KR20180011193A - A pattern forming method, an electronic device manufacturing method, and a resist composition - Google Patents

Abstract

Provided are a pattern forming method, an electronic device manufacturing method, and a resist composition, which have high sensitivity and high resolving power at the time of forming a very fine pattern. The pattern forming method comprises: (A) a resin represented by the general formula (1) in the specification, which contains a repeating unit having a ClogP value of 2.2 or less and whose solubility in a developer containing an organic solvent is decreased by the action of an acid; (B) a compound which generates an acid upon irradiation with an actinic ray or radiation, (C) a step of forming a film using an actinic ray-sensitive or radiation-sensitive resin composition containing a solvent, (1) A step (2) of exposing using radiation, and a step (3) of forming a negative pattern by developing the exposed film in the step (2) using a developer containing an organic solvent.

Description

A pattern forming method, an electronic device manufacturing method, and a resist composition

The present invention relates to a pattern using a developer containing an organic solvent, which is suitably used in a super-microlithography process such as the manufacture of a large scale integrated circuit (large-scale integrated circuit) or a high-capacity microchip or other photo- A method of manufacturing an electronic device, and a resist composition. More specifically, the present invention relates to a pattern formation method using a developer containing an organic solvent, which can be suitably used for microfabrication of a semiconductor device using an electron beam or EUV light (extreme ultra violet (wavelength: about 13 nm) A production method thereof, and a resist composition.

2. Description of the Related Art Conventionally, in a manufacturing process of a semiconductor device such as an IC (Integrated Circuit) or an LSI, fine processing by lithography using a photoresist composition is performed. In recent years, with the increase in integration of integrated circuits, ultrafine pattern formation in a submicron region or a quarter micron region has been required. Accordingly, the exposure wavelength tends to be shorter in wavelength as in the g line to the i line and also in the excimer laser light, and lithography using electron beams, X-rays, or EUV light is under development at present.

[0004] Incidentally, in the case of the positive active ray-sensitive or radiation-sensitive resin composition, there are generally used a "positive type" and a "positive type" in which an insoluble or insoluble resin is used in an alkaline developer and the pattern is formed by solubilizing the exposed portion with an alkali developer , And a "negative type" in which a resin soluble in an alkali developer is used and a pattern is formed by hardening or insolubilizing the exposed portion with an alkali developer by exposure.

As the actinic ray-sensitive or radiation-sensitive resin composition suitable for such a lithography process, a chemically amplified positive resist composition mainly using an acid catalyst reaction from the viewpoint of high sensitivity is studied, and an alkali developer as a main component is insoluble or poorly soluble, A resin having a property of being soluble in an alkali developing solution by the action of an acid, and a chemically amplified positive resist composition comprising an acid generator are effectively used (for example, Patent Documents 1 to 3).

On the other hand, in the production of semiconductor devices and the like, there is a demand for pattern formation having various shapes such as lines, trenches, and holes. In order to meet the demand for pattern formation having various shapes, not only a positive type but also a negative type active ray-sensitive or radiation-sensitive resin composition have been developed.

In the formation of ultrafine patterns, a method has been proposed in which an acid-decomposable resin is developed using a developing solution other than an alkali developing solution in order to improve the resolving power and further improve the pattern shape (see, for example, Patent Documents 4 to 6 ).

Patent Document 1: JP-A-2013-100471 Patent Document 2: JP-A-2013-100472 Patent Document 3: JP-A-2013-100473 Patent Document 4: JP-A-2013-68675 Patent Document 5: JP-A-2011-221513 Patent Document 6: JP-A-2015-31851

However, in the above-described pattern formation method, a very fine pattern (for example, a line-and-space pattern with a line width of 50 nm or less, a dot with a diameter of 50 nm or less, Pattern), pattern collapse or the like occurred, and sufficient resolution was not obtained.

SUMMARY OF THE INVENTION An object of the present invention is to provide a pattern forming method, a method of manufacturing an electronic device, a method of manufacturing an electronic device, and a method of manufacturing the same, which have high sensitivity and high resolution at the time of forming a very fine pattern (for example, a dot pattern with a diameter of 50 nm or less) And a resist composition.

As a result of intensive studies, the inventors of the present invention have found that a resist composition comprising a resin having a high-polarity repeating unit, a compound capable of generating an acid upon irradiation with an actinic ray or radiation and a solvent is used, To form a pattern, thereby achieving the above objects.

That is, the above problems can be solved by the following means.

[One]

(A) a resin represented by the following general formula (1) and containing a repeating unit having a ClogP value of 2.2 or less and having a reduced solubility in a developer containing an organic solvent by the action of an acid; (B) (1) a step of forming a film by using an actinic ray-sensitive or radiation-sensitive resin composition containing a compound capable of generating an acid upon irradiation with (C) a solvent,

A step (2) of exposing the film using an actinic ray or radiation, and

And a step (3) of developing the exposed film in the step (2) using a developing solution containing an organic solvent to form a negative type pattern.

[Chemical Formula 1]

In formula (1), R ₁ represents a hydrogen atom, an alkyl group or a halogen atom, R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group or a carboxyl group, L represents a single bond or a divalent linking group . R ₂ or R ₃ and L may be connected to each other to form a ring. In this case, either R ₂ or R ₃ represents a divalent linking group, and L represents a trivalent linking group. Ar represents an aromatic group. R ₄ represents a substituent, and n represents an integer of 0 or more. When R ₄ is present a plurality, the plurality of R ₄ may be the same and different.

[2]

The pattern forming method according to [1], wherein the resin (A) comprises a repeating unit having an acid-decomposable group.

[3]

The pattern forming method according to [1] or [2], wherein at least one of R ₄ in the general formula (1) is a hydroxyl group.

[4]

The pattern forming method according to any one of [1] to [3], wherein the general formula (1) is represented by the following general formula (2).

(2)

In formula (2), R ₁ represents a hydrogen atom, an alkyl group or a halogen atom, R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group or a carboxyl group, L represents a single bond or a divalent linking group . R ₂ or R ₃ and L may be connected to each other to form a ring. In this case, either R ₂ or R ₃ represents a divalent linking group, and L represents a trivalent linking group. R ₄ represents a substituent, and n ² represents an integer of 0 to 4. When R ₄ is present a plurality, the plurality of R ₄ may be the same and different.

[5]

The pattern forming method according to any one of [1] to [4], wherein the general formula (1) is represented by the following general formula (3)

(3)

In the general formula (3), R ₁ represents a hydrogen atom, an alkyl group, or a halogen atom, and L represents a single bond or a divalent linking group. R ₄ represents a substituent. n ² represents an integer of 0 to 4; When R ₄ is present a plurality, the plurality of R ₄ may be the same and different.

[6]

The pattern forming method according to any one of [1] to [4], wherein the general formula (1) is represented by the following general formula (4)

[Chemical Formula 4]

In the general formula (4), A represents a single bond or a divalent linking group. R ₄ represents a substituent. n ³ represents an integer of 0 to 4; When R ₄ is present a plurality, the plurality of R ₄ may be the same and different.

[7]

The pattern forming method according to [6], wherein the general formula (4) is represented by the following general formula (4a).

[Chemical Formula 5]

In the general formula (4a), R ₄ represents a substituent. p represents an integer of 0 to 4, and n ³ represents an integer of 0 to 4. When R ₄ is present a plurality, the plurality of R ₄ may be the same and different.

[8]

Wherein R ₄ is a group represented by the following formula (N1), a group represented by the following formula (N2), a group represented by the following formula The pattern forming method according to any one of [1] to [7], wherein the group represented by formula (S1) represents a group represented by formula (S2)

[Chemical Formula 6]

In the general formula (N1), R _N1 and R _N2 each independently represent a hydrogen atom or a substituent. * Represents the bonding hands bonding to the benzene ring.

In the general formula (N2), R _N3 represents a substituent and R _N4 represents a hydrogen atom or a substituent. * Represents the bonding hands bonding to the benzene ring.

(7)

In the general formula (S1), R _S1 represents a substituent. * Represents the bonding hands bonding to the benzene ring.

In the general formula (S2), R _S4 represents a substituent, and R _S5 represents a hydrogen atom or a substituent. * Represents the bonding hands bonding to the benzene ring.

[9]

The compound according to any one of [1] to [8], wherein R ₄ is a hydroxyl group, a hydroxymethyl group, a carboxyl group, a group represented by the general formula (S1) Pattern formation method.

[10]

Method of forming patterns according to the n ² is 1 or 2, [4] or [5].

[11]

The pattern forming method according to [6] or [7], wherein the n ³ is an integer of 0 to 2.

[12]

The pattern forming method according to any one of [1] to [11], wherein the compound (B) is a sulfonium salt.

[13]

The compound (B) is the volume of the acid generated 130Å 2000Å ³ or more ³ or less, pattern formation method described in [12].

[14]

The pattern forming method according to any one of [1] to [13], wherein the resin (A) further comprises a repeating unit having a lactone group.

[15]

A method of manufacturing an electronic device comprising the pattern forming method according to any one of [1] to [14].

[16]

A resist composition comprising a resin having a repeating unit represented by the following general formula (4).

[Chemical Formula 8]

In the general formula (4), A represents a single bond or a divalent linking group. R ₄ represents a substituent. n ³ represents an integer of 0 to 4; When R ₄ is present a plurality, the plurality of R ₄ may be the same and different.

[17]

The resist composition according to [16], wherein the formula (4) is represented by the following formula (4a).

[Chemical Formula 9]

In the general formula (4a), R ₄ represents a substituent. p represents an integer of 0 to 4, and n ³ represents an integer of 0 to 4. When R ₄ is present a plurality, the plurality of R ₄ may be the same and different.

[18]

Wherein R ₄ is a group represented by the following formula (N1), a group represented by the following formula (N2), a group represented by the following formula The resist composition according to [16] or [17], wherein the group represented by the formula (S1) or the group represented by the following formula (S2)

[Chemical formula 10]

In the general formula (N1), R _N1 and R _N2 each independently represent a hydrogen atom or a substituent. * Represents the bonding hands bonding to the benzene ring.

In the general formula (N2), R _N3 represents a substituent and R _N4 represents a hydrogen atom or a substituent. * Represents the bonding hands bonding to the benzene ring.

(11)

In the general formula (S1), R _S1 represents a substituent. * Represents the bonding hands bonding to the benzene ring.

In the general formula (S2), R _S4 represents a substituent, and R _S5 represents a hydrogen atom or a substituent. * Represents the bonding hands bonding to the benzene ring.

According to the present invention, it is possible to provide a method of forming a pattern having high sensitivity and high resolution at the time of forming a very fine pattern (for example, a line and space pattern having a line width of 50 nm or less and a dot pattern having a diameter of 50 nm or less) Method, and a resist composition.

Hereinafter, an example of a mode for carrying out the present invention will be described.

In the present specification, the numerical range indicated by using "~ " means a range including numerical values described before and after" to "as a lower limit value and an upper limit value.

In the present invention, "actinic ray" or "radiation" means, for example, a line spectrum of a mercury lamp, far ultraviolet ray, extreme ultraviolet ray, X-ray or electron ray typified by an excimer laser. In the present invention, "light" means an actinic ray or radiation. The term "exposure" in this specification refers to not only exposure by a bright line spectrum of a mercury lamp, deep ultraviolet ray represented by an excimer laser, X-ray, extreme ultraviolet ray (EUV light) Or the like is also included in the exposure.

In the notation of the group (atomic group) in the present specification, the notation in which substitution or non-substitution is not described includes those having a substituent in addition to a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In this specification, "(meth) acryl-based monomer" is "CH ₂ = CH-CO-" or refers to at least one of a monomer having a structure of _{"CH 2 = C (CH 3} ) -CO-". Similarly, the terms "(meth) acrylate" and "(meth) acrylic acid" mean "at least one of acrylate and methacrylate" and "at least one of acrylic acid and methacrylic acid", respectively.

In the present specification, the weight average molecular weight of the resin is a polystyrene reduced value measured by GPC (Gel Permeation Chromatography). GPC was prepared by using TSK gel Multipore HXL-M (manufactured by Tosoh Corporation, 7.8 mm ID x 30.0 cm) as a column and THF (tetrahydrofuran) as an eluent using HLC-8120 (manufactured by TOSOH CORPORATION) You can follow the method.

[Pattern formation method]

First, the pattern forming method of the present invention will be described.

The pattern forming method of the present invention comprises:

(A) a resin represented by the following general formula (1) and containing a repeating unit having a ClogP value of 2.2 or less and having a reduced solubility in a developer containing an organic solvent by the action of an acid; (B) (1) a step of forming a film by using an actinic ray-sensitive or radiation-sensitive resin composition containing a compound capable of generating an acid upon irradiation with (C) a solvent,

A step (2) of exposing the film using an actinic ray or radiation, and

And a step (3) of developing the exposed film in the step (2) using a developer containing an organic solvent to form a negative pattern.

[Chemical Formula 12]

In formula (1), R ₁ represents a hydrogen atom, an alkyl group or a halogen atom, R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group or a carboxyl group, L represents a single bond or a divalent linking group . R ₂ or R ₃ and L may be connected to each other to form a ring. In this case, either R ₂ or R ₃ represents a divalent linking group, and L represents a trivalent linking group. Ar represents an aromatic group. R ₄ represents a substituent, and n represents an integer of 0 or more. When R ₄ is present a plurality, the plurality of R ₄ may be the same and different.

The pattern forming method of the present invention has high sensitivity and high resolution when forming a very fine pattern (for example, a dot pattern with a diameter of 50 nm or less). The reason for this is not clear, but it is estimated as follows.

The main reasons that a very fine pattern can not be formed are pattern collapse and collapse of the pattern, and these phenomena occur when the developer penetrates into the pattern and swells the pattern. By including a high-polarity repeating unit in the resin, the affinity between the resin and a developer containing an organic solvent is lowered, and it is conceivable that swelling is suppressed because a developer containing an organic solvent hardly penetrates into the pattern . However, in a dot pattern in which the adhesion area with the substrate is smaller than that of the line-and-space pattern, the influence of the swelling due to penetration of the developer is larger, and simply using a resin containing a high- I can not. The reason why the problem is solved by the present invention is not clear, but it is presumed that the high-polarity repeating unit according to the present invention has a strong interaction with the substrate surface specifically, thereby enhancing the adhesion to the substrate.

[Sensitive actinic ray-sensitive or radiation-sensitive resin composition]

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

The actinic ray-sensitive or radiation-sensitive resin composition used in the pattern-forming method of the present invention is a negative-type development (a phenomenon in which solubility decreases with exposure to a developing solution and remains as an exposure part pattern and the unexposed part is removed) . Further, the actinic ray-sensitive or radiation-sensitive resin composition used in the pattern forming method of the present invention is a sensitizing actinic ray or radiation-sensitive resin composition for organic solvent development used for development using a developer containing an organic solvent . Here, the ease of organic solvent development refers to a use provided at least in a developing process using a developing solution containing an organic solvent.

The above active radiation-sensitive or radiation-sensitive resin composition is typically a resist composition, preferably a chemically amplified resist composition.

(A) a repeating unit represented by the following general formula (1) and having a ClogP value of 2.2 or less and having a repeating unit having a ClogP value of 2.2 or less, (B) a compound which generates an acid upon irradiation with an actinic ray or radiation, and (C) a solvent.

Examples of the additional component that can be contained in the actinic ray-sensitive or radiation-sensitive resin composition used in the present invention include a resin other than the resin (A), a basic compound, a crosslinking agent, a surfactant, an organic carboxylic acid, and a carboxylic acid onium salt .

Hereinafter, each of the above-described components will be described in order.

[Resin (A)]

In the present invention, the resin (A) is a resin represented by the following general formula (1) and containing a repeating unit having a ClogP value of 2.2 or less and having a reduced solubility in a developer containing an organic solvent by the action of an acid .

[Chemical Formula 13]

In formula (1), R ₁ represents a hydrogen atom, an alkyl group or a halogen atom, R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group or a carboxyl group, L represents a single bond or a divalent linking group . R ₂ or R ₃ and L may be connected to each other to form a ring. In this case, either R ₂ or R ₃ represents a divalent linking group, and L represents a trivalent linking group. Ar represents an aromatic group. R ₄ represents a substituent, and n represents an integer of 0 or more. When R ₄ is present a plurality, the plurality of R ₄ may be the same and different.

