl group of R ¹⁴ portion of the alkylsulfonyl group includes, for example, the first listed as an alkyl group of R _13, R ₁₄ or R _15. In addition, there may be mentioned that as a cycloalkyl cycloalkyl part of the alkylsulfonyl group of R _14, for example, first, listed as the cycloalkyl group of R _13, R ₁₄ or R _15. As these alkylsulfonyl groups or cycloalkylsulfonyl groups, methanesulfonyl group, ethanesulfonyl group, n-propanesulfonyl group, n-butanesulfonyl group, cyclopentanesulfonyl group and cyclohexanesulfonyl group are particularly preferable.

l is preferably 0 or 1, more preferably 1. r becomes like this. Preferably it is 0-2.

Each group of R ₁₃ , R ₁₄ or R ₁₅ may further have a substituent. As this substituent, For example, halogen atoms, such as a fluorine atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, a cycloalkyloxy group, an alkoxyalkyl group, a cycloalkyloxyalkyl group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an alkoxycarbon A carbonyloxy group and a cycloalkyloxycarbonyloxy group are mentioned.

The alkoxy group may be linear or branched. As this alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, etc. are mentioned, for example. C1-C20 thing is mentioned.

As a cycloalkyloxy group, C3-C20 things, such as a cyclopentyloxy group and a cyclohexyloxy group, are mentioned, for example.

The alkoxyalkyl group may be linear or branched. As this alkoxyalkyl group, C2-C21 things, such as a methoxymethyl group, an ethoxymethyl group, 1-methoxyethyl group, 2-methoxyethyl group, 1-ethoxyethyl group, and 2-ethoxyethyl group, are mentioned, for example. .

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. As this alkoxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, and t- C2-C21 things, such as a butoxycarbonyl group, are mentioned.

As a cycloalkyloxycarbonyl group, C4-C21 things, such as a cyclopentyloxycarbonyl group and cyclohexyloxycarbonyl, are mentioned, for example.

The alkoxycarbonyloxy group may be linear or branched. As this alkoxycarbonyloxy group, a methoxycarbonyloxy group, an ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i-propoxycarbonyloxy group, n-butoxycarbonyl octa, for example C2-C21 thing, such as a timing and a t-butoxycarbonyloxy group, is mentioned.

As a cycloalkyloxycarbonyloxy group, C4-C21 things, such as a cyclopentyloxycarbonyloxy group and a cyclohexyloxycarbonyloxy group, are mentioned, for example.

As a ring structure which two R <_15> couple | bonds and may form, together with S atom in general formula (ZI-1A), a 5-membered ring or a 6-membered ring, Especially preferably, a 5-membered ring (ie, tetrahydro thiophene ring) The structure to form is preferable.

This ring structure may further have a substituent. As this substituent, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group are mentioned, for example.

As R <_15> , the bivalent group in which a methyl group, an ethyl group, and two R <_15> combine with each other and form the tetrahydrothiophene ring structure with a sulfur atom is especially preferable.

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

Below, the specific example of a 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 represent an organic group containing no aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a hetero atom.

The organic group containing no aromatic ring as R _{201 to} R ₂₀₃ is, for example, 1 to 30 carbon atoms, and preferably 1 to 20 carbon atoms.

R _{201 to} R ₂₀₃ are each independently an alkyl group, a 2-oxoalkyl group, an alkoxycarbonylmethyl group, an allyl group, or a vinyl group. More preferably, they are a linear, branched or cyclic 2-oxoalkyl group or an alkoxycarbonyl methyl group, Especially preferably, they are a linear or branched 2-oxoalkyl group.

The alkyl group as R _{201 to} R ₂₀₃ may be any of linear, branched and cyclic, and as a preferred example, a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group or pen) And a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group or norbornyl group).

The 2-oxoalkyl group as R _{201 to} R ₂₀₃ may be any of linear, branched, and cyclic, and preferably groups having> C═O at the 2-position of the alkyl group.

Preferable examples of the alkoxy group in the alkoxycarbonylmethyl group as R _{201 to} R ₂₀₃ include an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group).

