JP2018128477A - Pattern forming method and method for manufacturing electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pattern forming method by which a pattern having excellent CDU can be formed, and a method for manufacturing an electronic device.SOLUTION: The pattern forming method includes: a film formation step of forming a film by using an actinic ray-sensitive or radiation-sensitive resin composition on an undercoat layer of a support body having the undercoat layer and a substrate; an exposure step of exposing the film; a development step of developing the film after the exposure step to form a resist pattern and exposing at least a part of the undercoat layer; and an etching step of etching the exposed undercoat layer by using a plasma generated from a process gas including a deposition gas, and depositing a deposit on a side surface of the resist pattern. The composition comprises a resin having a weight average molecular weight of 5,000 or more and having an acid-decomposable group. In the development step, either an alkaline development step or an organic solvent development step is carried out and then the other step is carried out.SELECTED DRAWING: None

Description

  The present invention relates to a pattern forming method used in a semiconductor manufacturing process such as an IC (Integrated Circuit), a circuit board such as a liquid crystal or a thermal head, and a lithography process for other photo applications, and the pattern forming method. The present invention relates to an electronic device manufacturing method and an electronic device. In particular, the present invention relates to an ArF exposure apparatus using far ultraviolet light having a wavelength of 300 nm or less as a light source, a pattern forming method suitable for exposure in an ArF immersion projection exposure apparatus, a method for manufacturing an electronic device, and an electronic device About.

  In the manufacture of semiconductors such as ICs, layers such as spin-on carbon (SOC) layers and antireflection films (BARC) (hereinafter referred to as “underlayers” are collectively referred to as layers on a substrate (for example, a silicon wafer). (Also called) is used. Here, a resist film was formed on the support, a resist pattern (patterned resist film) was formed by exposure and development, and then the resist pattern was once transferred to the underlayer by etching and formed by transfer. The substrate is patterned by etching the substrate through a laminated body of the base pattern and the resist pattern (“laminated body of resist pattern and resist pattern” is also simply referred to as “pattern”).

  In recent years, there has been a demand for production of finer wiring in response to the need for higher functionality of various electronic devices. For example, Patent Document 1 discloses a technique for forming a narrow pattern of openings by depositing deposits on the side surfaces of openings (holes) of a resist film by using a deposition gas for etching an antireflection film or the like. It is disclosed.

  On the other hand, as a technique for miniaturizing the resist pattern itself, for example, Patent Document 2 proposes a double development technique using a positive developer and a negative developer. More specifically, by utilizing the fact that the polarity of the resin in the resist composition by exposure is high in regions where light intensity is high and low in regions where light intensity is low, a specific resist is used. By dissolving the high exposure area of the film in a developer containing water and dissolving the low exposure area in a developer containing an organic solvent, the intermediate exposure area remains undissolved and removed by development. A line and space pattern having a half pitch is formed.

JP 2011-82577 A JP 2008-292975 A

  Under these circumstances, the inventors transferred a resist pattern formed by double development to a base layer using a deposition gas with reference to Patent Document 1, and the critical dimension uniformity of the formed pattern ( It has been found that CDU (Critical Dimension Uniformity) may be low. If the CDU of the pattern is low, the uniformity of the pattern of the substrate finally formed is also a problem.

  Therefore, in view of the above circumstances, an object of the present invention is to provide a pattern forming method capable of forming a pattern having an excellent CDU and a method for manufacturing an electronic device including the pattern forming method.

As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by using a resin having a specific molecular weight in the actinic ray-sensitive or radiation-sensitive resin composition (resist composition). .
That is, the present inventors have found that the above problem can be solved by the following configuration.

(1) A film forming step of forming a film using the actinic ray-sensitive or radiation-sensitive resin composition on the base layer of the support having the base layer and the substrate;
An exposure step of exposing the film;
Developing the film after the exposure step to form a resist pattern and exposing at least a portion of the underlayer; and
Etching the exposed underlayer using plasma generated from a processing gas containing a deposition gas, and an etching step of depositing a deposit on the side surface of the resist pattern,
The actinic ray-sensitive or radiation-sensitive resin composition contains a resin having an acid-decomposable group having a weight average molecular weight of 5,000 or more,
The development step is carried out by performing either one of an alkali development step of developing with an alkali developer and an organic solvent development step of developing with a developer containing an organic solvent, and then performing the other step. A pattern forming method as a process.
(2) The pattern formation method as described in said (1) whose said acid-decomposable group is a group which decomposes | disassembles by the effect | action of an acid and produces a carboxy group.
(3) The resin includes a repeating unit having an acid-decomposable group,
The pattern forming method according to (1) or (2), wherein the content of the repeating unit having an acid-decomposable group contained in the resin is 50 mol% or more based on all repeating units of the resin. .
(4) The pattern forming method according to any one of (1) to (3), wherein the resin includes a repeating unit having a lactone structure, a sultone structure, a cyclic ketone structure, or a cyclic sulfone structure.
(5) A method for manufacturing an electronic device, including the pattern forming method according to any one of (1) to (4).

  As described below, according to the present invention, it is possible to provide a pattern forming method capable of forming a pattern having an excellent CDU and a method for manufacturing an electronic device including the pattern forming method.

It is process drawing which shows one embodiment of the pattern formation method of this invention, (A) represents sectional drawing of the resist pattern formed after image development with an alkali developing solution, (B) is a developing solution containing the organic solvent. A cross-sectional view of a pattern formed after development is represented, and (C) a cross-sectional view of the pattern after the etching step is represented. It is a top view of the reticle used in the embodiment.

Hereinafter, embodiments of the present invention will be described in detail.
In the description of the group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In the present specification, “active light” or “radiation” means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB), etc. To do. In the present invention, light means actinic rays or radiation.
In addition, “exposure” in the present specification is not limited to exposure to far ultraviolet rays, extreme ultraviolet rays, X-rays, EUV light and the like represented by mercury lamps and excimer lasers, but also electron beams, ion beams, and the like, unless otherwise specified. The exposure with the particle beam is included in the exposure.
In the specification of the present application, “to” is used in the sense of including the numerical values described before and after it as lower and upper limits.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.