R ₁ represents a hydrogen atom, an alkyl group, or a halogen atom.

The alkyl group represented by R ₁ is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group.

Examples of the halogen atom of R ₁ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

R ₁ is preferably a hydrogen atom or a methyl group.

L represents a single bond or a divalent linking group. As the divalent linking group represented by L, monocyclic ring which may have a substituent having 6 to 18 or polycyclic aromatic ring, -C (= O) -, -OC (= O) -, -CH 2 -OC (= O) (Preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), a linear or branched alkenylene group (preferably having 2 to 10 carbon atoms, more preferably 2 to 10 carbon atoms, (Preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms), a sulfonyl group, -O-, -NH-, -S-, a cyclic lactone structure, or a combination thereof And a divalent linking group (preferably having 1 to 50 carbon atoms in total, more preferably 1 to 30 carbon atoms in total, and more preferably 1 to 20 carbon atoms in total).

L is a single bond, -COO-, -CONH-, -O-, -OCO- , -NHCO-, -COOCH 2 -, -COOCH 2 CH 2 -, -CONHCH 2 -, or -CONHCH ₂ CH ₂ - .

L may be linked to R ₂ or R ₃ to form a ring, and L in this case represents a trivalent linking group. Examples of the trivalent linking group in this case include a group formed by removing one hydrogen atom from the bivalent linking group, particularly -CONH-L _A - (wherein L _A represents a divalent linking group, LA), which is a divalent linking group represented by the following formula (1).

R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group or a carboxyl group.

When R ₂ and R ₃ represent an alkyl group, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is more preferable.

R ₂ or R ₃ and L may be connected to each other to form a ring. In this case, R ₂ or R ₃ represents a divalent linking group. The divalent linking group in this case is preferably a carbonyl group, an alkylene group, -O-, -NH-, or a divalent linking group composed of a combination thereof, and is preferably a carbonyl group, an alkylene group, -CONH-, More preferably a carbonyl group, and more preferably a carbonyl group.

R ₂ and R ₃ are preferably a hydrogen atom or a linkage with L to form a ring.

Ar represents an aromatic group. Preferable examples of the aromatic group represented by Ar include an aromatic hydrocarbon ring which may have a substituent having 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring and a phenanthrene ring, or an aromatic hydrocarbon ring such as a thiophene ring, An aromatic heterocycle such as a furan ring, a pyrrole ring, a benzothiophen ring, a benzofuran ring, a benzopyrrole ring, a triazin ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, . Ar is more preferably a benzene ring or a naphthalene ring, and most preferably a benzene ring.

R ₄ represents a substituent, and at least one of them is preferably a hydroxyl group.

R ₄ is a group represented by the following formula (N1), a group represented by the following formula (N2), a group represented by the following formula (S1), a group represented by the following formula A hydroxyl group, a carboxyl group, an alkyl group, a group represented by the following formula (S1), or a group represented by the following formula (S2), or a group represented by the following formula , More preferably a group represented by the formula (S2), a hydroxyl group, a hydroxyalkyl group (preferably a hydroxymethyl group), a carboxyl group, a group represented by the formula (S1) More preferably a hydroxyl group, a carboxyl group, or a hydroxymethyl group.

[Chemical Formula 14]

In the general formula (N1), R _N1 and R _N2 each independently represent a hydrogen atom or a substituent. * Represents the bonding hands bonding to the benzene ring.

In the general formula (N2), R _N3 represents a substituent and R _N4 represents a hydrogen atom or a substituent. * Represents the bonding hands bonding to the benzene ring.

[Chemical Formula 15]

In the general formula (S1), R _S1 represents a substituent. * Represents the bonding hands bonding to the benzene ring.

In the general formula (S2), R _S4 represents a substituent, and R _S5 represents a hydrogen atom or a substituent. * Represents the bonding hands bonding to the benzene ring.

In the general formula (N1), R _N1 and R _N2 each independently represent a hydrogen atom or a substituent, preferably a hydrogen atom or a methyl group.

In the general formula (N2), R _N3 represents a substituent and preferably represents a methyl group. R _N4 represents a hydrogen atom or a substituent, and preferably represents a hydrogen atom.

In the general formula (S1), R _S1 represents a substituent, and preferably represents a methoxy group or an amino group. When R _S1 represents an amino group, the general formula (S1) is represented by formula (S3) to.

[Chemical Formula 16]

In the general formula (S3), R _S2 and R _S3 each independently represent a hydrogen atom or a substituent. * Represents the bonding hands bonding to the benzene ring.

In the general formula (S3), R _S2 and R _S3 each independently represent a hydrogen atom or a substituent, preferably a hydrogen atom or a methyl group.

In the general formula (S2), R _S4 represents a substituent and preferably represents a methyl group. R _S5 is a hydrogen atom or a substituent, preferably represents a hydrogen atom.

The alkyl group as R ₁ in general formula (1), the alkyl group as R ₂ and R ₃ , the divalent linking group as R ₄ and L, and Ar may each have a substituent. Examples of the substituent include an alkyl group (preferably a straight chain or a branched alkyl group having 1 to 12 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms), an alkynyl group (preferably having 2 to 12 carbon atoms) (Preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 18 carbon atoms), a hydroxyl group, an alkoxy group, an alkyl and aryloxycarbonyl group, a carbamoyl group, Alkyl and aryloxycarbonylamino groups, acylamino groups, alkyl and arylthio groups, aminocarbonylamino groups, sulfamoyl groups, alkyl and arylsulfonylamino groups, halogen atoms, haloalkyl groups and alkyl and aryloxaphone groups . Preferred examples thereof include an alkyl group, a cycloalkyl group, a halogen atom, a haloalkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, an alkyl group and an aryloxycarbonyl group and an aryl group. More preferred examples thereof include an alkyl group, An alkoxy group, and the like. Examples of the halogen atom include the same ones as those exemplified above for R < ₁ >.

The substituent may have an additional substituent. Examples of the substituent include a hydroxyl group, a halogen atom (e.g., a fluorine atom), an alkyl group, a cycloalkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, An alkoxyalkyl group, and a group obtained by combining these groups. The number of carbon atoms is preferably 8 or less.

n represents an integer of 0 or more, preferably an integer of 1 to 3;

The above-mentioned general formula (1) is preferably represented by the following general formula (2).

[Chemical Formula 17]

In formula (2), R ₁ represents a hydrogen atom, an alkyl group or a halogen atom, R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group or a carboxyl group, L represents a single bond or a divalent linking group . R ₂ or R ₃ and L may be connected to each other to form a ring. In this case, either R ₂ or R ₃ represents a divalent linking group, and L represents a trivalent linking group. R ₄ represents a substituent, and n ² represents an integer of 0 to 4. When R ₄ is present a plurality, the plurality of R ₄ may be the same and different.

Formula (2) of, R _1, R _2, R _3, R ₄ and L are represented by the general formula (1), in R _1, R _2, R _3, R ₄ and L and copper, and specific examples and preferred ranges .

In the general formula (2), n ² represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1 or 2.

The repeating unit represented by the general formula (1) is more preferably represented by the following general formula (3) or (4).

[Chemical Formula 18]

In the general formula (3), R ₁ represents a hydrogen atom, an alkyl group, or a halogen atom, and L represents a single bond or a divalent linking group. R ₄ represents a substituent. n ² represents an integer of 0 to 4; When R ₄ is present a plurality, the plurality of R ₄ may be the same and different.

[Chemical Formula 19]

In the general formula (4), A represents a single bond or a divalent linking group. R ₄ represents a substituent. n ³ represents an integer of 0 to 4; When R ₄ is present a plurality, the plurality of R ₄ may be the same and different.

In the general formula (3), R _1, R ₄ and L are represented by the general formula (1), in R _1, R ₄ and L and copper, are also the same embodiments, and a preferred range.

In the general formula (3), n ² and n ² is synonymous with the general formula (2), preferably 0 to 2, more preferably 1 or 2;

In the general formula (4), R ₄ is synonymous with R ₄ in the general formula (1), and specific examples and preferred ranges are also the same.

In the general formula (4), n ³ represents an integer of 0 to 4, preferably 0 to 2.

In the general formula (4), A represents a single bond or a divalent linking group, and A is a single bond or a divalent linking group represented by the following general formula (LA).

[Chemical Formula 20]

In formula (LA), A ₁ represents an alkylene group or an arylene group, and A ₂ represents O, S, C═O, C (═O) -O, OC (═O) -NR, NR-C (= O) (R represents a hydrogen atom or an alkyl group), or a single bond, and na represents an integer of 1 or more. When A ₁ and A ₂ are a plurality is present, a plurality of A ₁ and A ₂ may be the same and different. * Represents the bonding hands bonding to the nitrogen atom of maleimide.

A ₁ is preferably an alkylene group, and A ₂ is preferably O, C (= O) -O, OC (= O), or a single bond, and na is preferably an integer of 1 to 4.

The formula (4) is preferably represented by the following formula (4a).

[Chemical Formula 21]

In the general formula (4a), R ₄ represents a substituent. p represents an integer of 0 to 4, and n ² represents an integer of 0 to 4; When R ₄ is present a plurality, the plurality of R ₄ may be the same and different.

In the general formula (4a), R ₄ is synonymous with R ₄ in the general formula (1), and specific examples and preferred ranges are also the same.

In the general formula (4a), n ³ and n ³ is an agreement in the general formula (4), and preferably 0-2.

In the general formula (4a), p represents an integer of 0 to 4, preferably an integer of 0 to 2.

The resin (A) needs to have a ClogP value of 2.2 or less, preferably 2.0 or less, and particularly preferably 1.8 or less, from the viewpoint of lowering the affinity with a developer containing an organic solvent and suppressing penetration into a pattern . In order to improve the solubility of the unexposed portion in the developing solution and to improve the resolution, the ClogP value is preferably -0.2 or more, more preferably -0.06 or more.

Generally, the logP value can be obtained by actual measurement using n-octanol and water, but in the present invention, the distribution coefficient (ClogP value) calculated from the logP value estimation program is used. Specifically, the "ClogP value" in the present specification refers to the ClogP value obtained from "Chem Bio Draw ultra ver. 12".

The ClogP value of the repeating unit in the present specification is a value calculated by the above method for a compound in which both terminals of the repeating unit are methyl groups.

The content ratio of the repeating unit represented by the general formula (1), (2), (3), (4) or (4a) Is preferably 2 to 70 mol%, more preferably 5 to 50 mol%, and particularly preferably 5 to 30 mol%, based on the total amount of the copolymer.

The repeating unit represented by the general formula (1), (2), (3), (4) or (4a) contained in the resin (A) may be one kind or two or more kinds.

From the viewpoint of securing a sufficient developer solubility in the unexposed portion, the resin (A) is preferably nonionic.

Specific examples of the repeating unit represented by the general formula (1), (2), (3), (4) or (4a) include the following structures. Also, in the example, the ClogP value obtained by the above method is added.

[Chemical Formula 22]

(23)

≪ EMI ID =

The resin (A) may contain a repeating unit having a ClogP value of more than 2.2 or a repeating unit having a ClogP value of more than 2.2, which has a phenolic hydroxyl group.

The content of the repeating unit having a ClogP value of more than 2.2 or the repeating unit having a phenolic hydroxyl group having a ClogP value of more than 2.2 is preferably from 0 to 50 mol% Is 0 to 45 mol%, more preferably 0 to 40 mol%.

Resin (A) is a resin whose solubility in a developer containing an organic solvent decreases due to the action of an acid.

The resin (A) preferably contains a repeating unit having an acid-decomposable group, and it is preferable that the resin (A) has a repeating unit having a group which is decomposed by the action of an acid to generate a carboxyl group.

Further, when the resin has a repeating unit having a carboxyl group by decomposition by the action of an acid, the solubility in an alkaline developer increases due to the action of an acid, and the solubility in an organic solvent decreases.

The repeating unit having a group which is decomposed by the action of an acid and which generates a carboxyl group is a repeating unit having a group substituted with a group in which the hydrogen atom of the carboxyl group is decomposed and cleaved by the action of an acid.

The group is eliminated with an acid, for example, _{-C (R 36) (R 37} ) (R 38), -C (R 36) (R 37) (OR 39), -C (R 01) (R 02) (OR ₃₉ ), and the like.

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

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

As the repeating unit having a group capable of decomposing by the action of an acid and generating a carboxyl group, a repeating unit represented by the following general formula (AI) is preferable.

(25)

In the general formula (AI)

Xa ₁ represents a hydrogen atom or an alkyl group.

T represents a single bond or a divalent linking group.

Rx ₁ to Rx ₃ each independently represent an alkyl group (straight chain or branched chain) or a cycloalkyl group (monocyclic or polycyclic). However, when all Rx ₁ to Rx ₃ are alkyl groups (straight chain or branched), at least two of Rx ₁ to Rx ₃ are preferably methyl groups.

Two of Rx ₁ to Rx _{3 may} combine to form a cycloalkyl group (monocyclic or polycyclic).

The alkyl group represented by Xa ₁ may have a substituent, and examples thereof include a methyl group or a group represented by -CH ₂ -R ₁₁ . R ₁₁ represents a halogen atom (such as a fluorine atom), a hydroxyl group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, preferably an alkyl group having 3 or less carbon atoms And more preferably a methyl group. Xa ₁ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group in an embodiment.

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

T is a single bond or -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.

As the alkyl group of Rx ₁ to Rx ₃ , those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group are preferable.

As the cycloalkyl group of Rx ₁ to Rx ₃ , a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclododecanyl group, a tetracyclododecanyl group and an adamantyl group is preferable .

Examples of the cycloalkyl group formed by combining two of Rx ₁ to Rx ₃ include a monocyclic cycloalkyl group such as cyclopentyl group and cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group Cycloalkyl groups are preferred. Particularly preferred is a monocyclic cycloalkyl group having 5 to 6 carbon atoms.

The cycloalkyl group formed by combining two of Rx ₁ to Rx ₃ may be substituted with, for example, one of the methylene groups constituting the ring is a heteroatom such as an oxygen atom, or a group having a heteroatom such as a carbonyl group .

The repeating unit represented by the general formula (AI) is, for example, an embodiment wherein Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are combined to form the above-mentioned cycloalkyl group.

Examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, an alkoxycarbonyl group (having 2 to 6 carbon atoms) , And the number of carbon atoms is preferably 8 or less.

The repeating unit represented by the general formula (AI) is preferably an acid-decomposable (meth) acrylic acid tertiary alkyl ester repeating unit (Xa ₁ represents a hydrogen atom or a methyl group, and T represents a single bond) . More preferably, Rx ₁ to Rx ₃ are each independently a repeating unit showing a straight-chain or branched alkyl group, and more preferably, each of Rx ₁ to Rx ₃ is a repeating unit independently representing a linear alkyl group.

Specific examples of the repeating unit having a group capable of decomposing by the action of an acid to generate a carboxyl group are shown below, but the present invention is not limited thereto.

In the specific examples, R x 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. Z represents a substituent containing a polar group, and when there are a plurality of Z groups, they are independent of each other. p represents 0 or a positive integer. Examples of the substituent containing a polar group represented by Z include a straight chain or branched alkyl group or cycloalkyl group having a hydroxyl group, a cyano group, an amino group, an alkylamido group or a sulfonamido group, preferably a hydroxyl group Lt; / RTI > As the branched alkyl group, an isopropyl group is particularly preferable.

(26)

The content of the repeating unit having a group capable of decomposing by the action of an acid to generate a carboxyl group is preferably from 20 to 90 mol%, more preferably from 25 to 80 mol%, further preferably from 25 to 80 mol%, based on the total repeating units in the resin (A) And preferably 30 to 75 mol%.

The resin (A) may contain a repeating unit represented by the following general formula (VI).

(27)

In the general formula (VI)

R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. However, R ₆₂ may combine with Ar ₆ to form a ring, and R ₆₂ in this case represents a single bond or an alkylene group.

X ₆ represents a single bond, -COO-, or -CONR ₆₄ -. R ₆₄ represents a hydrogen atom or an alkyl group.