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

Two of R _{201 to} R ₂₀₃ may be bonded to each other to 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. Examples of R groups to R _{~ 201} formed by combining two of the dog ₂₀₃ may be selected from among an alkylene group (e.g., a butylene group or a pentylene group).

Next, the compound (ZI-3) will be described.

A compound (ZI-3) is a compound represented by the following general formula (ZI-3), and is a compound which has a phenacylsulfonium salt structure.

In the formula, each of R _1c to R _5c independently represents 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 represent 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. In addition, R _x and R _y may be bonded to each other to form a ring structure. These ring structures may contain an oxygen atom, a sulfur atom, an ester bond and / or an amide bond.

In the formula (ZI-3) X ^- X is in formula (ZI) ^- are as defined.

As a specific example of a compound (ZI-3), the compound described in the compound illustrated by stage 0047 and 0048 of Unexamined-Japanese-Patent No. 2004-233661, or paragraph 0040-0046 of Unexamined-Japanese-Patent No. 2003-35948 is mentioned. have.

Next, a compound (ZI-4) is demonstrated.

Compound (ZI-4) is a compound having a cation represented by the following General Formula (ZI-4). This compound (ZI-4) is effective for suppressing out gas.

In general formula (ZI-4),

R ¹ to R ¹³ each independently represent a hydrogen atom or a substituent. At least one of R ¹ to R ¹³ is preferably a substituent containing an alcoholic hydroxy group. In addition, an "alcoholic hydroxy group" means the hydroxy group couple | bonded with the carbon atom of an alkyl group here.

Z is a single bond or a divalent linking group.

When R <^1> -R <^13> is a substituent containing an alcoholic hydroxyl group, it is preferable that R <^1> -R <^13> is group represented by-(WY). Wherein Y is an alkyl group substituted with a hydroxy group, and W is a single bond or a divalent linking group.

Preferred examples of the alkyl group represented by Y include ethyl group, propyl group and isopropyl group. Y particularly preferably comprises a structure represented by -CH ₂ CH ₂ OH.

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

When R <^1> -R <^13> is a substituent containing an alcoholic hydroxyl group, carbon number contained becomes like this. Preferably it is 2-10 pieces, More preferably, it is 2-6 pieces, Especially preferably, it is 2-4 pieces.

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

The number of alcoholic hydroxy groups which the compound represented by general formula (ZI-4) has is 1-10 in total of all R <^1> -R <^13> , Preferably it is 1-6, More preferably, it is 1-3. .

When R ¹ to R ¹³ do not contain an alcoholic hydroxy group, examples of the substituent for R ¹ to R ¹³ include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, and a 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 (anyl Lino group), ammonia group, acyl amino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group , Heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocycle Azo group, imido group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, silyl group, hydrazino group, ureido group, boric acid group [-B (OH) ₂ ], phosphate group [ -OPO (OH) ₂ ], a sulfate group (-OSO ₃ H), and other known substituents.

When R ¹ to R ¹³ do not contain an alcoholic hydroxy 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, a 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, alkyl Thio group, arylthio group, sulfamoyl group, alkyl and arylsulfonyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, imido group, silyl group or ureido group.

When R ¹ to R ¹³ do not contain an alcoholic hydroxy 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, or an amino group. Carbonylamino group, alkoxycarbonylamino group, alkyl and arylsulfonylamino group, alkylthio group, sulfamoyl group, alkyl and arylsulfonyl group, alkoxycarbonyl group or carbamoyl group.

When R ¹ to R ¹³ do not contain an alcoholic hydroxy 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 two out of R <^1> -R <^13> may combine with each other, and may form the ring. These rings include aromatic and nonaromatic hydrocarbon rings and heterocycles. These rings may further combine to form a condensed ring.

Compound (ZI-4) preferably has a structure in which at least one of R ¹ to R ¹³ includes an alcoholic hydroxy group, and more preferably, at least one of R ⁹ to R ¹³ includes an alcoholic hydroxy group Have

Z represents a single bond or a divalent linking group as described above. As this bivalent coupling group, an alkylene group, arylene group, carbonyl group, sulfonyl group, carbonyloxy group, carbonylamino group, sulfonylamide group, ether group, thioether group, amino group, disulfide group, acyl group, Alkylsulfonyl group, -CH = CH-, an aminocarbonylamino group, and an aminosulfonylamino group are mentioned.