In the pattern forming method of the present invention, an actinic ray-sensitive or radiation-sensitive resin composition (hereinafter referred to as “composition”, “resist composition”, “resist film formation” is formed on the above-described underlayer of a support having an underlayer and a substrate. A film forming process for forming a film (hereinafter also referred to as a “resist film”), an exposure process for exposing the film, and developing the film after the exposure process to form a resist pattern. And etching the exposed underlayer using a plasma generated from a processing gas containing a deposition gas, and exposing the at least part of the underlayer to the side surface of the resist pattern. And an etching process for depositing the deposit.
Here, the actinic ray-sensitive or radiation-sensitive resin composition contains a resin having an acid-decomposable group having a weight average molecular weight of 5,000 or more. Further, the developing step is carried out by performing any one of an alkali developing step for developing with an alkali developer and an organic solvent developing step for developing with a developer containing an organic solvent, and then performing the other step. It is a process to implement.
Since the pattern forming method of the present invention has such a configuration, it is considered that a desired effect can be obtained. The reason is not clear, but it is presumed that it is as follows.

FIG. 1 is a cross-sectional view showing each step of an embodiment of the pattern forming method of the present invention. FIG. 1 shows an embodiment in which development is performed with an alkaline developer, followed by development with a developer containing an organic solvent. First, as shown in FIG. 1 (A), dissolved exposure is large area R _P in an alkali developer to form the base layer 5 and the resist pattern 12 over the base layer 10 of the support having a substrate 1 . Next, when developing the small region R _N of exposure with a developing solution containing an organic solvent, as shown in FIG. 1 (B), the resist pattern 14 is formed. In addition, a part of the underlayer is exposed. Here, when the underlying layer 7 exposed using the deposition gas is etched, the underlying layer is etched to form the underlying pattern 6, and the deposit 16 is deposited on the side surface of the resist pattern 14. At this time, the larger the width of the opening 8 of the resist pattern 14 is, the higher the incidence frequency of gas is. Therefore, more deposits 16 are deposited, and the smaller the width of the opening 8 is, the lower the incidence frequency of gas is. Less deposits accumulate. In other words, deposits are selectively deposited on the resist pattern having the wide opening 8. As a result, the variation in the width of the opening 8 is reduced, and the critical dimension uniformity (CDU) of the pattern 20 is increased.
On the other hand, from the study by the present inventors, when the molecular weight of the resin in the resist composition is low, the deposit is not sufficiently deposited on the resist pattern, and the effect of improving the CDU as described above is diminished. Is obtained.
In the present invention, since a resin having a high molecular weight is used for the resist composition, deposits are easily deposited on the side surface of the resist pattern by a high van der Waals force, and the deposition of the selective deposits described above is promoted. The uniformity is considered to be extremely high.

The pattern forming method of the present invention includes at least the following four steps.
(1) Film forming step for forming a film using the actinic ray-sensitive or radiation-sensitive resin composition on the base layer of the support having the base layer and the substrate (2) Exposure step for exposing the film ( 3) Developing the film after the exposure step to form a resist pattern and exposing at least part of the underlayer (4) Using plasma generated from a processing gas containing a deposition gas Etching process for etching the exposed underlayer and depositing a deposit on the side surface of the resist pattern. Each process will be described in detail below.

[Step (1): Film formation step]
Step (1) is a film forming step of forming a film using the actinic ray-sensitive or radiation-sensitive resin composition on the base layer of the support having the base layer and the substrate.
Here, the actinic ray-sensitive or radiation-sensitive resin composition contains a resin having an acid-decomposable group having a weight average molecular weight of 5,000 or more.

[Support]
The support has an underlayer and a substrate.
Here, the base layer is a layer that becomes a base of a resist film, which will be described later, and is etched into a pattern in an etching process described later.
Although it does not restrict | limit especially as a base layer, For example, a spin-on-carbon (SOC) layer, a spin-on-glass (SOG) layer, a silicon nitride oxide vapor deposition film, an antireflection film (BARC) etc. are mentioned. As the antireflection film, a known organic or inorganic antireflection film can be appropriately used.
Also, the substrate is not particularly limited, and is generally used in silicon, SiN, SiO _{2 and} other semiconductor manufacturing processes such as ICs, circuit board manufacturing processes such as liquid crystal and thermal heads, and other photofabrication lithography processes. The board | substrate used for can be used.

[Actinic ray-sensitive or radiation-sensitive resin composition]
The actinic ray-sensitive or radiation-sensitive resin composition used in the present invention will be described below.

The composition contains a resin having an acid-decomposable group (hereinafter also referred to as “resin (A)”) having a weight average molecular weight (Mw) of 5,000 or more.
First, the resin (A) and other optional components will be described in detail.

[1] Resin (A)
As described above, the weight average molecular weight of the resin (A) is 5,000 or more.
The weight average molecular weight of the resin (A) is preferably 7,000 to 200,000, more preferably 12,000 to 50,000, still more preferably 17,000 to 40,000,000, particularly preferably. 20,000 to 30,000. The upper limit of the weight average molecular weight is not particularly limited, but is preferably 500,000 or less.
In addition, in this-application specification, a weight average molecular weight is a standard polystyrene conversion value calculated | required from the gel permeation chromatography (GPC) of the following conditions.
Column type: TSK gel Multipore HXL-M (manufactured by Tosoh Corporation, 7.8 mm ID × 30.0 cm)
・ Developing solvent: THF (tetrahydrofuran)
-Column temperature: 40 ° C
・ Flow rate: 1 ml / min
Sample injection volume: 10 μl
-Device name: HLC-8120 (manufactured by Tosoh Corporation)

The dispersity (molecular weight distribution) (Pd; Mw / Mn) of the resin (A) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2. A value of 0, particularly preferably in the range of 1.4 to 2.0 is used. The smaller the molecular weight distribution, the better the resolution and the resist shape, the smoother the sidewall of the resist pattern, and the better the roughness.
In addition, the number average molecular weight (Mn) is a standard polystyrene conversion value obtained from gel permeation chromatography (GPC) similarly to Mw described above, and the GPC conditions are the same as Mw described above.