L ₆ represents a single bond or an alkylene group.

Ar ₆ represents an aromatic ring of (n + 1) valency, and when it forms a ring by combining with R ₆₂ , it represents (n + 2) valent aromatic ring.

Y < ₂ > represents a hydrogen atom or a group which is eliminated by the action of an acid when n ≥ Provided that at least one of Y ₂ represents a group which is eliminated by the action of an acid.

n represents an integer of 1 to 4;

The group Y ₂ desorbed by the action of an acid is more preferably a structure represented by the following formula (VI-A).

(28)

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined.

M represents a single bond or a divalent linking group.

Q represents an alkyl group, a cycloalkyl group which may contain a hetero atom, an aryl group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group.

At least two of Q, M and L ₁ may combine to form a ring (preferably a 5-membered or 6-membered ring).

The repeating unit represented by the formula (VI) is preferably a repeating unit represented by the following formula (13).

[Chemical Formula 29]

In the general formula (13)

Ar ₃ represents aromatic ring.

R ₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group or a heterocyclic group.

M ₃ represents a single bond or a divalent linking group.

Q ₃ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.

At least two of Q ₃ , M ₃ and R _{3 may be} bonded to form a ring.

The aromatic ring represented by Ar ₃ is the same as Ar ₆ in the general formula (VI) when n in the general formula (VI) is 1, more preferably a phenylene group or a naphthylene group , More preferably a phenylene group.

Specific examples of the repeating unit represented by formula (VI) are shown below, but the present invention is not limited thereto.

(30)

It is also preferable that the resin (A) contains a repeating unit represented by the following general formula (15).

(31)

In the general formula (15)

R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₄₂ may combine with L ₄ to form a ring, and R ₄₂ in this case represents an alkylene group.

L ₄ represents a single bond or a divalent linking group, and when R ₄₂ forms a ring, it represents a trivalent linking group.

R ₄₄ and R ₄₅ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group or a heterocyclic group.

M ₄ represents a single bond or a divalent linking group.

Q ₄ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.

At least two of Q ₄ , M ₄ and R _{44 may be} bonded to form a ring.

R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. R ₄₂ may combine with L ₄ to form a ring, and R ₄₂ in this case represents an alkylene group.

L ₄ represents a single bond or a divalent linking group, and when R ₄₂ forms a ring, it represents a trivalent linking group.

R ₄₄ and R ₄₅ are the same as R ₃ in the above-mentioned general formula (13), and their preferable ranges are also the same.

M ₄ agrees with M ₃ in the above-mentioned general formula (13), and the preferable range thereof is also the same.

Q ₄ agrees with Q ₃ in the above-mentioned general formula (13), and the preferable range thereof is also the same. The ring formed by bonding at least two of Q ₄ , M ₄ and R ₄₄ is a ring formed by bonding at least two of Q ₃ , M ₃ and R ₃ , and the preferable range is also the same.

The alkyl group represented by R ₄₁ to R _{43 in} the general formula (15) is preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, An ethylhexyl group, an octyl group, and a dodecyl group; and more preferably an alkyl group having 8 or less carbon atoms, particularly preferably an alkyl group having 3 or less carbon atoms.

The alkyl group contained in the alkoxycarbonyl group is preferably the same as the alkyl group in R ₄₁ to R ₄₃ .

The cycloalkyl group may be either monocyclic or polycyclic. A cycloalkyl group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group, which may have a substituent.

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

Examples of preferable substituents in the respective groups include alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, An acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group and a nitro group, and the number of carbon atoms of the substituent is preferably 8 or less.

When R ₄₂ is an alkylene group and forms a ring with L ₄ , the alkylene group is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and an octylene group . More preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably an alkylene group having 1 to 2 carbon atoms. It is particularly preferable that the ring formed by combining R ₄₂ and L ₄ is a 5 or 6-membered ring.

As R ₄₁ and R ₄₃ , a hydrogen atom, an alkyl group and a halogen atom are more preferable and a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (-CF ₃ ), a hydroxymethyl group (-CH ₂ -OH) -CH ₂ -Cl), and a fluorine atom (-F) are particularly preferable. R ₄₂ is more preferably a hydrogen atom, an alkyl group, a halogen atom or an alkylene group (forming a ring with L ₄ ), and is preferably a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (-CF ₃ ), a hydroxymethyl group CH ₂ -OH), a chloromethyl group (-CH ₂ -Cl), a fluorine atom (-F), a methylene group (forming a ring with L ₄ ), and an ethylene group (forming a ring with L ₄ ).

Examples of the divalent linking group represented by L ₄ include an alkylene group, a divalent aromatic ring, -COO-L ₁ -, -OL ₁ -, and a group formed by combining two or more of these groups. Herein, L ₁ represents an alkylene group, a cycloalkylene group, a divalent aromatic ring, or a combination of an alkylene group and a bivalent aromatic ring.

L ₄ is preferably a single bond, a group represented by -COO-L ₁ - or a divalent aromatic ring. L ₁ is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene group or a propylene group. As the bivalent aromatic ring, 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group and 1,4-naphthylene group are preferable, and 1,4-phenylene group is more preferable.

As the trivalent linking group represented by L ₄ in the case where L ₄ is bonded to R ₄₂ to form a ring, a group obtained by removing one arbitrary hydrogen atom from the above specific example of the divalent linking group represented by L ₄ Can be suitably selected.

Specific examples of the repeating unit represented by the general formula (15) are shown below, but the present invention is not limited thereto.

(32)

The resin (A) may contain a repeating unit represented by the following general formula (BZ).

(33)

In the general formula (BZ), AR represents an aryl group. Rn represents an alkyl group, a cycloalkyl group or an aryl group. Rn and AR may combine with each other to form a non-aromatic ring.

R ₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkyloxycarbonyl group.

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

(34)

The number of the repeating units having an acid-decomposable group may be one, or two or more kinds may be used in combination.

The content of the repeating units having an acid-decomposable group in the resin (A) (the total of the repeating units having a plurality of types) is preferably 20 mol% or more and 90 mol% or less based on the total repeating units in the resin (A) More preferably 25 mol% or more and 80 mol% or less, and still more preferably 25 mol% or more and 75 mol% or less.

The resin (A) preferably further contains a repeating unit having a lactone group.

As the lactone group, any contribution can be used as far as it contains a lactone structure, preferably a group containing a 5- to 7-membered cyclic lactone structure, and a bicyclic structure and a spiro structure in a 5- to 7-membered cyclic lactone structure It is preferable that other ring structures are ringed. It is more preferable to have a repeating unit having a group having a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-17). The group having a lactone structure may be directly bonded to the main chain. Preferred lactone structures are groups represented by the general formulas (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14).

(35)

The lactone structure moiety may or may not have a substituent (Rb ₂ ). Examples of the preferable substituent (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, An anion group, and an acid-decomposable group. n ₂ represents an integer of 0 to 4; n Rb ₂ to ₂ when 2 or more, a plurality is present, be the same or be different, and may be also bonded to form a plurality presence ring is bonded between the _two Rb.

Examples of the repeating unit having a group having a lactone structure represented by any one of formulas (LC1-1) to (LC1-17) include repeating units represented by the following formula (AI).

(36)

In the general formula (AI), Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having from 1 to 4 carbon atoms.

The preferable substituent which the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom.

Examples of the halogen atom of Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Rb ₀ is preferably a hydrogen atom or a methyl group.

Ab represents a divalent linking group having a single bond, an alkylene group, a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group combining these groups. Preferably a single bond, a linking group represented by -Ab ₁ -CO ₂ -. Ab ₁ is a straight chain, branched alkylene group, monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.

V represents a group represented by any one of formulas (LC1-1) to (LC1-17).

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

Specific examples of the repeating unit having a group having a lactone structure are set forth below, but the present invention is not limited thereto.

(37)

The content of the repeating unit having a lactone group is preferably from 1 to 30 mol%, more preferably from 5 to 25 mol%, and still more preferably from 5 to 20 mol%, based on the total repeating units in the resin (A).

The resin (A) may further have a repeating unit containing an organic group having a polar group, particularly a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. As a result, the permeability of the developer is further lowered, and the swelling of the pattern can be further suppressed. As the alicyclic hydrocarbon structure of the alicyclic hydrocarbon structure substituted with a polar group, adamanthyl group, dianthmyl group and novone are preferred. As the polar group, a hydroxyl group and a cyano group are preferable.

Specific examples of the repeating unit having a polar group are set forth below, but the present invention is not limited thereto.

(38)

When the resin (A) has a repeating unit containing an organic group having a polar group, its content is preferably from 1 to 30 mol%, more preferably from 5 to 25 mol%, based on the total repeating units in the resin (A) %, More preferably 5 to 20 mol%.

As the repeating units other than the above, a repeating unit having a group (photo-acid generator) capable of generating an acid by irradiation with an actinic ray or radiation may be included. In this case, it can be considered that the repeating unit having this photoacid generator corresponds to the compound (B) which generates an acid by irradiation of an actinic ray or radiation described later.

Examples of such a repeating unit include repeating units represented by the following general formula (14).

[Chemical Formula 39]

R ⁴¹ represents a hydrogen atom or a methyl group. L ⁴¹ represents a single bond or a divalent linking group. L ⁴² represents a divalent linking group. R ⁴⁰ represents a structural moiety that is decomposed by irradiation with an actinic ray or radiation to generate an acid on the side chain.

Specific examples of the repeating unit represented by formula (14) are shown below, but the present invention is not limited thereto.

(40)

In addition, examples of the repeating unit represented by the general formula (14) include repeating units described in paragraphs [0094] to [0105] of JP-A No. 2014-041327.

When the resin (A) contains a repeating unit having a photoacid generator, the content of the repeating unit having a photoacid generator is preferably from 1 to 40 mol%, more preferably from 1 to 40 mol%, based on all repeating units in the resin (A) 5 to 35 mol%, and more preferably 5 to 30 mol%.

The resin (A) may contain a repeating unit represented by the following formula (V-1) or the following formula (V-2).

(41)

Wherein,

R ₆ and R ₇ each independently represent a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group or an acyloxy group, a cyano group, a nitro group, A halogen atom, an ester group (-OCOR or -COOR: R represents an alkyl group or a fluorinated alkyl group having 1 to 6 carbon atoms), or a carboxyl group.

n ₃ represents an integer of 0 to 6;

and n ₄ represents an integer of 0 to 4.

X ⁴ is a methylene group, an oxygen atom or a sulfur atom.

Specific examples of the repeating unit represented by the formula (V-1) or (V-2) are shown below, but are not limited thereto.

(42)

The resin (A) containing the repeating unit represented by the general formula (1) can be obtained by a method described in, for example, "Fifth Edition Experimental Chemistry Lecture", page 42, "Macromolecules", 46, (2013) , Pp. 8887, or the method described in "Bioorganic and Medicinal Chemistry Letters ", 20, (2010) 74-77.

The resin (A) can be synthesized by a conventional method (for example, radical polymerization). Examples of the general synthesis method include a batch polymerization method in which a monomer species and an initiator are dissolved in a solvent and heated to effect polymerization, a drop polymerization method in which a solution of a monomer species and an initiator is added dropwise to a heating solvent for 1 to 10 hours And a dropwise polymerization method is preferable.

Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; An ester solvent such as ethyl acetate; Amide solvents such as dimethylformamide and dimethylacetamide; A solvent for dissolving the actinic ray-sensitive or radiation-sensitive composition of the present invention such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone described below; And the like. More preferably, the polymerization is carried out by using the same solvent as the solvent used in the active radiation-sensitive or radiation-sensitive composition of the present invention. This makes it possible to suppress the generation of particles during storage.

The polymerization reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon. As the polymerization initiator, polymerization is initiated by using a commercially available radical initiator (azo type initiator, peroxide, etc.). As the radical initiator, azo-based initiators are preferable, and azo-based initiators having an ester group, a cyano group and a carboxyl group are preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, and dimethyl 2,2'-azobis (2-methylpropionate). An initiator is added according to the purpose or added in portions. After completion of the reaction, the polymer is added to a solvent to recover a desired polymer by a method such as powder or solid recovery. The concentration of the reaction is 5 to 50 mass%, preferably 10 to 30 mass%. The reaction temperature is usually from 10 to 150 캜, preferably from 30 to 120 캜, more preferably from 60 to 100 캜.

The purification may be carried out by a liquid-liquid extraction method in which residual monomer or oligomer component is removed by combining water or an appropriate solvent, a purification method in a solution state such as ultrafiltration in which only a substance having a specific molecular weight or less is extracted and removed, A conventional method such as a reprecipitation method in which residual monomer or the like is removed by coagulating the resin in a poor solvent or a solid state purification method such as washing a resin slurry separated by filtration with a poor solvent can be applied.

The weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 3,000 to 30,000, and most preferably 5,000 to 20,000 in terms of polystyrene by GPC. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, deterioration of developability or viscosity can be prevented and deterioration of film formability can be prevented.

Another particularly preferred form of the weight-average molecular weight of the resin (A) is 5,000 to 15,000 in terms of polystyrene conversion by the GPC method. By setting the weight average molecular weight to 5,000 to 15,000, resist residues (hereinafter also referred to as "scum") are suppressed, and a better pattern can be formed.

The dispersion degree (molecular weight distribution) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. The smaller the degree of dispersion, the better the resolution and pattern shape, and the sidewall of the resist pattern is smooth and the roughness is excellent.

In the actinic ray-sensitive or radiation-sensitive composition of the present invention, the content of the resin (A) is preferably 50 to 99.9 mass%, more preferably 60 to 99.0 mass%, of the total solid content.

In the actinic ray-sensitive or radiation-sensitive composition according to the present invention, the resin (A) may be used singly or in combination.

[Compound (B) that generates an acid upon irradiation with an actinic ray or radiation]

The actinic ray-sensitive or radiation-sensitive composition used in the pattern forming method of the present invention may be a compound that generates an acid upon irradiation with an actinic ray or radiation ("photoacid generator" PAG: (B) ").

The photoacid generator may be in the form of a low molecular weight compound or may be introduced into a part of the polymer. The form of the low molecular compound and the form introduced into a part of the polymer may be used in combination.

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

In the case where the photoacid generator is introduced into a part of the polymer, the photoacid generator may be introduced into a part of the resin (A) or may be introduced into a resin different from the resin (A).

In the present invention, the photoacid generator is preferably in the form of a low molecular weight compound.

The photoacid generator is not particularly limited as long as it is a known photoacid generator. The photoacid generator may be an organic acid such as sulfonic acid, bis (alkylsulfonyl) imide, or tris (ethylsulfonyl) imide by irradiation with actinic rays or radiation, preferably electron beam or extreme ultraviolet Alkylsulfonyl) methide are preferred.

The photoacid generator is preferably a sulfonium salt.

The photoacid generator may more preferably be a compound represented by the following general formula (ZI), (ZII) or (ZIII).

(43)

In the above general formula (ZI)

R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.

The number of carbon atoms of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.

Also, R ₂₀₁ and R ~ form a ring structure by combining two of the dogs _203, may contain an oxygen atom, a sulfur atom, an ester bond in the ring, an amide bond, a carbonyl group. Examples of R groups R ~ to ₂₀₁ formed by combining any two of the ₂₀₃ dogs, may be mentioned an alkylene group (e.g., tert-butyl group, a pentylene group).

Z ^- represents an unconjugated anion (an anion having a remarkably low ability to cause a nucleophilic reaction).

Examples of the non-nucleophilic anion include sulfonic acid anions (aliphatic sulfonic acid anions, aromatic sulfonic acid anions, camphorsulfonic acid anions, etc.), carboxylic acid anions (aliphatic carboxylic acid anions, aromatic carboxylic acid anions, aralkyl carboxylic acid anions, A bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methide anion.

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

The aromatic group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion is preferably an aryl group having 6 to 14 carbon atoms such as a phenyl group, a tolyl group and a naphthyl group.

The alkyl group, cycloalkyl group and aryl group exemplified above may have a substituent. Specific examples thereof include halogen atoms such as a nitro group and a fluorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms) , An aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms (Preferably having 1 to 15 carbon atoms) (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably having 1 to 15 carbon atoms) (Preferably having 6 to 20 carbon atoms), an alkylaryloxaphonyl group (preferably having 7 to 20 carbon atoms), a cycloalkylaryloxaphonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group (Having from 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having from 8 to 20 carbon atoms), and the like. All. The aryl group and the ring structure of each group may further include an alkyl group (preferably having from 1 to 15 carbon atoms) as a substituent.