This divalent linking group may have a substituent. As these substituents, the thing similar to what was enumerated about R <^1> -R <^13> first is mentioned, for example.

Z is preferably a bond or group having no electron withdrawing properties such as a single bond, an alkylene group, an arylene group, an ether group, a thioether group, an amino group, -CH = CH-, an aminocarbonylamino group and an aminosulfonylamino group More preferably, they are a single bond, an ether group, or a thioether group, Especially preferably, they are a single bond.

Hereinafter, general formula (ZII) and (ZIII) are demonstrated.

In General Formulas (ZII) and (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group, or a cycloalkyl group. These aryl groups, alkyl groups and cycloalkyl groups may have a substituent.

Preferred examples of the aryl group as R ₂₀₄ to R ₂₀₇ include the same groups as listed above for R ₂₀₁ to R ₂₀₃ in the compound (ZI-1).

As a preferable example of the alkyl group and cycloalkyl group as R <_204> -R <_207> , the linear, branched, or cycloalkyl group listed about R <_201> -R <_203> in a compound (ZI-2) is mentioned first.

Further, in the general formula (ZII) and (ZIII) X ^- X is in formula (ZI) ^- is as defined and.

As another preferable example of a photoacid generator, the compound represented by the following general formula (ZIV), (ZV) or (ZVI) is mentioned.

In general formulas (ZIV) to (ZVI),

Ar ₃ and Ar ₄ each independently represent a substituted or unsubstituted aryl group.

R ₂₀₈ each independently represents an alkyl group, a cycloalkyl group or an aryl group in formulas (ZV) and (ZVI). These alkyl groups, cycloalkyl groups, and aryl groups may be substituted or may not be substituted.

It is preferable that these groups are substituted by the fluorine atom. This makes it possible to increase the strength of the acid generated by the photoacid generator.

R ₂₀₉ and R ₂₁₀ each independently represent an alkyl group, a cycloalkyl group, an aryl group or an electron withdrawing group. These alkyl groups, cycloalkyl groups, aryl groups, and electron withdrawing groups may or may not be substituted.

Preferred R ₂₀₉ includes a substituted or unsubstituted aryl group.

Preferred R _{210 includes an} electron withdrawing group. As this electron-withdrawing group, a cyano group and a fluoroalkyl group are mentioned preferably.

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

Moreover, the compound which has two or more structures represented by general formula (ZVI) as a photo-acid generator is also preferable. As such a compound, for example, a compound having an R ₂₀₉ or structure R ₂₁₀ are bonded to each other in the other one of the compound represented by R ₂₀₉ or R ₂₁₀ and the general formula (ZVI) of the compound represented by the general formula (ZVI) Can be mentioned.

As a photo-acid generator, the compound represented by general formula (ZI)-(ZIII) is more preferable, The compound represented by general formula (ZI) is still more preferable, A compound (ZI-1)-(ZI-3) is especially desirable.

Although the specific example of a photo-acid generator is shown below, the scope of the present invention is not limited to these.

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 using 2 or more types in combination, it is preferable to combine the compound which produces the 2 types of organic acids in which 2 or more whole atoms except the hydrogen atom generate | occur | produce.

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 0.5 to 30% by mass, more preferably based on the total solids of the composition. Preferably it is 1-20 mass%.

[5] solvents

The solvent that can be used when preparing the composition is not particularly limited as long as it dissolves each component. Examples thereof include alkylene glycol monoalkyl ether carboxylates (propylene glycol monomethyl ether acetate and the like) and alkylene glycol monoalkyl. Ether (propylene glycol monomethyl ether, etc.), lactic acid alkyl ester (ethyl lactate, methyl lactate, etc.), cyclic lactone (γ-butyrolactone, etc., preferably 4-10 carbon atoms), chain or cyclic ketone (2-hep Tanon, cyclohexanone, etc., Preferably it is 4-10 carbon atoms, Alkylene carbonate (ethylene carbonate, propylene carbonate, etc.), Alkyl carboxylic acid (The alkyl acetate, such as butyl acetate is preferable), and Alkoxy acetic acid alkyl ( Ethyl ethoxy propionate), and the like. As other usable solvents, there may be mentioned, for example, the solvents described later in US 2008/0248425 A1.

