TW201526077A - Method for forming pattern, method for producing electronic device, electronic device and aqueous developing solution - Google Patents

Abstract

A method for forming pattern includes following steps: a step of forming an actinic ray-sensitive or radiation-sensitive resin film using an actinic ray-sensitive or radiation-sensitive resin composition, wherein the actinic ray-sensitive or radiation-sensitive resin composition contains a resin decomposed by effect of an acid to generate an acid functional group; a step of exposing the actinic ray-sensitive or radiation-sensitive resin film; and an alkali-developing step of developing the exposed actinic ray-sensitive or radiation-sensitive resin film using an aqueous developing solution containing an alkali compound having two or more alkali functional groups.

Description

Pattern forming method, method of manufacturing electronic component, electronic component, and Water developer

The present invention relates to a semiconductor manufacturing process such as an integrated circuit (IC), a circuit substrate such as a liquid crystal or a thermal head, and further photolithography lithography steps. A pattern forming method used in the method, a water-based developing solution used in the pattern forming method, a method of producing an electronic component, and an electronic component. More particularly, the present invention relates to a pattern forming method suitable for exposure using an ArF exposure apparatus and a liquid immersion type projection exposure apparatus using far ultraviolet light having a wavelength of 300 nm or less as a light source, and an aqueous developing solution used in the pattern forming method, A method of manufacturing an electronic component and an electronic component.

Since the development of a resist for KrF excimer laser (248 nm), in order to compensate for the decrease in sensitivity due to light absorption, a chemically amplified image forming method has been used as an image forming method of a resist. An example of the image forming method of the positive type chemical amplification is described as an image forming method in which an acid generator is decomposed in an exposed portion by exposure of an excimer laser, an electron beam, or an extreme ultraviolet light. and An acid is formed, and the generated acid is used as a reaction catalyst in the baking after exposure, and the alkali-insoluble group is changed to an alkali-soluble group, and the exposed portion is removed by an alkali developing solution. At present, as the alkali developing solution, an aqueous developing solution of 2.38 mass% of Tetramethyl ammonium hydroxide (TMAH) is widely used as a standard solution.

In order to achieve the miniaturization of semiconductor elements, the short wavelength of the exposure light source, and the high numerical aperture (higher numerical aperture) of the projection lens, an exposure of an ArF excimer laser having a wavelength of 193 nm as a light source is currently being developed. machine. When an ArF excimer laser is used as an exposure light source, a compound having an aromatic group exhibits a large absorption in the region of 193 nm, and an ArF excimer laser having a resin having an alicyclic hydrocarbon structure is being developed. A resist (for example, refer to Patent Document 1). In addition, as a technique for further improving the resolving power, a method of filling a liquid having a high refractive index between the projection lens and the sample (hereinafter also referred to as "liquid immersion liquid") (that is, a liquid immersion method) is proposed. In addition, Extreme Ultraviolet (EUV) lithography that uses exposure to shorter wavelength (13.5 nm) ultraviolet light is also advocated.

In recent years, a pattern forming method including an organic solvent developing solution (hereinafter referred to as "organic solvent developing solution") for developing an organic solvent developing process, for example, in Patent Document 2, is being developed. As a double patterning technique for further improving the resolving power, there is disclosed a dual developing process for performing an alkali developing process and an organic solvent developing process using an alkali developing solution for development. If the dual development process of "alkali development-organic solvent development" is described using FIG. 2, the resin in the resist composition is exposed by exposure. The polarity becomes high polarity in a region where the light intensity is high, and is maintained at a low polarity in a region where the light intensity is low. In this case, a region (exposure portion) 11 of a high exposure amount of the resist film is dissolved in the alkali development. In the liquid (see FIGS. 2( a ) and 2 ( b )), a region (unexposed portion) 13 having a low exposure amount is dissolved in the organic solvent developing solution, whereby the intermediate exposure amount region (intermediate exposure portion) 12 is left undissolved and removed during development, and a line and gap pattern having a half pitch of the exposure mask is formed (see FIGS. 2(b) and 2(c)).

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 9-73173

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2008-292975

In the double development process of "alkali development - organic solvent development", when the dissolution contrast of the region of the intermediate exposure amount (hereinafter referred to as "intermediate exposure portion") is insufficient, the residual amount of the pattern is small, and as a result, the roughness ( The line width roughness (LWR) is a big problem.

In addition, the problem of the LWR is not only a further improvement in the pattern formed by the dual development process, but also a further improvement in the pattern formed by the single development process by alkali development.

An object of the present invention is to provide a pattern forming method capable of forming a pattern having improved LWR, a water-based developing solution used in the method, and an electronic component. Manufacturing methods and electronic components. Further, an object of the present invention is to provide a pattern forming method capable of forming a pattern having good pattern remnancy and improved LWR in pattern formation including a double development process including an alkali developing process and an organic solvent developing process, and a water system used in the method. Developer solution, method of manufacturing electronic component, and electronic component.

The present invention is as follows in one aspect.

[1] A pattern forming method comprising the steps of: forming a photosensitive ray-sensitive or radiation-sensitive film using a photosensitive ray-sensitive or radiation-sensitive resin composition, wherein the sensitizing ray-sensitive or radiation-sensitive resin The composition contains a resin which decomposes by an action of an acid to generate an acidic functional group; a step of exposing the sensitizing ray-sensitive or radiation-sensitive film; and an alkalinity containing a basic functional group having two or more An aqueous developing solution of a compound, an alkali developing step of developing the exposed sensitizing ray-sensitive or radiation-sensitive film.

[2] The pattern forming method according to [1], wherein after the alkali developing step, an organic developing step of developing the photosensitive ray-sensitive or radiation-sensitive film using a developing solution containing an organic solvent is included.

[3] The pattern forming method according to [1], wherein the basic compound is a compound capable of preparing an aqueous solution having an equivalent concentration of a base of 0.1 N or more at 23 °C.

[4] The pattern forming method according to any one of [1] to [3] wherein The basic compound is a compound having at least one selected from the group consisting of a tertiary amino group and a quaternary ammonium group as a basic functional group.

[5] The pattern forming method according to [4], wherein the basic compound is a compound having at least one quaternary ammonium group as a basic functional group.

[6] The pattern forming method according to any one of [1] to [5] wherein the basic compound is a compound having three or more basic functional groups.

[7] The pattern forming method according to any one of [2] to [6] wherein, between the exposing step and the alkali developing step, the sensitizing sensation or feeling after exposure is included a heating step A of heating the radiation film, between the alkali development step and the organic development step, comprising a heating step B of heating the sensitized ray-sensitive or radiation-sensitive film after alkali development, and The heating temperature in the heating step B is higher than the heating temperature in the heating step A by 30 ° C or more.

[8] The pattern forming method according to any one of [1], wherein the exposing step is to bring a liquid into contact with the sensitizing ray-sensitive or radiation-sensitive film, and perform exposure through the liquid. A step of.

[9] A method of producing an electronic component, comprising the pattern forming method according to any one of [1] to [8].

[10] An electronic component produced by the method of producing an electronic component according to [9].

[11] An aqueous developing solution for use in a pattern forming method comprising the steps of: forming a sensitized ray-sensitive or radiation-sensitive film using a sensitizing ray-sensitive or radiation-sensitive resin composition, wherein Photosensitive rayiness or sensation The radiation-linear resin composition contains a resin which is decomposed by an action of an acid to generate an acidic functional group; a step of exposing the photosensitive ray-sensitive or radiation-sensitive film; and the exposure of the exposed light using an aqueous developing solution An alkali developing step of developing a ray-sensitive or radiation-sensitive film; and the aqueous developing solution contains a basic compound having two or more basic functional groups.

[12] The aqueous developing solution according to [11], wherein the basic compound is a compound capable of preparing an aqueous solution having an equivalent concentration of a base of 0.1 N or more at 23 °C.

[13] The aqueous developing solution according to [11], wherein the basic compound is a compound having at least one selected from the group consisting of a tertiary amino group and a quaternary ammonium group as a basic functional group.

[14] The aqueous developing solution according to [13], wherein the basic compound is a compound having at least one quaternary ammonium group as a basic functional group.

[15] The aqueous developing solution according to any one of [11], wherein the basic compound is a compound having three or more basic functional groups.

According to the present invention, it is possible to provide a pattern forming method capable of forming a pattern in which LWR is improved, a water-based developing solution used in the method, a method of manufacturing an electronic component, and an electronic component. Further, according to the present invention, it is possible to provide a pattern forming method capable of forming a pattern having good pattern remnancy and improved LWR in pattern formation including a double development process including an alkali developing process and an organic solvent developing process, and a water system used in the method. Developer solution, method of manufacturing electronic component, and electronic component.

1‧‧‧ pattern (unexposed part)

2‧‧‧Resin resin (deprotected resin)

3‧‧‧Basic compound (polybasic compound) of the present invention

4‧‧‧Substrate

11‧‧‧High exposure area (exposure section)

12‧‧‧Intermediate exposure area (intermediate exposure section)

13‧‧‧Low exposure area (unexposed part)

Fig. 1 is a pattern cross-sectional image view for explaining a mechanism for improving roughness characteristics in a pattern forming method of the present invention.

2(a) to 2(c) are views for schematically explaining a dual development process.

Hereinafter, embodiments of the present invention will be described in detail.

In the expression of the group (atomic group) in the present specification, the unsubstituted and unsubstituted expressions are not described as including a group having no substituent (atomic group) and also a group having a substituent (atomic group). For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In addition, the term "actinic ray" or "radiation" as used herein means, for example, a bright line spectrum of a mercury lamp, a far ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (EUV light), an X-ray, and an electron beam (Electron Beam). , EB) and so on. Further, the term "light" as used in the present invention means actinic ray or radiation.

In addition, the term "exposure" as used herein means not only exposure by far ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light, etc. represented by mercury lamps or excimer lasers, but also electron beams and ion beams. The drawing of the equal particle beam is also included in the exposure.

Hereinafter, each step included in the pattern forming method of the present invention will be described in detail, and then a sensitized ray-sensitive or radiation-sensitive resin composition which can be preferably used in the pattern forming method will be described in detail.

<pattern forming method>

As described above, the pattern forming method of the present invention includes the step of forming a photosensitive ray-sensitive or radiation-sensitive film using a sensitizing ray-sensitive or radiation-sensitive resin composition, wherein the sensitizing ray or feeling The radiation-linear resin composition contains a resin which decomposes by an action of an acid to generate an acidic functional group; a step of exposing the photosensitive ray-sensitive or radiation-sensitive film; and a use containing two or more basic functional groups An aqueous developing solution of an alkaline compound, an alkali developing step of developing the exposed sensitizing ray-sensitive or radiation-sensitive film.

The pattern forming method of the present invention may further include a plurality of development steps in one form, for example, preferably after the alkali development step, including using the developer containing an organic solvent to the sensitized ray-sensitive or radiation-sensitive film. An organic development step for developing.

In addition, the pattern forming method of the present invention may include a heating step in other forms, and may further include a plurality of heating steps.

Further, the pattern forming method of the present invention may include a rinsing step in other forms.

Further, the pattern forming method of the present invention may include a plurality of exposure steps in other forms.

Hereinafter, each step will be described. First, the development step will be described.

[Development Step]

The pattern forming method of the present invention includes the following alkali development step as a first feature: a basic compound containing two or more basic functional groups (hereinafter also referred to as "polybasic compound" or "basic compound of the present invention" is used. The water-based developing solution of the "other" develops the sensitized ray-sensitive or radiation-sensitive film after exposure.

At present, an aqueous developing solution of TMAH (monobasic) is widely used as an alkali developing solution for photoresist, but the inventors of the present invention have found that the pattern side wall is roughened by changing it to a water-based developing solution of a polybasic compound. The degree is improved. Further, it has been found that in the pattern formation of a dual development process including "alkali development - organic solvent development" (hereinafter referred to as "dual development process"), a water-based developer containing a polybasic compound is used as an alkali developer, and pattern sidewalls are used. The roughness is improved, and the pattern residual property is improved.

It is presumed that the improvement of the roughness characteristic of the pattern obtained by changing the aqueous developing solution for the photoresist from the aqueous developing solution of TMAH to the aqueous developing solution of the polybasic compound is due to the following mechanism. Fig. 1 is a view for explaining the mechanism of the mechanism, and will be described with reference to the drawing. In other words, the TMAH is a monobasic base. In contrast, since the basic compound of the present invention is a polybasic base, the polybasic compound 3 which acts on the developing solution of the side wall of the pattern (unexposed portion) 1 is further exposed to the exposed portion. The deprotection acid group action in the resin (deprotected resin) 2 is covered with the side wall portion of the pattern 1 by the deprotected resin 2 as shown in Fig. 1, whereby the roughness of the pattern side wall is improved.

Further, in the double development process, as described above, the intermediate exposure portion remains without being dissolved and removed during development, but when the dissolution contrast of the intermediate exposure portion is insufficient, the residual amount of the pattern is small, and as a result, the roughness is large. Become a problem. By light In the water-based developing solution in which the alkali developing solution is changed from the aqueous developing solution of TMAH to the polybasic compound, the roughness of the pattern side wall is improved, and the pattern residual property is improved. This is presumed to be due to the following mechanism. That is, an acid group is generated in the intermediate exposure portion by exposure and post-exposure heating (Post Exposure Bake (PEB)), which is subjected to contact by alkali in the developer during alkali development. And, form a salt. It is considered that in addition to the polarity transition due to deprotection, the salt formation contributes to a decrease in the dissolution rate at the time of development of the organic solvent in the intermediate exposure portion. It is presumed that by setting the base of the developer to a polybasic base, a salt of a plurality of points is formed between the acid group of the resin in the intermediate exposure portion and the alkali, whereby the degree of insolubilization becomes higher.

In the case where the pattern forming method of the present invention includes the organic developing step as the developing step after the alkali developing step, the alkali developing step is sometimes referred to as a "first developing step", and the developing solution used in the step is expressed as "the first The developing solution or the like describes the organic developing step as "second developing step", and the developing solution used in the step is referred to as "second developing solution" or the like.

. Alkali development step (first development step)

In the alkali development step, an aqueous developing solution containing a polybasic compound having two or more basic functional groups is used as a developing solution. Here, the term "water system" means that water is contained as a main component, and specifically, the content of water exceeds 50% by mass based on the total amount of the developer.

The polybasic compound of the present invention may be a low molecular compound or a high molecular compound. Here, the low molecular compound is, for example, a compound having a molecular weight of 500 or less, and the polymer compound is, for example, a compound having a molecular weight of more than 500. a compound or a compound obtained by polymerization of a monomer.

When the basic compound of the present invention is a polymer compound, the basic functional group may be contained in any of the main chain and the side chain of the polymer compound as will be described later.

In one aspect of the invention, the polybasic compound preferably has three or more basic functional groups.

The basic functional group which the polybasic compound has may, for example, be a substitutable amine group, a substitutable ammonium group or the like.

The term "substitutable amine group" as used in the present invention is a concept including a primary amino group, a secondary amino group and a tertiary amino group, such as a cyclic secondary such as pyrrolidinyl, piperazinyl or hexahydrotriazinyl. An amine group or a tertiary amino group which is a partial structure constituting a nitrogen-containing aromatic ring such as pyrazine is also included in the amine group. Hereinafter, the substitutable amine group is simply referred to as "amine group".

The "substitutable ammonium group" in the present invention means a nitrogen atom-containing group represented by the following formula, and is a concept including a primary ammonium group, a secondary ammonium group, a tertiary ammonium group, and a quaternary ammonium group. Further, the ammonium group also includes a group having a positive charge on a nitrogen atom of the nitrogen-containing aromatic ring. For example, a quaternary ammonium group which is a partial structure constituting a nitrogen-containing aromatic ring such as pyridinium is also included in the ammonium group. Hereinafter, the substitutable ammonium group is simply referred to as "ammonium group".

In one aspect of the invention, the polybasic compound of the present invention preferably contains at least one selected from the group consisting of a tertiary amino group and a quaternary ammonium group as a basic functional group, and more preferably contains at least one quaternary ammonium group.

In another aspect of the invention, the polybasic compound of the invention is preferably a low molecular compound having two or three ammonium groups.

Hereinafter, the polybasic compound of the present invention will be described.

First, a polybasic compound having an ammonium group will be described.

The ammonium group in the present invention, as described above, represents a nitrogen atom-containing group represented by the following formula, and is a concept including a primary ammonium group, a secondary ammonium group, a tertiary ammonium group, and a quaternary ammonium group. Further, the ammonium group also includes a group having a positive charge on a nitrogen atom of the nitrogen-containing aromatic ring, and for example, a quaternary ammonium group as a partial structure constituting a nitrogen-containing aromatic ring such as pyridinium is also included in the ammonium group.

When the polybasic compound of the present invention has an ammonium group, it is preferably in the form of an ammonium salt compound.

In addition, the anion contained in the ammonium salt compound (ammonium salt structure) is only The alkalinity of the developer composition may be any anion, and may be a monovalent ion or a multivalent ion.