The aralkyl group in the aralkylcarboxylic acid anion is preferably an aralkyl group having 7 to 12 carbon atoms such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group and a naphthylvinyl group.

The sulfonylimide anion includes, for example, a saccharin anion.

The alkyl group in the bis (alkylsulfonyl) imide anion and the tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of the substituent of these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxaphonyl group, an aryloxylphenyl group, a cycloalkylaryloxaphonyl group, Or an alkyl group substituted with a fluorine atom are preferable.

The alkyl group in the bis (alkylsulfonyl) imide anion may be bonded to each other to form a ring structure. As a result, acid strength is increased.

Examples of other non-nucleophilic anions include fluorinated phosphorus (for example, PF ₆ ^- ), boron fluoride (for example, BF ₄ ^- ), fluorinated antimony (for example, SbF ₆ ^- have.

Examples of the non-nucleophilic anion include an aliphatic sulfonic acid anion in which at least the? -Position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonic acid anion in which the alkyl group is substituted with a fluorine atom or a fluorine atom, bis (alkylsulfonyl) Anion, and a tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom. The non-nucleophilic anion is more preferably a perfluoro aliphatic sulfonic acid anion (more preferably having 4 to 8 carbon atoms), a benzenesulfonic acid anion having a fluorine atom, still more preferably a nonafluorobutane sulfonic acid anion, Perfluorooctanesulfonic acid anion, pentafluorobenzenesulfonic acid anion, and 3,5-bis (trifluoromethyl) benzenesulfonic acid anion.

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

As the non-nucleophilic anion, the anion represented by the following general formula (AN1) may also be mentioned as a preferable embodiment.

(44)

Wherein,

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

R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom, or an alkyl group, and R ¹ and R ² in the case where a plurality of R ¹ and R ² are present may be the same or different.

L represents a divalent linking group, and L in a case where a plurality is present may be the same or different.

A represents a cyclic organic group.

x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

The general formula (AN1) will be described in more detail.

The alkyl group in the fluorine atom-substituted alkyl group of Xf preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. 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. Specific examples of Xf example, a fluorine _{atom, CF 3, C 2 F 5} , C 3 F 7, C 4 F 9, CH 2 CF 3, CH 2 CH 2 CF 3, CH 2 C 2 F 5, CH 2 CH 2 C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ and CH ₂ CH ₂ C ₄ F ₉ , among which a fluorine atom and CF ₃ are preferable . Particularly, it is preferable that both Xf's are fluorine atoms.

The alkyl group of R ¹ and R ² may have a substituent (preferably a fluorine atom), and preferably has 1 to 4 carbon atoms. More preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having a substituent of R ¹ and R ² include CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F _{17, CH 2 CF 3, CH} 2 CH 2 CF 3, CH 2 C 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH 2 C 4 F ₉ , and CH ₂ CH ₂ C ₄ F ₉ , among which CF ₃ is preferable.

R ¹ and R ² are preferably a fluorine atom or CF ₃ .

x is preferably 1 to 10, more preferably 1 to 5.

y is preferably 0 to 4, more preferably 0.

z is preferably 0 to 5, more preferably 0 to 3.

L is not particularly limited and is preferably -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO ₂ -, an alkylene group, a cycloalkylene group, an alkenylene group Or a linking group in which a plurality of them are connected, and the like, and a linking group having a total carbon number of 12 or less is preferable. Of these, -COO-, -OCO-, -CO- and -O- are preferable, and -COO- and -OCO- are more preferable.

The cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and examples thereof include a cyclic group, an aryl group, and a heterocyclic group (including not only aromatic groups but also aromatic groups).

The cyclic group may be monocyclic or polycyclic, and may be a monocyclic cycloalkyl group such as cyclopentyl group, cyclohexyl group or cyclooctyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclododecanyl group, a tetracyclododecanyl group, And a t-butyl group. Among them, an alicyclic group having a bulky structure having 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, etc., And is preferable from the viewpoint of MEEF improvement.

Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring and an anthracene ring.

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

Examples of the cyclic organic group include a lactone structure. Specific examples thereof include the lactone structures represented by the aforementioned general formulas (LC1-1) to (LC1-17).

The cyclic organic group may have a substituent, and examples of the substituent include an alkyl group (any of linear, branched and cyclic, preferably 1 to 12 carbon atoms), a cycloalkyl group (monocyclic, polycyclic, (Preferably having from 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfone group Amide group, sulfonic acid ester group and the like. In addition, carbon constituting the cyclic organic group (carbon contributing to ring formation) may be carbonyl carbon.

_Examples of the organic group of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include an aryl group, an alkyl group, and a cycloalkyl group.

At least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is preferably an aryl group, and more preferably all three are aryl groups. As the aryl group, a heteroaryl group such as an indole moiety and a pyrrole moiety may be used in addition to a phenyl group and a naphthyl group. The alkyl group and the cycloalkyl group represented by R ₂₀₁ to R ₂₀₃ preferably include a straight chain or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. The alkyl group is more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group or an n-butyl group. More preferred examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. These groups may further have a substituent. Examples of the substituent include a halogen atom such as a nitro group and a fluorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms) , An aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms ), But the present invention is not limited thereto.

Among the general formulas (ZII) and (ZIII)

Each of R ₂₀₄ to R ₂₀₇ independently represents an aryl group, an alkyl group or a cycloalkyl group.

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

The aryl group, alkyl group and cycloalkyl group represented by R ₂₀₄ to R ₂₀₇ may have a substituent. Examples of the substituent include those having an aryl group, an alkyl group and a cycloalkyl group of R ₂₀₁ to R _{203 in} the above-mentioned compound (ZI).

Z ^- represents an unconjugated anion and is the same as the non-nucleophilic anion of Z ^- in formula (ZI).

In the present invention, the photo acid generator is, from the point of view to suppress the diffusion of the unexposed portion of the acid generated by the exposure to be improved the resolution, electron beams or by the irradiation of EUV, the volume 130Å least ^three sizes acid of (More preferably, a sulfonic acid), more preferably a compound generating an acid having a size of 190 Å ³ or more (more preferably a sulfonic acid), and more preferably an acid having a size of 270 Å ³ or more More preferably a sulfonic acid), particularly preferably a compound which generates an acid having a size of 400 Å ³ or more (more preferably, a sulfonic acid). However, in view of the sensitivity and the solubility in coating solvent, wherein the volume is ³ to 2000Å or less are preferred, and more preferably not more than, 1500Å ^3. The value of the volume was obtained using "WinMOPAC" manufactured by Fujitsu Kabushiki Kaisha. That is, first, the chemical structure of the acid in each example is input, and then the most stable steric body of each acid is determined by calculating the molecular force field using the MM3 method using this structure as an initial structure, By performing molecular orbital calculation using the PM3 method for the most stable three-dimensional fundus, the "accessible volume" of each acid can be calculated.

In the present invention, a photoacid generator that generates an acid exemplified below by irradiation with actinic rays or radiation is preferable. In some of the examples, the calculated value of the volume is added (unit A ³ ). The calculation value obtained here is the volume value of the acid to which the proton is bonded to the anion portion.

1 Å is 1 × 10 ^-10 m.

[Chemical Formula 45]

(46)

(47)

Examples of photoacid generators include those described in JP-A-2014-41328 [0368] to [0377], JP-A-2013-228681, paragraphs 0240 to 0262 (corresponding U.S. Patent Application Publication No. 2015/004533 And the contents of which are incorporated herein by reference. Specific preferred examples include, but are not limited to, the following compounds.

(48)

(49)

(50)

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

The content of the photoacid generator in the actinic ray-sensitive or radiation-sensitive composition is preferably from 0.1 to 50% by mass, more preferably from 5 to 50% by mass, more preferably from 8 to 8% by mass, based on the total solid content of the composition. To 40% by mass. In particular, in order to achieve high sensitivity and high resolution at the time of electron beam or extreme ultraviolet exposure, the photoacid generator content is preferably high, more preferably 10 to 40 mass%, and most preferably 10 to 35 mass%.

[Solvent (C)]

The actinic ray-sensitive or radiation-sensitive composition used in the pattern forming method of the present invention includes a solvent (C). The solvent may be selected from the group consisting of (M1) propylene glycol monoalkyl ether carboxylate, (M2) propylene glycol monoalkyl ether, lactic acid ester, acetic acid ester, alkoxypropionic acid ester, chain ketone, cyclic ketone, And at least one selected from the group consisting of an alkylene carbonate and an alkylene carbonate. The solvent may further contain components other than the components (M1) and (M2).

The component (M1) is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether acetate is particularly preferred.

As the component (M2), the followings are preferable.

As the propylene glycol monoalkyl ether, propylene glycol monomethyl ether or propylene glycol monoethyl ether is preferable.

As the lactic acid ester, ethyl lactate, butyl lactate, or propyl lactate is preferable.

As the acetic acid ester, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate is preferable.

Butyl butyrate is also preferred.

As the alkoxypropionic acid ester, methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferable.

Examples of the chain ketone include ketones such as 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, Ethyl ketone, methyl isobutyl ketone, acetyl acetone, acetone diacetone, ionone, diacetone diol, acetyl carbinol, acetophenone, methyl naphthyl ketone, or methyl amyl ketone is preferable.

As the cyclic ketone, methylcyclohexanone, isophorone, or cyclohexanone is preferable.

As the lactone,? -Butyrolactone is preferable.

As the alkylene carbonate, propylene carbonate is preferable.

As the component (M2), propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, pentyl acetate,? -Butyrolactone or propylene carbonate is more preferable Do.

It is preferable to use an ester solvent in which the number of carbon atoms is 7 or more (preferably 7 to 14, more preferably 7 to 12, more preferably 7 to 10), and the number of heteroatoms is 2 or less.

Preferable examples of the ester type solvent having 7 or more carbon atoms and 2 or less hetero atoms include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, butyl propionate, isobutyrate iso Butyl, heptyl propionate, and butyl butanoate, and isoamyl acetate is particularly preferable.

As the component (M2), those having a flash point (hereinafter also referred to as fp) of 37 ° C or higher are preferably used. Examples of such a component (M2) include propylene glycol monomethyl ether (fp: 47 ° C), ethyl lactate (fp: 53 ° C), ethyl 3-ethoxypropionate (fp: 49 ° C), methyl amyl ketone : 42 ° C), cyclohexanone (fp: 44 ° C), pentyl acetate (fp: 45 ° C), methyl 2-hydroxyisobutyrate (fp: 45 ° C), γ-butyrolactone Or propylene carbonate (fp: 132 DEG C). Of these, propylene glycol monoethyl ether, ethyl lactate, pentyl acetate, and cyclohexanone are more preferable, and propylene glycol monoethyl ether or ethyl lactate is particularly preferable. The "flash point" used herein means the value described in the reagent catalog of TOKYO KASEI KOGYO Co., Ltd. or Sigma-Aldrich Co.

The solvent preferably contains the component (M1). It is more preferable that the solvent consist essentially of the component (M1) alone or a mixed solvent of the component (M1) and other components. In the latter case, it is more preferable that the solvent includes both of the component (M1) and the component (M2).

The mass ratio of the component (M1) to the component (M2) is preferably in the range of 100: 0 to 15:85, more preferably in the range of 100: 0 to 40:60, 40 < / RTI > That is, it is preferable that the solvent comprises only the component (M1), or both the component (M1) and the component (M2), and the mass ratio thereof is as follows. That is, in the latter case, the mass ratio of the component (M1) to the component (M2) is preferably 15/85 or more, more preferably 40/60 or more, and even more preferably 60/40 or more. By employing such a configuration, it becomes possible to further reduce the number of development defects.

When the solvent contains both of the component (M1) and the component (M2), the mass ratio of the component (M1) to the component (M2) is, for example, 99/1 or less.

As described above, the solvent may further contain components other than the components (M1) and (M2). In this case, the content of the components other than the components (M1) and (M2) is preferably in the range of 5% by mass to 30% by mass with respect to the total amount of the solvent.

The content of the solvent in the actinic ray-sensitive or radiation-sensitive composition is preferably determined such that the solid content of the whole component is 0.5 to 30 mass%, more preferably 1 to 20 mass%. By doing so, the applicability of the actinic ray-sensitive or radiation-sensitive composition can be further improved.

≪ Basic compound >

The actinic ray-sensitive or radiation-sensitive composition of the present invention preferably contains a basic compound in order to reduce the change in performance over time from exposure to heating.

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

(51)

In the general formulas (A) and (E), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and each represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group 20) or an aryl group (preferably having 6 to 20 carbon atoms), wherein R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring.

As the alkyl group having a substituent for the alkyl group, 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 is preferable.

R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and represent an alkyl group having 1 to 20 carbon atoms.

The alkyl groups in these general formulas (A) and (E) are more preferably amorphous.

Preferred examples of the compound include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like. More preferred compounds include imidazole structure, diazabicyclic An onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, an aniline derivative having a hydroxyl group and / or an ether bond, etc. .

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole and the like. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] Javancyclo [5,4,0] undec-7-ene, and the like. Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacysulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide, tris (t -Butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide and the like. As the compound having an onium carboxylate structure, the anion portion of the compound having an onium hydroxide structure is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate and perfluoroalkyl carboxylate . Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine. Examples of the aniline compound include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutyl aniline and N, N-dibutylaniline. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, tris (methoxyethoxyethyl) amine and the like. Examples of the aniline derivative having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline and the like.

Preferred examples of the basic compound include an amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group.

As the amine compound, primary, secondary, and tertiary amine compounds can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable. The amine compound is more preferably a tertiary amine compound. When the at least one alkyl group (preferably 1 to 20 carbon atoms) is bonded to the nitrogen atom, the amine compound may contain, in addition to the alkyl group, a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group ) May be bonded to a nitrogen atom.

It is preferable that the amine compound has an oxygen atom in the alkyl chain and an oxyalkylene group. The number of oxyalkylene groups is one or more, preferably 3 to 9, more preferably 4 to 6, in the molecule. Among oxyalkylene groups, an oxyethylene group (-CH ₂ CH ₂ O-) or an oxypropylene group (-CH (CH ₃ ) CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-) is preferable, Oxyethylene group.

The ammonium salt compound is preferably an ammonium salt compound in which primary, secondary, tertiary or quaternary ammonium salt compounds can be used and at least one alkyl group is bonded to a nitrogen atom. When the at least one alkyl group (preferably 1 to 20 carbon atoms) is bonded to the nitrogen atom, the ammonium salt compound may contain, in addition to the alkyl group, a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group ) May be bonded to a nitrogen atom.

It is preferable that the ammonium salt compound has an oxygen atom and an oxyalkylene group in the alkyl chain. The number of oxyalkylene groups is one or more, preferably 3 to 9, more preferably 4 to 6, in the molecule. Among oxyalkylene groups, an oxyethylene group (-CH ₂ CH ₂ O-) or an oxypropylene group (-CH (CH ₃ ) CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-) is preferable, Oxyethylene group.

Examples of the anion of the ammonium salt compound include a halogen atom, a sulfonate, a borate, and a phosphate. Among them, a halogen atom and a sulfonate are preferable. The halogen atom is particularly preferably chloride, bromide or iodide, and as the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is particularly preferable. Examples of the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates. The alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, alkoxy group, acyl group, and aryl group. Specific examples of the alkyl sulfonate include methanesulfonate, ethanesulfonate, butainesulfonate, hexanesulfonate, octanesulfonate, benzylsulfonate, trifluoromethanesulfonate, pentafluoroethanesulfonate , Nonafluorobutane sulfonate, and the like. The aryl group of the arylsulfonate includes a benzene ring, a naphthalene ring and an anthracene ring. The benzene ring, naphthalene ring and anthracene ring may have a substituent, and the substituent is preferably a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. Specific examples of the linear or branched alkyl group and cycloalkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl and cyclohexyl. Examples of other substituents include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, an acyl group, and an acyloxy group.