Of these solvents, alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, and ethyl lactate are particularly preferred.

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

As a solvent containing a hydroxyl group, alkylene glycol monoalkyl ether or lactic acid alkyl ester is preferable, and as a solvent which does not contain a hydroxyl group, alkylene glycol monoalkyl ether carboxylate is preferable. It is especially preferable to use the solvent whose 50 mass% or more of a solvent is propylene glycol monomethyl ether.

In addition, the usage-amount of a solvent is set so that the total solid content concentration of a composition may become 2.0 to 4.0 weight%, More preferably, it is 2.0 to 3.0 mass%.

[6] surfactants

The composition according to the present invention may further contain a surfactant. As this surfactant, a fluorine type and / or silicon type surfactant is especially preferable.

As this surfactant, Dainippon Ink and Chemicals, Inc., for example. Megafac F176 and Megafac R08 from OMNOVA, PF656 and PF6320 from Troy Chemical Industries Inc. Products of Troysol S-366, Sumitomo 3M Inc. Products of Florad FC430, and Shin-Akita Kasei K.K. The polysiloxane polymer KP-341 of a product is mentioned.

In addition, surfactants other than fluorine-based and / or silicon-based surfactants may be used. More specifically, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, etc. are mentioned.

In addition, well-known surfactant can be used suitably. As the surfactant that can be used, for example, the surfactants described after the specification of US Patent 2008/0248425 A1 can be given.

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 to 1% by mass, based on the total solids of the composition.

[7] dissolution inhibiting compounds

The composition according to the present invention may further contain a dissolution inhibiting compound having a molecular weight of 3000 or less (hereinafter, also referred to as a "dissolution inhibiting compound"), which is decomposed by the action of an acid to increase the solubility in the alkaline developer.

As this dissolution inhibiting compound, an alicyclic or aliphatic compound containing an acid-decomposable group such as a cholic acid derivative containing an acid-decomposable group described in Proceeding of SPIE, 2724, 355 (1996) is preferable in order not to lower the permeability of 220 nm or less. Do. As this acid-decomposable group, the thing similar to what was previously demonstrated about "OY" of resin (P) is mentioned, for example.

In addition, when exposing the composition by this invention by KrF excimer laser or irradiating with an electron beam, the compound containing the structure which substituted the phenolic hydroxyl group of the phenol compound by the acid-decomposable group as a dissolution inhibiting compound is preferable. It is preferable to contain 1-9 phenol skeletons, and, as for a phenol compound, it is more preferable to contain 2-6 pieces. 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 solids of the composition.

Although the specific example of a dissolution inhibiting compound is shown below, this invention is not limited to these.

[8] other additives

The composition according to the present invention may further contain a dye, a plasticizer, a photosensitizer, a light absorbent, a compound for promoting dissolution in a developer (hereinafter also referred to as a dissolution promoting compound), and the like. Moreover, the compound provided with the proton acceptor functional group described in Unexamined-Japanese-Patent No. 2006-208781, 2007-286574, etc. can also be used suitably.

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

The addition amount of these dissolution accelerating compounds is preferably 0 to 50% by mass, more preferably 5 to 30% by mass, based on the mass of the resin (P). It is preferable to make this addition amount 50 mass% or less from a viewpoint of suppressing image development residue, and preventing pattern distortion at the time of image development.

In addition, the said dissolution promoting compound can be easily referred to, for example, with reference to the methods described in Japanese Patent Application Laid-Open No. 4-122938, Japanese Patent Application Laid-Open No. 2-28531, US Pat. Can be synthesized.

[9] pattern formation methods

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. As for the thickness of this film | membrane, 0.02-0.1 micrometer is preferable. As a method of apply | coating on a board | substrate, spin coating is preferable and the rotation speed of 1000-3000 rpm is preferable.

