KR20110025105A - 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 a pattern using the same are provided to obtain a pattern with the superior focus degree of freedom. CONSTITUTION: An active ray-sensitive or radiation-sensitive resin composition includes a resin and a compound. The solubility of the resin with respect to an alkaline developing agent is increased. The compound is represented by a general formula 1-1 or a general formula 1-2. The compound generates acid based on the radiation of active ray-sensitive ray or radiation-sensitive ray. The resin includes a repeating unit with an acid depositing group.

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 used in the manufacturing of semiconductor substrates such as ICs, the production of circuit boards such as liquid crystals and thermal heads, and other lithography processes of photofabrication, and pattern forming methods using the same. It is about. In particular, the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition for immersion exposure, and a pattern forming method using the same, for exposing to a liquid immersion projection exposure apparatus having an ultraviolet light having a wavelength of 300 nm or less as a light source.

In addition, in this invention, "active light" or "radiation" means the bright 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 the present invention, light means actinic light or radiation.

With the miniaturization of semiconductor devices, shortening of the exposure light source and high aperture number (high NA) of the projection lens have progressed, and an exposure apparatus of NA 0.84 using an ArF excimer laser having a wavelength of 193 nm as a light source has been developed. These can be represented by the following formulas as are generally well known.

(Resolution) = k ₁ (λ / NA)

(Depth of focus) = ± k ₂ λ / NA ²

Is the wavelength of the exposure light source, NA is the numerical aperture of the projection lens, and k ₁ and k ₂ are coefficients related to the process.

In order to achieve higher resolution due to shorter wavelengths, an exposure machine using a F ₂ excimer laser having a wavelength of 157 nm as a light source has been studied. However, in order to shorten the wavelength, a lens material and a material used for a resist are used. Since it is very limited, the manufacturing cost and quality stabilization of an apparatus and a material are very difficult, and there exists a possibility that the exposure apparatus and resist which have sufficient performance and stability in the required period are not made.

As a technique for improving resolution in an optical microscope, a so-called immersion method is conventionally known in which a projection lens and a sample are filled with a liquid having a high refractive index (hereinafter also referred to as "immersion liquid").

This immersion effect is described above when λ ₀ is the wavelength in the exposure light air, and n is the refractive index of the immersion liquid with respect to air, θ is the convergence half angle of the light beam, and NA ₀ = sinθ. Resolution and depth of focus can be expressed by the following equation.

(Resolution) = k ₁ (λ ₀ / n) / NA ₀

(Depth of focus) = ± k ₂ · (λ ₀ / n) / NA ₀ ²

That is, the effect of immersion is equivalent to using an exposure wavelength whose wavelength is 1 / n. In other words, in the case of the projection optical system of the same NA, the depth of focus can be n times depending on the immersion. This is effective for all pattern shapes and can be combined with super-resolution techniques such as the phase shift method and the modified illumination method which are currently examined.

Patent examples 1 and 2 introduce examples of devices in which this effect is applied to the transfer of fine image patterns of semiconductor devices.

Recent advances in immersion exposure technology have been reported in Non-Patent Documents 1 to 3, Patent Documents 3 and 4, and the like.

When the ArF excimer laser is used as the light source, pure water (refractive index 1.44 at 193 nm) is considered to be the most promising liquid in terms of handling safety, transmittance at 193 nm and refractive index. In the case of using the F ₂ excimer laser as a light source, a solution containing fluorine has been studied from the balance between the transmittance and the refractive index at 157 nm, but a sufficient one has not yet been found from the viewpoint of environmental safety and the refractive index. From the degree of immersion effect and the degree of completion of the resist, the immersion exposure technique is considered to be mounted fastest in the ArF exposure machine.

After the resist for KrF excimer laser (248 nm), an image forming method called chemical amplification has been used as an image forming method of the resist in order to compensate for the decrease in sensitivity due to light absorption. Taking an example of a positive chemical amplification image forming method, an acid generator in an exposed portion is decomposed by exposure to generate an acid, and the generated acid is used as a reaction catalyst by post exposure baking (PEB). It is an image forming method in which an insoluble group is changed to an alkali soluble group and an exposure part is removed by alkali development.

Various compounds are also found about the acid generator which is a main component of a chemically amplified resist composition, and patent documents 5 and 6 disclose the resist composition containing a specific sulfonium salt compound as an acid generator.

Patent document 7 discloses a polyhydroxystyrene resin and an acid generator of 5 to 20% by mass in order to suppress high sensitivity, high resolution, good pattern shape, and line edge roughness in patterning by X-ray, electron beam, and EUV exposure. A positive resist composition containing is disclosed.

However, it is very difficult to find suitable combinations of resins, photoacid generators, additives, solvents, and the like used from the viewpoint of overall performance as a resist, and when forming a fine pattern such as a line width of 100 nm or less, ordinary dry exposure In particular, in liquid immersion exposure, there is a problem in that the originally designed pattern shape cannot be reproduced due to the roughness of the resist pattern sidewalls due to miniaturization, or the pattern shape is easily changed in response to focus fluctuations. have.

Japanese Patent Laid-Open No. 57-153433 Japanese Patent Laid-Open No. 7-220990 Japanese Patent Laid-Open No. 10-303114 International Publication No. 04/077158 Japanese Patent Laid-Open No. 10-232490 Japanese Patent Publication No. 2003-195489 Japanese Patent Publication No. 2004-271629

 International Journal of Optical Engineering (Proc. SPIE), 2002, Vol. 4688, p. 11  J. Vac. Sci. Tecnol. B 17 (1999)  International Journal of Optical Engineering (Proc. SPIE), 2000, Vol. 3995, Vol. 2

An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition which is effective in improving the roundness of a pattern and capable of forming a pattern having good focus margin, and a pattern forming method using the same.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, the present inventors came to complete this invention shown below.

<1> Resin whose solubility to alkaline developing solution increases by the action of (A) acid, and (B) by irradiation of actinic light or radiation represented by following General formula (1-1) or (1-2) An actinic ray-sensitive or radiation-sensitive resin composition comprising a compound that generates an acid, wherein the resin (A) contains a repeating unit having an acid-decomposable group, and the content rate of the repeating unit is all the repeating units in the resin (A). It is 45-75 mol% with respect to, and the actinic-ray-sensitive or radiation-sensitive resin composition characterized by the content rate of a compound (B) being 10-30 mass% based on the total solid of the said composition.

In general formula (1-1),

R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton.

When two or more R <_14> exists, they respectively independently represent the group which has an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group, a cycloalkylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, or a monocyclic or polycyclic cycloalkyl skeleton.

R _{15 's} each independently represent an alkyl group, a cycloalkyl group, a phenyl group, or a naphthyl group. However, the case where two R <_15> is a phenyl group at the same time is excluded. In addition, two R ₁₅ may be bonded to each other to form a ring.

l represents the integer of 0-2.

r represents the integer of 0-8.

X ⁻ represents a non-nucleophilic anion.

In general formula (1-2),

M represents an alkyl group, a cycloalkyl group, an aryl group or a benzyl group, and when it has a ring structure, the ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbon-carbon double bond.

R _1c and R _2c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.

R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

R _x and R _y may be bonded to each other to form a ring.

At least two of M, R _1c and R _2c may be bonded to each other to form a ring, and the ring structure may contain a carbon-carbon double bond.

X ⁻ represents a non-nucleophilic anion.

<2> The actinic ray-sensitive or radiation-sensitive resin composition according to <1>, further comprising a hydrophobic resin having at least one of a fluorine atom and a silicon atom.

<3> The actinic ray-sensitive or radiation-sensitive resin composition according to <1> or <2>, wherein the resin (A) further contains a repeating unit containing a lactone structure.

<4> The resin according to any one of <1> to <3>, wherein the resin (A) contains a repeating unit having an acid-decomposable group containing at least a monocyclic or polycyclic alicyclic structure as a repeating unit having an acid-decomposable group. Actinic ray-sensitive or radiation-sensitive resin composition.

<5> The actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <4>, wherein liquid immersion exposure is applied.

<6> It comprises the process of forming a film | membrane using the actinic-ray-sensitive or radiation-sensitive resin composition in any one of <1>-<5>, the process of exposing the said film, and the process of developing. Pattern formation method.

<7> The pattern formation method according to <6>, wherein the exposure is immersion exposure.

(Effects of the Invention)

According to the present invention, it has become possible to provide an actinic ray-sensitive or radiation-sensitive resin composition which is effective in improving the roundness of a pattern and capable of forming a pattern having a good focus margin, and a pattern forming method using the same. Moreover, the actinic-ray-sensitive or radiation-sensitive resin composition of this invention is suitable as a positive resist composition.

EMBODIMENT OF THE INVENTION Hereinafter, the best form for implementing this invention is demonstrated.

In addition, in description of group (atom group) in this specification, the description which is not describing substitution and unsubstitution includes what has a substituent with the thing which does not have a substituent. For example, an "alkyl group" includes 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.

In addition, unless otherwise indicated, "exposure" in this specification exposes not only the exposure by the ultraviolet rays, X-rays, EUV light, etc. which are represented by a mercury lamp, an excimer laser, but also the drawing also by particle beams, such as an electron beam and an ion beam. Include it in

[1] resins, which increase the dissolution rate in alkaline developer by the action of acid

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is a resin (hereinafter referred to as "resin (A)" or "acid-decomposable resin (A)") which has increased solubility in an alkaline developer by the action of an acid. It contains.

The acid-decomposable resin (A) has a group (hereinafter also referred to as an "acid-decomposable group") that is decomposed by the action of an acid on both the main chain or the side chain of the resin or both the main chain and the side chain to generate an alkali-soluble group.

The resin (A) is preferably insoluble or poorly soluble in an alkaline developer.

The acid-decomposable group preferably has a structure protected by a group in which the alkali-soluble group decomposes and detaches by the action of an acid.

As an alkali-soluble group, a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonyl imide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) Imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris ( Alkyl sulfonyl) methylene group etc. are mentioned.

Preferred alkali-soluble groups include carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol), and sulfonic acid groups.

Preferred groups as acid-decomposable groups are groups in which the hydrogen atoms of these alkali-soluble groups are substituted with a group which is separated by an acid.

Examples of the group detached by an acid include, for example, -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), and -C (R ₀₁ ) (R ₀₂ (OR ₃₉ ), and the like.

In the formula, each of R ₃₆ to R ₃₉ independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

R ₀₁ to R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

As an acid-decomposable group, Preferably it is a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group, etc. More preferably, it is a tertiary alkyl ester group.

As a repeating unit which has an acid-decomposable group which resin (A) may contain, the repeating unit represented with the following general formula (AI) is preferable.

In general formula (AI),

Xa ₁ represents a hydrogen atom, a methyl group which may have a substituent, or a group represented by -CH ₂ -R ₉ . R ₉ represents a hydroxy group or a monovalent organic group, and examples of the monovalent organic group include an alkyl group having 5 or less carbon atoms and an acyl group, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. Xa ₁ preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

T represents a single bond or a divalent linking group.

Rx _{1 to} Rx ₃ each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic).

At least two of Rx _{1 to} Rx ₃ may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the divalent linking group for T include an alkylene group, a -COO-Rt- group, and an -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkylene group.

T is preferably a single bond or a -COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a -CH ₂ -group or a-(CH ₂ ) ₃ -group.

The alkyl group of Rx ₁ ~Rx ₃ is preferably 1 to 4 carbon atoms such as methyl group, ethyl group, n- propyl group, isopropyl group, n- butyl group, an isobutyl group, a t- butyl group.

As the cycloalkyl group of Rx ₁ ~Rx ₃ cyclopentyl group, a cyclohexyl group, etc. The cycloalkyl group of monocyclic, norbornyl group, a tetracyclo decamethylene group, the tetracyclododecanyl group is also big, adamantyl preferably a polycyclic cycloalkyl group such as a group .

Examples of the cycloalkyl group formed by bonding at least two of Rx _{1 to} Rx ₃ to each other include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group. Polycyclic cycloalkyl groups are preferred.

It is preferable that Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the cycloalkyl group described above.

Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (C 1-4), a halogen atom, a hydroxyl group, an alkoxy group (C 1-4), a carboxyl group, an alkoxycarbonyl group (C 2-6), and the like. And C8 or less is preferable.

As for the content rate as the sum total of the repeating unit which has an acid-decomposable group, 45-75 mol% is preferable with respect to all the repeating units in resin (A), More preferably, it is 50-60 mol%. When the ratio of the acid-decomposable group is 45 mol% or more, since the collision between the generated acid and the acid-decomposable group can be sufficiently secured, the deprotection reaction proceeds efficiently even if the amount of generated acid changes due to the focus change or the like. Do. However, when the acid-decomposable group exceeds 75 mol%, since the excessive deprotection reaction proceeds even in the micro-exposure portion, dissolution contrast is hardly imparted, which tends to be disadvantageous for resist pattern formation. In addition, when the acid-decomposable group is less than 45 mol%, since the alkali-soluble group generated by the deprotection reaction is insufficient, the resolution of the resist tends to be low. When the acid-decomposable group is 50 to 60 mol%, the balance of the deprotection reaction probability and the dissolution contrast after the deprotection reaction is optimal, and the resist pattern shape is particularly preferable.

Although the specific example of the repeating unit which has a preferable acid-decomposable group is shown below, this invention is not limited to this.

In the specific examples, Rx and Xa ₁ represent a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each represent an alkyl group having 1 to 4 carbon atoms. Z represents a substituent containing a polar group, and when two or more exist, they are each independently. p represents 0 or a positive integer.

It is more preferable that resin (A) has a repeating unit represented by the following general formula (I) at least as a repeating unit represented by general formula (AI).

In formula (I),

R ₁ is ₁ and Xa consent in the formula (AI), similarly preferable specific examples, a methyl group or a hydroxymethyl group of a hydrogen atom, a methyl group, and trifluoromethyl.

R <_2> represents a C2 or more linear or branched alkyl group, It is preferable that it is C2-C4, An ethyl group, i-propyl group, n-propyl group, n-butyl group, sec-butyl group is mentioned.

R represents an atomic group necessary for forming an alicyclic structure together with carbon atoms. The alicyclic structure formed by R may be a monocyclic structure or a polycyclic structure. As monocyclic structure, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, etc. are preferable, As a polycyclic structure, an adamantyl group, diamantyl group, decahydronaphthyl group, norbornyl group , Tricyclodecanyl group, or tetracyclododecanyl is preferable.

In one embodiment, the resin (A) preferably has at least two of the repeating units represented by the general formula (I) as the repeating unit represented by the general formula (AI), and in another embodiment, the general formula It is preferable to have a repeating unit represented by (I) and the repeating unit represented by following General formula (II).

In general formula (II), R <_3> is synonymous with Xa <_1> in general formula (AI), and a preferable specific example is a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group similarly.

R ₄ , R ₅ , and R ₆ each independently represent an alkyl group or a cycloalkyl group. The alkyl group in R ₄ , R ₅ , R ₆ may be linear or branched, and may have a substituent. As an alkyl group, a C1-C4 thing, such as a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, is preferable.

The cycloalkyl group in R ₄ , R ₅ , R ₆ may be monocyclic or polycyclic, and may have a substituent. As a cycloalkyl group, polycyclic cycloalkyl groups, such as monocyclic cycloalkyl groups, such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclo decanyl group, a tetracyclo dodecanyl group, and an adamantyl group, are preferable.

It is preferable to illustrate below as a preferable combination at the time of using together the repeating unit which resin (A) has an acid-decomposable group. In the following formulae, each R independently represents a hydrogen atom or a methyl group.

It is preferable that resin (A) contains the repeating unit which has a lactone structure represented by the following general formula (III).

In formula (III),

A represents an ester bond (group represented by -COO-) or an amide bond (group represented by -CONH-).

When there are a plurality of R _{0 's} , each independently represents an alkylene group, a cycloalkylene group, or a combination thereof.

In the case where a plurality of Z's are present, they are each independently an ether bond, an ester bond, an amide bond, or a urethane bond.

Or urea bond

. Here, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, and an aryl group.

R ₈ represents a monovalent organic group having a lactone structure.

n is the number of repetition of the structure represented by -R ₀ -Z-, represents an integer of 1 to 5.

R ₇ represents a hydrogen atom, a halogen atom or an alkyl group.

The alkylene group and cycloalkylene group of R ₀ may have a substituent.

Z is preferably an ether bond or an ester bond, particularly preferably an ester bond.

The alkyl group of R ₇ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group and an ethyl group, and particularly preferably a methyl group. The alkyl group in R ₇ may be substituted, and examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom, mercapto group, hydroxy group, methoxy group, ethoxy group, isopropoxy group and t- Acetoxy groups, such as an alkoxy group, such as a butoxy group and a benzyloxy group, an acetyl group, and a propionyl group, are mentioned. R ₇ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

As a preferable linear alkylene group in R <_0> , C1-C10 linear alkylene is preferable, More preferably, it is C1-C5, For example, a methylene group, ethylene group, a propylene group, etc. are mentioned. . Preferable cycloalkylene is C1-C20 cycloalkylene, for example, cyclohexylene, cyclopentylene, norbornylene, adamantylene, etc. are mentioned. In order to express the effect of this invention, a linear alkylene group is more preferable, and a methylene group is especially preferable.