For example, the monovalent anion may, for example, be a hydroxy anion, a sulfonate anion, a formate anion, a carboxylate anion, a sulfinate anion, a boron anion, a halide ion, a phenol anion, an alkoxy anion, a hydroxide ion or the like. Further, examples of the divalent anion include oxalate ion, phthalate ion, maleate ion, fumarate ion, tartrate ion, malate ion, lactate ion, sulfate ion, and diethylene glycol. Acid ion, 2,5-furandicarboxylate ion, and the like.

More specifically, the monovalent anion may be exemplified by OH ^- , Cl ^- , Br ^- , I ^- , AlCl ₄ ^- , Al ₂ Cl ₇ ^- , BF ₄ ^- , PF ₆ ^- , ClO ₄ ^- , NO ₃ ^- , CH ₃ COO ^- , CF ₃ COO ^- , CH ₃ SO ₃ ^- , CF ₃ SO ₃ ^- , (CF ₃ SO ₂ ) ₂ N ^- , (CF ₃ SO ₂ ) ₃ C ^- , AsF ₆ ^- , SbF ₆ ^- , NbF ₆ ^- , TaF ₆ ^- , F(HF) _n ^- , (CN) ₂ N ^- , C ₄ F ₉ SO ₃ ^- , (C ₂ F ₅ SO ₂ ) ₂ N ^- , C ₃ F ₇ COO ^- , (CF ₃ SO ₂ )(CF ₃ CO)N ^- , C ₉ H ₁₉ COO ^- , (CH ₃ ) ₂ PO ₄ ^- , (C ₂ H ₅ ) ₂ PO ₄ ^- , C ₂ H ₅ OSO ₃ ^- , C ₆ H ₁₃ OSO ₃ ^- , C ₈ H ₁₇ OSO ₃ ^- , CH ₃ (OC ₂ H ₄ ) ₂ OSO ₃ ^- , C ₆ H ₄ (CH ₃ )SO ₃ ^- , (C ₂ F ₅ ) ₃ PF ₃ ^- , CH ₃ CH(OH)COO ^- , B(C ₆ F ₅ ) ₄ ^- , FSO ₃ ^- , C ₆ H ₅ O ^- , (CF ₃ ) ₂ CHO ^- , (CF ₃ ) ₃ CHO ^- , C ₆ H ₃ ( CH ₃ ) ₂ O ^- , C ₂ H ₅ OC ₆ H ₄ COO ^- and the like.

Among them, preferred are OH ^- , sulfonate anion, carboxylate anion, bis(alkylsulfonyl)guanamine anion, tris(alkylsulfonyl)methide anion, BF ₄ ^- , PF ₆ ^- , SbF ₆ ^-, etc., more preferably OH ^- .

Specific examples of the cations contained in the ammonium salt structure of the polybasic compound of the present invention are exemplified below.

Specific examples of the anion contained in the ammonium salt structure are exemplified below.

[Chem. 3-2]

Specific examples of the ammonium salt structure are exemplified below.

[Chemical 3-3]

In a preferred aspect of the effect of the present invention, preferred examples of the ammonium salt compound include an onium salt compound represented by the formula (1-1) and a phosphonium salt compound represented by the formula (1-2). And at least one of the group consisting of the ammonium salt compounds represented by the formula (1-3).

In addition, the onium salt compound represented by the formula (1-1) may be used alone or in combination of two or more. In addition, the onium salt compound represented by the formula (1-2) may be used alone or in combination of two or more. In addition, the ammonium salt compound represented by the formula (1-3) may be used alone or in combination of two or more. In addition, two or more kinds of the onium salt compound represented by the formula (1-1), the onium salt compound represented by the formula (1-2), and the ammonium salt compound represented by the formula (1-3) may be selected. And use it.

[Chemical 4]

In the formula (1-1), R ₁ each independently represents a hydrogen atom, an aliphatic hydrocarbon group which may contain a hetero atom, an aromatic hydrocarbon group which may contain a hetero atom, or a group in which two or more of these groups are combined. . Wherein at least one R ₁ is an aliphatic hydrocarbon group or an aromatic hydrocarbon group containing an ammonium group or an amine group.

The aliphatic hydrocarbon group may be any of a linear chain, a branched chain, and a cyclic group. Further, the number of carbon atoms contained in the aliphatic hydrocarbon group is not particularly limited, and from the viewpoint of more excellent effects of the present invention, it is preferably from 1 to 15, more preferably from 1 to 5.

Examples of the aliphatic hydrocarbon group include an alkyl group, a cycloalkyl group, an alkene group, an alkyne group, or a combination of two or more kinds of these groups.

The aliphatic hydrocarbon group may also contain a hetero atom. That is, it may be a hydrocarbon group containing a hetero atom. The type of the hetero atom to be contained is not particularly limited, and examples thereof include a halogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, and a ruthenium atom. For example, including -Y ₁ H, -Y ₁ -, -N(R _a )-, -C(=Y ₂ )-, -CON(R _b )-, -C(=Y ₃ )Y ₄ -, -SO The aspect of _t- , -SO ₂ N(R _c )-, a halogen atom or a group in which two or more of these groups are combined.

Y ₁ to Y ₄ are each independently selected from the group consisting of an oxygen atom, a sulfur atom, a selenium atom, and a ruthenium atom. Among them, an oxygen atom or a sulfur atom is preferred in terms of ease of operation.

The R _a , R _b , and R _c are each independently selected from a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

t represents an integer from 1 to 3.

The number of carbon atoms contained in the aromatic hydrocarbon group is not particularly limited, and is preferably from 6 to 20, more preferably from 6 to 10, in terms of the effect of the present invention being more excellent.

Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.

The aromatic hydrocarbon group may also contain a hetero atom. The aspect containing a hetero atom is as described above. Further, when a hetero atom is contained in the aromatic hydrocarbon group, an aromatic heterocyclic group may be formed.

In a more preferable aspect of the effect of the present invention, preferred examples of R ₁ include an alkyl group which may contain a hetero atom, an olefin group which may contain a hetero atom, a cycloalkyl group which may contain a hetero atom, and may contain a hetero The aryl group of the atom.

Further, a plurality of R ₁ may be bonded to each other to form a ring. The type of the ring to be formed is not particularly limited, and examples thereof include a 5-membered ring to a 6-membered ring structure.

In the formula (1-2), R ₂ each independently represents a hydrogen atom, an aliphatic hydrocarbon group which may contain a hetero atom, an aromatic hydrocarbon group which may contain a hetero atom, or a group in which two or more of these groups are combined. . R ₃ represents a hydrogen atom, an aliphatic hydrocarbon group which may contain a hetero atom, an aromatic hydrocarbon group which may contain a hetero atom, or a group in which two or more of these groups are combined. Here, at least one of R ₂ and R ₃ is an aliphatic hydrocarbon group or an aromatic hydrocarbon group containing an ammonium group or an amine group. Specific examples of the respective groups are the same as those exemplified above for R ₁ in the formula (1-1).

A plurality of selected from R ₂ and R ₃ may be bonded to each other to form a ring. The type of the ring to be formed is not particularly limited, and examples thereof include a 5-membered ring to a 6-membered ring structure. In one embodiment of the present invention, an imidazolium ring represented by the formula (11) is preferred.

In the formula (11), R _{2 is} as defined above. Rv each independently represents a hydrogen atom or an alkyl group. A plurality of Rvs may also be bonded to each other to form a ring.

X ^- represents a monovalent anion. The definition of monovalent anions is as described above.

The definition of X ^- in the formula (1-3) is as described above. Further, in the formula (1-3), two X ^{- are} contained.

R ₄ each independently represents a hydrogen atom, an aliphatic hydrocarbon group which may contain a hetero atom, an aromatic hydrocarbon group which may contain a hetero atom, or a group in which two or more of these groups are combined.

L represents a divalent linking group. The divalent linking group may be exemplified by a substituted or unsubstituted divalent aliphatic hydrocarbon group (preferably having a carbon number of 1 to 8, such as a methylene group, an ethyl group, a propyl group or the like), substituted or Unsubstituted divalent aromatic hydrocarbon group (preferably having a carbon number of 6 to 12, such as a phenyl group), -O-, -S-, -SO ₂ -, -N(R)-(R:alkyl) , -CO-, -NH-, -COO-, -CONH- or a combination of two or more of these groups (for example, an alkoxy group, an alkoxycarbonyl group, an alkyl carbonyl oxide) Base, etc.).

Among them, in terms of the more excellent effects of the present invention, a divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group is preferred.

Further, in terms of the more excellent effects of the present invention, other preferred embodiments of the ammonium salt compound include a polymer having an ammonium salt. The polymer having an ammonium salt means a polymer having an ammonium salt structure in a side chain or a main chain. More preferably, it is a polymer containing a repeating unit having an ammonium salt structure.

The definition of the ammonium salt structure is as described above, and the definitions of the cation and the anion are also the same.

In a more preferable aspect of the effect of the present invention, a polymer having an ammonium salt may, for example, be a polymer containing a repeating unit represented by the formula (5-1).

In the formula (5-1), R _p represents a hydrogen atom or an alkyl group. The number of carbon atoms contained in the alkyl group is not particularly limited, and from the viewpoint of more excellent effects of the present invention, it is preferably from 1 to 20, more preferably from 1 to 10.

L _p represents a divalent linking group. The definition of the divalent linking group represented by L _p is the same as the definition of L represented by the above formula (1-2).

Among them, in terms of the more excellent effects of the present invention, L _{a is} preferably an alkyl group, an aryl group, a -COO- group, and a group in which two or more of these groups are combined (- Alkyl-alkyl-, -COO-alkylene-, etc.), more preferably an alkylene group.

A _p represents a residue obtained by removing one hydrogen atom from the ammonium salt represented by any one of the formula (1-1), the formula (1-2) and the formula (1-3). In addition, the term "residue" means a group which can be bonded to the structure of the _Lp by removing one hydrogen atom at an arbitrary position in the structural formula of the ammonium salt. Usually, one hydrogen atom in R is removed to become a group which can be bonded to the structure of the L _p .

The definition of each group in the formula (1-1), the formula (1-2) and the formula (1-3) is as described above.

The content of the repeating unit represented by the formula (5-1) in the polymer is not particularly limited, and in terms of the more excellent effects of the present invention, it is preferably 30 mol with respect to all the repeating units in the polymer. % (% by mole) ~ 100 mol%, more preferably 50 mol% - 100 mol%.

The weight average molecular weight of the polymer is not particularly limited, and from the viewpoint of more excellent effects of the present invention, it is preferably from 1,000 to 30,000, more preferably from 1,000 to 10,000.

A preferred embodiment of the repeating unit represented by the formula (5-1) is a repeating unit represented by the formula (5-2).

In the formula (5-2), R, R _p , L _p and X ^- are as defined above.

Further, preferred examples of the repeating unit represented by the formula (5-2) include repeating units represented by the formulae (5-3) to (5-5).

In the formula (5-3), R, R _p and X ^- are as defined above.

In the formula (5-4), R, R _p and X ^- are as defined above.

A represents -O-, -NH- or -NR-. The definition of R is the same as the definition of R in the formula (1-1).

B represents an alkylene group.

In the formula (5-5), R, R _p and X ^- are as defined above.

Specific examples of the repeating unit represented by the formula (5-2) are shown below.

Next, a polybasic compound having an amine group will be described.

The polybasic compound having two or more amine groups is, for example, a compound represented by the following formula (6).

In the above formula (6), R ⁴ and R ⁵ each independently represent a hydrogen atom, a hydroxyl group, a decyl group, an alkoxy group, an alkoxycarbonyl group, a chain hydrocarbon group having 1 to 30 carbon atoms, and a carbon number of 3 to 3; An alicyclic hydrocarbon group of 30, an aromatic hydrocarbon group having 6 to 14 carbon atoms, or a group obtained by combining two or more kinds of these groups. R ⁶ is an n-valent chain hydrocarbon group having 1 to 30 carbon atoms, an n-valent alicyclic hydrocarbon group having 3 to 30 carbon atoms, an n-valent aromatic hydrocarbon group having 6 to 14 carbon atoms, or two of these groups. An n-valent group of the above combinations. n is an integer of 2 or more. A plurality of R ⁴ and R ⁵ may be the same or different. Further, any two of R ⁴ to R ⁶ may be bonded and form a ring structure together with the nitrogen atom to which they are bonded.

Examples of the chain hydrocarbon group having 1 to 30 carbon atoms represented by R ⁴ and R ⁵ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 2-methylpropyl group, and 1- Methyl propyl, tert-butyl, and the like.

Examples of the aliphatic cyclic hydrocarbon group having 3 to 30 carbon atoms represented by R ⁴ and R ⁶ include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and a norbornyl group.

Examples of the alkyl group in the alkoxy group and the alkoxycarbonyl group represented by R ⁴ and R ⁵ include a linear or branched alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms. Specific examples thereof include the same groups as the specific examples of the chain hydrocarbon group and the aliphatic cyclic hydrocarbon group.

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R ⁴ and R ⁶ include a phenyl group, a tolyl group, and a naphthyl group.

Examples of the group in which two or more of these groups are a combination of R ⁴ and R ⁵ include a carbon number of 6 such as a benzyl group, a phenethyl group, a naphthylmethyl group or a naphthylethyl group. 12 aralkyl groups and the like.

The n-valent chain hydrocarbon group having 1 to 30 carbon atoms represented by R ⁶ is, for example, a group exemplified as the chain hydrocarbon group having 1 to 30 carbon atoms represented by R ⁴ and R ⁵ . A group obtained by removing (n-1) hydrogen atoms from the same group and the like.

The aliphatic cyclic hydrocarbon group having 3 to 30 carbon atoms represented by R ⁶ is, for example, the same as those exemplified as the aliphatic cyclic hydrocarbon group having 3 to 30 carbon atoms represented by R ⁴ and R ⁵ . A group obtained by removing (n-1) hydrogen atoms from the group.

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R ⁶ include the same groups as those exemplified as the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R ⁴ and R ⁵ . A group obtained by removing (n-1) hydrogen atoms from the group.

Examples of the group in which two or more of these groups are combined by R ⁶ are exemplified by two or more kinds of these groups represented by the above R ⁴ and R ⁵ . A group obtained by removing (n-1) hydrogen atoms from the group having the same group as exemplified in the group represented by the group.

The group represented by R ⁴ to R ⁶ may also be substituted. Specific examples of the substituent include a methyl group, an ethyl group, a propyl group, a n-butyl group, a tert-butyl group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and the like. Further, examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

Examples of the compound represented by the formula (6) include a (cyclo)alkylamine compound, a nitrogen-containing heterocyclic compound, a guanamine group-containing compound, and a urea compound.

Examples of the (cyclo)alkylamine compound include a compound having two nitrogen atoms, a compound having three or more nitrogen atoms, and the like.

Examples of the (cyclo)alkylamine compound having two nitrogen atoms include: Amine, tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4 , 4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, 2,2-bis(4-aminophenyl)propane, 2-(3-aminophenyl) -2-(4-Aminophenyl)propane, 1,4-bis[1-(4-aminophenyl)-1-methylethyl]benzene, 1,3-bis[1-(4- Aminophenyl)-1-methylethyl]benzene, bis(2-dimethylaminoethyl)ether, bis(2-diethylaminoethyl)ether, 1-(2-hydroxyethyl) Bis-2-imidazolidinone, 2-quinoxalinol, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, and the like.

Examples of the (cyclo)alkylamine compound having three or more nitrogen atoms include polymers such as polyethyleneimine, polyallylamine, and 2-dimethylaminoethyl acrylamide.

Examples of the nitrogen-containing heterocyclic compound include a nitrogen-containing aromatic heterocyclic compound and a nitrogen-containing aliphatic heterocyclic compound.

Examples of the nitrogen-containing aromatic heterocyclic compound include imidazole, 4-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, 2-phenylbenzimidazole, and 1-benzyl-2-methyl. Imidazoles such as imidazole, 1-benzyl-2-methyl-1H-imidazole, pyrazine, pyrazole, pyridazine, quinazoline, anthracene, and the like.

Examples of the nitrogen-containing aliphatic heterocyclic compound include piperazines such as piperazine and 1-(2-hydroxyethyl)piperazine; valine acid, 1,4-diazabicyclo[2.2.2]octane, and the like. .

Examples of the urea compound include urea, methyl urea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, and 1,3-diphenyl. Urea, tri-n-butyl thiourea, and the like.

Further, in terms of the more excellent effects of the present invention, other preferred embodiments of the polybasic compound of the present invention include compounds represented by the formula (3).

In the formula (3), A represents a single bond or an n-valent organic group.

Specific examples of A include the following groups: a single bond or a group represented by the following formula (1A), a group represented by the following formula (1B), -NH-, -NR _W -, -O-, -S-, carbonyl, alkylene, alkenyl, alkynyl, cycloalkyl, aromatic, heterocyclic, and the groups An n-valent organic group of a combination of two or more kinds. Here, in the formula, R _W represents an organic group, preferably an alkyl group, an alkylcarbonyl group or an alkylsulfonyl group. Further, in the combination, the hetero atoms are not linked to each other.

Among them, an aliphatic hydrocarbon group (alkylene group, alkenyl group, alkynylene group, cycloalkylene group), a group represented by the above formula (1B), -NH-, -NR _W - is preferred. .