For example, the composition is applied by a suitable coating method such as spinners and coaters onto substrates (such as silicon / silicon dioxide coatings, silicon nitride and chromium deposited quartz substrates, etc.) used in the manufacture of precision integrated circuit devices and the like. Thereafter, this is dried to obtain an actinic ray-sensitive or radiation-sensitive film (hereinafter also referred to as photosensitive film). Moreover, a well-known antireflection film can also be apply | coated beforehand.

Next, actinic light or a radiation is irradiated to this photosensitive film | membrane, Preferably it bakes (80-150 degreeC normally, More preferably, it is 90-130 degreeC), and develops. Thereby, a favorable pattern can be obtained. Then, using this pattern as a mask, etching treatment, ion implantation, and the like are appropriately performed to prepare a semiconductor fine circuit, an imprint mold structure, and the like.

In addition, about the detail of the process at the time of creating the imprint mold using the composition of this invention, Unexamined-Japanese-Patent No. 4,090,853, Unexamined-Japanese-Patent No. 2008-162101, and "The basis of nanoimprint and technology development are mentioned, for example. Application Development-Nanoimprint Substrate Technology and Latest Technology Development-Hirai Yoshihiko (Frontier Publishing). In addition, regarding the manufacturing method of the mold structure especially suitable for manufacture of an information recording medium, Unexamined-Japanese-Patent No. 4,049085 and Unexamined-Japanese-Patent No. 2008-162101 can be referred.

In the developing step, an alkaline developer is usually used. The developing method suitably uses known methods such as paddle formation, dipping and dynamic dispensing. Various alkali aqueous solutions are applicable as alkaline developing solution, Usually, tetramethylammonium hydroxide alkaline aqueous solution is used. An appropriate amount of alcohols and / or surfactants may be added to the alkaline developer.

The density | concentration of alkaline developing solution is 0.1-20 mass% normally. The pH of alkaline developing solution is 10.0-15.0 normally.

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

[Suzy]

First, monomers (M-1) to (M-9) shown below were synthesized. Furthermore, 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. The solution which melt | dissolved 3.35 mass parts lithium hydroxide monohydrate in 48 mass parts methanol was dripped at the obtained solution, and it stirred over 1 hour at room temperature. Thereafter, methanol was removed under reduced pressure to obtain a reaction product.

This reaction was redissolved in 55 parts by mass of dimethyl sulfoxide. Next, 12.2 mass parts of chloromethylstyrene (CMS-14, the product of SEIMI CHEMICAL CO., LTD.) Was added to this, and it stirred at 80 degreeC over 4 hours. Subsequently, ethyl acetate and saturated aqueous ammonium chloride solution were added thereto, followed by extraction and washing. The organic layer was concentrated and 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 = 8.4Hz, 1H), 7.90 (d, J = 8.7Hz, 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 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). Next, 0.015 mass part of camphorsulfonic acid was added to this solution, and it stirred at room temperature over 30 minutes. 0.1 mass part triethylamine was added to the reaction liquid, and the solvent was distilled off under reduced pressure, and it refine | purified using column chromatography. This obtained 12.6 mass parts of monomers (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)

15.2 parts by mass of monomers were prepared 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 ( M-3) was synthesized.

Synthesis Example 4: Synthesis of Monomer (M-4)

10.1 parts by mass of monomer (M-4) as in Synthesis Example 2, except that 2.4 parts by mass of 3,5-dihydroxy-2-naphthoic acid was used instead of 5 parts by mass of 2-cyclohexylethyl vinyl ether. Synthesized.

Synthesis Example 5: Synthesis of Monomer (M-5)

First, 6-vinyl-2-naphthol (m-5a) was synthesize | combined as follows. That is, 24 mass parts methyltriphenylphosphonium bromide and 130 mass parts toluene were added to 7.6 mass parts tert-butoxy potassium and 90 mass parts tetrahydrofuran, and it stirred at room temperature over 2 hours. 5.0 mass parts of 6-hydroxy-2-naphthoaldehyde was added to this reaction liquid, and it stirred further at room temperature over 4 hours. The reaction was extracted and washed with ethyl acetate and saturated aqueous ammonium chloride solution, and column chromatography purified using hexane / ethyl acetate. This obtained 2.6 mass parts 6-vinyl-2-naphthol (m-5a).