The substituent having a lactone structure represented by R ₈ is not limited as long as it has a lactone structure, and examples thereof include lactone structures represented by general formulas (LC1-1) to (LC1-17) described later. Particularly preferred is a structure represented by (LC1-4). In addition, n ₂ in (LC1-1) to (LC1-17) is more preferably 2 or less.

R ₈ is preferably a monovalent organic group having an unsubstituted lactone structure or a monovalent organic group having a lactone structure having a methyl group, cyano group, or alkoxycarbonyl group as a substituent, and a lactone structure having a cyano group as a substituent More preferred is a monovalent organic group having nolactone).

Although the specific example of the repeating unit which has group which has a lactone structure represented by general formula (III) below is shown, this invention is not limited to this.

In the following specific examples, R represents a hydrogen atom, an alkyl group which may have a substituent or a halogen atom, and preferably a hydrogen atom, a methyl group, a hydroxymethyl group or an acetoxymethyl group.

As a repeating unit which has a lactone structure, the repeating unit represented with the following general formula (III-1) is more preferable.

In general formula (III-1),

R <_7> , A, R <_0> , Z, and n are synonymous with the said general formula (III).

When there are a plurality of R _{9 's} , they each independently represent an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, a cyano group, a hydroxyl group or an alkoxy group, and when there are a plurality of them, two R _{9' s} may be bonded to each other to form a ring.

X represents an alkylene group, an oxygen atom or a sulfur atom.

m is the number of substituents and shows the integer of 0-5. It is preferable that m is 0 or 1.

As an alkyl group of R <_9> , a C1-C4 alkyl group is preferable, a methyl group and an ethyl group are more preferable, and a methyl group is the most preferable. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl groups. Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, and the like. As an alkoxy group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, butoxy group etc. are mentioned. These groups may have a substituent and halogen atoms, such as an alkoxy group, a cyano group, and a fluorine atom, such as a hydroxyl group, a methoxy group, and an ethoxy group, are mentioned as said substituent. R ₉ is more preferably a methyl group, cyano group or alkoxycarbonyl group, and more preferably cyano group.

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

When m is 1 or more, at least one R ₉ is preferably substituted at the α-position or β-position of the carbonyl group of the lactone, and particularly preferably at the α-position.

Although the specific example of the repeating unit which has group which has a lactone structure represented by general formula (III-1) is shown, this invention is not limited to this. In the following specific examples, R represents a hydrogen atom, an alkyl group which may have a substituent or a halogen atom, and preferably a hydrogen atom, a methyl group, a hydroxymethyl group or an acetoxymethyl group.

When containing two or more types of content rates of the repeating unit represented by General formula (III), 10-55 mol% is preferable with respect to all the repeating units in resin in total, More preferably, it is 20-50 mol%, More preferably Preferably it is 30-45 mol%.

Resin (A) may contain the repeating unit which has a lactone group other than the unit represented by General formula (III).

As the lactone group, any one can be used as long as it has a lactone structure. Preferably, the lactone group is a 5- to 7-membered ring lactone structure, and the other ring structure is condensed in the form of forming a bicyclo structure and a spiro structure to the 5- to 7-membered ring lactone structure, It is desirable to have. It is more preferable to have a repeating unit having a lactone structure represented by any one of the following General Formulas (LC1-1) to (LC1-17). In addition, the lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), (LC1-17), and specific lactones By using the structure, LWR and development defects are improved.

The lactone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and an acid decomposable. And the like can be mentioned. More preferably, they are a C1-C4 alkyl group, cyano group, and an acid-decomposable group. n ₂ represents an integer of 0 to 4. n ₂ is the substituent (Rb ₂₎ a plurality exists when two or more may be the same or different, or may form a ring by combining with each other the substituent (Rb ₂₎ to present a plurality.

As a repeating unit which has a lactone structure other than the unit represented by general formula (III), the repeating unit represented by the following general formula (AII ') is also preferable.

In general formula (AII '),

Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. As a preferable substituent is an alkyl group of Rb ₀ may be mentioned which may have a hydroxyl group, a halogen atom. Examples of the halogen atom of Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Preferably, they are a hydrogen atom, a methyl group, a hydroxymethyl group, and a trifluoromethyl group, and a hydrogen atom and a methyl group are especially preferable.

V represents a group having a structure represented by any one of General Formulas (LC1-1) to (LC1-17).

Although the specific example of the repeating unit which has lactone groups other than the unit represented by General formula (III) is illustrated below, this invention is not limited to these.

The following repeating unit is mentioned as a repeating unit which has lactone groups other than the unit represented by especially preferable general formula (III). By selecting the optimal lactone group, the pattern profile and the roughness dependency become good.

The repeating unit having a lactone group usually has an optical isomer, but any optical isomer may be used. Moreover, 1 type of optical isomers may be used individually, or several optical isomers may be mixed and used. When one type of optical isomer is mainly used, the optical purity (ee) is preferably 90 or more, more preferably 95 or more.

When the content rate of the repeating unit which has lactone other than the repeating unit represented by General formula (III) contains two or more types, 15-60 mol% is preferable with respect to all the repeating units in resin in total, More preferably, it is 20 It is -50 mol%, More preferably, it is 30-50 mol%.

In order to heighten the effect of this invention, it is also possible to use together 2 or more types of lactone repeating units chosen from general formula (III). When using together, it is preferable to select and use 2 or more types together from the lactone repeating unit whose n is 1 in general formula (III).

It is preferable that resin (A) has a repeating unit which has hydroxyl groups or cyano groups other than general formula (AI) and (III). This improves substrate adhesion and developer affinity. It is preferable that the repeating unit which has a hydroxyl group or a cyano group is a repeating unit which has an alicyclic hydrocarbon structure substituted by a hydroxyl group or a cyano group, and it is preferable that it does not have an acid-decomposable group. As an alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted by the hydroxyl group or the cyano group, an adamantyl group, diamantyl group, and norbornane group are preferable. As an alicyclic hydrocarbon structure substituted by the preferable hydroxyl group or cyano group, the partial structure represented by the following general formula (VIIa)-(VIId) is preferable.

In the general formulas (VIIa) to (VIIc),

R ₂ c to R ₄ c each independently represent a hydrogen atom, a hydroxyl group or a cyano group. Provided that at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c are hydroxyl groups, and the rest are hydrogen atoms. In general formula (VIIa), More preferably, _two of R < ₂ > c-R <_4> c are hydroxyl groups, and the remainder is a hydrogen atom.

As a repeating unit which has the partial structure represented by general formula (VIIa)-(VIId), the repeating unit represented by the following general formula (AIIa)-(AIId) is mentioned.

In General Formulas (AIIa) to (AIId), R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

R ₂ is R ₂ c~R c~R ₄ c ₄ c and agreement in the formula (VIIa) ~ (VIIc).

As for the content rate of the repeating unit which has a hydroxyl group or a cyano group, 5-40 mol% is preferable with respect to all the repeating units in resin (A), More preferably, it is 5-30 mol%, More preferably, it is 10-25 mol%. .

Although the specific example of the repeating unit which has a hydroxyl group or a cyano group is illustrated below, this invention is not limited to these.

Resin used for actinic-ray-sensitive or radiation-sensitive resin composition of this invention may have a repeating unit which has alkali-soluble group. As an alkali-soluble group, a carboxyl group, a sulfonamide group, a sulfonyl imide group, a bissulfonyl imide group, and the aliphatic alcohol (for example, hexafluoroisopropanol group) by which the (alpha) position was substituted by the electron withdrawing group are mentioned, A carboxyl group is mentioned. It is more preferable to have a repeating unit having By containing repeating units having alkali-soluble groups, the resolution in contact hole applications is increased. As the repeating unit having an alkali-soluble group, a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin such as a repeating unit of acrylic acid or methacrylic acid, or a repeating unit in which an alkali-soluble group is bonded to the main chain of the resin through a linking group, and The polymerization initiator or chain transfer agent which has alkali-soluble group is used at the time of superposition | polymerization, and what is introduce | transduced into the terminal of a polymer chain is preferable, and a linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure. Especially preferably, it is a repeating unit by acrylic acid and methacrylic acid.

As for the content rate of the repeating unit which has alkali-soluble group, 0-20 mol% is preferable with respect to all the repeating units in resin (A), More preferably, it is 3-15 mol%, More preferably, it is 5-10 mol%.

Although the specific example of the repeating unit which has alkali-soluble group is shown below, this invention is not limited to this.

In the specific examples, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

Resin (A) of this invention may further have an alicyclic hydrocarbon structure which does not have a polar group, and may have a repeating unit which does not show acid decomposability. As such a repeating unit, the repeating unit represented by general formula (IV) is mentioned.

In general formula (IV), R <_5> represents the hydrocarbon group which has at least 1 cyclic structure and does not have any of a hydroxyl group and a cyano group.

Ra represents a hydrogen atom, an alkyl group or a -CH ₂ -O-Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group or an acyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

The cyclic structure which R <_5> has contains a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. As a monocyclic hydrocarbon group, C3-C12 cycloalkenyl groups, such as a C3-C12 cycloalkyl group, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, and a cyclohexenyl group, are mentioned, for example. Can be. As a preferable monocyclic hydrocarbon group, it is a C3-C7 monocyclic hydrocarbon group, More preferably, a cyclopentyl group and a cyclohexyl group are mentioned.

The polycyclic hydrocarbon group includes a ring group hydrocarbon group and a temporary exchange hydrocarbon group, and examples of the ring group hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, and the like. As a temporary exchange type hydrocarbon ring, For example, bicyclic type, such as an evacuation, a boran, a norpinan, a norbornan, a bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Hydrocarbon rings, tricyclic hydrocarbon rings such as homobredan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [4.3.1.1 ^2,5 ] undecane ring, tetracyclo [4.4.0.1 ^{2 , 5.1 7,10} ] tetracyclic hydrocarbon rings such as dodecane, perhydro-1,4-methano-5,8-methanonaphthalene ring, and the like. In addition, condensed cyclic hydrocarbon rings include, for example, perhydronaphthalene (decarin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydrophenalene ring. The condensed ring which condensed two or more 5- to 8-membered cycloalkane ring of is also included.

As a preferable crosslinkable hydrocarbon ring, a norbornyl group, adamantyl group, bicyclooctanyl group, tricyclo [5, 2, 1, 0 ^2,6 ] decanyl group, etc. are mentioned. As a more preferable crosslinkable hydrocarbon ring, a norbornyl group and an adamantyl group are mentioned.

These alicyclic hydrocarbon groups may have a substituent and a halogen atom, an alkyl group, the hydroxyl group protected by the protecting group, the amino group protected by the protecting group, etc. are mentioned as a preferable substituent. Preferred halogen atoms include bromine, chlorine and fluorine atoms, and preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups. The alkyl group may further have a substituent, and examples of the substituent which may have a substituent include a halogen atom, an alkyl group, a hydroxyl group protected with a protecting group, and an amino group protected with a protecting group.

As a protecting group, an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group is mentioned, for example. As a preferable alkyl group, it is a C1-C4 alkyl group, As a preferable substituted methyl group, As a methoxymethyl, methoxy thiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl group, As a preferable substituted ethyl group, 1-ethoxyethyl And 1-methyl-1-methoxyethyl, and preferred acyl groups include aliphatic acyl groups and alkoxycarbonyl groups having 1 to 6 carbon atoms, such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, and pivaloyl groups. C1-C4 alkoxycarbonyl group etc. are mentioned.

As for the content rate of the repeating unit which has an alicyclic hydrocarbon structure which does not have a polar group, and does not show acid decomposability, 0-40 mol% is preferable with respect to all the repeating units in resin (A), More preferably, it is 0-20 mol%. .

Although the specific example of the repeating unit which has an alicyclic hydrocarbon structure which does not have a polar group and does not show acid decomposability is illustrated below, this invention is not limited to these. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

The resin (A) used in the composition of the present invention, in addition to the above-mentioned repeating structural unit, is for the purpose of controlling dry etching resistance, standard developer aptitude, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc. which are general necessary characteristics of resist. Can have multiple repeat structural units.

Although the repeating structural unit corresponding to the following monomer is mentioned as such a repeating structural unit, It is not limited to these.

Thereby, the performance calculated | required by resin used for the composition of this invention, especially,

(1) solubility in coating solvents,

(2) film forming property (glass transition point),

(3) alkali developability,

(4) membrane reduction (selection of hydrophilic, alkali-soluble groups),

(5) adhesion to the unexposed portion of the substrate,

(6) dry etching resistance,

Fine adjustment of such a thing becomes possible.

As such a monomer, for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like Can be mentioned.

In addition, as long as it is an addition-polymerizable unsaturated compound copolymerizable with the monomer corresponded to the said various repeating structural unit, you may copolymerize.

In the resin (A) used in the composition of the present invention, the molar ratio of each repeating structural unit is determined by the dry etching resistance of the resist, the standard developer aptitude, the substrate adhesion, the resist profile, and the resolving power, heat resistance, and sensitivity, which are general necessary capabilities of the resist. It is appropriately set to adjust the back.

When the composition of the present invention is for ArF exposure, the resin (A) used in the composition of the present invention preferably has no aromatic group from the point of transparency to ArF light, and the resin (A) is a monocyclic or polycyclic alicyclic hydrocarbon structure. It is preferred to have

In addition, it is preferable that resin (A) does not contain a fluorine atom and a silicon atom from a compatible viewpoint with hydrophobic resin (C) mentioned later.

As resin (A) used for the composition of this invention, Preferably, all the repeating units are comprised from the (meth) acrylate type repeating unit. In this case, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, and all of the repeating units are based on methacrylate repeating units and acrylate repeating units. Although either may be used, it is preferable that an acrylate type repeating unit is 50 mol% or less of all the repeating units. More preferably, alicyclic hydrocarbon structure substituted with 20-50 mol% of (meth) acrylate type repeating units which have an acid-decomposable group, 20-50 mol% of (meth) acrylate type repeating units which have a lactone group, a hydroxyl group, or a cyano group It is a copolymer polymer containing 5-30 mol% of (meth) acrylate type repeating units which have a further, and 0-20 mol% of other (meth) acrylate type repeating units.

When irradiating the composition of this invention with KrF excimer laser beam, an electron beam, an X-ray, and high energy ray (EUV etc.) of wavelength 50nm or less, it is preferable that resin (A) further has a hydroxystyrene type repeating unit. . More preferably, it is preferable to have an acid-decomposable repeating unit, such as a hydroxystyrene repeating unit, the hydroxystyrene repeating unit protected by the acid-decomposable group, and (meth) acrylic acid tertiary alkylester.

As a repeating unit which has a preferable hydroxy styrene-type acid-decomposable group, the repeating unit by t-butoxycarbonyloxy styrene, 1-alkoxy ethoxy styrene, (meth) acrylic acid tertiary alkyl ester, etc. are mentioned, for example. More preferred are repeating units of 2-alkyl-2-adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate.

Resin (A) of this invention can be synthesize | combined according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, the batch polymerization method which superposes | polymerizes by melt | dissolving and heating a monomeric species and an initiator in a solvent, and the dropping polymerization method which adds the solution of a monomeric species and an initiator dropwise to a heating solvent over 1 to 10 hours, etc. are mentioned. The dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, dimethylformamide and dimethyl. Amide solvents, such as acetamide, and the solvent which melt | dissolves the composition of this invention, such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone mentioned later, are mentioned. More preferably, it is preferable to superpose | polymerize using the same solvent as the solvent used for the photosensitive composition of this invention. As a result, generation of particles during storage can be suppressed.

It is preferable that a polymerization reaction is performed in inert gas atmosphere, such as nitrogen and argon. As a polymerization initiator, superposition | polymerization is started using a commercial radical initiator (azo initiator, peroxide, etc.). As a radical initiator, an azo initiator is preferable, and the azo initiator which has an ester group, a cyano group, and a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate) and the like. If desired, an initiator is added or added in portions, and after completion of the reaction, the initiator is added to a solvent to recover a desired polymer by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is usually 10 ° C to 150 ° C, preferably 30 ° C to 120 ° C, and more preferably 60 ° C to 100 ° C.

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

Dispersion degree (molecular weight distribution) is 1-3 normally, Preferably it is 1-2.6, More preferably, it is 1-2, Especially preferably, the thing of the range of 1.4-2.0 is used. The smaller the molecular weight distribution, the better the resolution and the resist shape, and the smoother the sidewall of the resist pattern, the better the roughness.

In this invention, 30-99 mass% is preferable in the total solid of the compounding ratio in the whole composition of resin (A), More preferably, it is 60-95 mass%.

In addition, the resin of this invention may be used by 1 type, and may use multiple together.

[2] compounds generating acids by irradiation with actinic radiation or radiation

The composition of this invention contains the compound (henceforth an "acid generator") which generate | occur | produces an acid by irradiation of actinic light or a radiation.

The composition of the present invention contains at least a compound represented by the following general formula (1-1) or (1-2) as an acid generator (hereinafter also referred to as "compound (B)"). The content rate of a compound (B) is 10-30 mass% based on the total solid of the composition of this invention, Preferably it is 18-30 mass%, More preferably, it is 20-26 mass%. By adding many compounds (B), there exists an effect which makes a resist pattern shape favorable.