As described above, the resin (A) has an acid-decomposable group. Here, the acid-decomposable group means a group that decomposes by the action of an acid to generate a polar group.
As the resin (A), the main chain or side chain of the resin, or both the main chain and the side chain are decomposed by the action of an acid to have a group that generates a polar group (hereinafter referred to as “acid-decomposable resin” Also called).
The acid-decomposable group preferably has a structure in which a polar group is protected by a group that decomposes and leaves under the action of an acid.
The polar group is not particularly limited as long as it is a group that is hardly soluble or insoluble in a developer containing an organic solvent, but it is a phenolic hydroxyl group, a carboxy group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group. , Sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkyl Sulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group and other acidic groups (2.38 mass% tetra, conventionally used as a resist developer) Methyl ammo Group dissociates in um hydroxide aqueous solution), or alcoholic hydroxyl group.

The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group and means a hydroxyl group other than a hydroxyl group directly bonded on an aromatic ring (phenolic hydroxyl group). An aliphatic alcohol substituted with a functional group (for example, a fluorinated alcohol group (such as a hexafluoroisopropanol group)) is excluded. The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa of 12 or more and 20 or less.
Preferred polar groups include carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), and sulfonic acid groups.
A preferable group as the acid-decomposable group is a group in which the hydrogen atom of these groups is substituted with a group capable of leaving with an acid.
Examples of the group leaving with an acid include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), -C (R ₀₁ ) (R ₀₂ ). ) (OR ₃₉ ) and the like.
In the formula, R _{36 to} R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
R ₀₁ and R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

The alkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl. Group, octyl group and the like.
The cycloalkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and the polycyclic type is preferably a cycloalkyl group having 6 to 20 carbon atoms. Note that at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.
The aryl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
The aralkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an aralkyl group having 7 to 12 carbon atoms.
The alkenyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms.
The ring formed by combining R ₃₆ and R ₃₇ is preferably a cycloalkyl group (monocyclic or polycyclic). The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable, and a monocyclic cycloalkyl group having 5 carbon atoms is particularly preferable.

  The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.

The resin (A) preferably has a repeating unit having an acid-decomposable group.
Moreover, it is preferable that resin (A) has a repeating unit represented by the following general formula (AI) as a repeating unit which has an acid-decomposable group. The repeating unit represented by the general formula (AI) generates a carboxyl group as a polar group by the action of an acid.

In general formula (AI),
Xa ₁ represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom.
T represents a single bond or a divalent linking group.
Rx _{1 to} Rx ₃ each independently represents an alkyl group or a cycloalkyl group.
Two of Rx _{1 to} Rx ₃ may be bonded to form a ring structure.

Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and a phenylene group. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a divalent linking group in that the effect of the present invention is more excellent. When T is a divalent linking group, the mobility of the polar group generated by the action of an acid is improved, and the effect of the present invention is more excellent.
In addition, as a bivalent coupling group, -COO-Rt- group is preferable. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group, — (CH ₂ ) ₂ — group, or — (CH ₂ ) ₃ — group.

The alkyl group of Xa ₁ may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).
The alkyl group of Xa ₁ preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a methyl group is preferable.
Xa ₁ is preferably a hydrogen atom or a methyl group.

The alkyl group of Rx ₁ , Rx ₂ and Rx ₃ may be linear or branched, and is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group. A group having 1 to 4 carbon atoms such as a t-butyl group is preferable.
Examples of the cycloalkyl group of Rx ₁ , Rx ₂ and Rx ₃ include polycyclic rings such as a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group and an adamantyl group Are preferred.

The ring structure formed by combining two of Rx ₁ , Rx ₂ and Rx ₃ includes a monocyclic cycloalkane ring such as cyclopentyl ring and cyclohexyl ring, norbornane ring, tetracyclodecane ring, tetracyclododecane ring, adamantane ring A polycyclic cycloalkyl group such as is preferable. A monocyclic cycloalkane ring having 5 or 6 carbon atoms is particularly preferable.
Rx ₁ , Rx ₂ and Rx ₃ are preferably each independently an alkyl group, more preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

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

Specific examples of the repeating unit represented by formula (AI) are given below, but the present invention is not limited to these specific examples.
In specific examples, Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms. Xa ₁ represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Z represents a substituent, and when a plurality of Zs are present, the plurality of Zs may be the same as or different from each other. p represents 0 or a positive integer. Specific examples and preferred examples of Z are the same as the specific examples and preferred examples of the substituent that each group such as Rx _{1 to} Rx ₃ may have.

  One type of repeating unit having an acid-decomposable group may be used, or two or more types may be used in combination. When two types are used in combination, a preferable combination is a combination whose structure is exemplified after paragraph [0121] of US2012 / 0009522A (in addition, US2012 / 0009522A is described in this specification). Incorporated).

The content of the repeating unit having an acid-decomposable group contained in the resin (A) (when there are a plurality of repeating units having an acid-decomposable group, the total) is based on the total repeating units of the resin (A), It is preferably 15 mol% or more, more preferably 20 mol% or more, further preferably 25 mol% or more, and particularly preferably 40 mol% or more. Especially, it is preferable that it is 50 mol% or more, it is more preferable that it is 55 mol% or more, and it is still more preferable that it is 65 mol% or more.
Resin (A) has a repeating unit represented by the above general formula (AI), and a content of the repeating unit represented by the above general formula (AI) with respect to all repeating units of the resin (A) is 40 mol%. The above is preferable.
Since the content of the repeating unit having an acid-decomposable group with respect to all repeating units of the resin (A) is 40 mol% or more, the glass transition temperature (Tg) of the resin (A) can be reliably increased, The effect that the increase in process cost described above can be suppressed can be made more reliable.
The content of the repeating unit having an acid-decomposable group is preferably 90 mol% or less, more preferably 80 mol% or less, more preferably 70 mol based on all repeating units of the resin (A). More preferably, it is% or less.

The resin (A) may have a structure such as a lactone structure, a sultone structure, a cyclic ketone structure, a cyclic sulfone structure, or a cyclic ether structure.
The lactone structure and sultone structure will be described later.
Here, the cyclic ketone structure means a cyclic ketone structure excluding a lactone structure, and examples thereof include cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, and cyclooctanone.
The cyclic sulfone structure means a cyclic sulfone structure excluding a sultone structure, and examples thereof include sulfolane.
The cyclic ether structure means a cyclic ether structure excluding a lactone structure, and examples thereof include a cyclic ether structure having 2 to 6 carbon atoms in the cyclic portion, and specific examples thereof include an oxirane ring, an oxetane ring, Dioxetane rings such as 1,3-dioxetane ring; Dioxolane rings such as tetrahydrofuran ring and 1,3-dioxolane ring; Dioxane rings such as tetrahydropyran ring, 1,3-dioxane ring and 1,4-dioxane ring; Oxepan ring, 1 , 3-dioxepane ring, dioxepane ring such as 1,4-dioxepane ring; and the like.