The amine compound having a phenoxy group or the ammonium salt compound having a phenoxy group has a phenoxy group at the terminal on the opposite side to the nitrogen atom of the alkyl group of the amine compound or the ammonium salt compound. The phenoxy group may have a substituent. Examples of the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, Time and so on. The substitution of the substituent may be any of 2 to 6 above. The number of substituents may be in the range of 1 to 5.

It is preferable that at least one oxyalkylene group is present between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups is one or more, preferably 3 to 9, more preferably 4 to 6, in the molecule. Among oxyalkylene groups, an oxyethylene group (-CH ₂ CH ₂ O-) or an oxypropylene group (-CH (CH ₃ ) CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-) is preferable, Oxyethylene group.

The amine compound having a phenoxy group can be obtained by heating and reacting a primary or secondary amine having a phenoxy group with a haloalkyl ether and then adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium, , Chloroform and the like. Alternatively, a reaction may be carried out by heating a primary or secondary amine and a haloalkyl ether having a phenoxy group at the terminal thereof, and then adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium, Of an organic solvent.

(A compound (PA) which has a proton acceptor functional group and which decomposes by irradiation with an actinic ray or radiation to decrease or disappear the proton acceptor property or to generate a compound which changes from proton acceptor property to acidic property)

The actinic ray-sensitive or radiation-sensitive composition according to the present invention is a basic compound which has a proton acceptor functional group and is decomposed by irradiation with an actinic ray or radiation to decrease or disappear the proton acceptor property, (Hereinafter also referred to as compound (PA)) which generates a compound which changes from an acceptor property to an acidic property.

The proton acceptor functional group is a functional group having a group capable of electrostatically interacting with the proton or an electron, and includes, for example, a functional group having a macrocyclic structure such as a cyclic polyether or a non-conjugated electron pair Means a functional group having a nitrogen atom attached thereto. The nitrogen atom having a non-covalent electron pair not contributing to the pi bond is, for example, a nitrogen atom having a partial structure represented by the following general formula.

(52)

Preferable partial structures of the proton acceptor functional groups include, for example, crown ethers, azacrown ethers, primary to tertiary amines, pyridine, imidazole and pyrazine structures.

The compound (PA) is decomposed by irradiation with an actinic ray or radiation to generate a compound in which the proton acceptor property is decreased, disappears, or the proton acceptor property is changed to acidic. Here, the change of the proton acceptor property from the degradation, disappearance, or change from the proton acceptor property to the acid is a change of the proton acceptor property due to the addition of the proton to the proton acceptor functional group. Specifically, Means that the equilibrium constant in the chemical equilibrium is reduced when a proton adduct is produced from a compound (PA) having a functional group and a proton.

Specific examples of the compound (PA) include, for example, the following compounds. As specific examples of the compound (PA), those described in paragraphs 0421 to 0428 of JP-A No. 2014-41328 and paragraphs 0108 to 0116 of JP-A No. 2014-134686 may be cited. Are included in the specification.

(53)

(54)

(55)

These basic compounds may be used alone or in combination of two or more.

The amount of the basic compound to be used is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the solid content of the actinic ray-sensitive or radiation-sensitive composition.

The ratio of the acid generator to the basic compound in the composition is preferably from 2.5 to 300 as the acid generator / basic compound (molar ratio). That is, the mole ratio is preferably 2.5 or more in terms of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the resolution lowering due to the thickening of the resist pattern with time after the post-exposure heating treatment. The acid generator / basic compound (molar ratio) is more preferably 5.0 to 200, and still more preferably 7.0 to 150.

As the basic compound, for example, compounds described in paragraphs 0140 to 0144 of Japanese Laid-Open Patent Publication No. 2013-11833 (amine compound, amide group-containing compound, urea compound, nitrogen-nitrogen heterocycle compound, etc.) can be used.

≪ Hydrophobic resin &

The actinic ray-sensitive or radiation-sensitive composition used in the pattern forming method of the present invention may have a hydrophobic resin different from the resin (A) separately from the resin (A).

It is preferable that the hydrophobic resin is designed to be localized on the surface of the membrane. However, unlike the surfactant, it is not necessary to have a hydrophilic group in the molecule and contribute to uniformly mixing the polar / nonpolar material.

The effects of adding a hydrophobic resin include control of the static / dynamic contact angle of the film surface with water, suppression of outgassing, and the like.

The hydrophobic resin preferably has at least one of "fluorine atom", "silicon atom" and "CH ₃ partial structure contained in the side chain portion of the resin" from the viewpoint of the unevenness of the surface layer of the film, It is more preferable to have species or more. The hydrophobic resin preferably contains a hydrocarbon group having 5 or more carbon atoms. These groups may be contained in the main chain of the resin, or may be substituted in the side chain.

When the hydrophobic resin contains a fluorine atom and / or a silicon atom, the fluorine atom and / or the silicon atom in the hydrophobic resin may be contained in the main chain of the resin or may be contained in the side chain.

When the hydrophobic resin contains a fluorine atom, it is preferable that the fluorine atom-containing partial structure is a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom.

The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a straight chain or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom .

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

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

Examples of the repeating unit having a fluorine atom or a silicon atom include those illustrated in paragraph 0519 of US2012 / 0251948A1.

As described above, it is also preferable that the hydrophobic resin includes a CH ₃ partial structure in the side chain portion.

Here, in the CH ₃ a partial structure having a side chain part of a hydrophobic resin, to include a CH ₃ a partial structure having a methyl group, ethyl group, propyl group and the like.

On the other hand, the methyl group directly bonded to the main chain of the hydrophobic resin (for example, the? -Methyl group of the repeating unit having a methacrylic acid structure) has a small contribution to the surface unevenization of the hydrophobic resin due to the influence of the main chain, Is not included in the CH ₃ partial structure in the present invention.

With regard to the hydrophobic resin, reference can be made to the descriptions in [0348] to [0415] of JP-A-2014-010245, the contents of which are incorporated herein by reference.

Further, as the hydrophobic resin, those described in Japanese Patent Laid-Open Publication No. 2011-248019, Japanese Unexamined Patent Publication No. 2010-175859, and Japanese Unexamined Patent Publication No. 2012-032544 can be preferably used.

<Surfactant>

The actinic ray-sensitive or radiation-sensitive composition used in the present invention may further contain a surfactant. By containing a surfactant, it becomes possible to form a pattern having less adhesiveness and less development defects with good sensitivity and resolution when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less, is used.

As the surfactant, it is particularly preferable to use a fluorine-based and / or silicon-based surfactant.

Examples of the fluorine-based and / or silicon-based surfactants include the surfactants described in [0276] of U.S. Patent Application Publication No. 2008/0248425. In addition, FFA TOP EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Fluorad FC430, 431 or 4430 (manufactured by Sumitomo 3M Co., Ltd.); F171, F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC Corporation); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by Asahi Glass Co., Ltd.); Troisol S-366 (manufactured by Troy Chemical); GF-300 or GF-150 (manufactured by Toagosei Chemical Industry Co., Ltd.), Surflon S-393 (manufactured by Seiyaku Chemical Co., Ltd.); EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 or EF601 (Gemco Co., Ltd.); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA); Alternatively, FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (manufactured by NEOS) may be used. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone surfactant.

The surfactant can be synthesized using a fluoroaliphatic compound produced by the telomerization method (also referred to as the telomer method) or the oligomerization method (also referred to as the oligomer method) in addition to the publicly known ones as described above You can. Specifically, a polymer having a fluoroaliphatic group derived from the fluoroaliphatic compound may be used as a surfactant. This fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-90991.

Also, surfactants other than the fluorine-based and / or silicon-based surfactants described in [0280] of U.S. Patent Application Publication No. 2008/0248425 may be used.

These surfactants may be used singly or in combination of two or more kinds.

When the actinic ray-sensitive or radiation-sensitive composition used in the present invention contains a surfactant, the content thereof is preferably 0 to 2% by mass, more preferably 0 to 2% by mass, based on the total solid content of the composition 0.0001 to 2% by mass, and more preferably 0.0005 to 1% by mass.

<Other additives>

The actinic ray-sensitive or radiation-sensitive composition used in the present invention may be a compound which promotes solubility in a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a developer (for example, Or an alicyclic or aliphatic compound containing a carboxy group) may be further contained.

The actinic ray-sensitive or radiation-sensitive composition used in the present invention may further contain a dissolution inhibiting compound. The "dissolution inhibiting compound" is a compound having a molecular weight of 3,000 or less, which is decomposed by the action of an acid to decrease the solubility in a developing solution.

The developer of the present invention can be suitably applied also to non-chemically amplified resist compositions.

As the non-chemically amplified resist composition, for example,

(for example, Japanese Unexamined Patent Application Publication No. 2013-210411 [0025] Patent Document 1) discloses a resist material whose main chain is broken by irradiation with g line, h line, i line, KrF, ArF, EB or EUV and the molecular weight is lowered to change the solubility As a main component, a copolymer of an? -Chloroacrylic acid ester compound and an? -Methylstyrene-based compound described in U.S. Patent Nos. 2015/0008211 [0032] to [0033] and [0063] And the like),

Hydrogen silsesquioxane (HSQ) accompanied by a silanol condensation reaction generated by g line, h line, i line, KrF, ArF, EB or EUV, chlorine-

metal complexes (such as magnesium, chromium, manganese, iron, cobalt, nickel, copper, zinc, silver, cadmium, indium, tin, and the like) having absorption for light such as g line, h line, i line, KrF, ArF, EB, Zirconium, and hafnium are preferred from the viewpoint of pattern formation property), and are used in combination with a ligand elimination or an acid generator to form a resist material accompanied by a ligand exchange process (JP-A-2015-075500 [0017] to [0033], [0037] to [0047], JP-A-2012-185485 [0017] - [0032], [0043] - [0044] And resist materials described in Patent Publications 2012/0208125 [0042] to [0051], [0066] and the like).

As the resist composition, the resist compositions described in [0010] to [0062], [0129] to [0165] of JP-A No. 2008-83384 may also be used.

Hereinafter, each step of the pattern forming method of the present invention will be described.

&Lt; Process (1) >

The step (1) is a step of forming a film using the above-mentioned actinic ray-sensitive or radiation-sensitive composition, and can be carried out, for example, by the following method.

In order to form a film on the substrate using the active ray-sensitive or radiation-sensitive composition, the resin (A) and the compound (B) are dissolved in the solvent (C) to prepare an actinic ray- or radiation- , Filtered as necessary, and then coated on a substrate. The filter is preferably made of polytetrafluoroethylene, polyethylene or nylon having a pore size of 0.1 mu m or less, more preferably 0.05 mu m or less, and even more preferably 0.03 mu m or less.

In the pattern forming method of the present invention, a resist film (a resist film, typically a sensitized actinic ray or radiation-sensitive film, and a chemically amplified resist film Is preferable). The topcoat layer may be formed using the topcoat composition on the active ray-sensitive or radiation-sensitive film. The film thickness of this film is generally 200 nm or less, preferably 10 to 100 nm. The film thickness of the top coat layer is preferably 10 to 200 nm, more preferably 20 to 100 nm, particularly preferably 40 to 80 nm.

For example, in order to resolve a 1: 1 line and space pattern having a line width of 20 nm or less, the film thickness of the formed film is preferably 50 nm or less. When the film thickness is 50 nm or less, it is more difficult for the occurrence of pattern collapse to occur when applying the developing process, which will be described later, to obtain better resolution performance.

The film thickness is more preferably in the range of 15 nm to 45 nm. When the film thickness is 15 nm or more, sufficient etching resistance is obtained. The range of the film thickness is more preferably from 15 nm to 40 nm. When the film thickness is in this range, both the etching resistance and the better resolution performance can be satisfied at the same time.

As a method for forming the film, for example, an actinic ray-sensitive or radiation-sensitive composition is coated on a substrate (for example, silicon / silicon dioxide coating) used in the production of a precision integrated circuit device by a suitable coating method such as a spinner or a coater Coating, and drying to form a film. Furthermore, various known base films (inorganic film, organic film, antireflection film) may be formed on the lower layer of the film.

As a method of applying the actinic ray-sensitive or radiation-sensitive composition on the substrate, spin coating is preferable, and the number of revolutions is preferably 1000 to 3000 rpm.

Further, in the pattern forming method of the present invention, the top coat composition may be applied to the upper layer of the film by the same means as the above-mentioned film forming method and dried to form the top coat layer. It is preferable that the topcoat is not mixed with the film made of the actinic ray-sensitive or radiation-sensitive composition and can be uniformly applied to the upper layer of the film. It is preferable to dry the film before forming the top coat layer.

The topcoat preferably contains a compound containing at least one group or bond selected from the group consisting of ether bonding, thioether bonding, hydroxyl group, thiol group, carbonyl bonding and ester bonding, A topcoat conventionally known can be formed by a conventionally known method and a topcoat can be formed based on the description in paragraphs 0072 to 0082 of Japanese Laid-Open Patent Publication No. 2014-059543 .

In the development process, it is preferable to form a topcoat containing a basic compound described in, for example, JP-A-2013-61648 on a film. Specific examples of the basic compound that can be included in the topcoat are the same as the above-mentioned basic compounds.

As a drying method of the film and the top coat layer made of the active ray-sensitive or radiation-sensitive composition, a method of heating and drying is generally used. The heating may be performed by a means provided in a conventional exposure and development apparatus, or may be performed using a hot plate or the like. The heating temperature is preferably 80 to 150 占 폚, more preferably 80 to 140 占 폚, and more preferably 80 to 130 占 폚. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and still more preferably 60 to 600 seconds.

&Lt; Process (2) >

Step (2) is a step of exposing a film, and can be performed, for example, by the following method.

The film formed as described above is irradiated with an actinic ray or radiation through a predetermined mask. In addition, in the irradiation of an electron beam, drawing (direct writing) without a mask is generally used.

Examples of the actinic ray or radiation include KrF excimer laser, ArF excimer laser, EUV (Extreme Ultra Violet), EB (Electron Beam), and the like. Extreme ultraviolet rays or electron beams are particularly preferable. The exposure may be liquid immersion exposure.

<Bake>

In the pattern forming method of the present invention, it is preferable to perform baking (heating) after exposure and before development. The reaction of the exposed portion is promoted by the baking, and the sensitivity and the pattern shape become better.

The heating temperature is preferably 80 to 150 占 폚, more preferably 80 to 140 占 폚, and even more preferably 80 to 130 占 폚.

The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and still more preferably 60 to 600 seconds.

The heating may be performed by a means provided in a conventional exposure and development apparatus, or may be performed using a hot plate or the like.

&Lt; Process (3) >

Step (3) is a step of developing the exposed film in step (2) by a developing solution containing an organic solvent.

[developer]

The developer used in the present invention contains an organic solvent. A developer containing an organic solvent is also referred to as an "organic developer ". The content of the organic solvent in the organic developer is preferably more than 50 mass% and not more than 100 mass%, more preferably not less than 70 mass% nor more than 100 mass%, more preferably not less than 90 mass% nor more than 100 mass% , And particularly preferably 95 mass% or more and 100 mass% or less.

The organic solvent contained in the developing solution is not particularly limited, but at least one organic solvent selected from the group consisting of an ester solvent, a ketone solvent, an alcohol solvent, an ether solvent, an amide solvent, and a hydrocarbon hydrocarbon solvent desirable.

An ester solvent refers to a solvent having an ester bond in a molecule, and a ketone solvent refers to a solvent having a ketone group in a molecule. An alcohol solvent refers to a solvent having an alcoholic hydroxyl group in a molecule. An amide solvent means an amide bond Refers to a solvent having an ether bond in a molecule. Among them, there is a solvent having a plurality of the above-mentioned functional groups in one molecule, and in this case, it is suitable for all the solvent species including the functional group possessed by the solvent. For example, the diethylene glycol monomethyl ether is suitable for both the alcohol-based solvent and the ether-based solvent in the above-mentioned classification.