These compounds can maintain a high transmittance with respect to ArF light having a wavelength of 193 nm of the film to be formed, even in the above-mentioned amount, and, for example, as a 100 nm film, have a transmittance with respect to light having a wavelength of 193 nm of 60% or more and 85% or less. You can do High transmittance for ArF light results in good performance in patterning by ArF light.

The transmittance | permeability with respect to the light of wavelength 193nm, for example, apply | coats an actinic ray sensitive or radiation sensitive resin composition on a quartz glass board | substrate by spin coating, prebaking is performed at 100 degreeC, and the film | membrane of thickness 100nm is formed. The absorbance at a wavelength of 193 nm of the film can be calculated and calculated by the Elastomer EPM-222 (manufactured by Jay-A-Ulam Co., Ltd.) or the like.

It is preferable to contain 50 mass%-100 mass% of the compound represented by general formula (1-1) or (1-2) in the total amount of an acid generator, and it is more preferable to contain 75 mass%-100 mass%. It is especially preferable to contain 95-100 mass%.

In general formula (1-1),

R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton.

When a plurality of R _{14 's} are present, each independently represents a group having an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a monocyclic or polycyclic cycloalkyl skeleton.

R ₁₅ each independently represents an alkyl group, a cycloalkyl group, a phenyl group or a naphthyl group. However, the case where two R <_15> is a phenyl group at the same time is excluded. Two R _{15 's} may be bonded to each other to form a ring.

l represents the integer of 0-2.

r represents the integer of 0-8.

X ⁻ represents a non-nucleophilic anion.

In general formula (1-2),

M represents an alkyl group, a cycloalkyl group, an aryl group or a benzyl group, and when it has a ring structure, the ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbon-carbon double bond.

R _1c and R _2c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.

R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

R _x and R _y may be bonded to each other to form a ring. At least two of M, R _1c and R _2c may be bonded to each other to form a ring, and the ring structure may contain a carbon-carbon double bond.

X ⁻ represents a non-nucleophilic anion.

In general formula (1-1), as an alkyl group of R <_13> , R <_14> and R <_15> , it is linear or branched, and it is preferable that it is C1-C10, and 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- Ethyl hexyl group, n-nonyl group, n-decyl group, etc. are mentioned. Among these alkyl groups, methyl group, ethyl group, n-butyl group, t-butyl group and the like are preferable.

Examples of the cycloalkyl group of R ₁₃ , R ₁₄ and R ₁₅ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecanyl, cyclopentenyl, cyclohexenyl, cyclooctadienyl, and adamant A methyl group etc. are mentioned, Especially cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl is preferable.

As an alkoxy group of R <_13> and R <_14> , it is linear or branched, and C1-C10 is preferable, For example, a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy Period, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, n-pentyloxy group, neopentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, 2-ethylhexyloxy group, n-nonyloxy group, n-decyloxy group, etc. are mentioned. Among these alkoxy groups, methoxy group, ethoxy group, n-propoxy group, n-butoxy group and the like are preferable.

As an alkoxycarbonyl group of R <_13> and R <_{14>, it} is linear or branched, C2-C11 is preferable, For example, a methoxycarbonyl group, an ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n -Butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t-butoxycarbonyl group, n-pentyloxycarbonyl group, neopentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n- Octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, n-nonyloxycarbonyl group, n-decyloxycarbonyl group, etc. are mentioned. Among these alkoxycarbonyl groups, methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group and the like are preferable.

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

R ₁₃ and R ₁₄ monocyclic or polycyclic cycloalkyloxy groups is preferably not less than decimal 7 as the bullet of and and a small number of bullets more preferably less than 715, it is also desirable to have a framework of the monocyclic cycloalkyl. Monocyclic cycloalkyloxy group having 7 or more carbon atoms is cycloalkyloxy such as cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cyclofutyloxy group, cyclooctyloxy group and cyclododecanyloxy group To the group, optionally, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl, 2-ethylhexyl, isopropyl, sec-butyl, t-butyl, iso- Alkyl groups such as amyl groups, hydroxyl groups, halogen atoms (fluorine, chlorine, bromine, iodine), nitro groups, cyano groups, amide groups, sulfonamide groups, methoxy groups, ethoxy groups, hydroxyethoxy groups, propoxy groups, hydroxides Alkoxy groups such as oxypropoxy group, butoxy group, alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group, acyl groups such as formyl group, acetyl group and benzoyl group, acyloxy groups such as acetoxy group and butyryloxy group, Substituents such as carboxyl groups And cycloalkyloxy groups having a monocyclic, indicates that the small number of bullets combined with any of the substituents on the cycloalkyl group 7 or more.

In addition, examples of the polycyclic cycloalkyloxy group having 7 or more carbon atoms include norbornyloxy group, tricyclodecanyloxy group, tetracyclodecanyloxy group, adamantantyloxy group and the like, and these may have the substituents described above. .

As the alkoxy group having a monocyclic or polycyclic cycloalkyl skeleton of R ₁₃ and R ₁₄ , a total carbon number is preferably 7 or more, more preferably 7 to 15 carbon atoms, more preferably an alkoxy group having a monocyclic cycloalkyl skeleton. It is preferable. An alkoxy group having a monocyclic cycloalkyl skeleton having 7 or more carbon atoms is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptoxy, octyloxy, dodecyloxy, 2-ethylhexyloxy, The alkoxy group, such as isopropoxy, sec-butoxy, t-butoxy, and iso-amyloxy, substituted the monocyclic cycloalkyl group which may have the above-mentioned substituent, and shows that the total carbon number which the substituent also included is 7 or more. For example, a cyclohexyl methoxy group, a cyclopentyl ethoxy group, a cyclohexyl ethoxy group, etc. are mentioned, A cyclohexyl methoxy group is preferable.

Moreover, as an alkoxy group which has a polycyclic cycloalkyl frame | skeleton of 7 or more carbon atoms, a norbornyl methoxy group, norbornyl ethoxy group, a tricyclo decanyl methoxy group, a tricyclo decanyl ethoxy group, and a tetracyclo decanyl methoxy group And tetracyclodecanylethoxy group, adamantantylmethoxy group, adamantanetethoxy group, and the like, and among these, norbornylmethoxy group and norbornylethoxy group are preferable. These may have the substituent mentioned above.

As an alkyl group of the alkylcarbonyl group of R <_14>, the specific example similar to the alkyl group as R <_13> -R <_15> mentioned above is mentioned.

The alkylsulfonyl group and the cycloalkylsulfonyl group of R ₁₄ are linear, branched and cyclic, and those having 1 to 10 carbon atoms are preferable. For example, methanesulfonyl group, ethanesulfonyl group, n-propanesulfonyl group, n- Butanesulfonyl group, tert-butanesulfonyl group, n-pentanesulfonyl group, neopentanesulfonyl group, n-hexanesulfonyl group, n-heptanesulfonyl group, n-octanesulfonyl group, 2-ethylhexanesulfonyl group, n-nonanesulfo And a n-decanesulfonyl group, a cyclopentanesulfonyl group, a cyclohexanesulfonyl group, and the like. Among these alkylsulfonyl groups and cycloalkylsulfonyl groups, methanesulfonyl group, ethanesulfonyl group, n-propanesulfonyl group, n-butanesulfonyl group, cyclopentanesulfonyl group, cyclohexanesulfonyl group and the like are preferable.

Each of the groups may have a substituent, and examples of the substituent include a halogen atom (for example, a fluorine atom), 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. Can be mentioned.

As said 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, And a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms such as a cyclopentyloxy group and a cyclohexyloxy group.

Examples of the alkoxyalkyl group include straight chains having 2 to 21 carbon atoms such as methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 2-methoxyethyl group, 1-ethoxyethyl group and 2-ethoxyethyl group, A branched or cyclic alkoxyalkyl group etc. are mentioned.

As said alkoxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, t- And C2-C21 linear, branched or cyclic alkoxycarbonyl groups such as butoxycarbonyl group, cyclopentyloxycarbonyl group and cyclohexyloxycarbonyl.

As said alkoxycarbonyloxy group, a methoxycarbonyloxy group, an ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i-propoxycarbonyloxy group, n-butoxycarbonyl octa, for example Linear, branched or cyclic alkoxycarbonyloxy groups having 2 to 21 carbon atoms such as a time period, a t-butoxycarbonyloxy group, a cyclopentyloxycarbonyloxy group, and a cyclohexyloxycarbonyloxy group; Can be.

As a ring structure which two R <_15> may combine with each other, the 5- or 6-membered ring which two bivalent R <_15> forms with the sulfur atom in General formula (1-1), Especially preferably, 5-membered Ring (that is, tetrahydrothiophene ring) may be mentioned, and may be condensed with an aryl group or a cycloalkyl group. The divalent R ₁₅ may have a substituent, and examples of the substituent include 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. As R <_15> in General formula (1-1), a methyl group, an ethyl group, a naphthyl group, the bivalent group in which two R <_15> couple | bonds with each other, and forms the tetrahydrothiophene ring structure with a sulfur atom is preferable.

As a substituent which R <_13> and R <_14> may have, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, and a halogen atom (especially a fluorine atom) is preferable.

As l, 0 or 1 is preferable and 1 is more preferable.

As r, 0-2 are preferable.

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

Next, General formula (1-2) is demonstrated.

In the formula, R _1c and R _2c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.

R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

M represents an alkyl group, a cycloalkyl group, an aryl group or a benzyl group, and when it has a ring structure, the ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbon-carbon double bond.

R _x and R _y may be bonded to each other to form a ring. In addition, at least two of M, R _1c, and R _2c may be bonded to each other to form a ring, and the ring structure may contain a carbon-carbon double bond.

The alkyl group as M may be either a straight chain or a branch, for example, an alkyl group having 1 to 20 carbon atoms, preferably a straight and branched alkyl group having 1 to 12 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, and iso A propyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, and 2-ethylhexyl group are mentioned.

The cycloalkyl group as M is a cyclic alkyl group having 3 to 12 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclodecyl group.

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

Each group as M may have a cycloalkyl group, an alkoxy group, a halogen atom, a phenylthio group, etc. as a substituent. The cycloalkyl group and aryl group as M may further have an alkyl group as a substituent. As for carbon number of a substituent, 15 or less are preferable.

When M is a phenyl group, it is preferable to have at least 1 linear, branched, cyclic alkyl group, linear, branched, cyclic alkoxy group, or phenylthio group as a substituent, More preferably, the sum of carbon number of a substituent is 2-15. Thereby, solvent solubility improves more and generation | occurrence | production of a particle is suppressed at the time of storage.

The alkyl group as R _1c and R _2c includes, for example, an alkyl group having 1 to 12 carbon atoms, preferably a straight and branched alkyl group having 1 to 5 carbon atoms (for example, a methyl group, an ethyl group, a straight chain or a branched propyl group).

The cycloalkyl group as R _1c and R _2c is, for example, a cycloalkyl group having 3 to 12 carbon atoms, preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclodecyl group, or the like. Can be mentioned.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.

As an aryl group as R <_1c> and R <_2c> , Preferably it is C5-C15, For example, a phenyl group and a naphthyl group are mentioned.

As a ring structure formed by combining at least 2 of M, R <_1c>, and R <_2c> , Preferably it is a 3-12 membered ring, More preferably, it is a 3-10 membered ring, More preferably, it is a 3-6 membered ring. The ring skeleton may have a carbon-carbon double bond.

When R _1c and R _2c are bonded to each other to form a ring, as the group formed by R _1c and R _2c bonding, an alkylene group having 2 to 10 carbon atoms is preferable. For example, an ethylene group, a propylene group, a butylene group, a pentyl group And a hexylene group. In addition, the ring formed by bonding of R _1c and R _2c may have a hetero atom such as an oxygen atom in the ring.

Alkyl groups as R _x and R _y include the same alkyl groups as R _1c and R _2c .

As a cycloalkyl group, a C3-C8 cycloalkyl group is preferable, for example, a cyclopentyl group, a cyclohexyl group, etc. are mentioned.

2-oxoalkyl group is group which has> C = O at the 2nd position of the alkyl group as R <_1c> and R < _2c >.

The alkoxy group in the alkoxycarbonylalkyl group may be any of linear, branched or cyclic ones, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear and branched alkoxy group having 1 to 5 carbon atoms (for example, methoxide). A time period, an ethoxy group, a linear or branched propoxy group, a linear or branched butoxy group, a linear or branched pentoxy group, and a C3-C8 cyclic alkoxy group (for example, a cyclopentyloxy group, a cyclohexyloxy group) can be mentioned. have. Moreover, about the alkyl group in an alkoxycarbonylalkyl group, a C1-C12 alkyl group, Preferably, a C1-C5 linear chain (for example, a methyl group and an ethyl group) is mentioned.

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

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

As a ring structure in which R _x and R _y may be bonded to each other, divalent R _x and R _y (for example, methylene group, ethylene group, propylene group, etc.) are formed together with sulfur atoms in the general formula (1-2). And a 5- or 6-membered ring, particularly preferably a 5-membered ring (that is, tetrahydrothiophene ring).

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

As a cation of the compound represented by General formula (1-2) of this invention, the following specific examples are mentioned.

X <^-> in general formula (1-1) and (1-2) represents a non-nucleophilic anion, Preferably it is a sulfonic acid anion, a carboxylic acid anion, a bis (alkylsulfonyl) amide anion, and a tris (alkylsulfonyl) ) Methed anion, BF _4- , PF _6- , SbF ₆ -and the like, and are preferably organic anions containing carbon atoms.

As a preferable organic anion, the organic anion shown by a following formula is mentioned.

Rc ₁ represents an organic group.

Examples of the organic group in Rc ₁ include those having ₁ to 30 carbon atoms, preferably an alkyl group which may have a substituent, an aryl group, or a plurality of these monovalent single bonds, -O-, -CO _2- , -S And groups connected by a linking group such as-, -SO _3- , or -SO ₂ N (Rd ₁ )-.

Rd ₁ represents a hydrogen atom or an alkyl group.

Rc ₃ , Rc ₄ and Rc ₅ each independently represent an organic group.

Rc _3, Rc _4, preferably used as the organic group of Rc ₅ are like those preferred organic groups in Rc _1, and most preferably a perfluoroalkyl group having 1 to 4 carbons.

Rc ₃ and Rc ₄ may be bonded to each other to form a ring. Examples of the group formed by bonding of Rc ₃ and Rc ₄ include an alkylene group and an arylene group. Preferably it is a C2-C4 perfluoroalkylene group.

The organic group of Rc ₁ , Rc _{3 to} Rc ₅ is most preferably a phenyl group substituted with an alkyl group, a fluorine atom, or a fluoroalkyl group substituted in the 1 position with a fluorine atom or a fluoroalkyl group. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by light irradiation is increased, and the sensitivity is improved.

Moreover, as X <^-> , the anion represented by the following general formula (A1) is mentioned.

In general formula (A1), R represents a hydrogen atom or an organic group, Preferably it is a C1-C40 organic group, More preferably, it is a C3-C20 organic group, and is represented by following formula (A1a) Most preferred.

As an organic group of R, it is good to have one or more carbon atoms, Preferably the atom couple | bonded with the oxygen atom in the ester bond represented by general formula (A1) is a carbon atom, For example, an alkyl group, a cycloalkyl group, an aryl group, The aralkyl group and the group which has a lactone structure can be mentioned, You may have heteroatoms, such as an oxygen atom and a sulfur atom, in a chain. Moreover, you may have these as a substituent mutually and may have substituents, such as a hydroxyl group, an acyl group, an acyloxy group, an oxy group (= O), and a halogen atom.

In formula (A1a), Rc represents a C3-C30 monocyclic or polycyclic cyclic organic group which may contain cyclic ether, cyclic thioether, cyclic ketone, cyclic carbonate, lactone, and lactam structure. Y is a hydroxyl group, a halogen atom, a cyano group, a carboxyl group, a C1-C10 hydrocarbon group, a C1-C10 hydroxyalkyl group, a C1-C10 alkoxy group, a C2-C10 acyl group, a C2-C10 An alkoxycarbonyl group, a C2-C10 acyloxy group, a C2-C10 alkoxyalkyl group, and a C1-C8 halogenated alkyl group are shown. It is m = 0-6, and when two or more Y exists, they may mutually be same or different. n = 0-10.

The total number of carbon atoms constituting the R group represented by formula (AIa) is preferably 40 or less.

It is preferable that n = 0-3 and Rc is a C7-C16 monocyclic or polycyclic cyclic organic group.

Moreover, as X <^-> , the anion corresponding to the acid represented by the following general formula (A2) is mentioned.

In the formula,

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

R ¹ and R ² each independently 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, they may be the same or different.

L represents a single bond or a divalent linking group, and in the case where a plurality of L's are present, L may be the same or different.

A 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.

General formula (A2) is demonstrated in more detail.

As an alkyl group in the alkyl group substituted with the fluorine atom of Xf, Preferably it is C1-C10, More preferably, it is C1-C4. Moreover, it is preferable that the alkyl group substituted by the fluorine atom of Xf is a perfluoroalkyl group.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specifically, fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , CH ₂ CH ₂ include a C ₄ F _9, and, particularly preferably a fluorine atom, CF _3.

As an alkyl group in the alkyl group of R <^1> , R <^{2> and} the alkyl group substituted by at least 1 fluorine atom, a C1-C4 thing is preferable. More preferably, they are a C1-C4 perfluoroalkyl group. Specifically, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , CH ₂ CH ₂ C ₄ F ₉ And CF ₃ is particularly preferable.