  The resin (A) preferably has at least one structure selected from the group consisting of a lactone structure, a sultone structure, a cyclic ketone structure, and a cyclic sulfone structure, and a lactone structure, a sultone structure, a cyclic ketone structure, and More preferably, it contains a repeating unit having at least one structure selected from the group consisting of cyclic sulfone structures. Thereby, the effect of this invention is more excellent.

  Any lactone structure or sultone structure can be used as long as it has a lactone structure or sultone structure, but a 5- to 7-membered lactone structure or a 5- to 7-membered sultone structure is preferable. Other ring structures are condensed in a form that forms a bicyclo structure or spiro structure in a member ring lactone structure, or other rings that form a bicyclo structure or a spiro structure in a 5- to 7-membered ring sultone structure Those having a condensed ring structure are more preferable. A lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21), or a sultone structure represented by any of the following general formulas (SL1-1) to (SL1-3), More preferably, it has a repeating unit having A lactone structure or a sultone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), (LC1-17), especially A preferred lactone structure is (LC1-4). By using such a specific lactone structure, LER (Line edge Roughness) and development defects are improved.

The lactone structure part or sultone structure part may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferably, they are a C1-C4 alkyl group, a cyano group, and an acid-decomposable group. n ₂ represents an integer of 0-4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different. A plurality of substituents (Rb ₂ ) may be bonded to form a ring.

  The repeating unit having a lactone structure or a sultone structure usually has an optical isomer, but any optical isomer may be used. One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90% or more, more preferably 95% or more.

  The repeating unit having a lactone structure or a sultone structure is preferably a repeating unit represented by the following general formula (III).

In the general formula (III),
A represents an ester bond (a group represented by —COO—) or an amide bond (a group represented by —CONH—).
R ₀ independently represents an alkylene group, a cycloalkylene group, or a combination of two or more of them when there are a plurality of R ₀ .
Z is independently a single bond, an ether bond, an ester bond, an amide bond, or a urethane bond when there are a plurality of Zs.

Or urea bond

Represents. Here, each R independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
R ₈ represents a monovalent organic group having a lactone structure or a sultone structure.
n is the number of repetitions of the structure represented by —R ₀ —Z—, and represents an integer of 0 to 5, preferably 0 or 1, and more preferably 0. When n is 0, -R ₀ -Z- does not exist and becomes a single bond.

A preferable chain alkylene group for R ₀ is preferably a chain alkylene group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group. . A preferable cycloalkylene group is a cycloalkylene group having 3 to 20 carbon atoms, and examples thereof include a cyclohexylene group, a cyclopentylene group, a norbornylene group, and an adamantylene group. In order to exhibit the effect of the present invention, a chain alkylene group is more preferable, and a methylene group is particularly preferable.
Z is preferably an ether bond or an ester bond, and particularly preferably an ester bond.

R ₇ represents a hydrogen atom, a halogen atom or an alkyl group.
The alkyl group for R ₇ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
R ₇ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

The alkylene group of R ₀ , the cycloalkylene group, and the alkyl group in R ₇ may each be substituted. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom, mercapto group, hydroxyl group , Alkoxy groups, and acyloxy groups.

The monovalent organic group having a lactone structure or a sultone structure represented by R ₈ is not limited as long as it has a lactone structure or a sultone structure. As specific examples, general formulas (LC1-1) to ( LC1-21) and a lactone structure or a sultone structure represented by any one of (SL1-1) to (SL1-3), and among these, a structure represented by (LC1-4) is particularly preferable. preferable. Further, n ₂ in (LC1-1) to (LC1-21) is more preferably 2 or less.
R ₈ is preferably a monovalent organic group having an unsubstituted lactone structure or sultone structure, or a monovalent organic group having a lactone structure or sultone structure having a methyl group, a cyano group or an alkoxycarbonyl group as a substituent. A monovalent organic group having a lactone structure (cyanolactone) having a cyano group as a substituent is more preferable.

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

  In order to enhance the effect of the present invention, it is possible to use two or more kinds of repeating units having a lactone structure or a sultone structure in combination.

  When the resin (A) contains a repeating unit having a lactone structure or a sultone structure, the content of the repeating unit having a lactone structure or a sultone structure is 5 to 60 mol% with respect to all the repeating units in the resin (A). Is more preferable, more preferably 5-55 mol%, still more preferably 10-50 mol%.

  Moreover, the resin (A) may have a repeating unit having a cyclic carbonate structure.

The resin (A) may have a repeating unit having a hydroxyl group or a cyano group. This improves the substrate adhesion and developer compatibility. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and preferably has no acid-decomposable group.
In addition, the repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably different from the repeating unit having an acid-decomposable group (that is, it is a stable repeating unit with respect to an acid). preferable).
The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diamantyl group, or a norbornane group.
More preferable examples include a repeating unit represented by any one of the following general formulas (AIIa) to (AIIc).

In the formula, Rx represents a hydrogen atom, a methyl group, a hydroxymethyl group, or a trifluoromethyl group.
Ab represents a single bond or a divalent linking group.
Examples of the divalent linking group represented by Ab include an alkylene group, a cycloalkylene group, an ester bond, an amide bond, an ether bond, a urethane bond, a urea bond, or a combination of two or more thereof. As an alkylene group, a C1-C10 alkylene group is preferable, A C1-C5 alkylene group is more preferable, For example, a methylene group, ethylene group, a propylene group, etc. are mentioned.
In one embodiment of the present invention, Ab is preferably a single bond or an alkylene group.
Rp represents a hydrogen atom, a hydroxyl group, or a hydroxyalkyl group. The plurality of Rp may be the same or different, but at least one of the plurality of Rp represents a hydroxyl group or a hydroxyalkyl group.

  The resin (A) may or may not contain a repeating unit having a hydroxyl group or a cyano group, but when the resin (A) contains a repeating unit having a hydroxyl group or a cyano group, The content of the repeating unit having a cyano group is preferably from 1 to 40 mol%, more preferably from 3 to 30 mol%, still more preferably from 5 to 25 mol%, based on all repeating units in the resin (A). . The resin (A) may contain two or more types of repeating units having a hydroxyl group or a cyano group having different structures.