Examples of the ester solvents include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, propyl acetate, isopropyl acetate, amyl acetate (pentyl acetate), isoamyl acetate (isopentyl acetate, Butyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, isohexyl acetate, heptyl acetate, octyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethylether acetate (PGMEA; Methoxy-2-acetoxypropane), ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether Ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopro ester Ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2- Methoxybutyl acetate, 3-methoxybutylacetate, 3-methoxybutylacetate, 3-methoxybutylacetate, 3-methyl-3-methoxybutylacetate, Propyleneglycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl Methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol Diaceta And examples thereof include methyl formate, ethyl formate, propyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, butyl pyruvate, methyl acetoacetate Ethyl propionate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, pentyl propionate, hexyl propionate, heptyl propionate, butyl butyrate, butyl isobutanoate, pentyl butyrate, hexyl butyrate, isobutanoate, Propyl propionate, propyl pentanoate, propyl pentanoate, isopropyl pentanoate, butyl pentanoate, pentyl pentanoate, ethyl hexanoate, propyl hexanoate, butyl hexanoate, isobutyl hexanoate, methyl heptanoate, ethyl heptanoate, Acetic acid cycloheptyl, acetic acid 2-ethylhexyl, propionic acid cyclopene Methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-hydroxypropionate, Methoxy propionate, and the like. Of these, butyl acetate, amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, pentyl acetate, pentyl propylate, hexyl propionate, heptyl propionate and butyl butyrate are preferably used, And is particularly preferably used.

Examples of the ketone-based solvent include aliphatic ketones such as 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methylamyl ketone) But are not limited to, acetone, methyl ethyl ketone, acetone acetone, acetone diacetone, diacetone diol, acetylcarbinol, acetophenone, methylnaphthyl ketone, isophorone , Propylene carbonate,? -Butyrolactone, and the like, among which 2-heptanone is preferable.

The ketone solvent may have a branched alkyl group. Examples of the cyclic aliphatic ketone solvent having a branched alkyl group include 2-isopropylcyclohexanone, 3-isopropylcyclohexanone, 4-isopropylcyclohexanone, 2-isopropylcycloheptanone, Cycloheptanone, 4-isopropylcycloheptanone and 2-isopropylcyclooctanone.

Examples of the alicyclic ketone solvent having a branched alkyl group include diisobutylketone, methylisopentylketone, ethylisopentylketone, propylisopentylketone, diisopentylketone, methylisobutylketone, ethylisobutylketone, Propyl isobutyl ketone, diisobutyl ketone, diisopropyl ketone, ethyl isopropyl ketone, and methyl isopropyl ketone. Particularly preferred is diisobutyl ketone.

Examples of the cyclic aliphatic ether solvent having a branched alkyl group include cyclopentyl isopropyl ether, cyclopentyl sec-butyl ether, cyclopentyl tert-butyl ether, cyclohexyl isopropyl ether, cyclohexyl sec- Butylhexyl ether, and cyclohexyl tert-butyl ether.

Examples of the non-cyclic aliphatic ether-based solvent having a branched alkyl group include diisobutyl ether, methyl isopentyl ether, ethyl isopentyl ether, propyl isopentyl ether, diisopentyl ether, , Ethyl isobutyl ether, propyl isobutyl ether, diisobutyl ether, diisopropyl ether, ethyl isopropyl ether, methyl isopropyl ether and the like, and particularly preferably diisobutyl Ether or diisopentyl ether.

Examples of the alcoholic solvent include aliphatic alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, Butanol, 3-heptanol, 3-heptanol, 1-heptanol, 1-heptanol, 2-heptanol, Octanol, 3-methyl-3-pentanol, cyclopentanol, 2,3-dimethyl-2-butanol, 3,3- Methyl-3-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexane, Hexanol, 5-methyl-2-hexanol, 4-methyl-2-hexanol, 4,5-dimethyl-2-hexanol, (Monohydric alcohols) such as 8-methyl-2-nonanol, 9-methyl-2-decanol and 3-methoxy-1-butanol, ethylene glycol, diethylene glycol, tri Glycols such as ethylene glycol, ethylene glycol monomethyl ether, Methoxy-2-propanol), diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butanol, ethylene glycol (ethylene glycol) Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether , Glycol ether type solvents containing hydroxyl groups such as propylene glycol monophenyl ether, and the like. Among them, it is preferable to use a glycol ether solvent.

Examples of the ether-based solvent include, in addition to the above glycol ether type solvent containing a hydroxyl group, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, di Glycol ether solvents such as ethylene glycol diethylether, aromatic ether solvents such as anisole and phenol, dioxane, tetrahydrofuran, tetrahydropyran, perfluoro-2 -Butyltetrahydrofuran, perfluorotetrahydrofuran, 1,4-dioxane, and the like. Preferably, a glycol ether solvent or an aromatic ether solvent such as anisole is used.

Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 2-imidazolidinone and the like can be used.

Examples of the hydrocarbon solvents include pentane, hexane, octane, nonene, decane, dodecane, undecane, hexadecane, 2,2,4-trimethylpentane, 2,2,3 Aliphatic hydrocarbon solvents such as trimethyl hexane, perfluorohexane and perfluoroheptane; aliphatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, Aromatic hydrocarbon solvents such as benzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene and dipropylbenzene; aromatic hydrocarbon solvents such as octane, n-heptene, undecene, undecene, dodecene and hexadecene; Solvent.

The unsaturated hydrocarbon solvent may have a plurality of double bonds or triple bonds and may be located at any position of the hydrocarbon hydrocarbon chain. Cis and trans isomers may be mixed by having double bonds.

When the developing solution contains another solvent, the content of the other solvent is preferably 40 mass% or less, more preferably 20 mass% or less, further preferably 10 mass% or less, relative to the total mass of the developing solution, Preferably not more than 5% by mass. By setting the content of the other solvent to 40 mass% or less, the pattern ingot performance can be further improved.

The developer preferably contains a surfactant. As a result, the wettability to the film is improved, the developability is improved, and the generation of foreign matter tends to be suppressed.

As the surfactant, the same surfactants as those used in a sensitizing actinic ray or radiation-sensitive composition described later can be used.

When the developer contains a surfactant, the content of the surfactant is preferably 0.001 to 5 mass%, more preferably 0.005 to 2 mass%, and even more preferably 0.01 to 0.5 mass%, based on the total mass of the developer. Mass%.

The developer preferably contains an antioxidant. As a result, the generation of the oxidizing agent over time can be suppressed, and the content of the oxidizing agent can be further reduced.

As the antioxidant, known antioxidants can be used. When used for semiconductor applications, an amine antioxidant and a phenol antioxidant are preferably used.

Examples of the amine antioxidant include 1-naphthylamine, phenyl-1-naphthylamine, p-octylphenyl-1-naphthylamine, p-nonylphenyl-1-naphthylamine, Naphthylamine-based antioxidants such as -1-naphthylamine and phenyl-2-naphthylamine; N, N'-diisopropyl-p-phenylenediamine, N, N'-diisopropyl-p-phenylenediamine, N, Phenyl-N'-isopropyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine, dioctyl-p-phenylenediamine, phenylhexyl- Phenylene diamine-based antioxidants such as benzene and benzene; P'-di-tert-butyldiphenylamine, p, p'-di-tert-butyldiphenylamine, p, p'-dodecyldiphenylamine, p, p'-dodecyldiphenylamine, p, p'-dodecyldiphenylamine, p, Thiirlyldiphenylamine, p, p'-dimethoxydiphenylamine, 4,4'-bis (4 -?,? - dimethylbenzoyl) diphenylamine, p-isopropoxydiphenylamine, Diphenylamine antioxidants such as diallylamine; Phenothiazine antioxidants such as phenothiazine, N-methylphenothiazine, N-ethylphenothiazine, 3,7-dioctylphenothiazine, phenothiazinecarboxylic acid ester, and phenoscelenazine.

Examples of the phenol-based antioxidant include 2,6-di-tert-butylphenol (hereinafter referred to as t-butyl butyl), 2,6-di- Di-t-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4-dimethyl- Bis (2,6-di-tert-butylphenol), 4,4'-bis (2,6- Butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'- (2-methyl-6-t-butylphenol), 4,4'-isopropylidenebis (2,6- Hexylphenol), 2,2'-methylenebis (4-methyl-6-nonylphenol), 2,2'-isobutylidenebis (4,6-dimethylphenol), 2,6- 3-tert-butyl-5'-methylbenzyl) -4-methylphenol, 3-t-butyl- - (4-hydroxy-3,5-di-tert-butylphenyl) propion (3-hydroxy-3,5-di-tert-butylphenyl) propionic acid oleyl, 3 (4-hydroxy- 3- (4-hydroxy-3,5-di-tert-butylphenyl) propionate, 3- (4-hydroxy-3,5- (4-hydroxy-3,5-di-tert-butylphenyl) propionyloxymethyl} methane, 3- (4-hydroxy- Dihydroxy-3,5-di-tert-butylphenyl) propionic acid glycerin monoester, 3- (4-hydroxy-3,5-di-tert- butylphenyl) propionic acid and an ester of glycerin monooleylether, 3- (4-hydroxy-3,5-di-tert-butylphenyl) propionic acid butyleneglycol diester, 3- (3-methyl-6-t-butylphenol), 4,4'-thiobis (2-methyl-6-t-butylphenol), 2,2'- Di-t-butyl-4- (N, N-di-tert-butylphenol), 2,6- (3,5-di-t-butyl-4-hydroxybenzyl) sulfide, tris {(3,5- (3,5-di-t-butyl-4-hydroxyphenyl) isocyanurate, 1,3,5-tris (3,5-di-tert- butyl (3-n-alkylthiopropionyloxy) -5-t-butylphenyl} sulfide, 1,3,5-tris (4-hydroxybenzyl) isocyanurate, 4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, tetrapyralyl-di (2,6- ), 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4-bis (octylthio) -1,3,5-triazine, 2,2- (Diethyl-bis-3- (3,5-di-tert-butyl-4-hydroxyphenyl) (3,5-di-tert-butyl-4-hydroxy-hydrocinnamate), 3,9-bis [1,1-dimethyl-2- { - (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5- Hydroxybenzyl) benzene, bis {3,3'-bis- (4'-hydroxy-3'-t-butylphenyl) butyric acid} glycol ester.

The content of the antioxidant is not particularly limited, but is preferably 0.0001 to 1% by mass, more preferably 0.0001 to 0.1% by mass, and still more preferably 0.0001 to 0.01% by mass based on the total mass of the developer. When it is 0.0001 mass% or more, a better antioxidation effect is obtained, and when it is 1 mass% or less, development residue tends to be suppressed.

The developer preferably contains a basic compound. Specific examples of the basic compound include compounds exemplified as basic compounds that can be included in the actinic ray-sensitive or radiation-sensitive composition described below.

Of the basic compounds that can be included in the developing solution, nitrogen-containing compounds are preferably used.

Examples of the developing method include a method (dip method) in which the substrate is immersed in a tank filled with a developing solution for a predetermined time (dip method), a method in which the developing solution is raised by surface tension on the substrate surface for a predetermined period of time A method of spraying a developer on the surface (spray method), a method of continuously discharging a developer while scanning a developer discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispensing method), and the like.

After the step of developing, the step of stopping development may be performed while replacing the solvent with another solvent.

The developing time is not particularly limited as long as the resin of the unexposed portion is sufficiently dissolved, usually 10 to 300 seconds, preferably 20 to 120 seconds.

The temperature of the developing solution is preferably 0 to 50 캜, more preferably 15 to 35 캜.

As the developer, it is preferable to use the developer described above.

As the developer used in the development process, in addition to the development using the developer described above, development (so-called double development) with an alkali developer may be performed.

<Rinse process>

The rinsing step is a step of rinsing (rinsing) with a rinsing liquid after the developing step.

In the rinsing process, the developed wafer is cleaned using the rinsing solution described above.

The method of the rinsing treatment is not particularly limited. For example, a method of continuously discharging the rinsing liquid on a substrate rotating at a constant speed (rotary discharge method), a method of immersing the substrate in a tank filled with the rinsing liquid for a predetermined time ), A method of spraying a rinsing liquid onto the surface of the substrate (spray method), and the like. Among them, a cleaning process is carried out by a rotary discharge method, the substrate is rotated at a rotation number of 2000 rpm to 4000 rpm, It is preferable to remove it from the substrate.

The rinsing time is not particularly limited, but is preferably 10 seconds to 300 seconds, more preferably 10 seconds to 180 seconds, and most preferably 20 seconds to 120 seconds.

The temperature of the rinsing liquid is preferably 0 to 50 캜, more preferably 15 to 35 캜.

After the developing treatment or the rinsing treatment, the developer or rinsing liquid adhering to the pattern can be removed by supercritical fluid.

Further, after the developing treatment or the rinsing treatment or the treatment with the supercritical fluid, a heat treatment may be performed to remove the solvent remaining in the pattern. The heating temperature is not particularly limited as long as a good resist pattern can be obtained, and is usually 40 to 160 ° C. The heating temperature is preferably 50 to 150 ° C, and most preferably 50 to 110 ° C. The heating time is not particularly limited as long as a good resist pattern can be obtained, but is usually 15 to 300 seconds, preferably 15 to 180 seconds.

As the rinsing liquid, it is preferable to use a rinsing liquid containing an organic solvent. As the organic solvent, an organic solvent (preferably, an ester solvent, a ketone solvent, an alcohol solvent, an ether solvent, Based solvent, at least one organic solvent selected from the group consisting of a solvent, a hydrocarbon solvent and a hydrocarbon hydrocarbon solvent).

The organic solvent to be contained in the rinsing liquid is preferably a hydrocarbon hydrocarbon solvent.

As the organic solvent contained in the rinsing liquid, when EUV light (Extreme Ultra Violet) or EB (Electron Beam) is used in the exposure process, a hydrocarbon hydrocarbon solvent is preferably used among the above organic solvents, and an aliphatic hydrocarbon solvent Is more preferable. As the aliphatic hydrocarbon solvents for use in the rinsing liquid, aliphatic hydrocarbon solvents having 5 or more carbon atoms (for example, pentane, hexane, octane, decane, undecane, dodecane, Ketene, hexadecane, etc.), and aliphatic hydrocarbon solvents having 8 or more carbon atoms are preferable, and aliphatic hydrocarbon solvents having 10 or more carbon atoms are more preferable.

The upper limit value of the number of carbon atoms of the aliphatic hydrocarbon group-containing solvent is not particularly limited, but may be, for example, 16 or less, preferably 14 or less, and more preferably 12 or less.

Among the above-mentioned aliphatic hydrocarbon solvents, particularly preferred are decane, undecane, isodecane and dodecane, and more preferably undecane.

As the hydrocarbon-based solvent contained in the rinsing liquid, unsaturated hydrocarbon-based solvents may also be used, and examples thereof include unsaturated hydrocarbon solvents such as octene, nonene, decene, undecene, dodecene and hexadecene . The number of double bonds and triple bonds of the unsaturated hydrocarbon solvent is not particularly limited and may be any position of the hydrocarbon hydrocarbon chain. When the unsaturated hydrocarbon solvent has a double bond, a cis form and a trans form may be mixed.

By using a hydrocarbon hydrocarbon solvent (particularly, an aliphatic hydrocarbon solvent solvent) as the organic solvent contained in the rinse liquid, the developer that has been slightly absorbed in the film after development is washed away, the swelling is further suppressed, The effect is further exerted.

As the organic solvent contained in the rinsing liquid, a mixed solvent of the ester solvent and the hydrocarbon solvent, or a mixed solvent of the ketone solvent and the hydrocarbon solvent may be used. When such a mixed solvent is used, it is preferable to use a hydrocarbon solvent as a main component.

When an ester solvent and a hydrocarbon hydrocarbon solvent are used in combination, it is preferable to use butyl acetate or isoamyl acetate as the ester solvent. As the hydrocarbon solvent, it is preferable to use a saturated hydrocarbon solvent (for example, decane, dodecane, undecane, hexadecane, etc.) in view of the above-mentioned effect.

When a ketone solvent and a hydrocarbon hydrocarbon solvent are used in combination, it is preferable to use 2-heptanone as the ketone solvent. As the hydrocarbon solvent, it is preferable to use a saturated hydrocarbon solvent (for example, decane, dodecane, undecane, hexadecane, etc.) in view of the above-mentioned effect.