0-4 are preferable and, as for y, 0 is more preferable. 1-8 are preferable and, as for x, 1-4 are especially preferable. z is preferably 0 to 8, and particularly preferably 0 to 4.

Is not particularly limited as the divalent linking group of L, -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO 2 -, an alkylene group, a cycloalkylene group, an alkenylene A lengi and the like. Among these, -COO-, -OCO-, -CO-, and -O- are preferable and -COO- and -OCO- are more preferable.

The group having a cyclic structure of A is not particularly limited as long as it has a cyclic structure, and includes an alicyclic group, an aryl group, and a group having a heterocyclic structure (not only having aromaticity but also having no aromaticity), and examples For example, tetrahydropyran ring and lactone ring structure are included, etc. are mentioned.

As an alicyclic group, monocyclic or polycyclic may be sufficient, and monocyclic cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group, norbornyl group, tricyclo decanyl group, tetracyclo decanyl group, tetracyclo dodecanyl group, and adamantyl group Polycyclic cycloalkyl groups, such as these, are preferable. Among these, alicyclic groups having a bulky structure having a carbon number of 7 or more of a norbonyl group, tricyclodecanyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group are diffused in the film in the PEB (post-exposure heating) step. It is possible to suppress the sex and is preferable from the viewpoint of MEEF improvement.

Examples of the aryl group include a benzene ring, naphthalene ring, phenanthrene ring, and anthracene ring. Among them, naphthalene having low absorbance is preferable from the viewpoint of light absorbance at 193 nm.

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

The group which has the said cyclic structure may have a substituent, As said substituent, an alkyl group (any linear, branched, cyclic may be sufficient, C1-C12 is preferable), an aryl group (C6-C14 is preferable), and a hydroxyl group. , Alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, sulfonamide group, sulfonic acid ester group and the like.

As counter ion represented by X <^-> , it is especially preferable to have a structure represented by following General formula (III).

It is preferable that the counter anion represented by said general formula (II) is a structure represented by the following general formula (III).

In general formula (III),

A represents an oxygen atom, a nitrogen atom, or a carbon atom.

R <_2> represents a fluorine atom, the alkyl group which may have a substituent, the cycloalkyl group which may have a substituent, or the aryl group which may have a substituent.

N = 1, m = 0 when A is an oxygen atom, n + m = 2 when A is a nitrogen atom, n = 1 or 2, m = 0 or 1 when A is a carbon atom, and n + m = 3 when A is a carbon atom It is an integer of n = 1-3, and an integer of m = 0-2. When n is 2 or more, R ₁ may be the same or different, and R ₁ may be bonded to each other to form a ring.

The alkyl group, cycloalkyl group, aryl group represented by R ₂ represents a chain alkyl group, a monocyclic alkyl group, a polycyclic hydrocarbon group, or a monocyclic aryl group, and the chain alkyl group, the monocyclic alkyl group, the polycyclic hydrocarbon group, and the monocyclic group The aryl group may have a substituent. It is preferable to have a fluorine atom as a substituent.

The chain alkyl group may be linear or branched, and may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl, 2-ethylhexyl, isopropyl, sec-butyl, t-butyl, iso-amyl, or the like. Can be mentioned.

The alkyl group may have a substituent, and as the substituent, a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, a methyl group, an ethyl group, a propyl group, an n-butyl group, Alkyl groups, such as alkyl groups, such as a sec-butyl group, a hexyl group, 2-ethylhexyl group, and an octyl group, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, butoxy group, Alkoxycarbonyl groups, such as an oxycarbonyl group and an ethoxycarbonyl group, Acyl groups, such as a formyl group, an acetyl group, and a benzoyl group, Acyloxy groups, such as an acetoxy group and butyryloxy group, and a carboxyl group are mentioned.

Examples of the monocyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclofutyl, cyclooctyl, cyclododecanyl, cyclopentenyl, cyclohexenyl, cyclooctadienyl, and the like, and in particular cyclopropyl and cyclo Pentyl, cyclohexyl, cyclooctyl is preferred.

The monocyclic alkyl group may have a substituent, and as the substituent, a halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, amide group, sulfonamide group, methyl group, ethyl group, propyl group, n-butyl group, Alkyl groups, such as alkyl groups, such as a sec-butyl group, a hexyl group, 2-ethylhexyl group, and an octyl group, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, butoxy group, Alkoxycarbonyl groups, such as an oxycarbonyl group and an ethoxycarbonyl group, Acyl groups, such as a formyl group, an acetyl group, and a benzoyl group, Acyloxy groups, such as an acetoxy group and butyryloxy group, and a carboxyl group are mentioned.

Examples of the polycyclic hydrocarbon group include bicyclo [4.3.0] nonanyl, decahydronaphthalenyl, tricyclo [5.2.1.0 (2,6)] decanyl, bornyl, isobornyl, norbornyl, adamantyl , Nor adamantyl, 1,7,7-trimethyltricyclo [2.2.1.0 ^2,6 ] heptanyl, 3,7,7-trimethylbicyclo [4.1.0] heptanyl, and the like. Bonyl, adamantyl, and noadamantyl are preferred.

Monocyclic aryl group means a substituted or unsubstituted phenyl group, and examples of the substituent include hydroxyl group, halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, amide group, sulfonamide group, methyl group, ethyl group, propyl group, alkyl groups such as n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, butoxy group, etc. And alkoxycarbonyl groups such as alkoxy group, methoxycarbonyl group and ethoxycarbonyl group, acyl groups such as formyl group, acetyl group and benzoyl group, acyloxy groups such as acetoxy group and butyryloxy group and carboxyl group.

R ₂ preferably has an electron withdrawing group from the viewpoint of acid strength. Although not particularly limited as the electron withdrawing group, cyano group, trifluoromethyl group, nitro group, carboxyl group, ketone group, acyloxy group, hydroxy group, perfluoroalkyl group, methoxy group, ethoxy group, isopropoxy group, Alkoxy groups, such as a t-butoxy group and a benzyloxy group, Halogen atoms, such as a fluorine atom and a chlorine atom, etc. are mentioned, It is especially preferable to have a fluorine atom. More preferably, R ₂ is a group having a fluorine atom having a molecular weight of 220 or less, and in particular, R ₂ is preferably a trifluoromethyl group.

When there are a plurality of R _{3 's} , each independently represents an alkyl group which may have a substituent, a cycloalkyl group which may have a substituent, or an aryl group which may have a substituent, and R ₄ represents a hydrogen atom.

L represents a single bond or a linking group.

p1 represents the integer of 1-8, p2 = 1 or 2, and p3 = 0 or 1.

When p2 = 2, two R <_3> may combine with each other and may form ring structure, and when n = 2 or more, two or more R <_3> may combine with each other and may form ring structure.

Specific examples of the alkyl group, cycloalkyl group and aryl group represented by R ₃ include the same groups as the groups exemplified in each of R ₂ .

It is preferable that R <_3> does not have a fluorine atom from a viewpoint of low fluorine content here.

L is a single bond, oxygen atom (-O-), sulfur atom (-S-), nitrogen atom (> N-), carboxyl group (-OC = O-, -CO = O-), amide group (> NC = O-) and sulfonamide groups (> NSO _2- ) are preferred. In particular, when p 2 = 2 and two R ₃ are bonded to each other to form a ring, L is preferably a linking group having a nitrogen atom such as an amide group or a sulfonamide group, wherein two R ₃ are bonded to each other To form a cyclic amine moiety having the nitrogen atom on L in the ring.

Cyclic amine residue structures include aziridine, azetidine, pyrrolidine, piperidine, hexamethyleneimine, heptamethyleneimine, piperazine, decahydroquinoline, decahydroquinoline, 8-azabicyclo [3.2.1] octane, indole And oxazolidine, thiazolidine, 2-azanorbornane, 7-azanorbornane, morpholine, thiamorpholine, and the like, and these may have a substituent. As a substituent, a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, an amide group, a sulfonamide group, a methyl group, an ethyl group, a propyl group, n-butyl group, sec-butyl group, hexyl group, 2 Alkoxy groups such as alkyl groups such as ethylhexyl group and octyl group, methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group and butoxy group, alkoxy such as methoxycarbonyl group and ethoxycarbonyl group And acyloxy groups such as acyl groups such as carbonyl group, formyl group, acetyl group, benzoyl group, and carbonyl carbon group forming a ring, acetoxy group and butyryloxy group, and carboxyl group.

In general formula (III), the site | part represented by a following formula:

In the formula, the content of fluorine represented by (mass of all fluorine atoms contained) / (mass of all atoms contained) is preferably 0.35 or less, more preferably 0.30 or less, particularly preferably 0.25 or less.

The following specific examples are mentioned as a counter anion structure represented by general formula (III) of this invention.

Moreover, as X <^-> , the anion represented by following General formula (A3) or (A4) described in Unexamined-Japanese-Patent No. 2005-221721 is mentioned.

In general formula (A3) and (A4),

Y is an alkylene group substituted with at least one fluorine atom, and preferably an alkylene group having 2 to 4 carbon atoms. The alkylene chain may contain an oxygen atom. More preferably, it is a C2-C4 perfluoro alkylene group, Most preferably, they are a tetrafluoroethylene group, a hexafluoropropylene group, and an octafluorobutylene group.

R in Formula (A4) represents an alkyl group or a cycloalkyl group. Moreover, the oxygen atom may be contained in the alkylene chain in an alkyl group or a cycloalkyl group.

As a compound which has an anion represented by general formula (A3) or (A4), the specific example described in Unexamined-Japanese-Patent No. 2005-221721 is mentioned.

Although the compound shown below is mentioned as a compound (B) represented by General formula (1-1) which generate | occur | produces an acid, It is not limited to these.

Although the compound shown below is mentioned as a compound (B) represented by General formula (1-2) which produces an acid, It is not limited to these.

The acid generator represented by general formula (1-1) or (1-2) can be used individually by 1 type or in combination of 2 or more types. In addition, the acid generator represented by general formula (1-1) or (1-2) may be used in combination with another acid generator.

As an acid generator, you may use together the compound represented by the following general formula (ZI), (ZII), or (ZIII) with a compound (B). Especially with respect to the total amount of the acid generator represented by said general formula (1-1) or (1-2), it is generally 50 mass% or less, Preferably it is 25 mass% or less, and in the range which maintains a favorable transmittance | permeability. Preferably it is 10 mass% or less, More preferably, it is 5 mass% or less.

In the 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 normally, Preferably it is 1-20.

In addition, two of R ₂₀₁ to R _{203 may be} bonded to each other to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbonyl group. An alkylene group (for example, butylene group, pentylene group) is mentioned as group which two of R <_201> -R <_203> combine and form.

Z ⁻ represents a non-nucleophilic anion (anion that is significantly less capable of causing nucleophilic reactions).

As Z ⁻ , for example, sulfonic acid anion (aliphatic sulfonic acid anion, aromatic sulfonic acid anion, camphorsulfonic anion, etc.), carboxylic acid anion (aliphatic carboxylic acid anion, aromatic carboxylic acid anion, aralkylcarboxylic acid anion, etc.), Sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methed anion and the like. Moreover, the anion as X <^-> in the acid generator represented by general formula (1-1) or (1-2) mentioned above may be sufficient.

The aliphatic moiety in the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion may be an alkyl group or a cycloalkyl group, and preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms.

As an aromatic group in an aromatic sulfonic acid anion and an aromatic carboxylic acid anion, Preferably, a C6-C14 aryl group, for example, a phenyl group, a tolyl group, a naphthyl group, etc. are mentioned.

The alkyl group, cycloalkyl group, and aryl group exemplified above may have a substituent. As this specific example, halogen atoms, such as a nitro group and a fluorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably C1-C15), a cycloalkyl group (preferably C3-C15), an aryl group ( Preferably, 6 to 14 carbon atoms, alkoxycarbonyl group (preferably 2 to 7 carbon atoms), acyl group (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), alkyl thi Ogi (preferably having 1 to 15 carbon atoms), alkylsulfonyl group (preferably having 1 to 15 carbon atoms), alkyliminosulfonyl group (preferably having 2 to 15 carbon atoms), and aryloxysulfonyl group (preferably having 6 carbon atoms) -20), alkylaryloxysulfonyl group (preferably C7-20), cycloalkylaryloxysulfonyl group (preferably C10-20), alkyloxyalkyloxy group (preferably C5-20) ), A cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms) Etc. can be mentioned. About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) is mentioned as a substituent.

As the aralkyl group in the aralkyl carboxylic acid anion, preferably aralkyl groups having 6 to 12 carbon atoms, for example, benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylbutyl group, etc. may be mentioned. .

As a sulfonylimide anion, saccharin anion is mentioned, for example.

The alkyl group in the bis (alkylsulfonyl) imide anion and the tris (alkylsulfonyl) methed anion is preferably an alkyl group having 1 to 5 carbon atoms. Substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like. Fluorine atoms or fluorine Preferred are alkyl groups substituted by atoms.

As other Z <^-> , phosphorus fluoride, a boron fluoride, antimony fluoride, etc. are mentioned, for example.

As Z ^−, an aliphatic sulfonic acid anion in which at least the α position of sulfonic acid is substituted with a fluorine atom, an aromatic sulfonic acid anion substituted with a fluorine atom or a group having a fluorine atom, a bis (alkylsulfonyl) imide anion in which an alkyl group is substituted with a fluorine atom, and an alkyl group are fluorine Preference is given to tris (alkylsulfonyl) methed anions substituted with atoms. As the non-nucleophilic anion, more preferably a perfluoro aliphatic sulfonic acid anion (more preferably 4 to 8 carbon atoms), a benzene sulfonic acid anion having a fluorine atom, more preferably a nonafluorobutane sulfonic acid anion and a perfluorooctane sulfonic acid Anion, pentafluorobenzenesulfonic acid anion, 3,5-bis (trifluoromethyl) benzenesulfonic acid anion.

From the viewpoint of acid strength, pKa of the generated acid is preferably -1 or less for the purpose of improving sensitivity.

R _201, R _202, and (the number of carbon atoms is preferably 6 to 15) aryl group as the organic group of R _203, a linear or branched alkyl group (having 1 to 10 carbon atoms is preferable), a cycloalkyl group (having a carbon number of 3 to 15 is preferred) Etc. can be mentioned.

It is preferable that at least 1 is an aryl group among R <_201> , R <_202>, and R <_203> , and it is more preferable that all three are an aryl group. As an aryl group, heteroaryl groups, such as an indole residue and a pyrrole residue, besides a phenyl group, a naphthyl group, etc. are possible. These aryl groups may further have a substituent. As the substituent, halogen atoms such as nitro group and fluorine atom, carboxyl group, hydroxyl group, amino group, cyano group, alkoxy group (preferably C1-15), cycloalkyl group (preferably C3-15), aryl group (preferably Preferably, 6 to 14 carbon atoms, alkoxycarbonyl group (preferably 2 to 7 carbon atoms), acyl group (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), etc. may be mentioned. However, it is not limited to these.

In addition, two selected from R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may be bonded via a single bond or a linking group. Examples of the linking group include an alkylene group (preferably having 1 to 3 carbon atoms), -O-, -S-, -CO-, -SO ₂ -and the like, but are not limited thereto.

R _201, R ₂₀₂ and R _203, preferred as the structure of, if at least one dog is not an aryl group, Japanese Laid-Open Patent Publication 2004-233661 of paragraph No. 0047, 0048, Japanese Patent Application Publication 2003-35948 paragraph of No. 0040-0046, Compounds exemplified by the formulas (I-1) to (I-70) in the US2003 / 0224288A1 specification, formulas (IA-1) to (IA-54) and formulas (IB-1) to the US2003 / 0077540A1 specification. Cation structures, such as a compound illustrated as (IB-24), are mentioned.

In general formula (ZII) or (ZIII),

R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group.

R ₂₀₄ ~R ₂₀₇ an aryl group, an alkyl group, a cycloalkyl group include the same aryl group as the aryl group described as the above-mentioned R ₂₀₁ ~R _203, an alkyl group, a cycloalkyl group.

The aryl group, alkyl group and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have a substituent. As this substituent, what may have the aryl group, alkyl group, and cycloalkyl group of said R <_201> -R <_203> is mentioned.

Z <^-> represents a non-nucleophilic anion and can illustrate the same thing as the non-nucleophilic anion of Z <^-> in general formula (ZI).

As an acid generator, the compound further represented by the following general formula (ZIV), (ZV), (ZVI) can also be illustrated.

In general formulas (ZIV) to (ZVI),

Ar ₃ and Ar ₄ each independently represent an aryl group.

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

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

As an acid generator which may be used together with the acid generator represented by General formula (1-1) or (1-2), a preferable example is given to the following.

[3] hydrophobic resins

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may contain a hydrophobic resin (HR).

It is preferable that hydrophobic resin (HR) is resin which has at least any one of a fluorine atom and a silicon atom, and a fluorine atom or a silicon atom may be substituted in the side chain, even if it has in the main chain of resin.

The hydrophobic resin (HR) is preferably a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom.

The alkyl group (preferably C1-C10, more preferably C1-C4) which has a fluorine atom is a linear or branched alkyl group in which at least 1 hydrogen atom was substituted by the fluorine atom, and may further have another substituent.