Next, the monomer (M-5) was synthesize | combined according to the following reaction schemes.

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

5 parts by mass of (m-5b) and 4.59 parts by mass of paratoluenesulfonyl chloride were dissolved in 50 parts by mass of pyridine and stirred at room temperature over 5 hours. The reaction was extracted and washed with ethyl acetate and saturated aqueous ammonium chloride solution, and column chromatography purified using hexane / ethyl acetate. This obtained 7.15 mass parts of said compounds (m-5c).

4.81 parts by mass of 4- (4-hydroxyphenyl) benzoic acid was dissolved in 60 parts by mass of methanol. The solution which melt | dissolved 0.94 mass parts lithium hydroxide monohydrate in 20 mass parts methanol was dripped at this solution, and it stirred at room temperature over 1 hour. Thereafter, methanol was removed under reduced pressure to obtain a reaction product.

This reaction was redissolved in 50 parts by mass of N-methylpyrrolidone. Next, 7.15 mass parts (m-5c) was added to this, and it stirred at 80 degreeC over 8 hours. Subsequently, ethyl acetate and saturated aqueous ammonium chloride solution were added thereto, followed by extraction and washing. The organic layer was concentrated, and then purified by column chromatography to obtain 5.1 parts by mass of monomer (M-5).

Synthesis Example 6 Synthesis of Monomer (M-6)

5 parts by mass of monomer (M-1) and 0.4 parts by mass of 4-dimethylaminopyridine were dissolved in 80 parts by mass of acetonitrile. 4.3 mass parts di-tert-butyl dicarbonate was added to the obtained solution, and it stirred at room temperature over 2 hours. Subsequently, chloroform and diluted hydrochloric acid aqueous solution were added to this, and extraction and washing were performed. 6.0 mass parts of monomers (M-6) were obtained by concentrating an organic layer.

Synthesis Example 7: Synthesis of Monomer (M-7)

The monomer (M-7) was synthesize | combined according to the following synthesis schemes.

Specifically, 400 mass parts acetonitrile was added to 5 mass parts 4-hydroxy indole, 5.64 mass parts succinic anhydride, and 38 mass parts triethylamine, and it refluxed over 16 hours. After distilling off the solvent, the residue was purified by column chromatography using hexane / ethyl acetate. This obtained 2.71 mass parts of compound (m-7a).

4 mass parts (m-7a) was dissolved in 100 mass parts methanol. The solution which melt | dissolved 0.72 mass parts lithium hydroxide monohydrate in 20 mass parts methanol was dripped at the obtained solution, and it stirred for 1 hour. The reaction was concentrated and redissolved in 100 parts by mass of N-methylpyrrolidone. 2.75 parts by mass of chloromethyl styrene (CMS-14, manufactured by SEIMI CHEMICAL CO., LTD.) Was added and stirred at 80 ° C. over 8 hours. Subsequently, ethyl acetate and saturated aqueous ammonium chloride solution were added thereto, followed by extraction and washing. The organic layer was concentrated and purified using column chromatography to obtain 4.25 parts by mass of compound (m-7b).

5 parts by mass of (m-7b) and 2.97 parts by mass of 2- (vinyloxy) ethylphenylcarbamate were dissolved in 100 parts by mass of propylene glycol monomethyl ether acetate (PGMEA). Next, 0.004 mass parts camphorsulfonic acid was added to the obtained solution, and the mixture was stirred at room temperature over 2 hours. 0.1 mass part triethylamine was added to the reaction liquid, and the solvent was distilled off under reduced pressure, and it refine | purified using column chromatography. This obtained 6.53 mass parts of monomers (M-7).

Synthesis Example 8: Synthesis of Monomer (M-8)

The monomer (M-8) was synthesize | combined according to the following synthesis schemes.

Specifically, 2.52 parts by mass of sodium hydride (oil, 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 over 1 hour. Subsequently, 5 mass parts chloromethylstyrene (CMS-14, the product of SEIMI CHEMICAL CO., LTD.) Was added, and it stirred at room temperature for 3 hours. The reaction solution was concentrated, ethyl acetate and saturated aqueous ammonium chloride solution were added, followed by extraction and washing. The organic layer was concentrated and purified using column chromatography to obtain 3.93 parts by mass of compound (m-8a).