Here, the alkyl group, the alkenyl group and the alkynylene group are preferably a carbon number of 1 to 40, more preferably a carbon number of 1 to 20, and more preferably a carbon number of 2 to 12. The alkyl group can be linear or divided Branches may also have substituents. Here, the cycloalkyl group is preferably a carbon number of 3 to 40, more preferably a carbon number of 3 to 20, and further preferably a carbon number of 5 to 12. The cycloalkyl group may be monocyclic or polycyclic, or may have a substituent on the ring.

The aromatic group may be a single ring or a polycyclic ring, and also includes a non-benzene aromatic group. Examples of the monocyclic aromatic group include a benzene residue, a pyrrole residue, a furan residue, a thiophene residue, an anthracene residue, and the like. Examples of the polycyclic aromatic group include a naphthalene residue, an anthracene residue, and a thick tetraphenyl residue. A base, a benzofuran residue, a benzothiophene residue and the like are exemplified. The aromatic group may have a substituent.

The n-valent organic group may have a substituent, and the kind thereof is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyl group, and an alkenyl group. , alkenyloxy, alkenylcarbonyl, alkenylcarbonyloxy, alkenyloxycarbonyl, alkynyl, alkynyloxy, alkynylcarbonyl, alkynylcarbonyloxy, alkynyloxycarbonyl, aralkyl, An aralkoxy group, an aralkylcarbonyl group, an aralkylcarbonyloxy group, an aralkoxycarbonyl group, a hydroxyl group, a decylamino group, a carboxyl group, a cyano group, a fluorine atom or the like.

B represents a single bond, an alkylene group, a cycloalkyl group or an aromatic group, and the alkylene group, the extended cycloalkyl group and the aromatic group may have a substituent. Here, the description of the alkyl group, the cycloalkyl group, and the aromatic group is the same as described above.

Among them, the case where A and B are both single bonds does not exist.

Rz each independently represents a hydrogen atom, an aliphatic hydrocarbon group which may contain a hetero atom, or an aromatic hydrocarbon group which may contain a hetero atom.

Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. The number of carbon atoms contained in the aliphatic hydrocarbon group is not particularly limited, and the effect of the present invention is more excellent. Preferably, it is preferably 1 to 20, more preferably 1 to 10.

Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.

The aliphatic hydrocarbon group and the aromatic hydrocarbon group may also contain a hetero atom. The definition and preferred aspect of the hetero atom are the same as the definition of the hetero atom described in the formula (1-1).

Further, the aliphatic hydrocarbon group and the aromatic hydrocarbon group may further contain a substituent (for example, a functional group such as a hydroxyl group, a cyano group, an amine group, a pyrrolidinyl group, a piperidinyl group, a morpholinyl group, a pendant oxy group, an alkoxy group, or a halogen atom). ).

n represents an integer of 2 to 8, preferably an integer of 3 to 8.

Further, the compound represented by the formula (3) preferably has three or more nitrogen atoms. In this aspect, in the case where n is 2, A contains at least one nitrogen atom. The term "A" in the A is a nitrogen atom, and means, for example, at least one selected from the group consisting of a group represented by the above formula (1B), -NH- and -NR _W -.

The compound represented by the formula (3) is exemplified below.

[Chemistry 13]

[Chemistry 14]

In other aspects in which the effects of the present invention are more excellent, other preferred aspects of the polybasic compound of the present invention are preferably exemplified by polymers having an amine group.

The amine group may be contained in either of the main chain and the side chain of the polymer.

Specific examples of the side chain in the case where the amine group is contained in a part of the side chain are shown below. Further, * indicates a connection portion with a polymer and/or an oligomer residue.

[化15]

Examples of the polymer having an amine group include polyallylamine, polyethyleneimine, polyvinylpyridine, polyvinylimidazole, polypyrimidine, polytriazole, polyquinoline, polyfluorene, polyfluorene. , polyvinylpyrrolidone, polybenzimidazole and the like.

Preferred examples of the polymer having an amine group include a polymer containing a repeating unit represented by the formula (2).

In the formula (2), R ¹ represents a hydrogen atom or an alkyl group. The number of carbon atoms contained in the alkyl group is not particularly limited, and from the viewpoint of more excellent effects of the present invention, it is preferably from 1 to 4, more preferably from 1 to 2.

R ² and R ³ each independently represent a hydrogen atom, an alkyl group which may contain a hetero atom, a cycloalkyl group which may contain a hetero atom, or an aromatic group which may contain a hetero atom.

The number of carbon atoms contained in the alkyl group and the cycloalkyl group is not particularly limited, and is preferably from 1 to 20, more preferably from 1 to 10.

Examples of the aromatic group include an aromatic hydrocarbon group or an aromatic heterocyclic group.

The alkyl group, the cycloalkyl group, and the aromatic group may further contain a hetero atom. The definition and preferred aspect of the hetero atom are the same as the definition of the hetero atom described in the formula (1-1).

Further, the alkyl group, the cycloalkyl group, and the aromatic group may further contain a substituent (for example, a functional group such as a hydroxyl group, a cyano group, an amine group, a pyrrolidinyl group, a piperidinyl group, a morpholinyl group, a pendant oxy group, or the like, or an alkane. Oxyl, halogen atom).

L _a represents a divalent linking group. The same definition of L L _a divalent represented by the formula (1-2) according to the definition above linking group represented.

Among them, in terms of the more excellent effects of the present invention, L _{a is} preferably an alkyl group, an aryl group, a -COO- group, and a group in which two or more of these groups are combined (- Alkyl-alkyl-, -COO-alkylene-, etc.), more preferably an alkylene group.

Furthermore, the divalent linking group of the R ¹ ~ R ³ and the group represented by L _a indicated substituents may further have a substituent group (e.g., hydroxyl group).

The repeating unit represented by the formula (2) is exemplified below.

[Chemistry 20]

The content of the repeating unit represented by the above formula (2) in the polymer is not particularly limited, and in terms of the more excellent effects of the present invention, it is preferably 40 mol% with respect to all the repeating units in the polymer. 100 mol%, more preferably 70 mol% to 100 mol%.

Further, the polymer may further contain other repeating units than the repeating unit represented by the formula (2).

The weight average molecular weight of the polymer having an amine group is not particularly limited, and from the viewpoint of more excellent effects of the present invention, it is preferably from 1,000 to 30,000, more preferably from 1,000 to 10,000.

In one aspect of the invention, the polybasic compound is preferably a compound which is easily dissolved in water. Specifically, a compound which can prepare an aqueous solution having an equivalent concentration of a base at 23 ° C of 0.1 N or more is preferable, and a compound which can prepare an aqueous solution of 0.2 N or more is more preferable. By using a compound which can prepare an aqueous solution of 0.1 N or more, it is easy to prepare a developing solution having an alkali concentration necessary for dissolving the resist.

The amount of the polybasic compound of the present invention added relative to the aqueous developer The present invention is not particularly limited, and is preferably from 0.1% by mass to 10% by mass, more preferably from 1% by mass to 10% by mass, even more preferably 1% by mass based on the total amount of the developer. %~5 mass%.

Further, in the present invention, the polybasic compound of the present invention may be used alone or in combination of two or more compounds having different chemical structures.

Further, in the aqueous developing solution, other basic compounds which are not plural kinds may be further added, for example, tetrabasic ammonium salts, inorganic bases, primary amines, secondary amines, tertiary amines which are not represented by tetramethylammonium hydroxide. An alcoholamine, a cyclic amine, or the like may be added with any other components such as a surfactant or an alcohol. Specific examples and amounts of the surfactant are the same as those of the organic developer described later.

The alkali concentration of the aqueous developing solution is usually 0.1% by mass to 20% by mass, and the pH of the aqueous developing solution is usually 10.0 to 15.0.

. Organic solvent development step (second development step)

In the organic solvent development step, a developer containing a solvent (hereinafter also referred to as an organic developer) is used as a developer.

The organic developer contains an organic solvent as a main component. In addition, the main component means that the content of the organic solvent exceeds 50% by mass based on the total amount of the developer.

The organic solvent to be contained in the organic developing solution is not particularly limited, and examples thereof include a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and a polar solvent such as an ether solvent, and a hydrocarbon solvent. Further, these may be mixed solvents.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, and 2-oxime. Ketone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutanone, cyclohexanone, methylcyclohexanone, phenylacetone, Methyl ethyl ketone, methyl isobutyl ketone, acetamidine acetone, acetone acetone, ionone, diacetone alcohol, acetamyl methanol, acetophenone, methylnaphthyl ketone, isophorone , propylene carbonate and so on.

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isoamyl acetate, amyl acetate, and propylene glycol monomethyl ether. Acid ester, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxy Butyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, etc. .

Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, third butanol, isobutanol, n-hexanol, n-heptanol, n-octanol, and anthracene. An alcohol solvent such as an alcohol, or a glycol solvent such as ethylene glycol, diethylene glycol or triethylene glycol, or ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether or two A glycol ether solvent such as ethylene glycol monomethyl ether, triethylene glycol monoethyl ether or methoxymethylbutanol.

The ether solvent may, for example, be dioxane or tetrahydrofuran in addition to the glycol ether solvent.

The guanamine-based solvent can be, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphonium triamine, 1 ,3-dimethyl-2- Imidazolidinone and the like.

Examples of the hydrocarbon-based solvent include an aromatic hydrocarbon solvent such as toluene or xylene, and an aliphatic hydrocarbon solvent such as pentane, hexane, octane or decane.

In particular, the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of a ketone solvent and an ester solvent, and particularly preferably contains butyl acetate as an ester solvent and a ketone solvent. A developer of methyl amyl ketone (2-heptanone).

The organic solvent may be mixed in a plurality of types, or may be used in combination with a solvent or water other than the above. In order to fully exert the effects of the present invention, it is preferred that the total moisture content of the developer is less than 10% by mass, and more preferably substantially no moisture.

In other words, the amount of the organic solvent to be used in the organic developing solution is preferably 90% by mass or more and 100% by mass or less, more preferably 95% by mass or more and 100% by mass or less based on the total amount of the developing solution.

The vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and still more preferably 2 kPa or less at 20 °C. By setting the vapor pressure of the organic developer to 5 kPa or less, evaporation of the developer onto the substrate or in the developing cup can be suppressed, and temperature uniformity in the wafer surface can be improved, resulting in uniform dimensional uniformity in the wafer surface. .

In the organic developer, an appropriate amount of a surfactant may be added as needed.

The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and/or a lanthanoid surfactant can be used. Examples of the fluorine- and/or lanthanum-based surfactants include, for example, Japanese Patent Laid-Open No. Sho 62-36663, Japanese Patent Laid-Open No. SHO 61-226746, Japanese Patent Laid-Open No. 61-226745, and Japanese Patent. JP-A-62-170950, JP-A-63-34540, JP-A-H07-230165, JP-A-H08-62834 Japanese Patent Laid-Open Publication No. Hei 9-5988, U.S. Patent No. 5,405, 720, U.S. Patent No. 5,360, 692, U.S. Patent No. 5,529, 881, U.S. Patent No. 5,296,330, U.S. Patent No. 5,436,098, U.S. Patent No. 5,576,143, The surfactant described in the specification, the specification of U.S. Patent No. 5,294,511, and the specification of U.S. Patent No. 5,824,451 is preferably a nonionic surfactant. The nonionic surfactant is not particularly limited, and a fluorine-based surfactant or a quinone-based surfactant is more preferably used.

The amount of the surfactant to be used is usually 0.001% by mass to 5% by mass, preferably 0.005% by mass to 2% by mass, and more preferably 0.01% by mass to 0.5% by mass based on the total amount of the developer.

The other steps will be described below.

[film forming step]

The application of the sensitizing ray-sensitive or radiation-sensitive resin composition of the substrate can be carried out by a generally known method. For example, a sensitizing ray-sensitive or radiation-sensitive resin composition can be applied to a substrate at a position at the center of the wafer, and then the substrate can be rotated by a rotator to form a sensitized ray-sensitive or radiation-sensitive film. A photosensitive ray-sensitive or radiation-sensitive linear composition is formed by applying a sensitizing ray-sensitive or radiation-sensitive resin composition while rotating.

[Exposure step]

The wavelength of the light source used in the exposure method of the present invention is not limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-ray, electron beam, etc., preferably 250 nm or less, more preferably 220 nm or less. Particularly preferred is a far-ultraviolet light having a wavelength of 1 nm to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm), electron beam, etc., preferably KrF excimer laser, ArF excimer laser, EUV or electron beam, more preferably ArF excimer laser.

Further, a liquid immersion exposure method can be applied to the exposure step of the present invention. The liquid immersion exposure method can be combined with a super-resolution technique such as a phase shift method or a deformation illumination method.

In the case of performing immersion exposure, the film may be heated after (1) after forming a film on the substrate, before performing the step of exposing, and/or after (2) exposing the film through the liquid immersion liquid. Before the step, a step of washing the surface of the film with a chemical liquid of a water system is performed.

The liquid immersion liquid is preferably a liquid which is transparent to the exposure wavelength and whose temperature coefficient of the refractive index is as small as possible to minimize deformation of the optical image projected onto the film, in particular, the exposure light source is an ArF excimer laser ( In the case of the wavelength; 193 nm), in addition to the above viewpoints, water is preferably used in terms of easiness of acquisition and ease of handling.

In the case of using water, an additive (liquid) which reduces the surface tension of water and increases the interfacial activity can also be added in a slight ratio. The additive preferably does not dissolve the resist layer on the wafer and has a negligible effect on the optical coating on the lower surface of the lens element.

Such an additive is preferably an aliphatic alcohol having a refractive index substantially equal to that of water, and specific examples thereof include methanol, ethanol, and isopropyl alcohol. By adding an alcohol having a refractive index substantially equal to that of water, it is possible to obtain an advantage that even if the alcohol component in the water evaporates and contains a change in concentration, the refractive index change of the entire liquid can be made extremely small.

On the other hand, when a substance which is opaque to 193 nm light or an impurity which is different in refractive index from water is mixed, deformation of the optical image projected onto the resist is caused, so that it is preferred to use water. Distilled water. More preferably, it is pure water filtered using an ion exchange filter or the like.

The electric resistance of the water used as the liquid immersion liquid is preferably 18.3 Mcm or more, and the total organic carbon (TOC) (organic matter concentration) is desirably 20 ppb or less, and desirably, a degassing treatment is performed.

In addition, the lithographic performance can be improved by increasing the refractive index of the liquid immersion liquid. From this point of view, an additive that increases the refractive index can be added to water, and heavy water (D ₂ O) can be used instead of water.

The receding contact angle of the resist film formed using the photosensitive ray-sensitive or radiation-sensitive resin composition of the present invention is 70° or more at a temperature of 23° C.±3° C. and a humidity of 45%±5%, and is suitable for a via liquid. The case where the medium is immersed for exposure is preferably 75 or more, more preferably 75 to 85.

If the receding contact angle is too small, it is not preferable to use it for exposure through a liquid immersion medium, and the effect of reducing water mark defects cannot be sufficiently exhibited. In order to achieve a preferable receding contact angle, it is preferred that the hydrophobic resin (HR) is contained in the sensitizing ray- or radiation-sensitive resin composition. Or, The receding contact angle is increased by forming a coating (so-called "top coat") of a hydrophobic resin composition on the resist film.

In the immersion exposure step, the liquid immersion liquid must follow the high-speed scanning of the exposure head on the wafer and form an exposure pattern to move on the wafer, so that the contact angle of the liquid immersion liquid to the resist film in the dynamic state becomes It is important that the resist is required to have no residual droplets and follow the performance of the high speed scanning of the exposure head.

[heating step]

The pattern forming method of the present invention may also include a heating step in one form.

The pattern forming method of the present invention may also include, for example, a pre-bake (Prebake (PB)) step between the film forming step and the exposure step.

Further, in another aspect of the pattern forming method of the present invention, a post-exposure heating (Post Exposure Bake (PEB)) step may be included between the exposure step and the alkali development step.

In addition, in the case where the pattern forming method of the present invention includes the organic solvent developing step, in order to further increase the amount of deprotection reaction of the pattern sidewall, a baking step may be included between the alkali developing step and the organic solvent developing step (first after Baking step).

Further, in the case where the pattern forming method of the present invention includes the organic solvent developing step, the heating step (second post-baking step) may be included after the organic solvent developing step.

The heating temperature in each heating step is, for example, preferably from 70 ° C to 150 ° C, more preferably from 80 ° C to 130 ° C.

The heating time in each heating step is, for example, preferably from 30 seconds to 300 seconds, more preferably from 30 seconds to 180 seconds, and even more preferably from 30 seconds to 90 seconds.

In the pattern forming method of the present invention, in a form, preferably, the heating temperature of the first post-baking between the alkali developing step and the organic solvent developing step is higher than the heating temperature in the PEB step between the exposing step and the alkali developing step More preferably, it is 30 °C higher. By setting the heating temperature of the first post-baking to a temperature higher than the heating temperature in the PEB step, an additional polarity shift reaction can be generated from the acid remaining on the sidewalls of the pattern to promote interaction with the alkali in the developer.