The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have another substituent.

Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have another substituent.

As an alkyl group which has a fluorine atom, the cycloalkyl group which has a fluorine atom, or the aryl group which has a fluorine atom, Preferably, group represented by following General formula (F2)-(F4) is mentioned, However, this invention is limited to this. It is not.

In general formula (F2)-(F4),

R ₅₇ to R ₆₈ each independently represent a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R ₅₇ to R ₆₁ , R ₆₂ to R ₆₄ and R ₆₅ to R ₆₈ represents an alkyl group (preferably having 1 to 4 carbon atoms) in which a fluorine atom or at least one hydrogen atom is substituted with a fluorine atom. ~R ₆₁ R ₅₇ and R ₆₅ ~R ₆₇ are preferably both fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are each preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

As a specific example of group represented by general formula (F2), a p-fluorophenyl group, a pentapulo phenyl group, a 3, 5- di (trifluoromethyl) phenyl group, etc. are mentioned, for example.

As a specific example of group represented by general formula (F3), a trifluoromethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexa Fluoro (2-methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluoro jade A methyl group, a perfluoro (trimethyl) hexyl group, a 2, 2, 3, 3- tetrafluoro cyclobutyl group, a perfluoro cyclohexyl group, etc. are mentioned. Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group, perfluoroisopentyl group are preferable. , Hexafluoroisopropyl group, and heptafluoroisopropyl group are more preferable.

Specific examples of the group represented by formula (F4), for example, _{-C (CF 3) 2 OH,} -C (C 2 F 5) 2 OH, -C (CF 3) (CH 3) OH, -CH (CF ₃ ) OH, and the like, -C (CF ₃ ) ₂ OH is preferable.

Hereinafter, although the specific example of the repeating unit which has a fluorine atom is shown, this invention is not limited to this.

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

Hydrophobic resin (HR) may contain a silicon atom. It is preferable that it is resin which has an alkylsilyl structure (preferably trialkylsilyl group) or cyclic siloxane structure as a partial structure which has a silicon atom.

Specific examples of the alkylsilyl structure or the cyclic siloxane structure include groups represented by general formulas (CS-1) to (CS-3) shown below.

In the general formulas (CS-1) to (CS-3),

R ₁₂ to R ₂₆ each independently represent a linear or branched alkyl group (preferably having 1 to 20 carbon atoms) or a cycloalkyl group (preferably having 3 to 20 carbon atoms).

L _{3 to} L ₅ represent a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, a phenylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a urethane group, or a combination of two or more groups selected from the group consisting of urea groups.

n represents the integer of 1-5. n becomes like this. Preferably it is an integer of 2-4.

Hereinafter, although the specific example of the repeating unit which has group represented by General Formula (CS-1)-(CS-3) is illustrated, this invention is not limited to this. In addition, in specific examples, X ₁ represents a hydrogen atom, -CH ₃ , -F or -CF ₃ .

In addition, hydrophobic resin (HR) may have at least 1 group chosen from the group of following (x) and (y).

(x) alkali soluble groups,

(y) groups decomposed by the action of acids.

(x) As an alkali-soluble group, a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonyl imide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (Alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) Methylene group, a tris (alkylsulfonyl) methylene group, etc. are mentioned.

Preferred alkali-soluble groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (carbonyl) methylene groups.

As a repeating unit which has alkali-soluble group (x), an alkali-soluble group is couple | bonded with the main chain of resin through the repeating unit in which alkali-soluble group was directly bonded to the main chain of resin, such as a repeating unit by acrylic acid or methacrylic acid, or a linking group. A repeating unit etc. can be mentioned, Moreover, the polymerization initiator and chain transfer agent which have alkali-soluble group can be used at the time of superposition | polymerization, and can also be introduce | transduced into the terminal of a polymer chain, and in any case, it is preferable.

As for the content rate of the repeating unit which has alkali-soluble group (x), 1-50 mol% is preferable with respect to all the repeating units in a polymer, More preferably, it is 3-35 mol%, More preferably, it is 5-20 mol%. .

Although the specific example of the repeating unit which has alkali-soluble group (x) is shown below, this invention is not limited to this.

The repeating unit which has group (y) decomposed by the action of an acid in hydrophobic resin (HR) is the same as the repeating unit having an acid-decomposable group exemplified in the resin (A). As for content of the repeating unit which has group (y) decomposed by the action of the acid in hydrophobic resin (HR), 1-80 mol% is preferable with respect to all the repeating units in a polymer, More preferably, it is 10-80 Mol%, More preferably, it is 20-60 mol%.

Hydrophobic resin (HR) may further have a repeating unit represented by the following general formula (III).

In general formula (III),

R _c31 represents a hydrogen atom, an alkyl group, or an alkyl group, cyano group or -CH ₂ -O-Rac ₂ group which may be substituted with a fluorine atom. In the formula, Rac ₂ represents a hydrogen atom, an alkyl group or an acyl group. R _c31 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

R _c32 represents a group having an alkyl, cycloalkyl, alkenyl, cycloalkenyl. These groups may be substituted with fluorine atoms and silicon atoms.

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

The alkyl group of R _c32 in General Formula (III) is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.

The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.

The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.

The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.

R _c32 is preferably an unsubstituted alkyl group or an alkyl group substituted with a fluorine atom.

The divalent linking group for L _c3 is preferably an ester group, an alkylene group (preferably having 1 to 5 carbon atoms), an oxy group, a phenylene group, or an ester bond (a group represented by -COO-).

It is also preferable that hydrophobic resin (HR) further has a repeating unit represented with the following general formula (CII-AB).

In formula (CII-AB),

R _c11 ′ and R _c12 ′ each independently represent a hydrogen atom, a cyano group, a halogen atom or an alkyl group.

Zc 'contains two carbon atoms (C-C) bonded to each other and represents an atomic group for forming an alicyclic structure.

Although the specific example of the repeating unit represented by general formula (III) and (CII-AB) below is illustrated below, this invention is not limited to these. In the formula, Ra represents H, CH ₃ , CH ₂ OH, CF ₃ or CN.

When hydrophobic resin (HR) has a fluorine atom, it is preferable that it is 5-80 mass% with respect to the molecular weight of hydrophobic resin (HR), and, as for content of a fluorine atom, it is more preferable that it is 10-80 mass%. Moreover, it is preferable that the repeating unit containing a fluorine atom is 10-100 mass% in hydrophobic resin (HR), and it is more preferable that it is 30-100 mass%.

When hydrophobic resin (HR) has a silicon atom, it is preferable that it is 2-50 mass% with respect to the molecular weight of hydrophobic resin (HR), and, as for content of a silicon atom, it is more preferable that it is 2-30 mass%. Moreover, it is preferable that it is 10-100 mass% in hydrophobic resin (HR), and, as for the repeating unit containing a silicon atom, it is more preferable that it is 20-100 mass%.

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

0.01-10 mass% is preferable with respect to the total solid in the composition of this invention, as for the content rate in the composition of hydrophobic resin (HR), 0.05-8 mass% is more preferable, 0.1-5 mass% is further more preferable.

As for the hydrophobic resin (HR), as in the resin of (A) component, it is natural that there are few impurities, such as a metal, It is preferable that 0-10 mass% of residual monomers and an oligomer component are preferable, More preferably, it is 0-5 mass% , 0-1 mass% is more preferable. Thereby, the resist which does not change with time, such as a foreign material in a liquid and a sensitivity, is obtained. In addition, the molecular weight distribution (Mw / Mn, also referred to as dispersion degree) is preferably in the range of 1 to 5, more preferably 1 to 3, even more preferably, in terms of resolution, resist shape, sidewall of the resist pattern, roughness, and the like. Preferably it is the range of 1-2.

Various commercial items can also be used for hydrophobic resin (HR), and it can synthesize | combine according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, the batch polymerization method which superposes | polymerizes by melt | dissolving and heating a monomeric species and an initiator in a solvent, and the dropping polymerization method which adds the solution of a monomeric species and an initiator dropwise to a heating solvent over 1 to 10 hours, etc. are mentioned. The dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, dimethylformamide and dimethyl. Amide solvents, such as acetamide, and the solvent which melt | dissolves the composition of this invention, such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone mentioned later, are mentioned. More preferably, it is preferable to polymerize using the same solvent as that used in the positive resist composition of the present invention. As a result, generation of particles during storage can be suppressed.

It is preferable that a polymerization reaction is performed in inert gas atmosphere, such as nitrogen and argon. As a polymerization initiator, superposition | polymerization is started using a commercial radical initiator (azo initiator, peroxide, etc.). As a radical initiator, an azo initiator is preferable, and the azo initiator which has an ester group, a cyano group, and a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate) and the like. The concentration of the reaction is 5 to 50% by mass, preferably 30 to 50% by mass. Reaction temperature is 10 degreeC-150 degreeC normally, Preferably it is 30 degreeC-120 degreeC, More preferably, it is 60-100 degreeC.

After completion of the reaction, the mixture is left to cool to room temperature and purified. Purification is carried out by washing with water or combining a suitable solvent to remove residual monomers and oligomer components, and purification methods in solution such as ultrafiltration for extracting and removing only those having a specific molecular weight or less, or by dropping a resin solution into a poor solvent. The conventional method, such as the reprecipitation method which removes residual monomer etc. by coagulating in a poor solvent, and the refinement | purification method in solid state, such as wash | cleaning the filtration-selected resin slurry with a poor solvent, is applicable. For example, the resin is precipitated as a solid by contacting a solvent (poor solvent) insoluble or insoluble in a volume amount of 10 times or less, preferably 10 to 5 times the volume of the reaction solution.

The solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent of the polymer, and may be hydrocarbon, halogenated hydrocarbon, nitro compound, ether, ketone, ester, It can select suitably from carbonate, alcohol, carboxylic acid, water, the mixed solvent containing these solvent, etc., and can use. Among these, as a precipitation or reprecipitation solvent, a solvent containing at least alcohol (especially methanol) or water is preferable.

The amount of precipitation or reprecipitation solvent can be appropriately selected in consideration of efficiency, yield, and the like, but is generally 100-10000 parts by mass, preferably 200-2000 parts by mass, and more preferably 100 parts by mass of the polymer solution. It is 300-1000 mass parts.

Although it can select suitably as temperature at the time of precipitation or reprecipitation, considering efficiency and operability, it is about 0-50 degreeC normally, Preferably it is near room temperature (for example, about 20-35 degreeC). Precipitation or reprecipitation operation can be performed by well-known methods, such as batch type and continuous type, using common mixing vessels, such as a stirring tank.

Precipitated or reprecipitated polymers are usually provided for conventional solid-liquid separation, such as filtration and centrifugation, and then dried and used for use. Filtration uses the solvent-proof filter medium, Preferably it is performed under pressure. Drying is performed at a temperature of about 30 to 100 ° C, preferably about 30 to 50 ° C, under normal pressure or reduced pressure (preferably under reduced pressure).

In addition, once the resin is precipitated and separated, it may be dissolved in a solvent again and the resin may be brought into contact with a poorly soluble or insoluble solvent. That is, after completion of the radical polymerization reaction, the polymer is contacted with a solvent insoluble or insoluble to precipitate the resin (step a), the resin is separated from the solution (step b), and dissolved in a solvent to prepare a resin solution A. (Step c), after that, a resin solid is precipitated by contacting the resin solution A with a solvent in which the resin is poorly soluble or insoluble in a volume amount of less than 10 times the volume of the resin solution A (preferably 5 times or less). (Step d) may be a method including separating the precipitated resin (step e).

The specific example of hydrophobic resin (HR) is shown below. In addition, in Table 1 below, the molar ratio of the repeating units in each resin (corresponding in order from each repeating unit to the left), the weight average molecular weight, and the degree of dispersion are shown.

TABLE 1

When the hydrophobic resin (HR) contains a repeating unit (c) having at least one polar converter which is decomposed by the action of the alkaline developer and the solubility in the alkaline developer is increased, it is particularly preferable in view of the development defect reduction. Hereinafter, what contains a repeating unit (c) in hydrophobic resin (HR) is also especially called "hydrophobic resin (C)."

Here, the polarity converter is a group which is decomposed by the action of the alkaline developer and increases the solubility in the alkaline developer. For example, a lactone group, a carboxylic acid ester group (-COO-), an acid anhydride group (-C (O) OC (O)-), an acid imide group (-NHCONH-), and a carboxylic acid thioester group ( -COS-), and the like carbonic ester group (-OC (O) O-), a sulfuric ester group (-OSO ₂ O-), sulfonate group (-SO ₂ O-).

In addition, since the ester group directly connected to the main chain of the repeating unit such as acrylate or the like decomposes due to the action of the alkaline developer, its ability to increase solubility in the alkaline developer is poor, and therefore, it is not included in the polarity converter in the present invention. .

As a repeating unit (c), the repeating unit represented by Formula (K0) is mentioned, for example.

In the formula, R _k1 represents a group containing a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group or a polar converter.

R _k2 represents a group containing an alkyl group, a cycloalkyl group, an aryl group or a polar converter.

However, at least one of R _k1 and R _k2 has a polarity converter.

In addition, the ester group directly connected to the main chain of the repeating unit represented by general formula (K0) is not included in the polarity converter in this invention as mentioned above.

As a polarity converter, the group represented by X in the partial structure represented by general formula (KA-1) or (KB-1) is preferable.

X in general formula (KA-1) or (KB-1) is a carboxylic ester group: -COO-, an acid anhydride group: -C (O) OC (O)-, an acid imide group: -NHCONH- , Carboxylic acid thioester group: -COS-, carbonate ester group: -OC (O) O-, sulfuric acid ester group: -OSO ₂ O-, sulfonic acid ester group: -SO ₂ O-.

Y ¹ and Y ² may be the same or different, and each represents an electron withdrawing group.

Further, the repeating unit (c) has a preferred polar converter by having a group having a substructure represented by the general formula (KA-1) or (KB-1), but a substructure represented by the general formula (KA-1), As in the case of the substructure represented by (KB-1) when Y ¹ and Y ² are monovalent, when the substructure does not have a bonding loss, the tile having the substructure is arbitrary in the substructure. It is group which has monovalent or more group except at least 1 hydrogen atom of. The partial structure represented by general formula (KA-1) or (KB-1) is connected to the main chain of resin (C) through a substituent at arbitrary positions.

The partial structure represented by general formula (KA-1) is a structure which forms ring structure with group as X.

As X in general formula (KA-1), Preferably, they are a carboxylic ester group (that is, when forming a lactone ring structure as KA-1), an acid anhydride group, and a carbonate ester group. More preferably, it is a carboxylic ester group.

Ring structure represented by the general formula (KA-1) is which may have a substituent, for example, which may have a substituent Z _ka1 nka dog.

When there are a plurality of Z _{ka1 's} , each independently represents an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group, or an electron withdrawing group.

Z _ka1 may be connected to each other and form a ring. As a ring formed by connecting _Zka1 , a cycloalkyl ring, a heterocyclic ring (cyclic ether ring, a lactone ring etc.) is mentioned, for example.

nka represents the integer of 0-10. Preferably it is an integer of 0-8, More preferably, it is an integer of 0-5, More preferably, it is an integer of 1-4, Most preferably, it is an integer of 1-3.

The electron withdrawing group as Z _{ka1 is the same} as the electron withdrawing group as Y ¹ and Y ² described later.

In addition, the said electron withdrawing group may be substituted by the other electron withdrawing group.

Z _ka1 is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, or an electron withdrawing group, and more preferably an alkyl group, a cycloalkyl group or an electron withdrawing group. Moreover, as an ether group, the thing substituted by the alkyl group, the cycloalkyl group, etc., ie, the alkyl ether group, etc. are preferable. An electron withdrawing group is synonymous with the above.

_Examples of the halogen atom as Z _ka1 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

The alkyl group as Z _ka1 may have a substituent, and either linear or branched may be used. As a linear alkyl group, Preferably it is C1-C30, More preferably, it is 1-20, For example, a methyl group, an ethyl group, n-propyl group, n-butyl group, sec-butyl group, t-butyl group, n- A pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group, etc. are mentioned. As a branched alkyl group, Preferably it is 3-30, More preferably, it is 3-20, For example, i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group, i -Hexyl group, t-hexyl group, i-heptyl group, t-heptyl group, i-octyl group, t-octyl group, i-nonyl group, t-decanoyl group, etc. are mentioned. It is preferable that it is C1-C4, such as a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group.

The cycloalkyl group as Z _ka1 may have a substituent, may be monocyclic, may be polycyclic, or may be Conjugated. For example, the cycloalkyl group may have a crosslinked structure. As monocyclic type, a C3-C8 cycloalkyl group is preferable and a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, a cyclooctyl group, etc. are mentioned, for example. Examples of the polycyclic type include groups having a bicyclo, tricyclo and tetracyclo structure having 5 or more carbon atoms, and a cycloalkyl group having 6 to 20 carbon atoms is preferable, for example, an adamantyl group, norbornyl group, isobornyl group, A campanyl group, a dicyclopentyl group, the (alpha)-pinenel group, a tricyclo decanyl group, the tetracyclo dodecyl group, an androstanyl group, or the following structure is mentioned. In addition, a part of carbon atoms in a cycloalkyl group may be substituted by hetero atoms, such as an oxygen atom.