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

Next, 17.58 parts by mass of the compound (m-8c) was obtained in the same manner as in Synthesis Example 1 except that 30.12 parts by mass (m-8b) was used instead of 12.2 parts by mass of chloromethyl styrene.

Next, 15.27 mass parts monomer (M-8) was obtained like synthesis example 2 except having used 12.89 mass parts (m-8c) instead of 10 mass parts of monomers (M-1).

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). Next, 0.015 mass part of camphorsulfonic acid was added to the obtained solution, and it stirred at room temperature over 1 hour. 0.1 mass part triethylamine was added to the reaction liquid, and the solvent was distilled off under reduced pressure, and it refine | purified using column chromatography. This obtained 12.1 mass parts monomers (M-9).

Next, resins were synthesized using these monomers.

Synthesis Example 10 Synthesis of Resin (P-1)

Resin (P-1) represented by following formula was synthesize | combined as follows.

That is, 3.86 mass parts of 1-methoxy-2-propanol were heated at 75 degreeC under nitrogen stream first. 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-methoxy-2-propanol, and 0.74 mass by stirring this liquid Negative 2,2'-azobisisobutyric acid dimethyl [V-601; Wako Pure Chemical Industries, Ltd. Product] was added dropwise over 4 hours. After completion of the dropwise addition, 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. Thereafter, 3.95 parts by mass of resin (P-1) was obtained by performing vacuum drying.

¹ H-NMR was measured for the obtained resin (P-1). This calculated the composition ratio (molar ratio) of resin (P-1). In addition, the weight average molecular weight (Mw: polystyrene conversion), number average molecular weight (Mn: polystyrene conversion), and dispersion degree (Mw / Mn, hereinafter "PDI") of resin (P-1) are also measured by GPC (solvent: THF) measurement. Was calculated. These results are shown in the above formulas and in Table 1 below.

Synthesis Example 11: Synthesis of Resin (P-2) to (P-8)>

Resins (P-2) to (P-8) were synthesized in the same manner as in Synthesis example 10. Structural unit used, its input amount (mass part), polymerization concentration (reaction liquid concentration: mass%), and the input amount of the polymerization initiator (mass part), and the composition ratio (molar ratio), weight average molecular weight and dispersion degree (PDI) of the obtained resin. Is shown in Table 1 below.

Hereinafter, a structure, a composition ratio, a weight average molecular weight, and dispersion degree are shown about each of resin (P-1)-(P-8).

[Mine generator]

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

Synthesis Example 12 PAG-1

(Synthesis of Tricyclohexylbenzene)

6.83 g of aluminum chloride was added to 20.0 g of benzene, and the mixture was cooled and stirred at 3 ° C, and 40.4 g of cyclohexyl chloride was slowly added dropwise. After dripping, it 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 degreeC. After further distilling under reduced pressure at 170 ° C, the mixture was cooled to room temperature and 50 ml of acetone was added 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 dropping, the mixture was stirred at room temperature for 5 hours, and 10 g of ice was added, followed by 40 g of a 50% aqueous sodium hydroxide solution. 20g of ethanol was further added, and after stirring at 50 degreeC for 1 hour, insoluble content was filtered off and distilled off under reduced pressure at 40 degreeC. 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 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, followed by extraction with chloroform. After the obtained organic layer was washed with water, the mixture was distilled off under reduced pressure at 40 ° C., and the obtained crystal was recrystallized with methanol / ethyl acetate solvent. This obtained 5.0g of compound 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, 1 H), 1.97-1.16 (m, 30 H).

[Basic compound]

As the basic compound, a compound represented by the following formula was used.

Surfactants and Solvents

The following were used as surfactant.

W-1: Megafac F176 from Dainippon Ink and Chemicals, Inc .; Fluorine

W-2: Megafac R08 (from Dainippon Ink and Chemicals, Inc .; fluorine and silicon based)

The following were used as a solvent.