  Specific examples of the repeating unit having a hydroxyl group or a cyano group are given below, but the present invention is not limited thereto.

In general formula (IV), R ₅ represents a hydrocarbon group having at least one cyclic structure and having no polar group.
Ra represents a hydrogen atom, an alkyl group, or a —CH ₂ —O—Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group or an acyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, particularly preferably a hydrogen atom or a methyl group.

The cyclic structure possessed by R ₅ includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. As the monocyclic hydrocarbon group, a cyclopentyl group and a cyclohexyl group are preferable.

The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group, and examples of the ring assembly hydrocarbon group include a bicyclohexyl group and a perhydronaphthalenyl group. As the bridged cyclic hydrocarbon ring, for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Hydrocarbon rings and tricyclic hydrocarbon rings such as homobredan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [4.3.1.1 ^2,5 ] undecane ring, tetracyclo [ 4.4.0.1 ^2,5 . 1 ^7,10 ] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene. A condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring are condensed is also included.

Preferred examples of the bridged cyclic hydrocarbon ring include a norbornyl group, an adamantyl group, a bicyclooctanyl group, a tricyclo [5,2,1,0 ^2,6 ] decanyl group, and the like. More preferable examples of the bridged cyclic hydrocarbon ring include a norbornyl group and an adamantyl group.

  These alicyclic hydrocarbon groups may have a substituent. Preferred examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom. It is done.

The resin (A) has an alicyclic hydrocarbon structure having no polar group, and may or may not contain a repeating unit that does not exhibit acid decomposability. 1 to 50 mol% is preferable with respect to all repeating units in the resin (A), more preferably 5 to 50 mol%, still more preferably 5 to 30 mol%. In addition, resin (A) may contain the repeating unit which has two or more types of alicyclic hydrocarbon structures which do not have a polar group, and which does not show acid-decomposability | different_conditions from which a structure differs.
Specific examples of the repeating unit having an alicyclic hydrocarbon structure having no polar group and not exhibiting acid decomposability are shown below, but the present invention is not limited thereto. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

  The resin (A) used in the composition is a general resin composition other than the above repeating structural units, and includes dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and actinic ray sensitive or radiation sensitive resin composition. It is possible to have various repeating structural units for the purpose of adjusting resolving power, heat resistance, sensitivity, and the like, which are necessary characteristics.

  Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.

Thereby, performance required for the resin used in the actinic ray-sensitive or radiation-sensitive resin composition, in particular,
(1) Solubility in coating solvent,
(2) Film formability (glass transition point),
(3) Alkali developability,
(4) Membrane slip (hydrophobic, alkali-soluble group selection),
(5) Adhesion of the unexposed part to the support,
(6) Fine adjustment such as dry etching resistance can be performed.

  As such a monomer, for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.

  In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.

  In the resin (A) used in the actinic ray-sensitive or radiation-sensitive resin composition, the content molar ratio of each repeating structural unit is the dry etching resistance or standard developer suitability of the actinic ray-sensitive or radiation-sensitive resin composition, It is suitably set to adjust the substrate adhesion, resist profile, and further the resolving power, heat resistance, sensitivity, etc., which are general required performances of the actinic ray-sensitive or radiation-sensitive resin composition.

The form of the resin (A) may be any of random type, block type, comb type, and star type. Resin (A) is compoundable by the radical, cation, or anion polymerization of the unsaturated monomer corresponding to each structure, for example. It is also possible to obtain the desired resin by conducting a polymer reaction after polymerization using an unsaturated monomer corresponding to the precursor of each structure.
When the actinic ray-sensitive or radiation-sensitive resin composition is for ArF exposure, the resin (A) has substantially no aromatic ring from the viewpoint of transparency to ArF light (specifically, In the resin, the ratio of the repeating unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, ideally 0 mol%, that is, it preferably has no aromatic group). The resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
In the case where the actinic ray-sensitive or radiation-sensitive resin composition contains a hydrophobic resin (D) described later, the resin (A) is a fluorine atom and a fluorine atom from the viewpoint of compatibility with the hydrophobic resin (D). Does not contain silicon atoms (specifically, the proportion of repeating units containing fluorine atoms or silicon atoms in the resin is preferably 5 mol% or less, more preferably 3 mol% or less, ideally 0 mol%) It is preferable.

  The resin (A) used in the actinic ray-sensitive or radiation-sensitive resin composition is preferably one in which all of the repeating units are composed of (meth) acrylate repeating units. In this case, all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are methacrylate repeating units and acrylate repeating units. Although it can be used, the acrylate-based repeating unit is preferably 50 mol% or less of the total repeating units.

  When the actinic ray-sensitive or radiation-sensitive resin composition is irradiated with KrF excimer laser light, electron beam, X-ray, high-energy light beam (EUV, etc.) having a wavelength of 50 nm or less, the resin (A) is further fragrant. It is preferable to have a repeating unit containing a ring structure, for example, a hydroxystyrene-based repeating unit. More preferably, it has a hydroxystyrene-based repeating unit, a hydroxystyrene-based repeating unit protected with an acid-decomposable group, and an acid-decomposable repeating unit such as a (meth) acrylic acid tertiary alkyl ester.

  Examples of the repeating unit having a preferred acid-decomposable group based on hydroxystyrene include, for example, t-butoxycarbonyloxystyrene, 1-alkoxyethoxystyrene, a repeating unit of (meth) acrylic acid tertiary alkyl ester, and the like. More preferred are repeating units of 2-alkyl-2-adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate.

  The resin (A) in the present invention can be synthesized according to a conventional method (for example, radical polymerization, living radical polymerization, anion polymerization). For example, reference can be made to the descriptions in paragraphs [0121] to [0128] of JP2012-074032A (paragraphs [0203] to [0211] of the corresponding US Patent Application Publication No. 2012/0777122). The contents are incorporated herein.

In the actinic ray-sensitive or radiation-sensitive resin composition, the blending ratio of the resin (A) in the entire composition is preferably 30 to 99% by mass, more preferably 60 to 95% by mass in the total solid content.
In the present invention, the resin (A) may be used alone or in combination.