Preferred examples of the alicyclic moiety include an adamantyl group, noadamantyl group, decarin group, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group, cycloheptyl group, cyclooctyl group, A cyclodecanyl group and a cyclododecanyl group are mentioned. More preferably, they are an adamantyl group, decalin group, norbornyl group, cedrol group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecanyl group, cyclododecanyl group, and tricyclodecanyl group.

As a substituent of these alicyclic structures, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group are mentioned. As the alkyl group, lower alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group are preferable, and more preferably methyl group, ethyl group, propyl group and isopropyl group. As said alkoxy group, Preferably, C1-C4 things, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, are mentioned. As a substituent which an alkyl group and an alkoxy group may have, a hydroxyl group, a halogen atom, an alkoxy group (preferably C1-C4), etc. are mentioned.

Moreover, as a new substituent which the said group may have, a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the said alkyl group, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, Alkoxycarbonyl groups such as hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, alkoxycarbonyl group such as methoxycarbonyl group and ethoxycarbonyl group, benzyl group, phenethyl group, cumyl group Acyloxy groups such as aralkyl groups such as aralkyl groups, aralkyloxy groups, formyl groups, acetyl groups, butyryl groups, benzoyl groups, cyanyl groups, valeryl groups, and acyloxy groups such as butyryloxy groups, the alkenyl groups, vinyloxy groups, and pros Alkenyloxy groups, such as a phenyloxy group, an allyloxy group, and butenyloxy group, aryloxy groups, such as the said aryl group and phenoxy group, and aryloxycarbonyl groups, such as a benzoyloxy group, etc. are mentioned.

It is preferable that X in general formula (KA-1) is a carboxylic ester group, and the partial structure represented by general formula (KA-1) is a lactone ring, and it is preferable that it is a 5-7 member cyclic lactone ring.

In addition, a bicyclo structure and a spiro structure are added to the 5- to 7-membered ring lactone ring as the partial structure represented by General Formula (KA-1) as in the following (KA-1-1) to (KA-1-17). It is preferable that the other ring structure is condensed by the form to form.

About the peripheral ring structure which the ring structure represented by general formula (KA-1) may couple | bond, for example, to the thing in following (KA-1-1)-(KA-1-17), or this The same thing can be mentioned.

As a structure containing the lactone ring structure represented by general formula (KA-1), the structure represented by either of following (KA-1-1) (KA-1-17) is more preferable. In addition, the lactone structure may be directly bonded to the main chain. Preferred structures include (KA-1-1), (KA-1-4), (KA-1-5), (KA-1-6), (KA-1-13) and (KA-1-14) , (KA-1-17).

The structure containing the said lactone ring structure does not need to have a substituent. As a preferable substituent, the same thing as the substituent which the ring structure represented by the said general formula (KA-1) may have is mentioned.

The lactone structure may have an optically active substance, but any optically active substance may be used. In addition, one type of optically active substance may be used alone, or a plurality of optically active substances may be mixed and used. When mainly using one type of optically active substance, it is preferable that the optical purity (ee) is 90 or more, More preferably, it is 95 or more, Most preferably, it is 98 or more.

As X of general formula (KB-1), Preferably, a carboxylic acid ester group (-COO-) is mentioned.

Y ¹ and Y ² in General Formula (KB-1) each independently represent an electron withdrawing group.

The electron withdrawing group is a partial structure represented by the following formula (EW). * In Formula (EW) represents the bond directly connected to (KA-1), or the bond directly connected to X in (KB-1).

In the formula (EW),

n _ew is the repeating number of the linking group represented by -C (R _ew1 ) (R _ew2 )-, and represents an integer of 0 or 1. When n _ew is 0, it represents a single bond and shows that Y _ew1 is directly bonded.

_Yew1 is a halogen atom, cyano group, nitrile group, nitro group, halo (cyclo) alkyl group, haloaryl group represented by -C (R _f1 ) (R _f2 ) -R _f3 , oxy group, carbonyl group, sulfonyl group, sulfi And a combination thereof. The electron withdrawing group may have the following structure, for example. In addition, a "halo (cyclo) alkyl group" shows the alkyl group and cycloalkyl group which at least one part was halogenated. R _{ew 3} and R _{ew 4} each independently represent an arbitrary structure. In any structure, R _{ew 3} and R _{ew 4} may have an electron- _relevant property in the structure represented by the formula (EW), and may be connected to the main chain of a resin, for example, but preferably an alkyl group, a cycloalkyl group, or an alkyl fluoride group.

When Y _ew1 is a divalent or higher group, the remaining bond is to form a bond with any atom or substituent. At least one of Y _ew1 , R _ew1 , and R _ew2 may be connected to the main chain of the resin (C) through a new substituent.

Y _ew1 is preferably a halogen atom or a halo (cyclo) alkyl group or haloaryl group represented by —C (R _f1 ) (R _f2 ) -R _f3 .

R _ew1 and R _ew2 each independently represent an arbitrary substituent, for example, a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.

At least two of R _ew1 , R _ew2 and Y _ew1 may be connected to each other to form a ring.

R _f1 represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group, or a perhaloaryl group, more preferably a fluorine atom, a perfluoroalkyl group or a perfluorocycloalkyl group, still more preferably a fluorine atom or a tree A fluoromethyl group is shown.

R _f2 and R _f3 each independently represent a hydrogen atom, a halogen atom or an organic group, and R _f2 and R _f3 may be linked to each other to form a ring. As an organic group, an alkyl group, a cycloalkyl group, an alkoxy group etc. are shown, for example. It is more preferable that R _f2 represents the same group as R _f1 , or forms a ring in conjunction with R _f3 .

You may connect with R <_f1> -R <_f3> and may form a ring, and a (halo) cycloalkyl ring, a (halo) aryl ring, etc. are mentioned as a ring to form.

As a (halo) alkyl group in R <_f1> -R <_f3> , the alkyl group in _Zka1 mentioned above and the structure which halogenated this are mentioned, for example.

R _{f1 f3} ~R in, or R _f2 and R _f3 is in a ring form by connecting (per) halo-cycloalkyl and (per) halo-aryl group includes, for example, a cycloalkyl in the above-described Z _ka1 A structure in which an alkyl group is halogenated, more preferably a fluoroalkyl group represented by -C _(n) F _(2n-2) H, and a perfluoroaryl group represented by -C _(n) F _(n-1) . Can be. Although carbon number n is not specifically limited here, It is preferable that it is 5-13, and 6 is more preferable.

As a _ring which at least two of R _ew1 , R _ew2 and Y _{ew1 may} be linked to each other, preferably, a cycloalkyl group or a heterocyclic group is mentioned, and a lactone ring group is preferable as a heterocyclic group. As a lactone ring, the structure represented by said formula (KA-1-1) (KA-1-17) is mentioned, for example.

In addition, a plurality of substructures represented by the general formula (KA-1) in the repeating unit (c), a plurality of substructures represented by the general formula (KB-1), or a substructure represented by the general formula (KA-1) You may have both the substructures of general formula (KB-1).

In addition, part or all of the partial structure of general formula (KA-1) may serve as the electron withdrawing group as Y <^1> or Y <^2> in general formula (KB-1). For example, when X in the general formula (KA-1) is a carboxylic ester group, the carboxylic ester group may function as an electron withdrawing group as Y ¹ or Y ^{2 in} the general formula (KB-1). It may be.

Although the repeating unit (c) is a repeating unit (c ') having at least one of a fluorine atom and a silicon atom on one side chain and a polar converter, the repeating unit (c) having a polar converter and not having a fluorine atom and a silicon atom *) Even if it is a repeating unit (c ") which has a polarity converter on one side chain, and has at least one of a fluorine atom and a silicon atom on the said side chain and another side chain in the same repeating unit, resin (C) may It is more preferable to have a repeating unit (c ') as a repeating unit (c).

Moreover, when resin (C) has a repeating unit (c *), it is preferable that it is a copolymer with the repeating unit (repeat unit (c1 mentioned later)) which has at least any one of a fluorine atom and a silicon atom. In addition, the side chain which has a polarity converter in a repeating unit (c "), and the side chain which has at least one of a fluorine atom and a silicon atom are couple | bonded with the same carbon atom in a principal chain, ie, the positional relationship of following formula (4) In the formula, B1 represents a partial structure having a polar converter, and B2 represents a partial structure having at least one of a fluorine atom and a silicon atom.

In addition, in the repeating unit (c *) and the repeating unit (c "), it is more preferable that the polarity converter is a partial structure represented by -COO- in the structure represented by general formula (KA-1).

The polarity converter is decomposed by the action of the alkaline developer to effect polarity conversion, so that the receding contact angle with water of the resin composition film after alkali development can be lowered.

The receding contact angle with water of the resin composition film after alkali development is 50 degrees or less, More preferably, it is 40 degrees or less, More preferably, at the temperature at the time of exposure, normal room temperature 23 +/- 3 degreeC, and humidity 45 +/- 5%. 35 degrees or less, Most preferably, it is 30 degrees or less.

The receding contact angle is a contact angle measured when the contact line at the droplet-substrate interface retreats, and it is generally known that it is useful when simulating the ease of movement of the droplet in a dynamic state. For simplicity, it can be defined as the contact angle when the droplet interface discharged from the needle tip onto the substrate and then the interface of the droplet retreats when the droplet is sucked back into the needle. It can measure using a measuring method of called contact angle.

It is preferable that the hydrolysis rate with respect to the alkaline developing solution of resin (C) is 0.001 nm / sec or more, It is more preferable that it is 0.01 nm / sec or more, It is still more preferable that it is 0.1 nm / sec or more, It is most preferable that it is 1 nm / sec or more Do.

Here, the hydrolysis rate of the resin (C) with respect to the alkali developer is reduced with the resin (C) when the resin film is formed only with respect to TMAH (aqueous solution of tetramethylammonium hydroxide) (2.38 mass%) at 23 ° C. That's the speed.

It is preferable that resin (C) of this invention is resin (C1) which contains the repeating unit (c) which has at least 2 or more polar converters, and has at least any one of a fluorine atom and a silicon atom.

When the repeating unit (c) has at least two polar converters, it is preferable to have a group having a partial structure having two polar converters represented by the following general formula (KY-1). In addition, when the structure represented by general formula (KY-1) does not have a bond, it is group which has monovalent or more group except at least one arbitrary hydrogen atom in the said structure.

In general formula (KY-1),

R _ky1 and R _ky4 each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, an ether group, a hydroxyl group, a cyano group, an amide group, or an aryl group. Alternatively, R _ky1 and R _ky4 may be bonded to the same atom to form a double bond, for example, R _ky1 and R _ky4 may be bonded to the same oxygen atom to form a part of carbonyl group (= O).

R _ky2 and R _ky3 are each independently an electron withdrawing group, or R _ky1 and R _ky2 are connected to form a lactone ring, and R _ky3 is an electron withdrawing group. As a lactone ring to form, the structure of said (KA-1-1) (KA-1-17) is preferable. Examples of electron withdrawing groups include the same groups as Y ¹ and Y ^{2 in} the formula (KB-1), and are preferably represented by a halogen atom or -C (R _f1 ) (R _f2 ) -R _f3 . It is a halo (cyclo) alkyl group or a haloaryl group. Preferably, R _ky3 is a halogen atom or a halo (cyclo) alkyl group or haloaryl group represented by -C (R _f1 ) (R _f2 ) -R _f3 , and R _ky2 is linked to R _ky1 to form a lactone ring or And an electron withdrawing group which does not have a halogen atom.

R _ky1 , R _ky2 and R _ky4 may be connected to each other to form a monocyclic or polycyclic structure.

R _ky1 and R _ky4 specifically include the same groups as Z _ka1 in formula (KA-1).

As a lactone ring which R _ky1 and R _ky2 connect and form, the structure of said (KA-1-1)-(KA-1-17) is preferable. Examples of the electron withdrawing group include those similar to Y ¹ and Y ^{2 in} the formula (KB-1).

As a structure represented by general formula (KY-1), it is more preferable that it is a structure represented by the following general formula (KY-2). In addition, the structure represented by general formula (KY-2) is group which has a monovalent or more group except at least one arbitrary hydrogen atom in the said structure.

In the formula (KY-2),

R _ky6 ~R _ky10 are independently represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a carbonyl group, carbonyloxy group, oxycarbonyl group, an ether group, a hydroxyl group, a cyano group, an amide group, or an aryl, respectively.

R _ky6 ~R _ky10 is to two or more connected to each other may form a monocyclic or polycyclic structure.

R _ky5 represents an electron withdrawing group. Examples of electron withdrawing groups include the same groups as Y ¹ and Y ^{2 in} the formula (KB-1), and preferably a halogen atom or a halo represented by -C (R _f1 ) (R _f2 ) -R _f3 . (Cyclo) alkyl group or haloaryl group.

Specific _examples of R _ky5 to R _ky10 include Z _ka1 in Formula (KA-1).

As for the structure represented by a formula (KY-2), it is more preferable that it is a partial structure represented by the following general formula (KY-3).

In the formula (KY-3),

Z _ka1 and nka are synonymous with the said general formula (KA-1), respectively. R _ky5 is _synonymous with the above formula (KY-2).

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

The repeating unit (c) is not limited as long as it is a repeating unit obtained by polymerization such as addition polymerization, condensation polymerization, addition condensation, but is preferably a repeating unit obtained by addition polymerization of a carbon-carbon double bond. For example, an acrylate repeating unit (including a system having a substituent at the α position and a β position), a styrene repeating unit (including a system having a substituent at the α position and a β position), a vinyl ether repeating unit, and a norvo Repeating units of n-ene repeating units and maleic acid derivatives (maleic anhydride or derivatives thereof, maleimide, etc.); and acrylate repeating units, styrene repeating units, vinyl ether repeating units, norbornene repeating units An acrylate repeating unit, a vinyl ether repeating unit, and a norbornene repeating unit are more preferable, and an acrylate repeating unit is the most preferable.

The repeating unit (c) may be a repeating unit having a partial structure shown below.

In general formula (cc),

Z ₁ each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and preferably an ester bond.

Z ₂ each independently represents a chain or cyclic alkylene group, and preferably represents an alkylene group having 1 or 2 carbon atoms or a cycloalkylene group having 5 to 10 carbon atoms.

Ta each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, a nitrile group, a hydroxyl group, an amide group, an aryl group or an electron withdrawing group [electron spheres as Y ¹ and Y ^{2 in} the general formula (KB-1) Synonymous with a group], preferably an alkyl group, a cycloalkyl group, an electron withdrawing group, and more preferably an electron withdrawing group. When there are two or more Ta, Ta may combine and form a ring.

L <_0> represents a single bond or m + monovalent hydrocarbon group (preferably C20 or less), Preferably it represents a single bond. The single bond as L ₀ is when m is 1. The m + monovalent hydrocarbon group as L _{0 represents} , for example, an m + monovalent hydrocarbon group excluding any hydrogen atom m −1 from an alkylene group, a cycloalkylene group, a phenylene group, or a combination thereof. When k is 2, two L ₀ may combine with each other and form a ring.

L each independently represents a carbonyl group, a carbonyloxy group or an ether group.

Tc is the electron withdrawing property group accept as Y ¹ and Y ² in the hydrogen atom, an alkyl group, a cycloalkyl group, a nitrile group, a hydroxyl group, an amide group, an aryl group or an electron withdrawing property group [the above general formula (KB-1) Is displayed.

* Represents a bond to the main chain or side chain of the resin. That is, the partial structure represented by the formula (cc) may be directly connected to the main chain, or the partial structure represented by the formula (cc) may be bonded to the side chain of the resin. In addition, the bond to a main chain is a bond of a nuclear reactor existing in the bond which comprises a main chain, and the bond to a side chain is a bond of a nuclear reactor other than the bond which comprises a main chain.

m represents the integer of 0-28, Preferably it is an integer of 1-3, More preferably, it is 1.

k represents the integer of 0-2, Preferably it is 1.

q represents the integer of 0-5, Preferably it is 0-2.

r represents the integer of 0-5.

In addition, -L _0- (Ta) m may be substituted instead of-(L) r-Tc.

It is also preferable to have a fluorine atom at the terminal of the sugar lactone and to have a fluorine atom on a side chain different from the side chain on the sugar lactone side in the same repeating unit (repeating unit (c ")).

As a more specific structure of a repeating unit (c), the repeating unit which has the partial structure shown below is preferable.

In general formula (ca-2) and general formula (cb-2),

Z ₁ , Z ₂ , Tc, Ta, L, q and r are synonymous with each in General Formula (cc).

Tb is independently an alkyl group, a cycloalkyl group, an alkoxy group, a nitrile group, a hydroxyl group, an amide group, an aryl group or an electron withdrawing group [electron spheres as Y ¹ and Y ^{2 in} the general formula (KB-1) Agree with the penis].

* Represents a bond to the main chain or side chain of the resin. That is, the partial structure represented by formula (ca-2) or formula (cb-2) may be directly connected to the main chain, and the partial structure represented by formula (ca-2) or formula (cb-2) in the side chain of the resin. May be combined.

m represents the integer of 1-28, Preferably it is an integer of 1-3, More preferably, it is 1.

n represents the integer of 0-11, Preferably it is an integer of 0-5, More preferably, it is 1 or 2.

p represents the integer of 0-5, Preferably it is an integer of 0-3, More preferably, it is 1 or 2.