Further, the heating can be performed by a mechanism provided in a general exposure/developer, and a heating plate or the like can be used.

[rinsing step]

The pattern forming method of the present invention may be in a form, after the alkali developing step and/or after the organic solvent developing step, including a rinsing step of washing with an eluent.

Pure water may be used as the eluent in the rinsing treatment after alkali development, and an appropriate amount of a surfactant may be added and used.

Further, after the development treatment or the rinsing treatment, the treatment for removing the developer or eluent adhering to the pattern by the supercritical fluid may be performed.

The eluent in the rinsing treatment after the organic solvent development is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a usual organic solvent can be used. The eluent preferably contains a group selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, a guanamine solvent, and an ether solvent. At least one organic solvent eluent.

Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the guanamine solvent, and the ether solvent include the same solvents as those described in the developer containing the organic solvent.

After the step of performing development using a developing solution containing an organic solvent, it is more preferred to use at least one organic solvent containing a group selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, and a guanamine solvent. The step of washing the eluent is preferably a step of washing with an eluent containing an alcohol solvent or an ester solvent, and particularly preferably a step of washing with a eluent containing a monohydric alcohol. A step of washing the eluent containing a monohydric alcohol having 5 or more carbon atoms.

Here, the monohydric alcohol used in the elution step may be a linear, branched or cyclic monohydric alcohol, and specifically, 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and the like.

The respective components may be mixed in a plurality of kinds, and may be used in combination with an organic solvent other than the above.

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

The vapor pressure of the eluent used after the step of performing development using the developing solution containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa or more at 20 ° C. , 3kPa or less. By setting the vapor pressure of the eluent to 0.05 kPa or more and 5 kPa or less, the wafer surface The temperature uniformity inside is improved, and the swelling caused by the penetration of the eluent is suppressed, and the dimensional uniformity in the wafer surface is improved.

An appropriate amount of a surfactant may be added to the eluent for use.

In the rinsing step, the wafer developed using the developer containing the organic solvent is subjected to a cleaning treatment using an eluent containing the organic solvent. The method of the cleaning treatment is not particularly limited, and for example, a method of continuously ejecting the eluent on a substrate rotating at a constant speed (spin coating method), and a method of immersing the substrate in a tank filled with the eluent for a predetermined period of time can be applied. (dipping method), a method of spraying the eluent onto the surface of the substrate (spraying method), etc., wherein it is preferably subjected to a washing treatment by a spin coating method, and after washing, the substrate is rotated at a number of revolutions of 2000 rpm to 4000 rpm to drip The wash solution is removed from the substrate. In addition, it is also preferred to include a heating step (Post Bake) after the rinsing step. The developer and the eluent remaining between the patterns and the inside of the pattern are removed by baking. The heating step after the rinsing step is usually carried out at 40 ° C to 160 ° C, preferably 70 ° C to 95 ° C for usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

The organic developing solution, the alkali developing solution, and/or the eluent used in the present invention preferably have less impurities such as various fine particles or metal elements. In order to obtain such a chemical liquid having a small amount of impurities, it is preferred to manufacture the chemical liquids in a clean room, and further to use a Teflon (registered trademark) filter, a polyolefin-based filter, and an ion exchange filter. Various filters are used for filtration to reduce impurities. The metal element preferably has a metal element concentration of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn of 10 ppm or less, more preferably 5 ppm or less.

In addition, the storage container of the developer or the eluent is not particularly limited, and a container such as a polyethylene resin, a polypropylene resin, or a polyethylene-polypropylene resin used for the use of an electronic material can be suitably used, in order to reduce dissolution from the container. The impurity is also preferably a container selected from the inner wall of the container to be eluted into the chemical liquid. Such a container may be a container in which the inner wall of the container is a perfluoro resin (for example, a Fluoro Pure perfluoroalkoxy (PFA) composite cylinder manufactured by Entegris Co., Ltd. (the inner surface of the liquid contact; PFA resin lining), steel cans manufactured by JFE Co., Ltd. (liquid inner surface; zinc phosphate film), and the like.

The present invention also relates to a method of manufacturing an electronic component including the pattern forming method of the present invention and an electronic component manufactured by the method.

The electronic component of the present invention can be preferably mounted on an electric and electronic device (home appliance, office automation (OA)/media related device, optical device, communication device, etc.).

<Photosensitized ray-sensitive or radiation-sensitive resin composition>

Hereinafter, a photosensitive ray-sensitive or radiation-sensitive resin composition which can be used in the pattern forming method of the present invention will be described.

As the photosensitive ray-sensitive or radiation-sensitive resin composition, a known positive-type resist for g-rays and i-rays can be suitably used, specifically, a carboxylic acid is produced by photoreaction of a naphthoquinonediazide group. Light resistance. More specifically: "New development of photoresist materials, CMC Publishing, Producer: "Resist" introduced in "Chapter 4 Existing Resistors" by Ueda, "Handbook of Resist Materials for Semiconductor Integrated Circuits, "Chapter 4 g-ray / i-ray resist material" of Realize Co., Ltd. The diazonaphthoquinone (DNQ)-novolac resin-based positive photoresist described above is not limited to these compositions.

Further, the sensitizing ray-sensitive or radiation-sensitive resin composition may be a resin containing a resin which is decomposed by an action of an acid to generate an acidic functional group, and a compound which generates an acid by irradiation with actinic rays or radiation. A ray- or radiation-sensitive linear resin composition.

The photosensitive ray-sensitive or radiation-sensitive resin composition is preferably the sensitized ray-sensitive or radiation-sensitive resin composition. The sensitizing ray-sensitive or radiation-sensitive resin composition is typically a chemically amplified resist composition.

Hereinafter, each component of the sensitizing ray-sensitive or radiation-sensitive resin composition (hereinafter simply referred to as "the composition of the present invention") will be described in detail.

[1] A resin which decomposes by an action of an acid to generate an acidic functional group

The resin which is decomposed by the action of an acid to generate an acidic functional group may, for example, be an acid functional group which is decomposed by the action of an acid in the main chain or the side chain of the resin or both the main chain and the side chain. A resin (hereinafter also referred to as "acid-decomposable group") (hereinafter also referred to as "acid-decomposable resin" or "resin (A)").

The acid-decomposable group is preferably a structure having a group in which an acidic functional group is desorbed by an action of an acid to be desorbed. Preferred polar groups include a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), and a sulfonic acid group.

Preferred groups as the acid-decomposable group are groups in which a hydrogen atom of the group is substituted with a group which is desorbed by an acid.

Examples of the group which is desorbed by an acid include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), -C(R ₀₁ )(R ₀₂ ) (OR ₃₉ ) and so on.

In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group (monocyclic or polycyclic), an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may also be bonded to each other to form a ring.

R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group (monocyclic or polycyclic), a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group. Further, in the case of performing the pattern forming method of the present invention by exposure of KrF light or EUV light or by electron beam irradiation, it is also preferred to use an acid decomposition which is obtained by protecting a phenolic hydroxyl group by an acid detachment group. Sexual basis.

The resin (A) preferably contains a repeating unit having an acid-decomposable group.

The repeating unit can be exemplified by the following repeating unit.

In the general formula (aI) and the general formula (aI'), Xa ₁ represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom.

T represents a single bond or a divalent linking group.

Rx ₁ to Rx ₃ each independently represent an alkyl group or a cycloalkyl group. Two of Rx ₁ to Rx ₃ may also be bonded to form a ring structure. Further, the ring structure may contain a hetero atom such as an oxygen atom in the ring.

The divalent linking group of T may, for example, be an alkyl group, a -COO-Rt- group, an -O-Rt- group, a phenylene group or the like. In the formula, Rt represents an alkylene group or a cycloalkyl group.

From the viewpoint of insolubilization of the resist in the organic solvent-based developing solution, T in the formula (aI) is preferably a single bond or a -COO-Rt- group, and more preferably a -COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a -CH ₂ - group, a -(CH ₂ ) ₂ - group or a -(CH ₂ ) ₃ - group.

T in the formula (aI') is preferably a single bond.

The alkyl group of X _a1 may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).

The alkyl group of X _a1 is preferably a group having 1 to 4 carbon atoms, preferably a methyl group.

X _{a1 is} preferably a hydrogen atom or a methyl group.

The alkyl group of Rx ₁ , Rx ₂ and Rx ₃ may be linear or branched.

The cycloalkyl group of Rx ₁ , Rx ₂ and Rx ₃ is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group, an adamantyl group or the like. Ring cycloalkyl.

The ring structure formed by the two bonds of Rx ₁ , Rx ₂ and Rx ₃ is preferably a monocyclic cycloalkane ring such as a cyclopentyl ring or a cyclohexyl ring, a norbornane ring, a tetracyclodecane ring or a tetracyclic ring. A polycyclic cycloalkyl group such as a dodecane ring or an adamantane ring. More preferably, it is a monocyclic cycloalkane ring having a carbon number of 5 or 6.

Rx ₁ , Rx ₂ and Rx ₃ are each independently preferably an alkyl group, more preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

Each of the groups may have a substituent, and examples of the substituent include an alkyl group (having a carbon number of 1 to 4), a cycloalkyl group (having a carbon number of 3 to 8), a halogen atom, and an alkoxy group (carbon number 1 to 4). ), a carboxyl group, an alkoxycarbonyl group (having a carbon number of 2 to 6), etc., preferably having a carbon number of 8 or less. Among them, from the viewpoint of further improving the dissolution contrast in the developer containing the organic solvent before and after the acid decomposition, it is more preferably a substituent having no hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom (for example, more preferably not The alkyl group substituted by a hydroxyl group, etc.) is preferably a group containing only a hydrogen atom and a carbon atom, and more preferably a linear or branched alkyl group or a cycloalkyl group.

Specific examples of the repeating unit having an acid-decomposable group are listed, but are not limited to these specific examples.

In a specific example, Rx represents 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. Xa ₁ represents a hydrogen atom, CH ₃ , CF ₃ or CH ₂ OH. Z represents a substituent, and when there are a plurality of cases, a plurality of Z may be the same or different from each other. p represents 0 or a positive integer. Specific examples and preferred examples of Z are the same as the specific examples and preferred examples of the substituent which each group such as Rx ₁ to Rx ₃ may have.

[化22]

[Chem. 24]

In the following specific examples, Xa represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom. child.

[化29]

[化30]

[化31]

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

[化32]

The repeating unit having an acid-decomposable group may be one type or two or more types may be used in combination. By using two or more types together, it is also possible to adjust the depth of focus (Depth Of Focus), exposure latitude (Exposure Latitude), and other various performances.

When two or more types are used in combination, any acid-decomposable group may be used in combination. For example, (i) a repeating unit which decomposes by an action of an acid to generate a carboxyl group, and a repeating unit which decomposes by an action of an acid to produce an alcoholic hydroxyl group, may be used in combination. Further, (ii) a combination of two or more repeating units represented by the following formula (I) and a repeating unit represented by the formula (II), and (iii) a repeating unit represented by the formula (I) are also preferable. A combination of at least two, etc.

In the formulae (I) and (II), R ₁ and R ₃ each independently have the same meaning as Xa ₁ in the above formula (aI), and the preferred embodiment is also the same.

R ₂ , R ₄ , R ₅ and R ₆ each independently represent an alkyl group or a cycloalkyl group.

R represents an atomic group necessary for forming an alicyclic structure together with a carbon atom to which R ₂ is bonded.

The alkyl group of R ₂ may be linear or branched, and may have a substituent.

The cycloalkyl group of R ₂ may be a single ring or a polycyclic ring or may have a substituent.

R _{2 is} preferably an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and examples thereof include a methyl group and an ethyl group.

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

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

The alkyl group of R ₄ , R ₅ or R ₆ may be linear or branched, and may have a substituent. The alkyl group is preferably a group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a t-butyl group.

The cycloalkyl group of R ₄ , R ₅ and R ₆ may be a monocyclic ring or a polycyclic ring, or may have a substituent. The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group or an adamantyl group.

Each of the groups may also have a substituent.

In the case of containing two or more repeating units of the formula (I), it is preferred that the repeating unit having an alicyclic structure in which an alicyclic structure formed by R together with a carbon atom is a monocyclic ring, and R form together with a carbon atom The alicyclic structure is both a repeating unit of a polycyclic alicyclic structure. The monocyclic alicyclic structure preferably has a carbon number of 5 to 8, more preferably a carbon number of 5 or 6, and particularly preferably a carbon number of 5. The polycyclic alicyclic structure is preferably a norbornyl group, a tetracyclic fluorenyl group, a tetracyclododecyl group or an adamantyl group.

Specific examples showing a preferred combination of the cases corresponding to (ii) and (iii) described above are shown. In the following formula, R each independently represents a hydrogen atom or a methyl group.

[化34]

The content of the repeating unit having an acid-decomposable group contained in the resin (A) (which is a total amount in the case where a plurality of repeating units having an acid-decomposable group are present) is preferable with respect to all the repeating units of the resin (A). It is 15 mol% or more, more preferably 20 mol% or more, further preferably 25 mol% or more, and particularly preferably 40 mol% or more.

The resin (A) may also contain a repeating unit having a lactone structure or a sultone structure.

Specific examples of the repeating unit containing a group having a lactone structure or a sultone structure are shown below, but the present invention is not limited thereto.

[化36]

[化37]

It is also possible to use two or more kinds of repeating units having a lactone structure or a sultone structure.

In the case where the resin (A) contains a repeating unit having a lactone structure or a sultone structure, the content of the repeating unit having a lactone structure or a sultone structure is preferable with respect to all the repeating units in the resin (A). It is 5 mol% to 60 mol%, more preferably 5 mol% to 55 mol%, and further preferably 10 mol% to 50 mol%.

Further, the resin (A) may also contain a repeating unit having a cyclic carbonate structure. Specific examples are given below, but the present invention is not limited to these specific examples.

Further, in the following specific examples, R _A ¹ represents a hydrogen atom or an alkyl group (preferably a methyl group).

The resin (A) may also contain a repeating unit having a hydroxyl group or a cyano group.

Specific examples of the repeating unit having a hydroxyl group or a cyano group are listed below, but the present invention is not limited to these specific examples.

[39]

The resin (A) may also contain a repeating unit having an acid group.

The resin (A) may contain a repeating unit having an acid group, or may not contain a repeating unit having an acid group, and in the case of containing a repeating unit having an acid group, has an acid group with respect to all the repeating units in the resin (A) The content of the repeating unit is preferably 25 mol% or less, more preferably 20 mol% or less. When the resin (A) contains a repeating unit having an acid group, the content of the repeating unit having an acid group in the resin (A) is usually 1 mol% or more.

Specific examples of the repeating unit having an acid group are shown below, but the present invention is not limited thereto.

In a specific example, Rx represents H, CH ₃ , CH ₂ OH or CF ₃ .

The resin (A) may further contain a repeating unit having an alicyclic hydrocarbon structure and/or an aromatic ring structure which does not contain a polar group (for example, the acid group, a hydroxyl group, or a cyano group) and which does not exhibit acid decomposition property.

The resin (A) may contain the repeating unit or may not contain the repeating unit, and when it contains the repeating unit, it is usually 1 mol% or more and 30 mol% or less with respect to all the repeating units in the resin (A), preferably 3 mol% or more and 25 mol% or less.

Specific examples of the repeating unit having an alicyclic hydrocarbon structure containing no polar group and exhibiting no acid decomposition property are listed below, but the present invention is not limited to these specific examples. In the formula, Ra represents H, CH ₃ , CH ₂ OH or CF ₃ .

[化44]

When the composition of the present invention is used for ArF exposure, the resin (A) used in the composition of the present invention preferably has substantially no aromatic ring in terms of transparency to ArF light (specifically, In the resin, the ratio of the repeating unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, desirably 0 mol%, i.e., no aromatic group, and the resin (A) preferably has a single ring. Or a polycyclic alicyclic hydrocarbon structure.

The form of the resin (A) of the present invention may be a random type, a block type, a comb type, or Any form of a star. The resin (A) can be synthesized, for example, by radical polymerization, cationic polymerization or anionic polymerization of an unsaturated monomer corresponding to each structure. Further, after the polymerization is carried out using an unsaturated monomer corresponding to the precursor of each structure, a polymer reaction is carried out to obtain a target resin.

When the composition of the present invention is used for ArF exposure, the resin (A) used in the composition of the present invention preferably has substantially no aromatic ring in terms of transparency to ArF light (specifically, In the resin, the ratio of the repeating unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, desirably 0 mol%, i.e., no aromatic group, and the resin (A) preferably has a single ring. Or a polycyclic alicyclic hydrocarbon structure.

When the composition of the present invention contains the resin (D) described later, the resin (A) preferably has no fluorine atom or ruthenium atom from the viewpoint of compatibility with the resin (D).

The resin (A) used in the composition of the present invention preferably has a repeating unit which is composed of a (meth) acrylate-based repeating unit. In this case, all of the repeating units may be methacrylate-based repeating units, and the repeating units are all acrylate-based repeating units, and the repeating units are all derived from methacrylate-based repeating units and acrylate-based repeating units. Any one of the repeating units is preferably 50 mol% or less of all the repeating units.