[2] Compound (B) that generates an acid upon irradiation with an actinic ray or radiation
The actinic ray-sensitive or radiation-sensitive resin composition used in the present invention is usually a compound (B) that generates an acid upon irradiation with actinic rays or radiation (hereinafter referred to as “acid generator” “compound (B ) ”)). The compound (B) that generates an acid upon irradiation with actinic rays or radiation is preferably a compound that generates an organic acid upon irradiation with actinic rays or radiation. In addition, the compound (B) may be contained in the resin (A) described above. More specifically, the compound (B) may be linked to the resin (A) via a chemical bond.
The compound (B) that generates an acid upon irradiation with actinic rays or radiation may be in the form of a low molecular compound or may be incorporated in a part of the polymer. Moreover, you may use together the form incorporated in a part of polymer and the form of a low molecular compound.
When the compound (B) that generates an acid upon irradiation with actinic rays or radiation is in the form of a low molecular compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and 1000 or less. Is more preferable.
When the compound (B) that generates an acid upon irradiation with actinic rays or radiation is in a form incorporated in a part of the polymer, it may be incorporated in a part of the acid-decomposable resin described above, and is acid-decomposable. It may be incorporated in a resin different from the resin.
In the present invention, the compound (B) that generates an acid upon irradiation with actinic rays or radiation is preferably in the form of a low molecular compound.
As an acid generator, photo-initiator of photocation polymerization, photo-initiator of photo-radical polymerization, photo-decoloring agent of dyes, photo-discoloring agent, irradiation of actinic ray or radiation, etc. The known compounds that generate an acid and mixtures thereof can be appropriately selected and used.

  For example, examples of the acid generator include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

  Preferred compounds among the acid generators include compounds represented by the following general formulas (ZI), (ZII), and (ZIII).

In the general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1-30, preferably 1-20.
Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).
Z ⁻ represents a non-nucleophilic anion.

Examples of the non-nucleophilic anion as Z ⁻ include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.

  A non-nucleophilic anion is an anion that has an extremely low ability to cause a nucleophilic reaction and is an anion that can suppress degradation over time due to an intramolecular nucleophilic reaction. Thereby, the temporal stability of the actinic ray-sensitive or radiation-sensitive resin composition is improved.

Examples of the sulfonate anion include an aliphatic sulfonate anion, an aromatic sulfonate anion, and a camphor sulfonate anion.
Examples of the carboxylate anion include an aliphatic carboxylate anion, an aromatic carboxylate anion, and an aralkylcarboxylate anion.

  The aliphatic moiety in the aliphatic sulfonate anion and aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably an alkyl group having 1 to 30 carbon atoms and a cyclohexane having 3 to 30 carbon atoms. Alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl , Undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, bornyl group, etc. Can be mentioned.

  The aromatic group in the aromatic sulfonate anion and aromatic carboxylate 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 in the aliphatic sulfonate anion and aromatic sulfonate anion may have a substituent. Examples of the substituent of the alkyl group, cycloalkyl group, and aryl group in the aliphatic sulfonate anion and aromatic sulfonate anion include, for example, a nitro group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), carboxyl group , Hydroxyl group, amino group, cyano group, alkoxy group (preferably having 1 to 15 carbon atoms), cycloalkyl group (preferably having 3 to 15 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), alkoxycarbonyl group ( Preferably 2 to 7 carbon atoms, acyl group (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), alkylthio group (preferably 1 to 15 carbon atoms), alkylsulfonyl group (Preferably 1 to 15 carbon atoms), alkyliminosulfonyl group (preferably 1 to 15 carbon atoms), ant Ruoxysulfonyl group (preferably having 6 to 20 carbon atoms), alkylaryloxysulfonyl group (preferably having 7 to 20 carbon atoms), cycloalkylaryloxysulfonyl group (preferably having 10 to 20 carbon atoms), alkyloxyalkyloxy group (Preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like. About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) and a cycloalkyl group (preferably C3-C15) can further be mentioned as a substituent.

  The aralkyl group in the aralkyl carboxylate 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 naphthylbutyl group.

  The alkyl group, cycloalkyl group, aryl group and aralkyl group in the aliphatic carboxylate anion, aromatic carboxylate anion and aralkylcarboxylate anion may have a substituent. Examples of this substituent include the same halogen atom, alkyl group, cycloalkyl group, alkoxy group, alkylthio group and the like as those in the aromatic sulfonate anion.

  Examples of the sulfonylimide anion include saccharin anion.

The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl. Group, sec-butyl group, pentyl group, neopentyl group and the like.
Two alkyl groups in the bis (alkylsulfonyl) imide anion may be linked to each other to form an alkylene group (preferably having 2 to 4 carbon atoms), and may form a ring together with the imide group and the two sulfonyl groups. The alkylene group formed by linking two alkyl groups in these alkyl groups and bis (alkylsulfonyl) imide anions may have a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group. , An alkyloxysulfonyl group, an aryloxysulfonyl group, a cycloalkylaryloxysulfonyl group, and the like, and an alkyl group substituted with a fluorine atom is preferred.
Examples of other non-nucleophilic anions include fluorinated phosphorus (for example, PF ₆ ⁻ ), fluorinated boron (for example, BF ₄ ⁻ ), fluorinated antimony (for example, SbF ₆ ⁻ ), and the like. .

As the non-nucleophilic anion of Z ⁻ , an aliphatic sulfonate anion in which at least α position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, an alkyl group Is preferably a bis (alkylsulfonyl) imide anion substituted with a fluorine atom, or a tris (alkylsulfonyl) methide anion wherein an alkyl group is substituted with a fluorine atom. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonic acid anion having 4 to 8 carbon atoms, a benzenesulfonic acid anion having a fluorine atom, still more preferably a nonafluorobutanesulfonic acid anion, a perfluorooctanesulfonic acid anion, It is a pentafluorobenzenesulfonic acid anion and 3,5-bis (trifluoromethyl) benzenesulfonic acid anion.

The acid generator is preferably a compound that generates an acid represented by the following general formula (V) or (VI) upon irradiation with actinic rays or radiation. Since it is a compound that generates an acid represented by the following general formula (V) or (VI) and has a cyclic organic group, the resolution and roughness performance can be further improved.
As said non-nucleophilic anion, it can be set as the anion which produces the organic acid represented by the following general formula (V) or (VI).