In general formula (2),

R <_2> represents a linear or cyclic alkylene group and may be same or different when there exist _two or more.

R ₃ represents a linear, branched or cyclic hydrocarbon group in which part or all of the hydrogen atoms on the constituent carbon are substituted with fluorine atoms.

R ₄ represents a halogen atom, a cyano group, a hydroxyl group, an amide group, an alkyl group, a cycloalkyl group, an alkoxy group, a phenyl group, an acyl group, an alkoxycarbonyl group, or a group represented by RC (= O)-or RC (= O) O- ( R represents an alkyl group or a cycloalkyl group.). When there are a plurality of R ₄ , they may be the same or different, and two or more R ₄ may be bonded to each other to form a ring.

X represents an alkylene group, an oxygen atom or a sulfur atom.

Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond, and in the case where there are a plurality, Z may be the same or different.

* Represents a bond to the main chain of the resin.

n represents a repeating number and represents the integer of 0-5.

m is the number of substituents and represents the integer of 0-7.

As the structure of -R ₂ -Z-, a structure preferably represented by-(CH ₂ ) ₁ -COO- is preferable (l represents an integer of 1 to 5).

The specific example of resin (C) is shown. In addition, the molar ratio of the repeating unit in each resin (corresponding in order from each repeating unit to the left), the weight average molecular weight (Mw), and the dispersion degree (Mw / Mn) are shown in the following table.

TABLE 2-1

Table 2-2

[Table 2-3]

Table 2-4

Resin (C) can be used individually by 1 type or in combination of 2 or more types.

Moreover, it is preferable to use in combination with resin (CP) which has at least any one of a fluorine atom and a silicon atom different from resin (C).

(CP) Resin having at least one of fluorine atom and silicon atom

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may further contain a resin (CP) having at least one of a fluorine atom and a silicon atom, separately from the resin (C). By containing the resin (C) and resin (CP), the resin (C) and resin (CP) are localized in the film surface layer, and when the liquid immersion medium is water, the receding contact angle of the surface of the resist film with respect to water when the film is formed into a film is obtained. Improve immersion yield. The receding contact angle of the membrane is preferably 60 ° to 90 °, more preferably 70 ° or more. Although the content rate of resin (CP) can be suitably adjusted and used so that the receding contact angle of a film may become the said range, It is preferable that it is 0.01-10 mass% based on the total solid of an actinic-ray-sensitive or radiation-sensitive resin composition, More preferably, it is 0.01-5 mass%, More preferably, it is 0.01-4 mass%, Especially preferably, it is 0.01-3 mass%.

The resin (CP) is ubiquitous at the interface as described above. However, unlike the surfactant, the resin (CP) does not necessarily have a hydrophilic group in the molecule, and does not necessarily contribute to uniformly mixing the polar / non-polar materials.

The fluorine atom or silicon atom in the resin (CP) having at least one of the fluorine atom and the silicon atom may be present in the main chain of the resin or may be substituted with the side chain.

It is preferable that resin (CP) is resin which has the alkyl group which has a fluorine atom, the cycloalkyl group which has a fluorine atom, or the aryl group which has a fluorine atom as a partial structure which has a fluorine atom.

The alkyl group (preferably C1-C10, more preferably C1-C4) which has a fluorine atom is a linear or branched alkyl group in which at least 1 hydrogen atom was substituted by the fluorine atom, and may further have another substituent.

The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have another substituent.

Examples of the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have another substituent.

As an alkyl group which has a fluorine atom, the cycloalkyl group which has a fluorine atom, or the aryl group which has a fluorine atom, Preferably, group represented by General formula (F2)-(F4) in the said resin (C) is mentioned, This invention is not limited to this.

In this invention, it is preferable that the group represented by general formula (F2)-(F4) is contained in a (meth) acrylate type repeating unit.

The resin (CP) is preferably a resin having an alkylsilyl structure (preferably trialkylsilyl group) or a cyclic siloxane structure as a partial structure having silicon atoms.

Specific examples of the alkylsilyl structure or the cyclic siloxane structure include groups represented by general formulas (CS-1) to (CS-3) in the resin (C).

In addition, resin (CP) may have at least 1 group further chosen from the group of following (x) and (z).

(x) alkali soluble groups,

(z) groups decomposed by the action of acids.

These groups can specifically mention the group similar to the thing in the said resin (C).

Specific examples of the resin (CP) include the above-mentioned (HR-1) to (HR-65) and the like.

For the film formed from the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, exposure (liquid immersion exposure) is performed by filling a liquid (immersion medium) having a higher refractive index than air between the film and the lens when irradiating actinic radiation or radiation. You may do it. Thereby, resolution can be improved. As the liquid immersion medium to be used, any liquid can be used as long as the liquid has a refractive index higher than that of air, but is preferably pure water.

The liquid immersion liquid used at the time of immersion exposure is demonstrated below.

The liquid immersion liquid is preferably liquid with a small temperature coefficient of refractive index as small as possible so as to be transparent to the exposure wavelength and to minimize the deformation of the optical image projected onto the resist film. In one case, in addition to the above point of view, it is preferable to use water from the point of availability and ease of handling.

In addition, since the refractive index can be further improved, a medium having a refractive index of 1.5 or more can be used. The medium may be an aqueous solution or an organic solvent.

When water is used as the immersion liquid, an additive (liquid) which does not dissolve the resist film on the wafer and can ignore the influence on the optical coat of the bottom surface of the lens element in order to reduce the surface tension of the water and increase the interfacial activity. ) May be added at a slight ratio. As the additive, an aliphatic alcohol having a refractive index almost the same as water is preferable, and specific examples thereof include methyl alcohol, ethyl alcohol, isopropyl alcohol, and the like. By adding an alcohol having a refractive index almost equal to that of water, an advantage can be obtained that the change in refractive index of the entire liquid can be made very small even if the alcohol component in the water evaporates and the content concentration is changed. On the other hand, distilled water is preferred as the water to be used when an opaque substance or an impurity whose refractive index is significantly different from water is mixed with 193 nm light, causing deformation of the optical image projected onto the resist film. In addition, pure water filtered through an ion exchange filter or the like may be used.

It is preferable that the electrical resistance of water is 18.3MQcm or more, It is preferable that TOC (organic concentration) is 20 ppb or less, It is preferable to carry out the degassing process.

It is also possible to improve the lithographic performance by improving the refractive index of the immersion liquid. From this point of view, the addition of an additive to increase the refractive index of the water, or may be used in a heavy water (D ₂ O) in place of water.

An immersion liquid poorly soluble film (hereinafter also referred to as a "top coat") may be formed between the film and the immersion liquid by the composition of the present invention so as not to directly contact the immersion liquid. Functions necessary for the top coat are application titration to the upper resist layer, radiation, especially transparency to 193 nm, and poor immersion liquid solubility. It is preferable that the top coat is not mixed with the resist and can be uniformly applied to the upper layer of the resist.

From the viewpoint of 193 nm transparency, the top coat is preferably a polymer that does not contain abundant aromatics, and specifically, a hydrocarbon polymer, an acrylic ester polymer, polymethacrylic acid, polyacrylic acid, polyvinyl ether, a silicon-containing polymer, fluorine Containing polymers; and the like. The above hydrophobic resin (HR) is also preferable as a top coat. From the viewpoint of contaminating the optical lens when impurities are eluted from the top coat to the immersion liquid, the less monomer residue of the polymer contained in the top coat is preferable.

When peeling a top coat, you may use a developing solution and you may use a peeling agent separately. As the release agent, a solvent having less penetration into the membrane is preferable. In that a peeling process is possible simultaneously with the image development process of a film | membrane, it is preferable that it can peel by alkaline developing solution. The top coat is preferably acidic from the viewpoint of being peeled off with an alkaline developer, but may be neutral or alkaline from the viewpoint of nonintermixing with the film.

The resolution without the difference in refractive index between the top coat and the immersion liquid is improved. In the ArF excimer laser (wavelength: 193 nm), when water is used as the immersion liquid, the ArF immersion exposure topcoat is preferably close to the refractive index of the immersion liquid. From the viewpoint of bringing the refractive index closer to the immersion liquid, it is preferable to have a fluorine atom in the top coat. Moreover, a thin film is preferable from a viewpoint of transparency and refractive index.

It is preferable that the topcoat is not mixed with the membrane and also with the immersion liquid. From this point of view, when the immersion liquid is water, it is preferable that the solvent used for the top coat is poorly soluble in the solvent used in the composition of the present invention and is a water-insoluble medium. In addition, when the immersion liquid is an organic solvent, the top coat may be water-soluble or water-insoluble.

[4] solvents

As a solvent which can be used when dissolving each said component and preparing a positive resist composition, For example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactic acid alkyl ester, alkoxypropionate alkyl, cyclic lactone (Preferably C4-10), the organic solvent, such as the monoketone compound which may contain a ring (preferably C4-10), alkylene carbonate, alkyl alkoxyacetic acid, alkyl pyruvate, is mentioned.

Examples of the alkylene glycol monoalkyl ether carboxylates include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, and propylene glycol monomethyl ether propionate. , Propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate are preferable.

As alkylene glycol monoalkyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether are mentioned preferably, for example. Can be.

As lactic acid alkyl ester, methyl lactate, ethyl lactate, propyl lactic acid, and butyl lactate are mentioned preferably, for example.

As alkyl alkoxy propionate, 3-ethoxy propionate ethyl, 3-methoxy methyl propionate, 3-ethoxy propionate methyl, and 3-methoxy ethylpropionate are mentioned preferably, for example.

As the cyclic lactone, for example, β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, and γ-valerolactone , γ-caprolactone, γ-octanoic lactone, and α-hydroxy-γ-butyrolactone are preferable.

As a monoketone compound which may contain a ring, for example, 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl- 2-pentanone, 2-methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-penta Paddy, 2-hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3 -Heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-decanone, 5-hexen-2-one, 3-penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2, 4,4-trimethylcyclopentanone, cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexa Paddy, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methylcycloheptanone is mentioned preferably.

As alkylene carbonate, a propylene carbonate, vinylene carbonate, ethylene carbonate, butylene carbonate is mentioned preferably, for example.

As an alkoxy acetic acid alkyl, for example, 2-methoxy ethyl acetate, 2-ethoxy ethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, Acetic acid-1-methoxy-2-propyl is mentioned preferably.

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

As a solvent which can be used preferably, the solvent of boiling point 130 degreeC or more is mentioned under normal temperature and normal pressure. Specifically, cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, ethyl pyruvate, and ethyl acetate-2-e Oxyethyl, acetic acid-2- (2-ethoxyethoxy) ethyl, and propylene carbonate.

In this invention, the said solvent may be used independently and may use two or more types together.

In this invention, you may use the mixed solvent which mixed the solvent containing a hydroxyl group in the structure, and the solvent which does not contain a hydroxyl group as an organic solvent.

Although the above-mentioned exemplary compound can be selected suitably as a solvent containing a hydroxyl group and a solvent which does not contain a hydroxyl group, As a solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate, etc. are preferable, A propylene glycol monomethyl ether, Ethyl lactate is more preferred. Moreover, as a solvent which does not contain a hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxy propionate, the monoketone compound which may contain a ring, cyclic lactone, alkyl acetate, etc. are preferable, Among these, propylene glycol monomethyl ether acetate is preferable. , Ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone and butyl acetate are particularly preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxy propionate and 2-heptanone are most preferred. desirable.

The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99-99/1, Preferably it is 10/90-90/10, More preferably, it is 20/80-60/40. . The mixed solvent which contains 50 mass% or more of solvents which does not contain a hydroxyl group is especially preferable at the point of coating uniformity.

It is preferable that a solvent is two or more types of mixed solvents containing propylene glycol monomethyl ether acetate.

[5] basic compounds

It is preferable that the composition of this invention contains a basic compound in order to reduce the performance change by time-lapse from exposure to heating.

As a basic compound, Preferably, the compound which has a structure represented by following formula (A)-(E) is mentioned.

In general formulas (A) and (E),

R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and may represent a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (having 6 to 20 carbon atoms). In this case, R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring. R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and represent an alkyl group having 1 to 20 carbon atoms.

As an alkyl group which has a substituent with respect to the said alkyl group, a C1-C20 amino alkyl group, a C1-C20 hydroxyalkyl group, or a C1-C20 cyanoalkyl group is preferable.

As for the alkyl group in these general formula (A) and (E), it is more preferable that it is unsubstituted.

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

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, 2-phenylbenzoimidazole, and the like. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] nona-5-ene and 1,8-diazabi Cyclo [5,4,0] undec-7-ene and the like. Examples of the compound having an onium hydroxide structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxide having a 2-oxoalkyl group, specifically triphenylsulfonium Hydroxide, tris (t-butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodine hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide and the like. Can be mentioned. As a compound which has an onium carboxylate structure, the anion part of the compound which has an onium hydroxide structure consists of carboxylates, For example, acetate, adamantane-1-carboxylate, perfluoroalkyl carboxylate, etc. Can be mentioned. Examples of the compound having a trialkylamine structure include tri (n-butyl) amine, tri (n-octyl) amine, and the like. Examples of the aniline compound include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline, and the like. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyl diethanolamine, tris (methoxyethoxyethyl) amine, and the like. As an aniline derivative which has a hydroxyl group and / or an ether bond, N, N-bis (hydroxyethyl) aniline etc. are mentioned.

As a preferable basic compound, the amine compound which has a phenoxy group, the ammonium salt compound which has a phenoxy group, the amine compound which has a sulfonic acid ester group, and the ammonium salt compound which has a sulfonic acid ester group are mentioned.

In the amine compound having a phenoxy group, the ammonium salt compound having a phenoxy group, the amine compound having a sulfonic acid ester group and the ammonium salt compound having a sulfonic acid ester group, at least one alkyl group is preferably bonded to a nitrogen atom. Moreover, it is preferable to have an oxygen atom in the said alkyl chain, and the oxyalkylene group is formed. The number of oxyalkylene groups is 1 or more in a molecule | numerator, Preferably it is 3-9, More preferably, it is 4-6. Among the oxyalkylene groups, the structures of —CH ₂ CH ₂ O—, —CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O— are preferred.

Specific examples of the amine compound having a phenoxy group, the ammonium salt compound having a phenoxy group, the amine compound having a sulfonic acid ester group and the ammonium salt compound having a sulfonic acid ester group include compounds (C1-1) exemplified in US2007 / 0224539A. Although (C3-3) is mentioned, it is not limited to these.

These basic compounds are used individually or in combination of 2 or more types.

The usage-amount of a basic compound is 0.001-10 mass% normally, Preferably it is 0.01-5 mass% based on the total solid of a composition.

The use ratio of the acid generator and the basic compound in the composition is preferably acid generator / basic compound (molar ratio) = 2.5 to 300. That is, a molar ratio of 2.5 or more is preferable from the point of sensitivity and resolution, and 300 or less is preferable from the point of suppression of the fall of the resolution by thickening of the resist pattern by the time-lapse until post-exposure heat processing. The acid generator / basic compound (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

[6] surfactants

The composition of this invention may contain surfactant further. When it contains, it is preferable to contain any 1 type, or 2 or more types of fluorine type and / or silicon type surfactant (surfactant which has both a fluorine type surfactant, a silicon type surfactant, and a fluorine atom and a silicon atom).

By the positive resist composition of the present invention containing the surfactant, it is possible to give a resist pattern with little adhesiveness and development defect with good sensitivity and resolution.

As a commercially available surfactant which can be used, for example, F-top EF301, EF303, [made by Shin-Akita Kasei Co., Ltd.], fluoride FC430, 431, 4430 (made by Sumitomo 3M Co., Ltd.), megapack F171, F173 , F176, F189, F113, F110, F177, F120, R08 [product made by Dainippon Ink & Chemicals Kagaku Kogyo Co., Ltd.], Suplon S-382, SC101, 102, 103, 104, 105, 106 [Asahi Glass. )], Troisol S-366 [made by Troy Chemical Co., Ltd.], GF-300, GF-150 [made by Toagosei Kagaku Co., Ltd.], Suplon S-393 [made by Seiko Chemical Co., Ltd.] Ftop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802, EF601 And fluorine-based surfactants or silicon-based surfactants such as 218G, 230G, 204D, 208D, 212D, 218D, and 222D (manufactured by Neos). In addition, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd.) can also be used as the silicon-based surfactant.

Moreover, as surfactant, in addition to the well-known thing shown above, the fluoro aliphatic compound introduce | transduced from the fluoro aliphatic compound manufactured by the telomerization method (also called teromer method) or the oligomerization method (also called oligomer method) is mentioned. Surfactants using polymers having aliphatic groups can be used. A fluoro aliphatic compound can be synthesize | combined by the method as described in [0015]-[0018] of Unexamined-Japanese-Patent No. 2002-90991. The polymer having a fluoro aliphatic group may be a copolymer of a monomer having a fluoro aliphatic group with (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate.

Examples of commercially available surfactants mentioned above include Mega Pack F178, F-470, F-473, F-475, F-476, and F-472 (manufactured by Dainippon Ink, Kakagu Kogyo Co., Ltd.). Further, copolymers of acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate (or methacrylate), acrylate (or methacrylate having a C ₃ F ₇ group) And copolymers of (poly (oxyethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate).