When an ester solvent and a hydrocarbon hydrocarbon solvent are used in combination, when a ketone solvent and a hydrocarbon hydrocarbon solvent are used in combination, an unsaturated hydrocarbon solvent may be used as the hydrocarbon hydrocarbon solvent. For example, , Unsaturated hydrocarbon solvents such as nonene, decene, undecene, dodecene and hexadecene. The number of double bonds and triple bonds of the unsaturated hydrocarbon solvent is not particularly limited and may be any position of the hydrocarbon hydrocarbon chain.

When the unsaturated hydrocarbon solvent has a double bond, a cis form and a trans form may be mixed.

The organic solvent to be contained in the rinsing liquid may be at least one selected from the group consisting of the ester solvent and the ketone solvent from the viewpoint of being particularly effective in reducing residues after development.

When the rinse liquid contains at least one selected from the group consisting of an ester solvent and a ketone solvent, the solvent is preferably selected from the group consisting of butyl acetate, isopentyl acetate (isoamyl acetate), n-pentyl acetate, ethyl 3-ethoxypropionate , Ethyl-3-ethoxypropionate), and 2-heptanone as a main component, and is preferably selected from the group consisting of butyl acetate and 2-heptanone It is particularly preferable to contain at least one kind of solvent as a main component.

When the rinse liquid contains at least one kind selected from the group consisting of an ester type solvent and a ketone type solvent, it is preferably selected from the group consisting of an ester type solvent, a glycol ether type solvent, a ketone type solvent and an alcohol type solvent (PGMEA), propylene glycol monomethyl ether (PGME), ethyl acetate, ethyl lactate, 3-methoxypropionic acid (PGME), and the like. A solvent selected from the group consisting of methyl, cyclohexanone, methyl ethyl ketone,? -Butyrolactone, propanol, 3-methoxy-1-butanol, N-methylpyrrolidone and propylene carbonate is preferable.

Among these, in the case of using an ester solvent as the organic solvent, it is preferable to use two or more kinds of ester solvents because the above effects can be further exerted. As specific examples of such a case, an ester solvent (preferably propylene glycol monomethyl ether acetate (PGMEA)) having a chemical structure different from that of the ester solvent (preferably, butyl acetate) as a main component is used as a subcomponent And the like.

In the case of using an ester solvent as the organic solvent, a glycol ether solvent may be used in addition to the ester solvent (one or more kinds) in view of the above effect being further exerted. As a specific example of this case, a glycol ether solvent (preferably propylene glycol monomethyl ether (PGME)) is used as a subcomponent with an ester type solvent (preferably, butyl acetate) as a main component have.

In the case of using a ketone solvent as the organic solvent, an ester solvent and / or a glycol ether solvent may be used in addition to the ketone solvent (one or more) . As specific examples of such a case, it is preferable to use a ketone solvent (preferably 2-heptanone) as a main component and an ester solvent (preferably propylene glycol monomethyl ether acetate (PGMEA)) and / Based solvent (preferably propylene glycol monomethyl ether (PGME)) is used as a subcomponent.

The term "main component" as used herein means that the content of the organic solvent with respect to the total mass is 50 to 100 mass%, preferably 70 to 100 mass%, more preferably 80 to 100 mass% By mass is 90 to 100% by mass, and particularly preferably 95 to 100% by mass.

When the subcomponent is contained, the content of the subcomponent is preferably 0.1 to 20 mass%, more preferably 0.5 to 10 mass%, and more preferably 1 to 5 mass% with respect to the total mass of the main component (100 mass% More preferably, it is in mass%.

The vapor pressure of the rinsing liquid at 20 캜 is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, most preferably 0.12 kPa or more and 3 kPa or less. When the rinse liquid is a mixed solvent of a plurality of solvents, the vapor pressure as a whole is preferably in the above range. By adjusting the vapor pressure of the rinsing liquid to 0.05 kPa or more and 5 kPa or less, temperature uniformity in the wafer surface is improved, swelling due to infiltration of the rinsing liquid is suppressed, and dimensional uniformity within the wafer surface is improved.

The rinsing liquid may contain a surfactant. When the rinsing liquid contains a surfactant, wettability to the film is improved, rinsing property is improved, and generation of foreign matter tends to be suppressed.

As the surfactant, the same surfactants as those used in a sensitizing actinic ray or radiation-sensitive composition described later can be used.

When the rinsing liquid contains a surfactant, the content of the surfactant is preferably 0.001 to 5 mass%, more preferably 0.005 to 2 mass%, and still more preferably 0.01 to 5 mass%, based on the total mass of the rinsing liquid. 0.5% by mass.

The rinse liquid may contain an antioxidant. The antioxidant that may be contained in the rinse liquid is the same as the antioxidant that may be contained in the developer.

When the rinse liquid contains an antioxidant, the content of the antioxidant is not particularly limited, but it is preferably 0.0001 to 1 mass%, more preferably 0.0001 to 0.1 mass%, and most preferably 0.0001 to 0.1 mass% based on the total mass of the rinse liquid. 0.01% by mass is more preferable.

(For example, a solvent, a developer, a rinsing liquid, a composition for forming an antireflection film, a composition for forming a top coat, etc.) used in the pattern forming method of the present invention may be a metal , A metal salt containing halogen, an acid, an alkali, and the like. The content of the impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb or less, more preferably 100 ppt or less, particularly preferably 10 ppt or less, and substantially no content Is most preferable.

Examples of a method for removing impurities such as metals from various materials include filtration using a filter. The filter hole diameter is preferably 10 nm or less in pore size, more preferably 5 nm or less, and further preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon is preferable. The filter may be a composite material obtained by combining these materials with an ion exchange medium. The filter may be previously washed with an organic solvent. In the filter filtering step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different hole diameters and / or different materials may be used in combination. In addition, the various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.

As a method for reducing impurities such as metals contained in various materials, it is possible to select a raw material having a small metal content as a raw material constituting various materials, filter the raw materials constituting various materials, Or ligning with Teflon (registered trademark) to perform distillation under the condition of suppressing contamination as much as possible. Preferable conditions for filter filtration performed on raw materials constituting various materials are the same as those described above.

In addition to filter filtration, impurities may be removed by the adsorbent, or a combination of filter filtration and adsorbent may be used. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.

<Storage container>

As the organic solvent (also referred to as "organic-based treatment solution") that can be used for the developer and rinse solution, it is preferable to use a product stored in a holding container for an organic processing solution for patterning of a chemically amplified or non- Do. As the accommodation container, for example, the inner wall in contact with the organic-based treatment liquid in the accommodation portion is made of a resin different from any one of polyethylene resin, polypropylene resin and polyethylene-polypropylene resin, It is preferable that the container is a container for an organic processing solution for patterning a film formed of a metal. An organic solvent to be used as an organic processing solution for patterning a film may be accommodated in the containing portion of the container and discharged from the accommodating portion at the time of patterning of the film.

In the case where the accommodating container has a sealing portion for sealing the accommodating portion, the sealing portion may also be made of a resin different from at least one resin selected from the group consisting of a polyethylene resin, a polypropylene resin, and a polyethylene-polypropylene resin , Or a metal subjected to anticorrosion and metal leaching prevention treatment.

Here, the sealing portion means a member capable of blocking the receiving portion and the outside air, and a packing, an O-ring, and the like are suitably used.

The resin different from at least one resin selected from the group consisting of a polyethylene resin, a polypropylene resin, and a polyethylene-polypropylene resin is preferably a perfluororesin.

Examples of the perfluororesin include polytetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkylvinylether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), tetrafluoroethylene- (ETFE), trifluoroethylene-ethylene copolymer resin (ECTFE), fluorinated vinylidene resin (PVDF), trifluoroethylene chloride copolymer resin (PCTFE), and vinyl fluoride resin (PVF).

Particularly preferred perfluororesins include tetrafluoroethylene resins, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers and tetrafluoroethylene-hexafluoropropylene copolymer resins.

Examples of the metal in the metal subjected to the rust prevention and metal elution prevention treatment include carbon steel, alloy steel, nickel chromium steel, nickel chromium molybdenum steel, chromium steel, chromium molybdenum steel, manganese steel and the like.

As the anti-rusting and metal leaching prevention treatment, it is preferable to apply the coating technique.

The coating technology is largely classified into three types of metal coating (various plating), inorganic coating (various chemical treatment, glass, concrete, ceramics, etc.) and organic coating (rust preventive oil, paint, rubber and plastic).

Preferable coating techniques include surface treatment with anti-corrosive oil, rust inhibitor, corrosion inhibitor, chelate compound, flexible plastic and lining agent.

Among them, corrosion inhibitors such as various chromium salts, nitrites, silicates, phosphates, carboxylic acids such as oleic acid, dimer acid and naphthenic acid, carboxylic acid metal soaps, sulfonates, amine salts and esters (glycerine ester or phosphate ester of higher fatty acid) Chelate compounds such as ethylenediaminetetraacetic acid, gluconic acid, nitrilotriacetic acid, hydroxyethylethylenediamine triacetic acid, and diethylenetriamine o acetic acid, and fluorine resin lining are preferable. Especially preferred are phosphating and fluororesin lining.

It is also preferable to adopt a "pretreatment" step prior to starting the anti-corrosive treatment as a treatment method that leads to an extension of the anti-corrosive period by the coating treatment, although it does not directly prevent the rusting as compared with the direct coating treatment.

As a specific example of such a pretreatment, a treatment for removing various corrosion factors such as chloride and sulfate present on the metal surface by washing or polishing is suitably used.

Specific examples of the container include the following.

· Fluoro Pure PFA composite drum manufactured by Entegris Inc. (Inside surface: PFA resin lining)

· Drum can made of steel (made of steel) (inner surface of contact liquid; zinc phosphate coating)

Examples of the container for use in the present invention include containers described in Japanese Laid-Open Patent Publication Nos. 11-021393 to 0030 and Japanese Laid-Open Patent Publication Nos. 10-45961 to 0012 .

The organic-based treatment liquid of the present invention may be added with a conductive compound in order to prevent the failure of the chemical liquid pipe and various parts (filter, O-ring, tube, etc.) caused by static electricity charging and subsequent electrostatic discharge. The conductive compound is not particularly limited, and examples thereof include methanol. The addition amount is not particularly limited, but is preferably not more than 10% by mass, more preferably not more than 5% by mass from the viewpoint of maintaining desirable developing characteristics. As for the member of the chemical liquid pipe, various pipes coated with SUS (stainless steel) or polyethylene, polypropylene, or fluorine resin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) subjected to antistatic treatment may be used . As for the filter and the O-ring, it is also possible to use polyethylene, polypropylene or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) subjected to antistatic treatment.

In general, the developer and the rinsing liquid are accommodated in a waste liquid tank through piping after use. At this time, in the case of using a hydrocarbon solvent as the rinsing liquid, in order to prevent the resist dissolved in the developer from depositing and adhering to the back surface of the wafer or the side surface of the pipe, the solvent through which the resist is dissolved is again passed through the pipe There is a way. As a method of passing through the pipe, there are a method in which the back surface or the side surface of the substrate is cleaned and washed with a solvent in which the resist is dissolved after the cleaning in the rinsing liquid and a method in which a solvent in which the resist is dissolved, Method.

The solvent to be passed through the pipe is not particularly limited as long as it can dissolve the resist, and examples thereof include the above-mentioned organic solvents, and propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl Ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monoethyl ether acetate, Ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, Ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, 2-heptanone, ethyl lactate, 1-propanol, acetone and the like, Can be used. Among them, PGMEA, PGME and cyclohexanone can be preferably used.

A semiconductor fine circuit, an imprint mold structure, a photomask, or the like can be manufactured by using the pattern obtained by the pattern forming method of the present invention as a mask and appropriately performing an etching treatment and an ion implantation.

The pattern formed by the above method can also be used for guiding pattern formation in DSA (Directed Self-Assembly) (see, for example, ACS Nano Vol. 4 No. 8 Page 4815-4823). The pattern formed by the above method can be used as a core (core) of a spacer process disclosed in, for example, Japanese Unexamined Patent Application Publication No. 3-270227 and Japanese Unexamined Patent Publication No. 2013-164509.

The process for producing the imprint mold using the composition of the present invention is described in, for example, Japanese Patent Publication No. 4109085, Japanese Laid-Open Patent Publication No. 2008-162101, and " Application Development - Nanoimprint Technology and Latest Technologies - Editing: Yoshihiko Hirai (Frontier Shotpan) ".

The photomask manufactured using the pattern formation method of the present invention may be a light transmission type mask used in an ArF excimer laser or the like or a light reflection type mask used in reflection type lithography using EUV light as a light source.

The present invention also relates to a manufacturing method of an electronic device including the above-described pattern forming method of the present invention, and an electronic device manufactured by the manufacturing method.

The electronic device manufactured by the method of manufacturing an electronic device of the present invention is suitably mounted on an electric / electronic appliance (appliance, OA (Office Appliance), media related equipment, optical equipment, communication equipment, etc.).

&Lt; Resist composition &

The present invention also relates to a resist composition comprising a resin having a repeating unit represented by the general formula (4) or (4a). The repeating unit represented by the general formula (4) or (4a) in the resist composition of the present invention, and specific examples and preferred ranges of the resin having the repeating unit are as described above.

The resist composition is a preferred embodiment of the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition. The components and contents thereof described in the aforementioned actinic ray-sensitive or radiation-sensitive resin composition, And the like.

Example

Hereinafter, the present invention will be described more concretely with reference to Examples, but the present invention is not limited to the following Examples unless it is beyond the scope of the present invention. Unless otherwise stated, "part" and "%" are based on mass.

<Synthesis of Resin A-1>

&Quot; Synthesis of monomer (a1) &quot;

(Synthesis of intermediate a1-1)

30 g of 4-aminophenol was dissolved in 250 ml of tetrahydrofuran, 27 g of maleic anhydride was carefully added to this solution so that excessive heat was not generated, and the mixture was stirred at room temperature for 3 hours. After the reaction, the solvent was distilled off, and the obtained crude crystals were washed with ethyl acetate to obtain 56 g of intermediate (a1-1).

¹ H-NMR (nuclear magnetic resonance) (DMSO (dimethyl sulfoxide) -d 6: ppm)?: 13.67 (br), 10.38 (s), 9.35 (s), 7.43 (d), 6.74 ), 6.30 (d)

(Synthesis of monomer (a1)) [

56 g of the intermediate (a1-1) was suspended in 240 ml of toluene, 3.7 g of para-toluenesulfonic acid and 28 ml of N, N-dimethylformamide were added, and the mixture was heated under reflux for 5 hours. After cooling to room temperature, the reaction solution was added to 3000 ml of water, and the powder was filtered. The residue was purified by silica gel column chromatography (eluent: ethyl acetate / n-hexane = 1/1) and recrystallized from isopropanol to obtain 22 g of monomer (a1).

^{1 H-NMR (DMSO-d6} : ppm) δ: 9.68 (s), 7.13 (s), 7.08 (d), 6.83 (d)

(56)

&Quot; Synthesis of Resin A-1 &

, 5.0 g of monomer (a1), 2.0 g of monomer (c1), t-butyl methacrylate of 7.7 g and 0.48 g of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) Of cyclohexanone. 29.3 g of cyclohexanone was added to the reaction vessel, and the mixture was dropped in a nitrogen gas atmosphere at 85 캜 for 4 hours. The reaction solution was heated and stirred for 2 hours, and then cooled to room temperature. The reaction solution was added dropwise to 990 g of a mixed solution of n-heptane and ethyl acetate (n-heptane / ethyl acetate = 9/1 (mass ratio)), and the polymer was precipitated and filtered. The filtered solid was washed with 300 g of a mixed solution of n-heptane and ethyl acetate (n-heptane / ethyl acetate = 9/1 (mass ratio)). The obtained polymer was dissolved in 82 g of cyclohexanone and 960 g of the polymer was added dropwise to a mixed solution of methanol and water (methanol / water = 4/6 (by mass ratio)) to precipitate the polymer. 290 g of the filtered solid was washed using a mixed solution of methanol and water (methanol / water = 4/6 (mass ratio)). Thereafter, the washed solid was subjected to reduced-pressure drying to obtain 12.3 g of Resin (A-1). The weight-average molecular weight by GPC was 12900 and the molecular weight dispersion (Mw / Mn) was 1.70.