When the composition of the present invention is irradiated with KrF excimer laser light, electron beam, X-ray, or high-energy light (EUV or the like) having a wavelength of 50 nm or less, the resin (A) may contain a repeating unit having an aromatic ring. The repeating unit having an aromatic ring is not particularly limited, and examples thereof include the styrene unit, the hydroxystyrene unit, and the phenyl (meth) acrylate unit. And a hydroxyphenyl (meth) acrylate unit. More specifically, the resin (A) includes a resin containing a hydroxystyrene-based repeating unit and a hydroxystyrene-based repeating unit protected by an acid-decomposable group, and the repeating unit having the aromatic ring and (meth)acrylic acid. A resin such as a repeating unit in which a carboxylic acid moiety is protected by an acid-decomposable group. Further, in particular, in the case of EUV exposure, high sensitivity is usually required, and therefore the resin (A) is preferably a repeating unit containing a protective group which is susceptible to acid decomposition. Specifically, the repeating unit may be exemplified by -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ) or -C(R ₀₁ ) in the structure described above as a group desorbed by an acid. (R ₀₂ ) (OR ₃₉ ) (generally referred to as the structure of an acetal type protecting group).

The resin (A) of the present invention can be synthesized and purified in accordance with a usual method (e.g., radical polymerization). For the synthesis method and purification method, for example, the descriptions of paragraphs 0201 to 0202 of JP-A-2008-292975 can be referred to.

The weight average molecular weight of the resin (A) of the present invention is 7,000 or more, preferably 7,000 to 200,000, as measured by a polystyrene conversion value obtained by a gel permeation chromatography (GPC) method, as described above. More preferably, it is 7,000 to 50,000, and further preferably 7,000 to 40,000,000, and particularly preferably 7,000 to 30,000. When the weight average molecular weight is less than 7,000, the solubility in the organic developer may become too high, and a precise pattern may not be formed.

The degree of dispersion (molecular weight distribution) is usually in the range of 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and particularly preferably 1.4 to 2.0. Molecular weight The smaller the cloth, the more excellent the resolution and the resist shape, and the smoother the side wall of the resist pattern, the more excellent the roughness. In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin (A) can be obtained, for example, by using HLC-8120 (manufactured by Tosoh Corporation) and using TSK gel Multipore HXL- M (manufactured by Tosoh Corporation, 7.8 mm ID × 30.0 cm) was used as a column, and Tetrahydrofuran (THF) was used as a solution.

In the chemically amplified resist composition of the present invention, the blending ratio of the resin (A) in the total composition is preferably from 30% by mass to 99% by mass, more preferably from 60% by mass to 95% by mass based on the total solid content. quality%.

Further, in the present invention, the resin (A) may be used alone or in combination of two or more.

Specific examples of the resin (A) are listed below (the composition ratio of the repeating unit is a molar ratio), but the present invention is not limited to these specific examples. In the following, the aspect in which the structure corresponding to the acid generator (B) described later is carried on the resin (A) is also exemplified.

[Chem. 46]

[化47]

[48]

The resin exemplified below is an example of a resin which can be preferably used especially in EUV exposure or electron beam exposure.

[化49]

[化53]

[54]

[化55]

[化56]

[2] Compounds which generate acid by irradiation with actinic rays or radiation

The sensitizing ray-sensitive or radiation-sensitive resin composition used in the present invention may also contain a compound which generates an acid by irradiation with actinic rays or radiation (hereinafter also referred to as "compound (B)" or "acid generator". ).

The acid generator may be in the form of a low molecular compound or may be in a form incorporated into a part of the polymer. In addition, the morphology and composition of low molecular compounds can also be incorporated. The form to a part of the polymer is used in combination.

When the acid generator is in the form of a low molecular compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,000 or less.

When the acid generator is in a form of being incorporated into a part of the polymer, it may be incorporated into a part of the acid-decomposable resin described above or may be incorporated into a resin different from the acid-decomposable resin.

In the present invention, the acid generator is preferably in the form of a low molecular compound. In one aspect of the invention, the acid generator may be a compound represented by the following formula (ZI), formula (ZII) or formula (ZIII).

In the above formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.

The organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ has a carbon number of usually 1 to 30, preferably 1 to 20.

Further, two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and may contain an oxygen atom, a sulfur atom, an ester bond, a guanamine bond or a carbonyl group in the ring. The group formed by bonding two of R ₂₀₁ to R ₂₀₃ may, for example, be an alkyl group (for example, a butyl group or a pentyl group).

Further, it may be a compound having a plurality of structures represented by the general formula (ZI). For example, it may be a compound having a structure in which at least one of R ₂₀₁ to R ₂₀₃ of the compound represented by the formula (ZI) is via a single bond or a linking group and R ₂₀₁ of another compound represented by the formula (ZI). At least one of ~R ₂₀₃ is bonded.

Z ^- represents a non-nucleophilic anion (an anion having a significantly lower ability to cause a nucleophilic reaction).

Examples of Z ^- sulfonate anion (aliphatic sulfonate anion, aromatic sulfonate anion, camphorsulfonate anion, etc.), carboxylate anion (aliphatic carboxylate anion, aromatic carboxylate anion, aralkyl carboxylate) An anion or the like), a sulfonyl quinone imine anion, a bis(alkylsulfonyl) quinone imine anion, a tris(alkylsulfonyl) methide anion, or the like.

The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number of 3 to 30. Cycloalkyl.

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

The alkyl group, cycloalkyl group and aryl group exemplified may also have a substituent. Specific examples thereof include a halogen atom such as a nitro group and a fluorine atom, a carboxyl group, a hydroxyl group, an amine group, a cyano group, an alkoxy group (preferably having a carbon number of 1 to 15), and a cycloalkyl group (preferably having a carbon number of 3~). 15) an aryl group (preferably having a carbon number of 6 to 14), an alkoxycarbonyl group (preferably having a carbon number of 2 to 7), a mercapto group (preferably having a carbon number of 2 to 12), and an alkoxycarbonyloxy group. (preferably carbon number 2~7), alkane Sulfur-based (preferably having a carbon number of 1 to 15), an alkylsulfonyl group (preferably having a carbon number of 1 to 15), an alkylimidosulfonyl group (preferably having a carbon number of 2 to 15), and an aryloxy group. A sulfonyl group (preferably having a carbon number of 6 to 20), an alkylaryloxysulfonyl group (preferably having a carbon number of 7 to 20), a cycloalkylaryloxysulfonyl group (preferably having a carbon number of 10) ~20), alkoxyalkoxy (preferably having a carbon number of 5 to 20), cycloalkylalkoxyalkoxy group (preferably having a carbon number of 8 to 20), and the like. The aryl group and the ring structure which each group has may further have an alkyl group (preferably having a carbon number of 1 to 15) as a substituent.

The aralkyl group in the aralkylcarboxylate anion is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylbutyl group, and the like. .

Examples of the sulfonyl quinone imine anion include a saccharin anion.

The alkyl group in the bis(alkylsulfonyl)phosphonium anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. The substituent of the alkyl group may, for example, be a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkoxysulfonyl group, an aryloxysulfonyl group or a cycloalkylaryloxysulfonate. The fluorenyl group or the like is preferably a fluorine atom or an alkyl group substituted by a fluorine atom.

Other Z ^- may, for example, be phosphorus fluoride (for example, PF ₆ ^- ), boron fluoride (for example, BF ₄ ^- ), or cesium fluoride (for example, SbF ₆ ^- ).

Z ^- preferably an aliphatic sulfonate anion having at least the α position of the sulfonic acid substituted by a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, or a bis (alkane) substituted with a fluorine atom by an alkyl group A tris(alkylsulfonyl)methide anion having a sulfonium iodide anion and an alkyl group substituted by a fluorine atom.

In one aspect of the invention, the number of fluorine atoms contained in the anion of Z ^- is preferably 2 or 3.

From the viewpoint of acid strength, in order to improve the sensitivity, it is preferred that the pKa of the generated acid is -1 or less.

The organic group of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may, for example, be an aryl group (preferably having a carbon number of 6 to 15), a linear or branched alkyl group (preferably having a carbon number of 1 to 10), or a cycloalkyl group (more preferably Good for carbon number 3~15).

Of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , at least one is preferably an aryl group, and more preferably all three are aryl groups. The aryl group may be a heteroaryl group such as an anthracene residue or a pyrrole residue, in addition to a phenyl group or a naphthyl group.

The aryl group, the alkyl group or the cycloalkyl group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may further have a substituent. Examples of the substituent include a halogen atom such as a nitro group or a fluorine atom, a carboxyl group, a hydroxyl group, an amine group, a cyano group, an alkoxy group (preferably having a carbon number of 1 to 15), and a cycloalkyl group (preferably having a carbon number of 3~). 15) an aryl group (preferably having a carbon number of 6 to 14), an alkoxycarbonyl group (preferably having a carbon number of 2 to 7), a mercapto group (preferably having a carbon number of 2 to 12), and an alkoxycarbonyloxy group. (preferably, carbon number 2 to 7), etc., but it is not limited to these groups.

Further, two of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may be bonded via a single bond or a linking group. The linking group may, for example, be an alkyl group (preferably having 1 to 3 carbon atoms), -O-, -S-, -CO- or -SO ₂ -, but is not limited to these groups.

A preferred structure of the case where at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is not an aryl group is exemplified by paragraphs 0046 and 0047 of Japanese Patent Laid-Open Publication No. 2004-233661, and Japanese Patent Laid-Open No. 2003-35948 The compound exemplified as the formula (I-1) to the formula (I-70) in the specification of the U.S. Patent Application Publication No. 2003/0224288A1, and the specification of the U.S. Patent Application Publication No. 2003/0077540 A1, The cation structure of the compound exemplified by IA-1) to the formula (IA-54) and the formula (IB-1) to the formula (IB-24).

More preferable examples of the compound represented by the formula (ZI) include the compounds represented by the formula (ZI-3) or the formula (ZI-4) which will be described below. First, the compound represented by the formula (ZI-3) will be described.

In the above formula (ZI-3), R ₁ represents an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkoxy group, an aryl group or an alkenyl group, and R ₂ and R ₃ each independently represent a hydrogen atom or an alkyl group. a cycloalkyl group or an aryl group, and R ₂ and R ₃ may be bonded to each other to form a ring, and R ₁ and R ₂ may be bonded to each other to form a ring, and R _X and R _y each independently represent an alkyl group or a cycloalkyl group. Alkenyl, aryl, 2-oxoalkyl, 2-oxocycloalkyl, alkoxycarbonylalkyl, alkoxycarbonylcycloalkyl, R _X and R _y may also be bonded to each other to form a ring, The ring structure may also contain an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond, or a guanamine bond.

Z ^- represents a non-nucleophilic anion.

The alkyl group as R ₁ is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and may have an oxygen atom, a sulfur atom or a nitrogen atom in the alkyl chain. Specifically, a branched alkyl group is mentioned. The alkyl group of R ₁ may also have a substituent.

The cycloalkyl group as R ₁ is preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom or a sulfur atom in the ring. The cycloalkyl group of R ₁ may also have a substituent.

The alkoxy group as R ₁ is preferably an alkoxy group having 1 to 20 carbon atoms. The alkoxy group of R ₁ may have a substituent.

The cycloalkoxy group as R ₁ is preferably a cycloalkyloxy group having 3 to 20 carbon atoms. The cycloalkoxy group of R ₁ may have a substituent.

The aryl group as R ₁ is preferably an aryl group having 6 to 14 carbon atoms. The aryl group of R ₁ may also have a substituent.

Examples of the alkenyl group of R ₁ include a vinyl group and an allyl group.

R ₂ and R ₃ represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R ₂ and R ₃ may be bonded to each other to form a ring. Here, at least one of R ₂ and R ₃ represents an alkyl group, a cycloalkyl group, or an aryl group. Specific examples and preferred examples of the alkyl group, the cycloalkyl group and the aryl group of R ₂ and R ₃ include the same groups as the specific examples and preferred examples described above for R ₁ . When R ₂ and R ₃ are bonded to each other to form a ring, the total number of carbon atoms contributing to the formation of the ring contained in R ₂ and R ₃ is preferably 4 to 7, more preferably 4 or 5.

R ₁ and R ₂ may also be bonded to each other to form a ring. In the case where R ₁ and R ₂ are bonded to each other to form a ring, R ₁ is preferably an aryl group (preferably a phenyl group or a naphthyl group which may have a substituent), and R ₂ is a from 1 to 4 carbon atoms. The group (preferably a methylene group or an ethyl group), and a preferred substituent may be the same one as the substituent which the aryl group of R ₁ described above may have. In another embodiment in which R ₁ and R ₂ are bonded to each other to form a ring, R ₁ is preferably a vinyl group, and R ₂ is an alkylene group having 1 to 4 carbon atoms.

The alkyl group represented by R _X and R _y is preferably an alkyl group having 1 to 15 carbon atoms.

The cycloalkyl group represented by R _X and R _y is preferably a cycloalkyl group having 3 to 20 carbon atoms.

The alkenyl group represented by R _X and R _y is preferably an alkenyl group of 2 to 30, and examples thereof include a vinyl group, an allyl group, and a styryl group.

The aryl group represented by R _X and R _y is, for example, an aryl group having 6 to 20 carbon atoms, preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.

Alkyl moiety and 2-oxo-alkyl alkoxycarbonyl group R _X and R _y include, for example, represented by the group R _X and R _y as enumerated above.

Examples of the cycloalkyl group of the 2-oxocycloalkyl group and the alkoxycarbonylcycloalkyl group represented by R _X and R _y include the groups exemplified above as R _X and Ry .

An aspect of R _X and R _y is preferably bonded to each other to form a ring structure. The ring structure preferably also includes a sulfur atom of the formula (ZI-3) and is a 5-membered ring or a 6-membered ring. Further, in the case where the ring structure contains an ether bond, it is preferable to reduce the decomposition of the decomposition product due to irradiation with actinic rays or radiation as an out gas.

Z ^- include, for example, as described above general formula (ZI) in the Z ^- those recited.

Specific examples of the cationic portion of the compound represented by the formula (ZI-3) are listed below.

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Next, the compound represented by the formula (ZI-4) will be described.

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In the formula (ZI-4), 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 cycloalkyl group. These groups may also have a substituent.

R ₁₄ independently represents hydroxy, alkyl, cycloalkyl, alkoxy, alkoxycarbonyl, alkylcarbonyl, alkylsulfonyl, cycloalkylsulfonyl, or a group of a cycloalkyl group. These groups may also have a substituent.

R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R ₁₅ may be bonded to each other to form a ring, and may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom as an atom constituting the ring. These groups may also have a substituent.

l represents an integer from 0 to 2.

r represents an integer from 0 to 8.

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

In the general formula (ZI-4), the alkyl group as R ₁₃ , R ₁₄ and R ₁₅ is linear or branched, and is preferably a group having 1 to 10 carbon atoms.

The cycloalkyl group of R ₁₃ , R ₁₄ and R ₁₅ may, for example, be a monocyclic or polycyclic cycloalkyl group.

The alkoxy group of R ₁₃ and R ₁₄ is linear or branched, and is preferably a group having 1 to 10 carbon atoms.

The alkoxycarbonyl group of R ₁₃ and R ₁₄ is linear or branched, and is preferably a group having 2 to 11 carbon atoms.

The group having a cycloalkyl group of R ₁₃ and R ₁₄ may, for example, be a group having a monocyclic or polycyclic cycloalkyl group. These groups may also have more substituents.

The alkyl group of the alkylcarbonyl group of R ₁₄ may be the same as the specific example of the alkyl group as R ₁₃ to R ₁₅ described above.

The alkylsulfonyl group and the cycloalkylsulfonyl group of R ₁₄ are linear, branched or cyclic, and preferably have a group having 1 to 10 carbon atoms.

The substituent which each of the groups may have may be 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 or an alkoxycarbonyl group. Oxyl and the like.

Ring structure 2 R ₁₅ may be bonded to each other include 2 formed by the general formula R ₁₅ together form a (ZI-4) the sulfur atom of a 5 or 6-membered, particularly preferably 5 to ring (ie, a tetrahydrothiophene ring or a 2,5-dihydrothiophene ring) may also be condensed with an aryl or cycloalkyl group. The two 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 alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkane group. Oxycarbonyloxy and the like. A plurality of substituents may be present for the ring structure, and in addition, the groups may be bonded to each other to form a ring.

R ₁₅ in the formula (ZI-4) is preferably a methyl group, an ethyl group, a naphthyl group, and two divalent groups in which R ^{15 is} bonded to each other and form a tetrahydrothiophene ring structure together with a sulfur atom, and the like. Two R ¹⁵ are bonded to each other and together with a sulfur atom form a divalent group of a tetrahydrothiophene ring structure.

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

l is preferably 0 or 1, more preferably 1.

r is preferably 0 to 2.