Moreover, in this invention, surfactant other than fluorine type and / or silicon type surfactant can also be used. Specifically, polyoxyethylene alkylaryl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether and the like, polyoxy Ethylene polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan fatty acid esters such as sorbitan tristearate, polyoxyethylene sorbitan monolaurate, Nonionic systems, such as polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate Surfactant etc. are mentioned.

These surfactants may be used alone or in any combination.

The amount of the surfactant to be used is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, particularly preferably based on the total solids (the total amount excluding the solvent) of the actinic ray-sensitive or radiation-sensitive resin composition. Preferably it is 0.0005-1 mass%.

[7] onium salts

The composition of this invention may contain carboxylic acid onium salt. As carboxylic acid onium salt, an iodonium salt and a sulfonium salt are preferable. As an anion part, a C1-C30 linear, branched, monocyclic or polycyclic cyclic alkylcarboxylic acid anion is preferable. More preferably, anions of carboxylic acids in which some or all of these alkyl groups are fluorine substituted. The alkyl chain may contain an oxygen atom. As a result, transparency to light of 220 nm or less is ensured, the sensitivity and resolution are improved, and the roughness dependency and exposure margin are improved.

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

The content in the composition of the onium salt of the carboxylic acid is generally 0.1 to 20% by mass, preferably 0.5 to 10% by mass, and more preferably 1 to 7% by mass, based on the total solids of the composition.

[8] A dissolution inhibiting compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid and increases in solubility in an alkaline developer.

As 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 and increases in solubility in an alkaline developer, a Proceeding of SPIE, Preference is given to alicyclic or aliphatic compounds containing acid-decomposable groups, such as cholic acid derivatives containing acid-decomposable groups described in 2724,355 (1996). As acid-decomposable group and alicyclic structure, the thing similar to what was demonstrated by the part of resin (A) is mentioned.

In addition, when exposing the composition of this invention with KrF excimer laser or irradiating with an electron beam, it is preferable that a dissolution inhibiting compound contains the structure which substituted the phenolic hydroxyl group of the phenol compound by the acid-decomposable group. As a phenolic compound, what contains 1-9 phenol skeletons is preferable, More preferably, it contains 2-6.

The addition amount of the dissolution inhibiting compound is preferably 3 to 50% by mass, more preferably 5 to 40% by mass relative to the solid content of the actinic ray-sensitive or radiation-sensitive resin composition.

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

[9] additives

The composition of the present invention includes a dye, a plasticizer, a photosensitizer, a light absorbing agent, and a compound for promoting solubility in a developer (for example, a phenol compound having a molecular weight of 1000 or less, an alicyclic having an carboxyl group, or an aliphatic compound), etc., if necessary. It can be contained further.

Such a phenol compound having a molecular weight of 1000 or less is referred to, for example, by the methods described in Japanese Patent Application Laid-Open No. 4-122938, Japanese Patent Application Laid-Open No. 2-28531, US Patent No. 4,916,210, European Patent No. 219294 and the like. It can be synthesized easily.

Specific examples of the alicyclic or aliphatic compound having a carboxyl group include carboxylic acid derivatives, adamantanecarboxylic acid derivatives, adamantanedicarboxylic acid, and cyclohexane having steroid structures such as cholic acid, dioxycholic acid, and lithocholic acid. Although carboxylic acid, cyclohexanedicarboxylic acid, etc. are mentioned, It is not limited to these.

Pattern Formation Method

It is preferable that the composition of this invention is used with a film thickness of 30-250 nm from a viewpoint of the resolution improvement, More preferably, it is used with a film thickness of 30-200 nm. It can be set as such a film thickness by setting solid content concentration in actinic ray or a radiation sensitive resin composition to an appropriate range, making it suitable viscosity, and improving applicability | paintability and film forming property.

The total solid content concentration in the actinic ray or the radiation-sensitive resin composition is generally 1 to 10% by mass, more preferably 1 to 8.0% by mass, still more preferably 1.0 to 6.0% by mass.

The composition of the present invention is used after dissolving the above components in a predetermined organic solvent, preferably the mixed solvent, filtering the filter, and then applying it onto a predetermined support as follows. The pore size of the filter used for filter filtration is preferably 0.1 µm or less, more preferably 0.05 µm or less, still more preferably 0.03 µm or less, made of polytetrafluoroethylene, polyethylene, or nylon.

For example, the actinic ray or radiation sensitive resin composition is applied to a substrate (eg, silicon / silicon dioxide coating) used for the manufacture of a precision integrated circuit device by a suitable coating method such as a spinner or a coater and dried to resist To form a film.

The film is irradiated with actinic light or radiation through a predetermined mask, and is preferably developed by baking (heating) and rinsing. Thereby, a favorable pattern can be obtained.

Examples of the active light or the radiation include infrared light, visible light, ultraviolet light, far-ultraviolet light, extreme ultraviolet light, X-ray, electron beam, and the like, but are preferably 250 nm or less, more preferably 220 nm or less, particularly preferably 1 to Ultraviolet light having a wavelength of 200 nm, specifically, a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F ₂ excimer laser (157 nm), an X-ray, an electron beam, or the like, and an ArF excimer laser, an F ₂ excimer Lasers, EUV (13 nm) and electron beams are preferred.

The anti-reflection film may be applied on the substrate in advance before the film is formed.

As the antireflection film, any of inorganic film types such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, and amorphous silicon, and an organic film type made of a light absorber and a polymer material can be used. As the organic antireflection film, commercially available organic antireflection films such as DUV30 series, DUV-40 series, and AR-2, AR-3, and AR-5, manufactured by Brewfrey, may be used.

As the alkali developer in the developing step, a quaternary ammonium salt usually represented by tetramethylammonium hydroxide is used, but besides this, alkalis such as inorganic alkali, primary amine, secondary amine, tertiary amine, alcohol amine and cyclic amine An aqueous solution can also be used.

Moreover, alcohol and surfactant can also be added and used for the said alkali developing solution.

The alkali concentration of alkaline developing solution is 0.1-20 mass% normally.

The pH of alkaline developing solution is 10.0-15.0 normally.

Moreover, alcohol and surfactant can be added to the alkaline aqueous solution in an appropriate amount.

Pure water can be used as a rinse liquid, and surfactant can also be used, adding an appropriate amount.

Moreover, the process which removes the developing solution or rinse liquid adhering on a pattern after a developing process or a rinse process with a supercritical fluid can be performed.

[Example]

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

Synthesis Example 1 [Synthesis of Resin (1)]

8.8 g of cyclohexanone was put into the three neck flask under nitrogen stream, and it heated at 80 degreeC. To this, 8.5 g of norbornane lactone methacrylate, 2.2 g of methacrylic acid hydroxyadamantyl, 9.0 g of 2-cyclohexyl isopropyl methacrylate, polymerization initiator V-60 [manufactured by Wako Pure Chemical Industries, Ltd.] The solution which melt | dissolved 13 mol% in 79 g of cyclohexanone with respect to the monomer was dripped over 6 hours. After completion of the dropwise addition, the mixture was further reacted at 80 ° C for 2 hours. After the reaction solution was left to cool, it was added dropwise to a mixed solution of 900 ml of methanol and 100 ml of water over 20 minutes, and the precipitated powder was collected by filtration and dried to obtain a white powdery solid polymer compound [resin (1)] having the structure shown below. 18g was obtained. As for the weight average molecular weight (Mw) of obtained resin (1), 10000 and dispersion degree (Mw / Mn) were 1.8 in GPC by polystyrene conversion.

In the same manner, other resins (2) to (14) shown below were synthesized.

The structure of the acid-decomposable resin (A) used in the Example and the comparative example is shown below. In addition, in the following table, the molar ratio of the repeating unit in each resin (from left to right in the structural formula), the weight average molecular weight (Mw), and the dispersion degree (Mw / Mn) are shown.

[Table 3]

Synthesis Example 2 (Synthesis of Acid Generator PAG-1)

The following PAG-1 was synthesized according to the following synthetic route.

Synthesis of Compound 1

After dissolving 20 g of bromomethylcyclohexane and 12.5 g of 1-naphthol in NMP 300 g in a three-necked flask, 12 g of potassium carbonate and 14 g of potassium iodide were added and heated to 120 ° C. for 8 hours. 300 g of water was added to the reaction solution, and the organic layer obtained by extraction three times with 100 g of hexane was combined, washed once with 100 g of 1N sodium hydroxide aqueous solution, once with 100 g of water, and once with 100 g of Brine, and then concentrated to compound 1 13g was obtained.

[Synthesis of Compound 2]

Compound 2 was synthesized with reference to the method described in JP 2005-266799 A.

[Synthesis of PAG-1]

After dissolving 13.1 g of compound 1 in 65 g of Eaton reagent in a three-necked flask, 5.7 g of tetramethylene sulfoxide was added dropwise while stirring, followed by stirring for 3 hours. The reaction solution was poured into 240 g of water, and then 25 g of Compound 2 and 50 g of chloroform were added. The organic layer was separated, and then further extracted twice using 50 g of chloroform from the aqueous layer. The obtained organic layer was combined and washed with water twice and concentrated. The obtained composition was recrystallized using 20 g of ethyl acetate to obtain 22 g of PAG1.

PAG-2 and 4-7 were also prepared by the same method as PAG-1. In addition, PAG-3 and PAG-8 were prepared by a well-known method.

The structure of the acid generator used in the Example and the comparative example is shown below.

<Synthesis of Hydrophobic Resin>

Synthesis Example 3 Synthesis of Hydrophobic Resin C-7

Monomers corresponding to the following repeating units were each added in a ratio of 10/10 (molar ratio), dissolved in PGMEA, and 450 g of a solution having a solid content concentration of 15% by mass was prepared. 1 mol% of the polymerization initiator V-60 made from Wako Pure Chemical Industries was added to this solution, and this was dripped at 50 g of PGMEA heated at 100 degreeC over 6 hours under nitrogen atmosphere. After completion of the dropwise addition, the reaction solution was stirred for 2 hours. The reaction liquid was cooled to room temperature after completion | finish of reaction, the white powder which crystallized and precipitated in 5 L of methanol was collected by filtration, and resin C-7 which is a target object was collect | recovered.

The polymer composition ratio determined from NMR was 90/10. In addition, the weight average molecular weight of standard polystyrene conversion calculated | required by GPC measurement was 8000, and dispersion degree 1.40.

In the same manner as in Synthesis Example 3, the composition ratios shown in Tables 1 and 2 described above for Resins C-8, C-94, HR-9, HR-26, HR-47, and HR-50; Each resin which has a weight average molecular weight (Mw) and dispersion degree (Mw / Mn) was synthesize | combined.

<Resist preparation>

The components shown in the following table were melt | dissolved in the solvent, the solution of 4 mass% of solid content concentration was prepared with respect to each, and this was filtered with the polyethylene filter which has a pore size of 0.1 micrometer, and the positive type resist composition was prepared. The prepared positive resist composition was evaluated by the following method, and the result was shown to the table | surface.

In addition, in Table 4, when the positive resist composition does not contain hydrophobic resin (HR) and forms a film, and then forms a top coat protective film containing hydrophobic resin (HR) on the upper layer, the addition form thereof. Denoted as "TC form".

Table 4-1

Table 4-2

<Image performance test>

Exposure Conditions: ArF Immersion Exposure

An organic antireflection film ARC29A (manufactured by Nissan Kagaku Co., Ltd.) was applied onto the silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film having a film thickness of 98 nm. The positive resist composition prepared thereon was apply | coated, and it baked at 120 degreeC for 60 second, and formed the resist film of film thickness 100nm. The obtained wafer was exposed through the 6% halftone mask of a pitch 130 nm contact hole pattern using ArF excimer laser immersion scanner (XT1700i by ASML, NA 1.20). Ultrapure water was used as the immersion liquid. Then, after heating at 100 degreeC for 60 second, it developed for 30 second by the aqueous tetramethylammonium hydrooxide solution (2.38 mass%), rinsed with pure water, spin-dried, and obtained the resist pattern.

In addition, in Table 3, when the positive resist composition does not contain a hydrophobic resin (C), and a top coat protective film containing a hydrophobic resin (HR) is formed on the upper layer after forming a resist film, the hydrophobic resin (C) The addition form of was made into "blank", and the use form of the top coat was described in Table 3 separately. In addition, after forming the photosensitive film at that time, the following operation was performed.

<Formation method of top coat>

On the photosensitive film, hydrophobic resin (HR) was dissolved in a solvent, applied by a spin coater, and the wafer was heated and dried at 115 ° C. for 60 seconds to form a top coat layer of 0.05 μm. At this time, the top coat coating stain was observed, and it was confirmed that it was applied uniformly without coating stain.

[Roundness evaluation]

The roundness in the contact hole pattern having a diameter of 65 nm was observed using a scanning electron microscope (S-9380II manufactured by Hitachi), the average diameter of the contact hole pattern was defined as a reference line, and the distance therefrom was measured by the length measurement SEM. The standard deviation was calculated by measuring 144 points, and 3σ was calculated. Smaller values indicate better performance.

[Focus Margin Evaluation]

When the focal point at the time of exposure is shifted up or down by 0.1 µm with respect to the optimum exposure amount for forming the contact hole pattern having a diameter of 65 nm obtained above, the line width falls within the range of ± 10% from 65 nm, which is the target line width, and further includes a pattern shape. The maximum value of the focus shift of the range which does not involve deterioration of was called focus margin. The larger the value, the greater the tolerance for the deviation of focus.

[Basic compound]

N-1: N, N-dibutylaniline

N-2: N, N-dihexyl aniline

N-3: 2,6-diisopropylaniline

N-4: tri-n-octylamine

N-5: N, N-dihydroxyethylaniline

N-6: 2,4,5-triphenylimidazole

N-7: tris (methoxyethoxyethyl) amine

[Surfactants]

W-1: Mega Pack F176 (Dai Nippon Ink Kagaku Kogyo Co., Ltd., fluorine series)

W-2: Megapack R08 (manufactured by Dainippon Ink & Chemicals Co., Ltd., fluorine and silicon system)

W-3: Polysiloxane Polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd., silicon)

W-4: Troisol S-366 (made by Troy Chemical Co., Ltd.)

W-5: PF656 (OMNOVA company, fluorine system)

W-6: PF6320 (OMNOVA, Fluorine)

[solvent]

SL-1: Cyclohexanone

SL-2: Propylene Glycol Monomethyl Ether Acetate (PGMEA)

SL-3: Ethyl Lactate

SL-4: Propylene Glycol Monomethyl Ether (PGME)

SL-5: γ-butyrolactone

SL-6: Propylene Carbonate

SL-7: 2-ethylbutanol

SL-8: Perfluorobutyltetrahydrofuran

Hydrophobic Resin (HR)

Table 3 shows that the resist pattern formed using the positive resist composition of this invention has the outstanding performance in roundness and focus margin.

Claims (7)

(A) Resin whose solubility to an alkaline developing solution increases by the action of an acid, and (B) acid is generate | occur | produced by irradiation of actinic light or radiation represented by following General formula (1-1) or (1-2). As actinic-ray-sensitive or radiation-sensitive resin composition containing the compound to make:
The said resin (A) contains the repeating unit which has an acid-decomposable group, the content rate of the said repeating unit is 45-75 mol% with respect to all the repeating units in the said resin (A), and the content rate of the said compound (B) is the said It is 10-30 mass% based on the total solid of a composition, The actinic-ray-sensitive or radiation-sensitive resin composition characterized by the above-mentioned.

[In general formula (1-1),
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton.
When two or more R <_14> exists, they respectively independently represent the group which has an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group, a cycloalkylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, or a monocyclic or polycyclic cycloalkyl skeleton.
R _{15 's} each independently represent an alkyl group, a cycloalkyl group, a phenyl group, or a naphthyl group. However, the case where two R <_15> is a phenyl group at the same time is excluded. In addition, two R ₁₅ may be bonded to each other to form a ring.
l represents the integer of 0-2.
r represents the integer of 0-8.
X ⁻ represents a non-nucleophilic anion.
In general formula (1-2),
M represents an alkyl group, a cycloalkyl group, an aryl group or a benzyl group, and when it has a ring structure, the ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbon-carbon double bond.
R _1c and R _2c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.
R _x and R _y may be bonded to each other to form a ring.
Two or more of M, R _1c and R _2c may be bonded to each other to form a ring, and the ring structure may contain a carbon-carbon double bond.
X ⁻ represents a non-nucleophilic anion.] The method of claim 1,
An actinic ray-sensitive or radiation-sensitive resin composition further comprising a hydrophobic resin having at least one of a fluorine atom and a silicon atom. The method of claim 1,
The actinic ray-sensitive or radiation-sensitive resin composition, wherein the resin (A) further contains a repeating unit containing a lactone structure. The method of claim 1,
Said resin (A) is a repeating unit which has an acid-decomposable group, and contains the repeating unit which has an acid-decomposable group containing at least a monocyclic or polycyclic alicyclic structure, The actinic-ray-sensitive or radiation-sensitive resin composition characterized by the above-mentioned. The method of claim 1,
Actinic-ray-sensitive or radiation-sensitive resin composition characterized by the immersion exposure is applied. A pattern forming method comprising the step of forming a film using the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, the step of exposing the film, and the step of developing. The method according to claim 6,
And the exposure is immersion exposure.