In the above general formula,
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ₁₁ and R ₁₂ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group.
L each independently represents a divalent linking group.
Cy represents a cyclic organic group.
Rf is a group containing a fluorine atom.
x represents an integer of 1 to 20.
y represents an integer of 0 to 10.
z represents an integer of 0 to 10.

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Xf is more preferably a fluorine atom or CF ₃ . In particular, it is preferable that both Xf are fluorine atoms.

R ₁₁ and R ₁₂ are each independently a hydrogen atom, a fluorine atom, or an alkyl group. This alkyl group may have a substituent (preferably a fluorine atom), and preferably has 1 to 4 carbon atoms. More preferably, it is a C1-C4 perfluoroalkyl group. The alkyl group having a substituent for R ₁₁ and R ₁₂ is preferably CF ₃ .

L represents a divalent linking group. Examples of the divalent linking group include —COO—, —OCO—, —CONH—, —NHCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, and an alkylene group. (Preferably having 1 to 6 carbon atoms), cycloalkylene group (preferably having 3 to 10 carbon atoms), alkenylene group (preferably having 2 to 6 carbon atoms) or a divalent linking group in which two or more of these are combined. It is done. Among these, —COO—, —OCO—, —CONH—, —NHCO—, —CO—, —O—, —SO ₂ —, —COO-alkylene group—, —OCO-alkylene group—, —CONH— alkylene group - or -NHCO- alkylene group - are preferred, -COO -, - OCO -, - CONH -, - SO 2 -, - COO- alkylene group - or -OCO- alkylene group - is more preferable.

Cy represents a cyclic organic group. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.
The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include alicyclic groups having a bulky structure of 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. From the viewpoint of suppressing diffusibility in the film in the PEB (post-exposure heating) step and improving MEEF (Mask Error Enhancement Factor).

  The aryl group may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. Among these, a naphthyl group having a relatively low light absorbance at 193 nm is preferable.

  The heterocyclic group may be monocyclic or polycyclic, but the polycyclic group can suppress acid diffusion more. Moreover, the heterocyclic group may have aromaticity or may not have aromaticity. Examples of the heterocyclic ring having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring not having aromaticity include a tetrahydropyran ring, a lactone ring or a sultone ring, and a decahydroisoquinoline ring. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable. Examples of the lactone ring or sultone ring include the lactone structure or sultone exemplified in the aforementioned resin (A).

  The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, preferably 1 to 12 carbon atoms), and a cycloalkyl group (monocyclic, polycyclic or spirocyclic). Well, preferably having 3 to 20 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), hydroxyl group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, sulfonamide group, and sulfonic acid An ester group is mentioned. The carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.

x is preferably 1 to 8, more preferably 1 to 4, and particularly preferably 1. y is preferably 0 to 4, and more preferably 0. z is preferably 0 to 8, particularly preferably 0 to 4.
Examples of the group containing a fluorine atom represented by Rf include an alkyl group having at least one fluorine atom, a cycloalkyl group having at least one fluorine atom, and an aryl group having at least one fluorine atom. .
These alkyl group, cycloalkyl group and aryl group may be substituted with a fluorine atom, or may be substituted with another substituent containing a fluorine atom. When Rf is a cycloalkyl group having at least one fluorine atom or an aryl group having at least one fluorine atom, other substituents containing a fluorine atom include, for example, alkyl substituted with at least one fluorine atom. Groups.
Further, these alkyl group, cycloalkyl group and aryl group may be further substituted with a substituent not containing a fluorine atom. As this substituent, the thing which does not contain a fluorine atom among what was demonstrated about Cy previously can be mentioned, for example.
Examples of the alkyl group having at least one fluorine atom represented by Rf include those described above as the alkyl group substituted with at least one fluorine atom represented by Xf. Examples of the cycloalkyl group having at least one fluorine atom represented by Rf include a perfluorocyclopentyl group and a perfluorocyclohexyl group. Examples of the aryl group having at least one fluorine atom represented by Rf include a perfluorophenyl group.

  Further preferred examples of the (ZI) component include compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described below.

The compound (ZI-1) will be described.
The compound (ZI-1) is at least one of the aryl groups R ₂₀₁ to R ₂₀₃ in formula (ZI), arylsulfonium compounds, namely, compounds containing an arylsulfonium as a cation.

In the arylsulfonium compound, all of R _{201 to} R ₂₀₃ may be an aryl group, or a part of R _{201 to} R ₂₀₃ may be an aryl group with the remaining being an alkyl group or a cycloalkyl group.

  Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

  The aryl group of the arylsulfonium compound is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.

  The alkyl group or cycloalkyl group that the arylsulfonium compound has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms, such as a methyl group, Examples thereof include an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

Aryl group, alkyl group of R ₂₀₁ to R _203, cycloalkyl group, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms) , An alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be substituted. Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, more preferably carbon. These are an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted with any one of the three R _{201 to} R ₂₀₃ , or may be substituted with all three. When R _{201 to} R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

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

The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, alkoxy group. A carbonylmethyl group, particularly preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group of R ₂₀₁ to R _203, preferably a linear or branched alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group). More preferred examples of the alkyl group include a 2-oxoalkyl group and an alkoxycarbonylmethyl group. More preferred examples of the cycloalkyl group include a 2-oxocycloalkyl group.

The 2-oxoalkyl group may be either linear or branched, and a group having> C = O at the 2-position of the above alkyl group is preferable.
The 2-oxocycloalkyl group is preferably a group having> C═O at the 2-position of the cycloalkyl group.

  The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group).

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

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

In general formula (ZI-3),
R _{1c to} R _5c are each independently a hydrogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen atom, hydroxyl group Represents a nitro group, an alkylthio group or an arylthio group.
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
R _x and R _y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

Any two or more of R _{1c to} R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y may be bonded to form a ring structure. In addition, this ring structure may contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, or a polycyclic fused ring formed by combining two or more of these rings. Examples of the ring structure include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.
Examples of the group formed by combining any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.
The group formed by combining R _5c and R _6c and R _5c and R _x is preferably a single bond or an alkylene group, and examples of the alkylene group include a methylene group and an ethylene group. .

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

The alkyl group as R _{1c to} R _7c may be either linear or branched, for example, an alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 12 carbon atoms ( Examples thereof include a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, and a linear or branched pentyl group. Examples of the cycloalkyl group include cyclohexane having 3 to 10 carbon atoms. An alkyl group (for example, a cyclopentyl group, a cyclohexyl group) can be mentioned.