Specific examples of the cation structure of the compound represented by the formula (ZI-3) or the formula (ZI-4) described above include the above-mentioned Japanese Patent Laid-Open Publication No. 2004-233661, and Japan. A cationic structure such as a compound exemplified in the specification of the Japanese Patent Application Laid-Open No. 2003/0224288A1, the specification of the US Patent Application Publication No. 2003/0077540 A1, and the like, for example, Japanese Patent Laid-Open The cationic structure in the chemical structure and the like exemplified in paragraph 0046, paragraph 0047, paragraph 0072 to paragraph 0077, paragraph 0107 to paragraph 0110 of the Japanese Patent Publication No. 2011-53360, paragraph 0135 to paragraph 0137 of Japanese Patent Laid-Open No. 2011-53430, The cationic structure or the like in the chemical structure or the like exemplified in paragraph 0151, paragraph 0196 to paragraph 0199.

In the general formula (ZII) and the general formula (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group.

The aryl group, the alkyl group and the cycloalkyl group of R ₂₀₄ to R _{207 are the same} as the aryl group, the alkyl group or the cycloalkyl group of R ₂₀₁ to R ₂₀₃ in the compound (ZI) described above.

The aryl group, the alkyl group or the cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have a substituent. The substituent may also be a substituent which the aryl group, the alkyl group or the cycloalkyl group of R ₂₀₁ to R ₂₀₃ in the compound (ZI) described above may have.

Z ^- include, for example, as described above general formula (ZI) in the Z ^- those recited.

Next, a preferred structure of the non-nucleophilic anion Z ^- will be described.

The non-nucleophilic anion Z ^{- is} preferably a sulfonate anion represented by the formula (2).

Xf in the formula (2) each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.

R ₇ and R ₈ each independently represent a hydrogen atom, a fluorine atom, an alkyl group or an alkyl group substituted with at least one fluorine atom. When a plurality of R ₇ and R ₈ are present, R ₇ and R ₈ may be the same or different.

L represents a divalent linking group, and in the case where there are a plurality of L, the L may be the same or different.

A represents an organic group having a cyclic structure.

x represents an integer from 1 to 20. y represents an integer from 0 to 10. z represents an integer from 0 to 10.

The anion of the formula (2) will be described in more detail.

As described above, Xf is a fluorine atom or an alkyl group substituted with at least one fluorine atom, and the alkyl group in the alkyl group substituted by a fluorine atom is preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. Alkyl. Further, the alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specifically, it is preferably a fluorine atom or CF ₃ . It is especially preferred that the two Xf are fluorine atoms.

As described above, R ₇ and R ₈ represent a hydrogen atom, a fluorine atom, an alkyl group or an alkyl group substituted with at least one fluorine atom, and the alkyl group is preferably a group having 1 to 4 carbon atoms. More preferably, it is a perfluoroalkyl group having 1 to 4 carbon atoms. A specific example of the alkyl group substituted with at least one fluorine atom of R ₇ and R ₈ is preferably CF ₃ .

L represents a divalent linking group, and examples thereof include: -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, -N(Ri)- (wherein Ri Represents a hydrogen atom or an alkyl group, an alkyl group (preferably having a carbon number of 1 to 6), a cycloalkyl group (preferably having a carbon number of 3 to 10), and an alkenyl group (preferably having a carbon number of 2 to 6). Or a divalent linking group or the like obtained by combining a plurality of the groups, preferably -COO-, -OCO-, -CO-, -SO ₂ -, -CON(Ri)-, -SO ₂ N (Ri)-, -CON(Ri)-alkylene-, -N(Ri)CO-alkylene-, -COO-alkylene- or -OCO-alkylene-, more preferably -COO- , -OCO-, -SO ₂ -, -CON(Ri)- or -SO ₂ N(Ri)-. The L of the case where there are a plurality of cases may be the same or different.

The alkyl group as Ri is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and may have an oxygen atom, a sulfur atom or a nitrogen atom in the alkyl chain. Specific examples thereof include a linear alkyl group and a branched alkyl group. The alkyl group having a substituent may, for example, be a cyanomethyl group, a 2,2,2-trifluoroethyl group, a methoxycarbonylmethyl group or an ethoxycarbonylmethyl group.

The organic group having a cyclic structure of A is not particularly limited as long as it has a cyclic structure, and examples thereof include an alicyclic group, an aryl group, and a heterocyclic group (including not only aromatics but also aromatic groups). For example, a tetrahydropyran ring, a lactone ring structure, and the like are also included.

The alicyclic group may be a single ring or a polycyclic ring. Further, a nitrogen atom-containing alicyclic group such as a piperidinyl group, a decahydroquinolyl group or a decahydroisoquinolyl group is also preferred. Wherein, a norbornyl group, a tricyclic fluorenyl group, a tetracyclic fluorenyl group, a tetracyclododecyl group, an adamantyl group, a decahydroquinolyl group, a decahydroisoquinolyl group, a steroid skeleton, or the like has a large carbon number of 7 or more. The alicyclic group having a volume structure suppresses the diffusibility in the film in the PEB (post-exposure heating) step, and is preferable from the viewpoint of improving the exposure latitude.

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

Examples of the heterocyclic group include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Among them, a furan ring, a thiophene ring, and a pyridine ring are preferred.

The cyclic organic group may have a substituent, and examples of the substituent include an alkyl group (which may be any of a straight chain, a branched group, and a cyclic group, preferably a carbon number of 1 to 12) and an aryl group. The carbon number is 6 to 14), a hydroxyl group, an alkoxy group, an ester group, a decylamino group, a urethane group, a urea group, a thioether group, a sulfonylamino group, a sulfonate group, a cyano group or the like.

Further, the carbon constituting the organic group having a cyclic structure (carbon which contributes to the formation of a ring) may also be a carbonyl carbon.

x is preferably from 1 to 8, more preferably from 1 to 4, and particularly preferably 1. y is preferably 0~4, More preferably 0 or 1, and thus preferably 0. z is preferably 0 to 8, more preferably 0 to 4, and further preferably 1.

Moreover, in one aspect of the present invention, the anion represented by the formula (2) preferably has 2 or 3 fluorine atoms. Thereby, the effect of the present invention can be further improved.

Specific examples of the sulfonate anion structure represented by the formula (2) are listed below, but the present invention is not limited to these specific examples.

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Z ^{- is} also preferably a sulfonate anion represented by the following formula (B-1).

In the above formula (B-1), R _b1 each independently represents a hydrogen atom, a fluorine atom or a trifluoromethyl group (CF ₃ ).

n represents an integer from 0 to 4.

n is preferably an integer of 0 to 3, more preferably 0 or 1.

X _b1 represents a single bond, an alkylene group, an ether bond, an ester bond (-OCO- or -COO-), a sulfonate bond (-OSO ₂ - or -SO ₃ -) or a combination thereof.

X _{b1 is} preferably an ester bond (-OCO- or -COO-) or a sulfonate bond (-OSO ₂ - or -SO ₃ -), more preferably an ester bond (-OCO- or -COO-).

R _b2 represents an organic group having 6 or more carbon atoms.

The organic group having 6 or more carbon atoms of R _b2 is preferably a large-volume group, and examples thereof include an alkyl group having 6 or more carbon atoms, an alicyclic group, an aryl group, and a heterocyclic group.

The alkyl group having 6 or more carbon atoms of R _b2 may be linear or branched, and is preferably a linear or branched alkyl group having 6 to 20 carbon atoms, and examples thereof include a linear or branched hexyl group and a linear chain. Or branched heptyl, linear or branched octyl, and the like. From the viewpoint of a large volume, a branched alkyl group is preferred.

The alicyclic group having 6 or more carbon atoms of R _b2 may be a monocyclic ring or a polycyclic ring. Among them, in terms of suppressing the diffusibility in the film in the PEB (post-exposure heating) step and improving the Mask Error Enhancement Factor (MEEF), it is preferably a norborne base, a tricyclic fluorenyl group, or a fourth An alicyclic group having a bulky structure having a carbon number of 7 or more, such as a cyclodecyl group, a tetracyclododecyl group, and an adamantyl group.

The aryl group having 6 or more carbon atoms of R _b2 may be a monocyclic ring or a polycyclic ring. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group and an anthracenyl group. Among them, a naphthyl group having a relatively low light absorbance at 193 nm is preferred.

The heterocyclic group having 6 or more carbon atoms of R _b2 may be a monocyclic ring or a polycyclic ring, and in the case of a polycyclic ring, the diffusion of the acid can be further suppressed. Further, the heterocyclic group may have aromaticity or may not have aromaticity. Examples of the aromatic heterocyclic ring include a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, and a dibenzothiophene ring. Examples of the heterocyclic ring having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.

The substituent having 6 or more carbon atoms of R _b2 may further have a substituent. Examples of the further substituent include an alkyl group (which may be either a straight chain or a branched group, preferably a carbon number of 1 to 12) or a cycloalkyl group (which may be a monocyclic ring, a polycyclic ring or a spiro ring). Preferred is a carbon number of 3 to 20), an aryl group (preferably having a carbon number of 6 to 14), a hydroxyl group, an alkoxy group, an ester group, a decylamino group, a urethane group, a urea group, a thioether group, Sulfonamide and sulfonate groups. Further, the carbon constituting the alicyclic group, the aryl group or the heterocyclic group described above (the carbon contributing to the formation of a ring) may also be a carbonyl carbon.

Specific examples of the sulfonate anion structure represented by the general formula (B-1) are listed below, but the present invention is not limited to these specific examples. Further, in the following specific examples, those corresponding to the sulfonate anion represented by the above formula (2) are also included.

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Z ^{- is} also preferably a sulfonate anion represented by the following formula (AI).

In the formula (AI), R ₁ is an alkyl group, a monovalent alicyclic hydrocarbon group, an aryl group or a heteroaryl group.

R ₂ is a divalent linking group.

Rf is a fluorine atom or an alkyl group substituted with at least one fluorine atom.

n ₁ and n ₂ are each independently 0 or 1.

The alkyl group represented by R ₁ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably a carbon number. 1 to 4 alkyl groups.

In addition, the alkyl group may have a substituent (preferably a fluorine atom), The alkyl group having a substituent is preferably a perfluoroalkyl group having 1 to 5 carbon atoms.

The monovalent alicyclic hydrocarbon group represented by R ₁ preferably has a carbon number of 5 or more. Further, the monovalent alicyclic hydrocarbon group preferably has a carbon number of 20 or less, more preferably 15 or less. The monovalent alicyclic hydrocarbon group may be a monocyclic alicyclic hydrocarbon group or a polycyclic alicyclic hydrocarbon group. A part of -CH ₂ - of the alicyclic hydrocarbon group may also be substituted with -O- or -C(=O)-.

The monocyclic alicyclic hydrocarbon group is preferably a group having 5 to 12 carbon atoms, preferably a cyclopentyl group, a cyclohexyl group or a cyclooctyl group.

The polycyclic alicyclic hydrocarbon group is preferably a group having 10 to 20 carbon atoms, preferably a norbornyl group, an adamantyl group or a noradamantyl group.

The aryl group represented by R ₁ preferably has a carbon number of 6 or more. Further, the aryl group preferably has a carbon number of 20 or less, more preferably 15 or less.

The heteroaryl group represented by R ₁ preferably has a carbon number of 2 or more. Further, the heteroaryl group preferably has a carbon number of 20 or less, more preferably 15 or less.

The aryl group and the heteroaryl group may be a monocyclic aryl group or a monocyclic heteroaryl group, or may be a polycyclic aryl group or a polycyclic heteroaryl group. Specific examples thereof include a phenyl group, a naphthyl group, an anthracenyl group, a pyridyl group, a thienyl group, a furyl group, a quinolyl group, an isoquinolyl group and the like.

The monovalent alicyclic hydrocarbon group, the aryl group and the heteroaryl group of the R ₁ may further have a substituent. Examples of such a further substituent include a hydroxyl group and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine). Atom, etc.), nitro, cyano, decylamino, sulfonylamino, alkyl, alkoxy, alkoxycarbonyl, decyl, decyloxy, carboxy.

R _{1 is} particularly preferably a cyclohexyl group or an adamantyl group.

The divalent linking group represented by R ₂ is not particularly limited, and examples thereof include: -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, and alkane. a base (preferably an alkylene group having 1 to 30 carbon atoms), a cycloalkyl group (preferably a cycloalkyl group having 3 to 30 carbon atoms), an alkenyl group (preferably a carbon number of 2 to 30) Alkenyl), an aryl group (preferably a aryl group having 6 to 30 carbon atoms), a heteroaryl group (preferably a heteroaryl group having 2 to 30 carbon atoms), and two of these groups A group of the above combinations. The alkylene group, the cycloalkyl group, the alkenyl group, the aryl group and the heteroaryl group may further have a substituent. Specific examples of such a substituent are as described above for the monovalent alicyclic ring as R ₁ . The hydrocarbon group, the aryl group and the heteroaryl group may have the same groups as described above.

The divalent linking group represented by R ₂ is preferably an alkylene group, a cycloalkyl group, an alkenyl group, an aryl group, a heteroaryl group, more preferably an alkyl group, and more preferably a carbon number of 1~ The alkyl group of 10 is particularly preferably an alkylene group having a carbon number of 1 to 5.

Rf is a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group preferably has a carbon number of 1 to 4. Further, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. More specifically, Rf is preferably a fluorine atom or CF ₃ .

n _{1 is} preferably 1.

n _{2 is} preferably 1.

Preferred specific examples of the sulfonate anion represented by the above formula (A-I) are listed below, but the present invention is not limited to these specific examples. Further, in the following specific examples, those corresponding to the sulfonate anion represented by the above formula (2) are also included.

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The non-nucleophilic anion Z ^- may also be a disulfonyl sulfinyl anion represented by the formula (2').

In the formula (2'), Xf is as defined in the above formula (2), and preferred examples are also the same. In the general formula (2'), two Xf may be bonded to each other to form a ring structure.

For Z ^- di (PEI) acyl sulfonic acid anion is preferably bis (alkylsulfonyl yl) acyl imide anion.

The alkyl group in the bis(alkylsulfonyl) quinone imine anion is preferably an alkyl group having 1 to 5 carbon atoms.

The two alkyl groups in the bis(alkylsulfonyl) quinone imine anion may also be bonded to each other to form an alkylene group (preferably having a carbon number of 2 to 4), and a quinone imine group and two sulfonyl groups. Form a ring together. The ring structure which the bis(alkylsulfonyl) quinone imine anion can form is preferably a 5-membered ring to a 7-membered ring, more preferably a 6-membered ring.

The substituent which the alkyl group and the two alkyl groups are bonded to each other to form an alkylene group may, for example, be a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group or an alkoxysulfonium group. The group, the aryloxysulfonyl group, the cycloalkylaryloxysulfonyl group and the like are preferably a fluorine atom or an alkyl group substituted by a fluorine atom.

Further, the acid generator may be a compound represented by the following formula (ZV).

In the formula (ZV), R ₂₀₈ represents an alkyl group, a cycloalkyl group or an aryl group.

A represents an alkyl group, an alkenyl group or an aryl group.

Specific examples of the aryl group of R ₂₀₈ include the same groups as the specific examples of the aryl group of R ₂₀₁ to R ₂₀₃ in the above formula (ZI).

Specific examples of the alkyl group and the cycloalkyl group of R ₂₀₈ include the same groups as the specific examples of the alkyl group and the cycloalkyl group of R ₂₀₁ to R ₂₀₃ in the above formula (ZI).

The alkylene group of A may be an alkylene group having 1 to 12 carbon atoms, the alkenyl group of A may be an alkenyl group having 2 to 12 carbon atoms, and the extended aryl group of A may be an alkyl group having 6 to 10 carbon atoms. .

Examples of the acid generator are listed below. However, the invention is not limited to the examples.

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The acid generator can be synthesized by a known method, for example, according to JP-A-2007-161707, JP-A-2010-100595, <0200> to <0210>, and International Publication No. 2011/093280. <0051>~<0058>, the method described in <0382> to <0385> of the International Publication No. 2008/153110, and the method described in JP-A-2007-161707, etc., is synthesized.

The acid generators may be used alone or in combination of two or more.

The content of the compound which generates an acid by irradiation with actinic rays or radiation is preferably from 0.1% by mass to 30% by mass, more preferably 0.5% by mass based on the total solid content of the composition of the present invention. %~25 mass%, and further preferably 3% by mass to 20% by mass, particularly preferably 3% by mass to 15% by mass.

Further, depending on the composition of the sensitizing ray-sensitive or radiation-sensitive resin, the structure corresponding to the acid generator is carried on the resin (A) (B'). Specifically, the structure described in Japanese Laid-Open Patent Publication No. 2011-248019 (especially the structure described in paragraphs 0164 to 0019 and the structure of the resin described in the example of paragraph 0555), and Japan The repeating unit (R) and the like described in paragraphs 0023 to 0210 of JP-A-2013-80002. Incidentally, even if the structure corresponding to the acid generator is carried on the resin (A), the sensitizing ray-sensitive or radiation-sensitive resin composition may additionally contain no resin ( Acid generator on A).

The aspect (B') may be exemplified by the following repeating unit, but is not limited thereto.

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[3] Solvent

The composition of the present invention usually contains a solvent.