S1: Propylene Glycol Monomethyl Ether Acetate (PGMEA)

S2: Propylene Glycol Monomethyl Ether (PGME)

[Examples 1-11 and Comparative Example 1]

Each component shown in following Table 2 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, the positive resist solution of the total solid concentration shown in Table 2 was prepared. In addition, the density | concentration of each component shown in Table 2 is a mass concentration based on the mass of all solid content.

Resist Evaluation

The prepared positive resist solution was uniformly coated on a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater. Next, heat drying was performed at 130 degreeC for 90 second using the hotplate. As a result, a resist film having a film thickness of 100 nm was formed.

This resist film was irradiated with an electron beam using an electron beam irradiation apparatus (HL750 manufactured by Hitachi, Ltd .; an acceleration voltage of 50 keV). Immediately after irradiation, it was heated on a hotplate at 120 ° C. for 90 seconds. Then, it developed for 60 second at 23 degreeC using the tetramethylammonium hydroxide aqueous solution of 2.38 mass% in concentration, and rinsed with pure water for 30 second, and dried. As a result, a line and space pattern (line: space = 1: 1) and an isolated line pattern (line: space = 1:> 100) were formed, respectively. In addition, below, the line and space pattern is abbreviated as L & S, and the isolated line pattern may be abbreviated as IL.

[Sensitivity]

The cross-sectional shape of each obtained pattern was observed using the scanning electron microscope (S-4800 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 called sensitivity (μC / cm ² ).

[definition]

The limit resolution (the minimum line width at which lines and spaces are separated and resolved) in the irradiation amount indicating the sensitivity was referred to as resolution (nm).

[Residual film rate (plasma etching resistance)]

A positive resist film with a film thickness of 100 nm was formed on the hexamethyldisilazane-treated wafer. This film was plasma-etched 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. And the remaining film ratio (%) was obtained by dividing the film thickness after this etching by the film thickness before etching, and 100 times. In addition, the larger the residual film ratio, the better the plasma etching resistance.

As shown in Table 2, the compositions according to Examples 1 to 11 had better sensitivity and resolution when forming IL patterns as compared with the compositions according to Comparative Example 1. In addition, the compositions according to Examples 1 to 11 were excellent in plasma etching resistance and resolution when forming L & S patterns.

Claims (8)

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

[Wherein, 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 including a plurality of aromatic rings, and the plurality of aromatic rings are condensed to form a polycyclic structure or connected to each other through a single bond. Y represents a group which is released by the action of a hydrogen atom or an acid, and when n ₁ is 2 or more, a plurality of Y may be the same as or different from each other. n ₁ represents the integer of 1-5.] The method of claim 1,
X is an actinic ray-sensitive or radiation-sensitive resin composition, characterized in that the structural unit represented by any one of the following general formula (X1) to (X6).

[In formula, when two or more R <^4> exists, each independently represents a monovalent substituent. R ⁵ represents a hydrogen atom, an alkyl group, a cycloalkyl group, or A ¹ above. n ₂ is an integer from 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 method of claim 1,
Y is a group represented by a hydrogen atom or the following general formula (2) actinic ray-sensitive or radiation-sensitive resin composition.

[Wherein, 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. Two or more of R ⁶ , R ⁷ , M and Q may be bonded to each other to form a ring.] The method of claim 1,
The resin is an actinic ray-sensitive or radiation-sensitive resin composition characterized in that it further comprises one or more of the repeating unit represented by the following general formula (3) and the repeating unit represented by the following general formula (4).

[Wherein, R ⁹ to R ¹⁴ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a cyano group. R ¹⁵ to R ¹⁷ each independently represent an alkyl group or a cycloalkyl group. Two or more 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 group leaving by the action of a hydrogen atom or an acid. L ³ represents a single bond or a divalent linking group.] The method of claim 1,
An actinic ray-sensitive or radiation-sensitive resin composition, which is exposed by electron beam, X-ray or EUV light. A film was formed using the actinic-ray-sensitive or radiation-sensitive resin composition of any one of Claims 1-5. The resist film characterized by the above-mentioned. Forming a film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5;
Exposing the film;
And developing the exposed film. The method of claim 7, wherein
The exposure is performed using an electron beam, X-rays or EUV light.