^{1 H-NMR (DMSO-d6} : ppm) δ: 9.80, 7.15-6.71, 4.76-4.26, 2.93-0.79 ( both the peak width is broad)

(57)

A resin having the following structure was synthesized in the same manner as in Synthesis Example of Resin A-1 except that the monomer used was changed. The composition ratio (molar ratio) of the resin was calculated by ¹ H-NMR or ¹³ C-NMR measurement. The weight average molecular weight (Mw: in terms of polystyrene) and the degree of dispersion (Mw / Mn) of the resin were calculated by GPC (solvent: THF) measurement. In Table 1, the composition ratio (molar ratio), the weight average molecular weight, the degree of dispersion, and the ClogP value of the repeating units are shown for each resin. The ClogP values shown in Table 1 below are the ClogP values of the recurring units listed at the leftmost of the repeating units contained in each resin.

(58)

[Chemical Formula 59]

(60)

(61)

[Table 1]

&Lt; Acid generating agent (B) >

The following acid generators were used.

(62)

&Lt; Basic compound >

As the basic compound, the following compounds were used.

(63)

&Lt; EMI ID =

&Lt; Solvent (C) >

As the solvent, the following were used.

C1: Propylene glycol monomethyl ether acetate

C2: propylene glycol monomethyl ether

C3: Ethyl lactate

C4: cyclohexanone

&Lt; Developer >

As the developer, the following were used.

SG-1: Anisole

SG-2: methyl amyl ketone

SG-3: isoamyl acetate

<Rinse liquid>

As the rinsing liquid, the following were used.

R-1: undecane

R-2: Isodecane

R-3: decane

R-4: 4-methyl-2-pentanol

<Cross-linking agent>

As the crosslinking agent, the following were used.

(65)

&Lt; Resist composition &

The components shown in Tables 2 to 4 below were dissolved in the solvents shown in Tables 2 to 4. This was filtered using a polyethylene filter having a pore size of 0.03 mu m to obtain a resist composition.

[Table 2]

[Table 3]

[Table 4]

<EUV exposure evaluation line and space pattern>

Using a resist composition, a resist pattern was formed by the following procedure.

[Application of resist composition and baking after application (PB)]

A resist composition was applied on a 4-inch silicon wafer subjected to HMDS (hexamethyldisilazane) treatment and baked at 120 캜 for 60 seconds to form a resist film having a thickness of 40 nm.

One inch is 25.4 mm.

[Exposure]

The wafer having the resist film formed thereon was subjected to EUV exposure with NA (lens numerical aperture) 0.3, dipole illumination. Specifically, EUV exposure was performed by changing the exposure dose through a mask containing a pattern for forming a 1: 1 line and space pattern having a line width of 50 nm.

[Post-exposure baking (PEB)]

After the exposure, the wafer was taken out of the EUV exposure apparatus and immediately baked for 60 seconds under the conditions shown in Table 5.

〔phenomenon〕

Thereafter, the developing solution (23 DEG C) shown in Table 5 was sprayed at a flow rate of 200 mL / min for a predetermined time while rotating the wafer at 50 rpm using a shower type developing device (ADE3000S manufactured by ACTES Co., Ltd.) And development was carried out.

〔Rinse〕

Thereafter, the rinsing solution (23 DEG C) described in Table 5 was sprayed and discharged at a flow rate of 200 mL / minute for a predetermined time while rotating the wafer at 50 rpm, and rinsing treatment was performed.

Finally, the wafer was dried at a high rotation speed of 2500 rpm for 120 seconds.

Evaluation of resist pattern

The obtained resist pattern was evaluated for sensitivity and resolving power by the following method. The resist pattern was observed using a scanning electron microscope (S-9380II, manufactured by Hitachi, Ltd.). The results are shown in Table 5 below.

(Sensitivity)

The optimum exposure amount at the time of resolving the 1: 1 line-and-space pattern having a line width of 50 nm was determined as the sensitivity (Eop1). The smaller this value is, the better the performance is.

(definition)

In Eop1, a line and space pattern having a different half pitch size was produced by changing the mask. At this time, the minimum half-pitch size at which a 1: 1 line-and-space pattern that is separated is obtained is defined as a resolution. The smaller this value is, the better the performance is.

[Table 5]

<EUV Exposure Evaluation Dot Pattern>

Using a resist composition, a resist pattern was formed by the following procedure.

[Application of resist composition and baking after application (PB)]

A resist composition was applied on a 4-inch silicon wafer subjected to HMDS (hexamethyldisilazane) treatment and baked at 120 캜 for 60 seconds to form a resist film having a thickness of 40 nm.

One inch is 25.4 mm.

[Exposure]

The wafer having the resist film formed thereon was subjected to EUV exposure with NA (lens numerical aperture) 0.3, dipole illumination. Specifically, EUV exposure was performed by changing the exposure dose through a mask containing a pattern for forming dots having a diameter of 30 nm at a pitch of 100 nm.

[Post-exposure baking (PEB)]

After the exposure, the wafer was taken out from the EUV exposure apparatus and immediately baked for 60 seconds under the temperature conditions shown in Table 6. [

〔phenomenon〕

Thereafter, the developing solution (23 DEG C) shown in Table 6 was sprayed at a flow rate of 200 mL / minute for a predetermined time while rotating the wafer at 50 rpm using a shower type developing device (ADE3000S manufactured by ACTES Co., Ltd.) And development was carried out.

〔Rinse〕

Thereafter, the rinse solution (23 DEG C) described in Table 6 was sprayed and discharged at a flow rate of 200 mL / minute for a predetermined time while rotating the wafer at 50 rpm to perform a rinse treatment.

Finally, the wafer was dried at a high rotation speed of 2500 rpm for 120 seconds.

Evaluation of resist pattern

The resolution of the obtained resist pattern was evaluated by the following method. The resist pattern was observed using a scanning electron microscope (S-9380II, manufactured by Hitachi, Ltd.). The results are shown in Table 6 below.

(Sensitivity)

The optimum exposure amount when resolving a dot having a diameter of 30 nm was determined as the sensitivity (Eop2).

(definition)

In Eop2, by changing the mask, the dot diameter was reduced from 30 nm in a state where the pitch (interval between dots and dots) was maintained at 100 nm, and the marginal minimum diameter of the separated dot patterns was taken as the resolution. The smaller this value is, the better the performance is.

[Table 6]

<EB exposure evaluation line and space pattern>

Using a resist composition, a resist pattern was formed by the following procedure.

[Application of resist composition and baking after application (PB)]

An organic film DUV44 (manufactured by Brewer Science) was applied on a 6-inch silicon wafer and baked at 200 DEG C for 60 seconds to form an organic film having a film thickness of 60 nm. A resist composition was applied thereon and baked at 120 DEG C for 60 seconds to form a resist film having a thickness of 40 nm.

[Exposure]

The wafer on which the resist film was formed was subjected to EB exposure using an electron beam irradiation apparatus (JEOL JBX6000FS / E; acceleration voltage: 50 keV). Specifically, a 1: 1 line and space pattern having a line width of 50 nm (0.12 mm in the longitudinal direction and 20 drawing lines) was exposed by changing the exposure amount.

[Post-exposure baking (PEB)]

After exposure, the wafer was taken out of the electron beam irradiating apparatus and immediately heated on a hot plate under the conditions shown in Table 7 for 60 seconds.

〔phenomenon〕

(23 ° C) shown in Table 7 was sprayed and discharged at a flow rate of 200 mL / minute for a predetermined time while rotating the wafer at 50 rpm using a shower type developing device (ADE3000S manufactured by ACTES Co., Ltd.) .

〔Rinse〕

Thereafter, the rinsing solution (23 DEG C) described in Table 7 was sprayed and discharged at a flow rate of 200 mL / minute for a predetermined time while rotating the wafer at 50 rpm, and rinsing treatment was performed.

Finally, the wafer was dried at a high rotation speed of 2500 rpm for 120 seconds.

The evaluation of the resist pattern was carried out in the same manner as the above-mentioned "EUV exposure evaluation line and space pattern ". The results are shown in Table 7. The resolution was evaluated by producing line and space patterns having different half pitch sizes by drawing.

[Table 7]

&Lt; EB exposure evaluation dot pattern >

Using a resist composition, a resist pattern was formed by the following procedure.

[Application of resist composition and baking after application (PB)]

An organic film DUV44 (manufactured by Brewer Science) was applied on a 6-inch silicon wafer and baked at 200 DEG C for 60 seconds to form an organic film having a film thickness of 60 nm. A resist composition was applied thereon and baked at 120 DEG C for 60 seconds to form a resist film having a thickness of 40 nm.

[Exposure]

The wafer on which the resist film was formed was subjected to EB exposure using an electron beam irradiation apparatus (JEOL JBX6000FS / E; acceleration voltage: 50 keV). Specifically, EB exposure was performed by changing the exposure amount so that a dot having a diameter of 30 nm was formed at a pitch of 100 nm.

[Post-exposure baking (PEB)]

After exposure, the wafer was taken out of the electron beam irradiating apparatus and immediately heated on a hot plate under the conditions shown in Table 8 for 60 seconds.

〔phenomenon〕

(23 ° C) shown in Table 8 was sprayed and discharged at a flow rate of 200 mL / minute for a predetermined time while rotating the wafer at 50 rpm using a shower type developing apparatus (ADE3000S manufactured by ACTES Co., Ltd.) .

〔Rinse〕

Thereafter, the rinsing solution (23 DEG C) shown in Table 8 was sprayed and discharged at a flow rate of 200 mL / minute for a predetermined time while rotating the wafer at 50 rpm, and rinsing treatment was performed.

Finally, the wafer was dried at a high rotation speed of 2500 rpm for 120 seconds.

The evaluation of the resist pattern was carried out in the same manner as the above-mentioned "EUV exposure evaluation dot pattern ". The results are shown in Table 8. The resolving power was evaluated by drawing the dot diameter so as to be smaller than 30 nm.

[Table 8]

As shown in Tables 5 to 8, the pattern formed by the pattern forming method of the present invention was excellent in sensitivity and resolution.

Claims (18)

(A) a resin represented by the following general formula (1) and containing a repeating unit having a ClogP value of 2.2 or less and having a reduced solubility in a developer containing an organic solvent by the action of an acid; (B) (1) a step of forming a film by using an actinic ray-sensitive or radiation-sensitive resin composition containing a compound capable of generating an acid upon irradiation with (C) a solvent,
A step (2) of exposing the film using an actinic ray or radiation, and
And a step (3) of developing the exposed film in the step (2) using a developing solution containing an organic solvent to form a negative type pattern.
[Chemical Formula 1]

In formula (1), R ₁ represents a hydrogen atom, an alkyl group or a halogen atom, R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group or a carboxyl group, L represents a single bond or a divalent linking group . R ₂ or R ₃ and L may be connected to each other to form a ring. In this case, either R ₂ or R ₃ represents a divalent linking group, and L represents a trivalent linking group. Ar represents an aromatic group. R ₄ represents a substituent, and n represents an integer of 0 or more. When R ₄ is present a plurality, the plurality of R ₄ may be the same and different. The method according to claim 1,
Wherein the resin (A) comprises a repeating unit having an acid-decomposable group. The method according to claim 1 or 2,
Wherein at least one of R ₄ in the general formula (1) is a hydroxyl group. The method according to any one of claims 1 to 3,
Wherein the general formula (1) is represented by the following general formula (2).
(2)

In formula (2), R ₁ represents a hydrogen atom, an alkyl group or a halogen atom, R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group or a carboxyl group, L represents a single bond or a divalent linking group . R ₂ or R ₃ and L may be connected to each other to form a ring. In this case, either R ₂ or R ₃ represents a divalent linking group, and L represents a trivalent linking group. R ₄ represents a substituent, and n ² represents an integer of 0 to 4. When R ₄ is present a plurality, the plurality of R ₄ may be the same and different. The method according to any one of claims 1 to 4,
Wherein the general formula (1) is represented by the following general formula (3).
(3)

In the general formula (3), R ₁ represents a hydrogen atom, an alkyl group, or a halogen atom, and L represents a single bond or a divalent linking group. R ₄ represents a substituent. n ² represents an integer of 0 to 4; When R ₄ is present a plurality, the plurality of R ₄ may be the same and different. The method according to any one of claims 1 to 4,
Wherein the general formula (1) is represented by the following general formula (4).
[Chemical Formula 4]

In the general formula (4), A represents a single bond or a divalent linking group. R ₄ represents a substituent. n ³ represents an integer of 0 to 4; When R ₄ is present a plurality, the plurality of R ₄ may be the same and different. The method of claim 6,
Wherein the general formula (4) is represented by the following general formula (4a).
[Chemical Formula 5]

In the general formula (4a), R ₄ represents a substituent. p represents an integer of 0 to 4, and n ³ represents an integer of 0 to 4. When R ₄ is present a plurality, the plurality of R ₄ may be the same and different. The method according to any one of claims 1 to 7,
Wherein R ₄ is a group represented by the following formula (N1), a group represented by the following formula (N2), a group represented by the following formula A group represented by the following formula (S1), or a group represented by the following formula (S2).
[Chemical Formula 6]

In the general formula (N1), R _N1 and R _N2 each independently represent a hydrogen atom or a substituent. * Represents the bonding hands bonding to the benzene ring.
In the general formula (N2), R _N3 represents a substituent and R _N4 represents a hydrogen atom or a substituent. * Represents the bonding hands bonding to the benzene ring.
(7)

In the general formula (S1), R _S1 represents a substituent. * Represents the bonding hands bonding to the benzene ring.
In the general formula (S2), R _S4 represents a substituent, and R _S5 represents a hydrogen atom or a substituent. * Represents the bonding hands bonding to the benzene ring. The method according to any one of claims 1 to 8,
Wherein R ₄ is a group represented by a hydroxyl group, a hydroxymethyl group, a carboxyl group, a group represented by the following formula (S1), or a group represented by the following formula (S2).

In the general formula (S1), R _S1 represents a substituent. * Represents the bonding hands bonding to the benzene ring.
In the general formula (S2), R _S4 represents a substituent, and R _S5 represents a hydrogen atom or a substituent. * Represents the bonding hands bonding to the benzene ring. The method according to claim 4 or 5,
And n &lt; ² &gt; is 1 or 2. The method according to claim 6 or 7,
And n ³ is an integer of 0 to 2. The method according to any one of claims 1 to 11,
Wherein the compound (B) is a sulfonium salt. The method of claim 12,
The compound (B) is the volume of the acid generated 130Å 2000Å ³ or less than ^3, the pattern forming method. The method according to any one of claims 1 to 13,
Wherein the resin (A) further comprises a repeating unit having a lactone group. A method of manufacturing an electronic device, comprising the pattern forming method according to any one of claims 1 to 14. A resist composition comprising a resin having a repeating unit represented by the following general formula (4).
[Chemical Formula 8]

In the general formula (4), A represents a single bond or a divalent linking group. R ₄ represents a substituent. n ³ represents an integer of 0 to 4; When R ₄ is present a plurality, the plurality of R ₄ may be the same and different. 18. The method of claim 16,
Wherein the general formula (4) is represented by the following general formula (4a).
[Chemical Formula 9]

In the general formula (4a), R ₄ represents a substituent. p represents an integer of 0 to 4, and n ³ represents an integer of 0 to 4. When R ₄ is present a plurality, the plurality of R ₄ may be the same and different. The method according to claim 16 or 17,
Wherein R ₄ is a group represented by the following formula (N1), a group represented by the following formula (N2), a group represented by the following formula A group represented by the following formula (S1), or a group represented by the following formula (S2).
[Chemical formula 10]

In the general formula (N1), R _N1 and R _N2 each independently represent a hydrogen atom or a substituent. * Represents the bonding hands bonding to the benzene ring.
In the general formula (N2), R _N3 represents a substituent and R _N4 represents a hydrogen atom or a substituent. * Represents the bonding hands bonding to the benzene ring.
(11)

In the general formula (S1), R _S1 represents a substituent. * Represents the bonding hands bonding to the benzene ring.
In the general formula (S2), R _S4 represents a substituent, and R _S5 represents a hydrogen atom or a substituent. * Represents the bonding hands bonding to the benzene ring.