Examples of the solvent which can be used in the preparation of the composition of the present invention include an alkylene glycol monoalkyl ether carboxylate, an alkylene glycol monoalkyl ether, an alkyl lactate, and an alkoxypropionic acid alkyl group. An ester, a cyclic lactone (preferably having a carbon number of 4 to 10), a monoketone compound which may have a ring (preferably having a carbon number of 4 to 10), an alkyl carbonate, an alkyl alkoxyacetate, and acetone. An organic solvent such as an acid alkyl ester.

Specific examples of the solvent include the solvents described in the specification of the U.S. Patent Application Publication No. 2008/0187860, <0441> to <0455.

In the present invention, a plurality of organic solvents may also be used in combination.

For example, a mixed solvent obtained by mixing a solvent having a hydroxyl group in the structure and a solvent containing no hydroxyl group may be used as the organic solvent. Solvent containing hydroxyl, not The hydroxyl group-containing solvent may be appropriately selected from the above-exemplified compounds, and the hydroxyl group-containing solvent is preferably an alkylene glycol monoalkyl ether, an alkyl lactate or the like, more preferably a propylene glycol monomethyl ether (Propylene Glycol Monomethyl Ether). , PGME, alias 1-methoxy-2-propanol), ethyl lactate. Further, the solvent containing no hydroxyl group is preferably an alkylene glycol monoalkyl ether acetate, an alkyl alkoxy propionate, a ring-containing monoketone compound, a cyclic lactone, an alkyl acetate, or the like. Particularly preferred among these are Propylene Glycol Monomethyl Ether Acetate (PGMEA, alias 1-methoxy-2-ethoxypropane), ethyl ethoxy propionate, 2- Heptone, γ-butyrolactone, cyclohexanone, butyl acetate, preferably propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone.

Further, it is of course also possible to use an organic solvent having no hydroxyl group in the structure in combination with each other. The combination thereof may be exemplified by PGMEA and cyclohexanone, PGMEA and cyclopentanone, PGMEA and γ-butyrolactone, PGMEA and 2-heptanone.

For example, when two solvents are used, the mixing ratio (mass) is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 60/40.

The solvent preferably contains propylene glycol monomethyl ether acetate, preferably propylene glycol monomethyl ether acetate alone solvent or two or more mixed solvents containing propylene glycol monomethyl ether acetate.

In addition, when a solvent having a relatively high boiling point such as γ-butyrolactone is used in an appropriate amount, the hydrophobic resin (D) described later is more biased toward the surface, and performance for immersion exposure is expected to be improved.

Further, three or more kinds of solvents may be used. Sometimes it’s also tiny Resist shape adjustment, viscosity adjustment, etc. Combinations include: PGMEA/PGME/γ-butyrolactone, PGMEA/PGME/cyclohexanone, PGMEA/PGME/2-heptanone, PGMEA/cyclohexanone/γ-butyrolactone, PGMEA/γ-butyrolactone /2-heptanone and the like.

[4] Hydrophobic resin (D)

The composition of the present invention may contain a hydrophobic resin (hereinafter also referred to as "hydrophobic resin (D)" or simply "resin (D)") particularly when applied to liquid immersion exposure. Further, the hydrophobic resin (D) is preferably different from the resin (A).

Thereby, the hydrophobic resin (D) is biased toward the surface layer of the film, and when the liquid immersion medium is water, the static/dynamic contact angle of the surface of the resist film with respect to water can be improved, and the liquid immersion liquid followability can be improved.

Further, even when the composition is not applied to the immersion exposure, the hydrophobic resin can be contained for various purposes. For example, when the composition is applied to EUV exposure, it is also preferred to use a hydrophobic resin in order to suppress outgassing, adjust the shape of the pattern, and the like.

The hydrophobic resin (D) is preferably designed to be biased toward the interface as described above, but unlike the surfactant, it is not necessarily required to have a hydrophilic group in the molecule, or may be uniformly mixed with a polar/nonpolar substance. Not helpful.

The hydrophobic resin (D) is preferably one or more of a "fluorine atom", a "deuterium atom", and a "CH ₃ partial structure contained in a side chain portion of the resin" from the viewpoint of the film surface layer. Furthermore, it is preferable to have two or more types.

The standard polystyrene-equivalent weight average molecular weight of the hydrophobic resin (D) is preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000, and still more preferably 2,000. ~15,000.

Further, the hydrophobic resin (D) may be used alone or in combination of two or more.

The content of the hydrophobic resin (D) in the composition is preferably from 0.01% by mass to 10% by mass, more preferably from 0.05% by mass to 8% by mass, based on the total solid content of the composition of the present invention, and further preferably 0.1% by mass to 7% by mass.

The hydrophobic resin (D) is preferably a small amount of impurities such as a metal as in the case of the resin (A), and the residual monomer or oligomer component is 0.01% by mass to 5% by mass, more preferably 0.01% by mass to 3% by mass. Further, it is more preferably 0.05% by mass to 1% by mass. Thereby, a chemically amplified resist composition having no change in the amount of foreign matter or sensitivity in the liquid can be obtained. Further, the molecular weight distribution (Mw/Mn, also referred to as dispersity) is preferably in the range of 1 to 5, in terms of resolution, resist shape, side wall of the resist pattern, roughness, and the like, and more preferably 1~3, and then the range of 1~2.

The hydrophobic resin (D) can also be used in various commercial products, and can be synthesized according to a usual method (for example, radical polymerization). For example, a general synthesis method may be a method in which a monomer type and an initiator are dissolved in a solvent and heated to carry out polymerization, and a monomer polymerization method is carried out by adding a monomer species to a heating solvent for 1 hour to 10 hours. The dropwise addition polymerization method of the solution of the initiator is preferably a dropping polymerization method.

The reaction solvent, the polymerization initiator, the reaction conditions (temperature, concentration, etc.) and the purification method after the reaction are the same as those described in the resin (A), and in the synthesis of the hydrophobic resin (D), the concentration of the reaction is preferably 30% by mass to 50% by mass. More specifically, the description in the vicinity of paragraphs 0320 to 0329 of Japanese Patent Laid-Open Publication No. 2008-292975 can be referred to.

Specific examples of the hydrophobic resin (D) are shown below. Further, the following table shows the molar ratio of the repeating unit in each resin (corresponding to each repeating unit from left to right), the weight average molecular weight, and the degree of dispersion.

[化85]

[化86]

[Table 1]

[化87]

[化88]

[化89]

[化90]

[table 2-1]

[Table 2-2]

[5] Basic compounds

The composition of the present invention preferably contains a basic compound.

(1) The composition of the present invention preferably contains a basic compound or an ammonium salt compound (hereinafter also referred to as "compound (N)") which is reduced in alkali by irradiation with actinic rays or radiation. As a basic compound.

The compound (N) is preferably a compound (N-1) having a basic functional group or an ammonium group and a group which generates an acidic functional group by irradiation with actinic rays or radiation. That is, the compound (N) is preferably a basic compound having a basic functional group and a group which generates an acidic functional group by irradiation with actinic rays or radiation, or has An ammonium salt and an ammonium salt compound which generates an acidic functional group by irradiation with actinic rays or radiation.

Specific examples of the compound (N) include the following compounds. Further, in addition to the compounds listed below, as the compound (N), for example, a compound of (A-1) to (A-44) described in the specification of the US Patent Application Publication No. 2010/0233629, or the United States, or the United States The compound of (A-1) to (A-23) described in the specification of Patent Application Publication No. 2012/0156617 is preferably used in the present invention.

These compounds can be synthesized in accordance with the synthesis examples and the like described in JP-A-2006-330098.

The molecular weight of the compound (N) is preferably from 500 to 1,000.

The composition of the present invention may contain the compound (N) or the compound (N). When the compound (N) is contained, the solid content of the composition is The content of the compound (N) is preferably from 0.1% by mass to 20% by mass, and more preferably from 0.1% by mass to 10% by mass.

(2) The composition of the present invention may contain a basic compound (N') different from the compound (N) as a basic compound in order to reduce the change in performance over time from exposure to heating. .

The basic compound (N') is preferably a compound having a structure represented by the following formula (A') to formula (E').

In the general formula (A') and the general formula (E'), RA ²⁰⁰ , RA ²⁰¹ and RA ²⁰² may be the same or different and each represents a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), or a cycloalkyl group ( Preferably, the carbon number is 3 to 20) or the aryl group (carbon number is 6 to 20), and here, the RA ²⁰¹ and the RA ²⁰² may be bonded to each other to form a ring. RA ²⁰³ , RA ²⁰⁴ , RA ²⁰⁵ and RA ²⁰⁶ may be the same or different and represent an alkyl group (preferably having a carbon number of 1 to 20).

The alkyl group may have a substituent, and the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms or a cyanoalkyl group having 1 to 20 carbon atoms. .

The alkyl groups in the general formula (A') and the general formula (E') are more preferably unsubstituted.

Preferred examples of the basic compound (N') include hydrazine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, etc., and further preferably Specific examples thereof include a compound having an imidazole structure, a diazabicyclo structure, a phosphonium hydroxide structure, a phosphonium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, and having a hydroxyl group and/or an ether bond. An alkylamine derivative, an aniline derivative having a hydroxyl group and/or an ether bond, or the like.

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole and the like. The compound having a diazabicyclo structure may, for example, be 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8- Diazabicyclo[5.4.0]undec-7-ene and the like. Examples of the compound having a ruthenium hydroxide structure include triaryl ruthenium hydroxide, benzamidine methyl hydrazine hydroxide, ruthenium hydroxide having a 2-oxoalkyl group, specifically triphenylphosphonium hydroxide, hydrogen Tris(t-butylphenyl)phosphonium oxide, bis(t-butylphenyl)phosphonium hydroxide, benzamidine methylthiophene hydroxide, 2-oxopropylthiophene hydroxide, and the like. The compound having a ruthenium carboxylate structure is one in which the anion portion of the compound having a ruthenium hydroxide structure is a carboxylate, and examples thereof include an acetate, an adamantane-1-carboxylate, and a perfluoroalkylcarboxylate. The compound having a trialkylamine structure may, for example, be tri(n-butyl)amine or tri(n-octyl)amine. The compound having an aniline structure may, for example, be 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline or N,N-dihexylaniline. The alkylamine derivative having a hydroxyl group and/or an ether bond may, for example, be ethanolamine, diethanolamine, triethanolamine or tris(methoxyethoxyethyl)amine. Examples of the aniline derivative having a hydroxyl group and/or an ether bond include N,N-bis(hydroxyethyl)aniline.

Further, preferred examples of the basic compound include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonate group, and an ammonium salt compound having a sulfonate group. Specific examples thereof include the compound (C1-1) to the compound (C3-3) exemplified in <0066> of the specification of US Patent Application Publication No. 2007/0224539, but are not limited thereto.

Nitrogen-containing organic compounds having further detached groups may also be included. Specific examples of the compound are shown below, for example.

The compound can be synthesized, for example, according to the method described in JP-A-2009-199021.

Further, as the basic compound (N'), a compound having an amine oxide structure can also be used. Specific examples of the compound can be used: triethylamine pyridine-N-oxide, tributylamine-N-oxide, triethanolamine-N-oxide, tris(methoxyethyl)amine-N-oxide , tris(2-(methoxymethoxy)ethyl)amine=oxide, 2,2',2"-azalkynyl triethylpropionate-N-oxide, N-2-(2 -methoxyethoxy)methoxyethylmorpholine-N-oxidation An amine oxide compound exemplified in Japanese Patent Laid-Open Publication No. 2008-102383.

The molecular weight of the basic compound (N') is preferably from 250 to 2,000, more preferably from 400 to 1,000. The molecular weight of the basic compound is preferably 400 or more, more preferably 500 or more, and still more preferably 600 or more from the viewpoint of further reduction of LWR and uniformity of local pattern size.

These basic compounds (N') may also be used in combination with the compound (N), and may be used singly or in combination of two or more.

The chemically amplified resist composition of the present invention may contain a basic compound (N') or a basic compound (N'), and in the case of a basic compound (N'), a chemically amplified resist The amount of the basic compound (N') to be used is usually 0.001% by mass to 10% by mass, preferably 0.01% by mass to 5% by mass based on the solid content of the agent composition.

(4) The composition of the present invention may contain, as another basic compound, a phosphonium salt represented by the following formula (6A) or (6B). Regarding the onium salt, it is expected that the diffusion of acid generated in the resist system is suppressed by the relationship with the acid strength of the photoacid generator generally used in the resist composition.

In the formula (6A), Ra represents an organic group. Among them, a fluorine atom is substituted for a group on a carbon atom directly bonded to a carboxylic acid group in the formula.

X ⁺ represents a phosphonium cation.

In the formula (6B), Rb represents an organic group. Wherein the fluorine atom is substituted for the group on the carbon atom directly bonded to the sulfonic acid group in the formula.

X ⁺ represents a phosphonium cation.

The organic group represented by Ra and Rb is preferably a carbon atom which is directly bonded to a carboxylic acid group or a sulfonic acid group in the formula. Wherein, in this case, in order to form an acid which is relatively weaker than the acid produced by the photoacid generator described above, the unsubstituted fluorine on the carbon atom directly bonded to the sulfonic acid group or the carboxylic acid group atom.

Examples of the organic group represented by Ra and Rb include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 3 to 30 carbon atoms. Some or all of the hydrogen atoms of the groups may also be substituted.

Examples of the substituent which the alkyl group, the cycloalkyl group, the aryl group, the arylalkyl group and the heterocyclic group may have include a hydroxyl group, a halogen atom, an alkoxy group, a lactone group, an alkylcarbonyl group and the like.

Examples of the phosphonium cation represented by X ⁺ in the general formula (6A) and the general formula (6B) include a phosphonium cation, an ammonium cation, a phosphonium cation, a phosphonium cation, a diazo cation, and the like. Among them, a phosphonium cation is more preferable.

The phosphonium cation is preferably, for example, an aryl cation having at least one aryl group. More preferably, it is a triarylsulfonium cation. The aryl group may also have a substituent, and the aryl group is preferably a phenyl group.

Examples of the phosphonium cation and the phosphonium cation are also preferably exemplified by the structure described in the compound (B).

The specific structure of the onium salt represented by the general formula (6A) or the general formula (6B) is shown below.

(5) The composition of the present invention may contain, in other forms, the following compound as a basic compound: a compound contained in the formula (I) of JP-A-2012-189977, Japanese Patent Laid-Open No. 2013-6827 The compound represented by the formula (I) of the publication, the compound represented by the formula (I) of JP-A-2013-8020, and the compound represented by the formula (I) of JP-A-2012-252124 A compound having both a phosphonium salt structure and an acid anion structure (hereinafter also referred to as a betaine compound) in one molecule. The structure of the cerium salt can be exemplified by cerium, lanthanum The structure is preferably a ruthenium or osmium salt structure. Further, the acid anion structure is preferably a sulfonate anion or a carboxylate anion. Examples of the compound include the following compounds.

[6] surfactants

The composition of the present invention may further contain a surfactant. When the composition of the present invention contains a surfactant, it is more preferable to contain a fluorine-based and/or a lanthanoid surfactant (a fluorine-based surfactant, a lanthanoid surfactant, and an interface having both a fluorine atom and a ruthenium atom). Either or two or more of the active agents).

When the composition of the present invention contains a surfactant, when an exposure light source of 250 nm or less, particularly 220 nm or less is used, a resist pattern having less adhesion and development defects can be formed with good sensitivity and resolution.

Examples of the fluorine-based and/or lanthanoid surfactants include the surfactants described in <0276> of the specification of U.S. Patent Application Publication No. 2008/0248425, for example, Fluorad FC430, Fluorad FC431. , Fluorad FC4430 (made by Sumitomo 3M (share)), Megafac series (Di Aisheng) (DIC) (manufactured by the stock), Surflon S-382, Surflon SC101, Surflon SC102, Surflon SC103, Surflon SC104 , Surflon SC105, Surflon SC106, Surflon KH-20 (made by Asahi Glass), Troy-sol S-366 (Troy-Troy- Chemical), GF-300, GF-150 (manufactured by East Asia Synthetic Chemicals Co., Ltd.), Surflon S-393 (made by Seimi Chemical Co., Ltd.), Aifutuo (F-top) EF121, F-top EF122A, F-top EF122B, F-top RF122C, F-top EF125M, Aifutuo (F-top) EF135M, F-top EF351, F-top EF352, F-top EF801, F-top EF802, Aifutuo (F-top) EF601 (manufactured by Jemco), PF636, PF656, PF6320, PF6520 (manufactured by OMNOVA), FTX-204G, FTX-208G, FTX-218G, FTX -230G, FTX-204D, FTX-208D, FTX-212D, FTX-218D, FTX-222D (manufactured by Neos). Further, a polyoxyalkylene polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as the lanthanoid surfactant.

Further, in addition to the well-known surfactants shown above, the surfactant may use a surfactant using a polymer having a telomerization method (also referred to as short). A fluoroaliphatic group derived from a fluoroaliphatic compound produced by a chain polymer method or an oligomerization method (also referred to as an oligomer method). Fluoroaliphatic compound The method described in JP-A-2002-90991 was synthesized.

The surfactant corresponding to the surfactant may, for example, be a Megafac F178, a Megafac F-470, a Megafac F-473, a Megafac F-475, or a good method. (Megafac) F-476, Megafac F-472 (manufactured by Dixon (DIC) Co., Ltd.), C ₆ F ₁₃ based acrylate (or methacrylate) and (poly(oxygen) Base) a copolymer of acrylate (or methacrylate), acrylate (or methacrylate) with a C ₃ F ₇ group and (poly(oxyethyl)) acrylate (or methacrylic acid) a copolymer of (ester) and (poly(oxypropyl)) acrylate (or methacrylate).

Further, in the present invention, other surfactants other than the fluorine-based and/or lanthanoid surfactants described in <0280> of the specification of US Patent Application Publication No. 2008/0248425 may be used.

These surfactants can be used singly or in combination of several kinds.

When the composition of the present invention contains a surfactant, the amount of the surfactant used is preferably 0.0001% by mass to 2% by mass, more preferably 0.0005% by mass, based on the total amount of the composition (excluding the solvent). ~1% by mass.

On the other hand, by setting the addition amount of the surfactant to 10 ppm or less with respect to the total amount of the sensitizing ray-sensitive or radiation-sensitive resin composition (excluding the solvent), the surface bias property of the hydrophobic resin is improved. The surface of the resist film can be made more hydrophobic, and the water followability during immersion exposure can be improved.

[7]Other additives (G)

The composition of the present invention may also contain a cerium carboxylate salt. Such a carboxylic acid sulfonium salt can be exemplified in the specification of US Patent Application Publication No. 2008/0187860, <0605> to <0606>.

When the composition of the present invention contains a cerium carboxylate salt, the content of the total solid content of the composition is usually 0.1% by mass to 20% by mass, preferably 0.5% by mass to 10% by mass, more preferably Preferably, it is 1% by mass to 7% by mass.

Further, the composition of the present invention may contain a so-called acid multiplying agent as needed. The acid multiplying agent is preferably used in the pattern forming method of the present invention by EUV exposure or electron beam irradiation. Specific examples of the acid multiplying agent are not particularly limited, and examples thereof include the following compounds.

[化97]

The composition of the present invention may further contain a dye, a plasticizer, a photosensitizer, a light absorbing agent, an alkali-soluble resin, a dissolution inhibitor, and a compound which promotes solubility in a developing solution (for example, a molecular weight of 1,000). The following phenol compound, alicyclic or aliphatic compound having a carboxyl group, and the like.

From the viewpoint of improving the resolution, the composition of the present invention is preferably used in a film thickness of 30 nm to 250 nm, and more preferably in a film thickness of 30 nm to 200 nm.

The solid content concentration of the composition of the present invention is usually 1.0% by mass to 10% The mass% is preferably 2.0% by mass to 5.7% by mass, more preferably 2.0% by mass to 5.3% by mass. By setting the solid content concentration to the above range, the resist solution can be uniformly applied onto the substrate.

The solid content concentration refers to the weight percentage of the weight of the other resist component excluding the solvent to the total weight of the chemically amplified resist composition.

In the composition of the present invention, the component is dissolved in a predetermined organic solvent, preferably in the mixed solvent, filtered through a filter, and applied to a predetermined support (substrate). The filter used for the filtration of the filter is preferably a polytetrafluoroethylene, polyethylene or nylon filter having a pore size of 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less. When the filter is filtered, for example, it can be circulated and filtered as in the case of Japanese Patent Laid-Open Publication No. 2002-62667, or a plurality of filters can be filtered in series or in parallel. Alternatively, the composition can be filtered multiple times. Further, the composition may be subjected to a degassing treatment or the like before and after the filter is filtered.

The pattern forming method of the present invention can also be preferably used for the formation of a guide pattern of Directed Self-Assembly (DSA) (for example, refer to "ACS Nano", Vol. .4, No. 8, pp. 4815-4823).

[Examples]

Hereinafter, the present invention will be described by way of examples, but the invention is not limited to the examples.

<Synthesis Example 1>

40 g of a 6/4 (mass ratio) mixed solvent of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether was placed in a three-necked flask under a nitrogen stream, and the mixture was heated to 80 ° C (solvent 1). The monomer corresponding to the repeating unit described below was dissolved in a 6/4 (mass ratio) mixed solvent of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether at a molar ratio of 30/10/60, respectively. A 22% by mass monomer solution (400 g) was prepared. Further, a solution in which a polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.), which was 8 mol% based on the monomer, was dissolved and dissolved therein was added dropwise to the solvent 1 over 6 hours. After completion of the dropwise addition, the mixture was further reacted at 80 ° C for 2 hours. The reaction solution was allowed to stand for cooling, and then poured into 400 ml of hexane (3,600 ml / ethyl acetate), and the precipitated product was collected by filtration and dried to obtain 74 g of a resin (P-1). The weight average molecular weight (Mw: polystyrene conversion), the number average molecular weight (Mn: polystyrene conversion), and the dispersion degree (Mw/Mn) were calculated from the obtained resin (P-1) by GPC (solvent: THF) measurement. . Further, the composition ratio (Morby ratio) was calculated by ¹ H-nuclear magnetic resonance (NMR) measurement.

A resin (P-2) to a resin (P-10) to be described later was synthesized in the same manner as in Synthesis Example 1 except that a monomer corresponding to each repeating unit was used in a desired composition ratio (mole ratio). And a hydrophobic resin (N-1) to a hydrophobic resin (N-3).

<Resist preparation>

The components shown in the following Table 3 were dissolved in a solvent shown in the table to prepare a solvent having a total solid content concentration of 3.5% by mass, and each solvent was filtered by a polyethylene filter having a pore diameter of 0.05 μm to prepare a solvent. The resist composition Ar-1 to the resist composition Ar-15.

The abbreviations in Table 3 are as follows.

[resin]

The composition ratio (molar ratio), weight average molecular weight, and degree of dispersion of the resin used in the examples are shown below.

[化99]

[acid generator]

The structural formula of the acid generator is shown below.

[化100]

[alkaline compound]

The structural formula of the basic compound is shown below.

[化101]

[hydrophobic resin]

The composition ratio (mol ratio), weight average molecular weight, and degree of dispersion of the hydrophobic resin used in the examples are shown below.

[化102]

[Surfactant]

W-1: Megafac F176 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) (fluorine system)

W-2: Megafac R08 (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) (fluorine and lanthanide)

W-3: Polyoxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)

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

[solvent]

A1: Propylene glycol monomethyl ether acetate (PGMEA)

A2: γ-butyrolactone

A3: cyclohexanone

B1: Propylene glycol monomethyl ether (PGME)

B2: ethyl lactate

B3: 2-heptanone

B4: propyl carbonate

. Alkali developer preparation

The components were mixed so that the equivalent concentration became a value shown in the following Table 4, and it was observed at 23 ° C whether or not the components were completely compatible. For the fully compatible level, the total amount was filtered using a polyethylene filter having a pore size of 0.05 μm, and for the phase separation level, the total amount of the aqueous phase was filtered using a polyethylene filter having a pore size of 0.05 μm to prepare Alkali developer D-1 ~ alkali developer D-11.

[Performance evaluation]

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

example 1

ARC29A (manufactured by Nissan Chemical Co., Ltd.) for forming an organic antireflection film was applied onto a ruthenium wafer having a diameter of 8 Å, and baked at 205 ° C for 60 seconds to form an antireflection film having a film thickness of 84 nm. The resist composition Ar-1 was applied thereon and baked at 100 ° C for 60 seconds to form a resist film having a film thickness of 100 nm. For the obtained wafer, an ArF excimer laser scanner (PAS5500/1100 manufactured by ASML), a numerical aperture (NA) of 0.75, a dipole, and an outer sigma were used. The initial σ (inner sigma) was 0.65), and the exposure was performed using an exposure mask (6% HTPSM, line/gap = 75 nm/75 nm) with an exposure amount of a line pattern having a line width of 112.5 nm. Thereafter, the film was heated at 100 ° C for 60 seconds, and then developed in D-1 for 30 seconds to develop, and after rinsing with pure water for 30 seconds, the wafer was rotated at 2000 rpm for 30 seconds. After heating at 100 ° C for 60 seconds, the solution was coated with butyl acetate for 30 seconds to develop, and after rinsing with MIBC for 30 seconds, the wafer was rotated at 2000 rpm for 30 seconds. Baking was performed at 90 ° C for 60 seconds, thereby obtaining a 1:1 line and gap resist pattern having a line width of 37.5 nm.

Example 2 to Example 10, Example 12 to Example 19, Comparative Example 1

A line width of 37.5 nm was obtained in the same manner as in the method of Example 1 except that the resist, the first developer, the first eluent, the second developer, the second eluent, and the conditions described in Table 5 were used. 1:1 line and gap resist pattern.

Example 11

ARC29SR (manufactured by Nissan Chemical Co., Ltd.) for forming an organic anti-reflection film was applied onto a 12-inch-diameter silicon wafer, and baked at 205 ° C for 60 seconds to form an anti-reflection film having a film thickness of 95 nm. The resist composition Ar-11 was applied thereon, and baked at 100 ° C for 60 seconds to form a resist film having a film thickness of 100 nm. An ArF excimer laser immersion scanner (XT1700i manufactured by ASML, NA of 1.20, quadrupole illumination (C-Quad), external σ of 0.981, internal σ of 0.895, XY deflection) was used for the obtained wafer. The mask (6% HTPSM, line/gap = 65 nm / 65 nm) was subjected to pattern exposure with an exposure amount of a line pattern having a line width of 97.5 nm. The liquid immersion liquid is ultrapure water. Thereafter, the film was heated at 100 ° C for 60 seconds, and the solution was applied to a D-2 solution for 30 seconds for development, and after rinsing with pure water for 30 seconds, the wafer was rotated at 2000 rpm for 30 seconds. After heating at 100 ° C for 60 seconds, the solution was developed by coating with Ethyl-3-ethoxypropionate (EEP) for 30 seconds, using methyl isobutyl methanol ( Methyl Isobutyl Carbinol (MIBC) was rinsed for 30 seconds, and then the wafer was rotated at 2000 rpm for 30 seconds and baked at 90 ° C for 60 seconds, thereby obtaining a line width of 32.5 nm. : 1 line and gap resist pattern.

Example 20

ARC29A (manufactured by Nissan Chemical Co., Ltd.) for forming an organic antireflection film was applied onto a ruthenium wafer having a diameter of 8 Å, and baked at 205 ° C for 60 seconds to form an antireflection film having a film thickness of 84 nm. The resist composition Ar-1 was applied thereon and baked at 100 ° C for 60 seconds to form a resist film having a film thickness of 100 nm. An ArF excimer laser scanner (PAS5500/1100 manufactured by ASML) was used for the obtained wafer. NA is 0.75, Dipole, external σ is 0.89, internal σ is 0.65), and exposure exposure is performed using an exposure mask (6% HTPSM, line/gap = 75 nm/75 nm) with a line width of the line pattern of 75 nm. Pattern exposure. Thereafter, the film was heated at 100 ° C for 60 seconds, and then developed in D-1 for 30 seconds to develop, and after rinsing with pure water for 30 seconds, the wafer was rotated at 2000 rpm for 30 seconds. The baking was performed at 90 ° C for 60 seconds, thereby obtaining a 1:1 line and gap resist pattern having a line width of 75 nm.

Comparative example 2

A resist pattern having a line width of 75 nm and a 1:1 line and a gap was obtained in the same manner as in the method of Example 20, except that the resist, the first developer, the first eluent, and the conditions described in Table 5 were used.

In Table 5, PB means heating before exposure, and PEB means heating after exposure. Further, in the columns of PB, PEB, first post-baking, and second post-baking, for example, "100 ° C, 60 s" means heating at 100 ° C for 60 seconds. EEP represents ethyl-3-ethoxypropionate and MIBC represents 4-methyl-2-pentanol.

. Double-developed pattern residual observation

Atomic Force Microscope (AFM) (trade name: Nanoscope 4) manufactured by Veeco Co., Ltd. The line pattern in the case forming area is scanned in the length direction. The results obtained by calculating the difference between the average height of the top of the pattern and the average height of the bottom of the pattern are shown in Table 6. A larger difference indicates that the pattern remains better.

. Line width roughness (LWR) observation

The line and gap resist patterns obtained in the respective examples were observed using a scanning electron microscope (SEM, Hitachi, Ltd., S-9380II). 50 points were measured at equal intervals in the range of the line width of the resist pattern in the longitudinal direction of the pattern of 2 μm, and 3σ (nm) was calculated from the standard deviation, thereby measuring the line width roughness (LWR). A smaller value indicates better performance.

According to the results shown in the above table, the pattern forming method including the alkali developing step of the aqueous developing solution containing the basic compound of the present invention is more excellent in roughness characteristics than the comparative example. Further, it has been found that in the dual development including the organic solvent development step, the pattern remaining property is also excellent.

Although the embodiments have been described above, the present invention is not limited to the embodiments. For example, the following aspects (the aspect X, the aspect Y, and the aspect Z) can be used to form a pattern.

Aspect X: A state in which about 1% by mass of a nitrogen-containing basic compound such as trioctylamine or the like is added to the second developing solution of the above embodiment is developed.

Aspect Y (the aspect of EUV exposure): In the embodiment, the exposure of the ArF excimer laser is replaced by the EUV exposure, and the above is used as "especially for EUV exposure or electron beam exposure. The resin which is preferably used in the case of a resin is used as a state of the resin in the resist composition.

Aspect Z: In the above examples, the evaluation by ArF dry exposure (exposure without liquid immersion liquid) was changed to the evaluation of exposure by ArF immersion exposure.

1‧‧‧ pattern (unexposed part)

2‧‧‧Resin resin (deprotected resin)

3‧‧‧Basic compound (polybasic compound) of the present invention

4‧‧‧Substrate

Claims (16)

A pattern forming method comprising the steps of: forming a photosensitive ray-sensitive or radiation-sensitive film using a photosensitive ray-sensitive or radiation-sensitive resin composition, wherein the sensitized ray-sensitive or radiation-sensitive resin composition contains a resin which is decomposed by an action of an acid to generate an acidic functional group; a step of exposing the sensitizing ray-sensitive or radiation-sensitive film; and a water system containing a basic compound having two or more basic functional groups A developing solution, an alkali developing step of developing the exposed sensitizing ray-sensitive or radiation-sensitive film. The pattern forming method according to claim 1, wherein after the alkali developing step, an organic developing step of developing the photosensitive ray or radiation sensitive film using a developing solution containing an organic solvent is included. The pattern forming method according to claim 1, wherein the basic compound is a compound capable of preparing an aqueous solution having an equivalent concentration of a base of 0.1 N or more at 23 °C. The pattern forming method according to claim 2, wherein the basic compound is a compound capable of preparing an aqueous solution having an alkali equivalent concentration of 0.1 N or more at 23 °C. The pattern forming method according to any one of claims 1 to 4, wherein the basic compound is at least one selected from the group consisting of a tertiary amine group and a quaternary ammonium group as the basicity A functional group of compounds. The pattern forming method according to claim 5, wherein the basic compound is a compound having at least one quaternary ammonium group as the basic functional group. The pattern forming method according to any one of claims 1 to 4, wherein the basic compound is a compound having three or more of the basic functional groups. The pattern forming method according to claim 2, wherein between the exposing step and the alkali developing step, a heating step of heating the exposed sensitizing ray-sensitive or radiation-sensitive film A, between the alkali development step and the organic development step, comprising a heating step B of heating the sensitized ray-sensitive or radiation sensitive film after alkali development, and the heating temperature in the heating step B is higher. The heating temperature in the heating step A is higher than 30 °C. The pattern forming method according to claim 1, wherein the exposing step is a step of bringing a liquid into contact with the sensitizing ray-sensitive or radiation-sensitive film and performing exposure through the liquid. A method of manufacturing an electronic component, comprising the pattern forming method according to claim 1 of the patent application. An electronic component manufactured by the method of manufacturing an electronic component according to claim 10 of the patent application. An aqueous developing solution for use in a pattern forming method comprising the steps of: forming a sensitized shot using a sensitizing ray-sensitive or radiation-sensitive resin composition a step of linear or radiation sensitive film, wherein the sensitizing ray-sensitive or radiation-sensitive resin composition contains a resin which decomposes by an action of an acid to generate an acidic functional group; and the sensitizing ray or radiation is linear a step of exposing the film; and an alkali developing step of developing the exposed photosensitive or radiation sensitive film using an aqueous developing solution; and the aqueous developing solution contains a basic functional group having two or more Basic compound. The aqueous developing solution according to claim 12, wherein the basic compound is a compound capable of preparing an aqueous solution having an alkali equivalent concentration of 0.1 N or more at 23 °C. The aqueous developing solution according to claim 12, wherein the basic compound is a compound having at least one selected from the group consisting of a tertiary amino group and a quaternary ammonium group as the basic functional group. . The aqueous developing solution according to claim 14, wherein the basic compound is a compound having at least one quaternary ammonium group as the basic functional group. The aqueous developing solution according to claim 12, wherein the basic compound is a compound having three or more of the basic functional groups.