The aryl group as R _{1c to} R _5c preferably has 5 to 15 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

The alkoxy group as R _{1c to} R _{5c may} be linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear or branched alkoxy group having 1 to 5 carbon atoms. (For example, methoxy group, ethoxy group, linear or branched propoxy group, linear or branched butoxy group, linear or branched pentoxy group), C3-C10 cyclic alkoxy group (for example, cyclopentyloxy group, cyclohexyloxy group) ).

Specific examples of the alkoxy group in the alkoxycarbonyl group as R _1c to R _5c are the same as specific examples of the alkoxy group as the R _1c to R _5c.

Specific examples of the alkyl group in the alkylcarbonyloxy group and alkylthio group as R _1c to R _5c are the same as specific examples of the alkyl group of the R _1c to R _5c.

Specific examples of the cycloalkyl group in the cycloalkyl carbonyl group as R _1c to R _5c are the same as specific examples of the cycloalkyl group of the R _1c to R _5c.

Specific examples of the aryl group in the aryloxy group and arylthio group as R _1c to R _5c are the same as specific examples of the aryl group of the R _1c to R _5c.
Preferably, any of R _{1c to} R _5c is a linear or branched alkyl group, a cycloalkyl group, or a linear, branched or cyclic alkoxy group, and more preferably the sum of the carbon number of R _{1c to} R _5c. Is 2-15. Thereby, solvent solubility improves more and generation | occurrence | production of a particle is suppressed at the time of a preservation | save.

The ring structure that any two or more of R _{1c to} R _5c may be bonded to each other is preferably a 5-membered or 6-membered ring, particularly preferably a 6-membered ring (for example, a phenyl ring). It is done.

The ring structure which may be formed by R _5c and R _6c are bonded to each other, bonded R _5c and R _6c are each other a single bond or an alkylene group (methylene group, ethylene group, etc.) by configuring the generally Examples thereof include a carbonyl carbon atom in formula (ZI-3) and a 4-membered ring (particularly preferably a 5- to 6-membered ring) formed together with the carbon atom.

The aryl group as R _6c and R _7c preferably has 5 to 15 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.
As an aspect of R _6c and R _7c , it is preferable that both of them are alkyl groups. In particular, the case where R _6c and R _7c are each a linear or branched alkyl group having 1 to 4 carbon atoms is preferred, and the case where both are methyl groups is particularly preferred.

In addition, when R _6c and R _7c are combined to form a ring, the group formed by combining R _6c and R _7c is preferably an alkylene group having 2 to 10 carbon atoms, such as an ethylene group , Propylene group, butylene group, pentylene group, hexylene group and the like. The ring formed by combining R _6c and R _7c may have a hetero atom such as an oxygen atom in the ring.

_Examples of the alkyl group and cycloalkyl group as R _x and R _y include the same alkyl group and cycloalkyl group as in R _{1c to} R _7c .

_Examples of the 2-oxoalkyl group and 2-oxocycloalkyl group as R _x and R _y include a group having> C═O at the 2-position of the alkyl group and cycloalkyl group as R _{1c to} R _7c. .

Examples of the alkoxy group in the alkoxycarbonylalkyl group as R _x and R _y include the same alkoxy groups as in R _{1c to} R _5c , and examples of the alkyl group include an alkyl group having 1 to 12 carbon atoms. Preferably, a C1-C5 linear alkyl group (for example, a methyl group, an ethyl group) can be mentioned.

The allyl group as R _x and R _y is not particularly limited, but is substituted with an unsubstituted allyl group or a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having 3 to 10 carbon atoms). An allyl group is preferred.

The vinyl group as R _x and R _y is not particularly limited, but is substituted with an unsubstituted vinyl group or a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having 3 to 10 carbon atoms). It is preferably a vinyl group.

The ring structure which may be formed by R _5c and R _x are bonded to each other, bonded R _5c and R _x each other a single bond or an alkylene group (methylene group, ethylene group, etc.) by configuring the generally Examples thereof include a 5-membered ring or more (particularly preferably a 5-membered ring) formed together with the sulfur atom and the carbonyl carbon atom in the formula (ZI-3).

As the ring structure that R _x and R _y may be bonded to each other, divalent R _x and R _y (for example, a methylene group, an ethylene group, a propylene group, and the like) are represented by the general formula (ZI-3). A 5-membered or 6-membered ring formed with a sulfur atom, particularly preferably a 5-membered ring (that is, a tetrahydrothiophene ring).

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

R _{1c to} R _7c , R _x and R _y may further have a substituent. Examples of such a substituent include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, and a nitro group. Group, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, acyl group, arylcarbonyl group, alkoxyalkyl group, aryloxyalkyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxycarbonyloxy group, aryl An oxycarbonyloxy group etc. can be mentioned.

In the general formula (ZI-3), R _1c , R _2c , R _4c and R _5c each independently represent a hydrogen atom, and R _3c is a group other than a hydrogen atom, that is, an alkyl group, a cycloalkyl group, More preferably, it represents an aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen atom, hydroxyl group, nitro group, alkylthio group or arylthio group.

  Examples of the cation of the compound represented by formula (ZI-2) or (ZI-3) in the present invention include the following specific examples. Here, Me represents a methyl group, Et represents an ethyl group, and Bu represents a butyl group.

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

In general formula (ZI-4),
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group. These groups may have a substituent.
When there are a plurality of R _{14 s,} each independently represents a group having a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group. Represent. These groups may have a substituent.
R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R ₁₅ may be bonded to each other to form a ring. These groups may have a substituent.
l represents an integer of 0-2.
r represents an integer of 0 to 8.
Z ^- represents a non-nucleophilic anion, in the general formula (ZI) Z ^- and include the same non-nucleophilic anion.

In the general formula (ZI-4), the alkyl group of R ₁₃ , R ₁₄ and R ₁₅ is linear or branched and preferably has 1 to 10 carbon atoms, and is preferably a methyl group, an ethyl group, n -A butyl group, a t-butyl group, etc. are preferable.

Examples of the cycloalkyl group represented by R ₁₃ , R ₁₄ and R ₁₅ include a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms), particularly cyclopropyl, cyclopentyl, cyclohexyl, Cycloheptyl and cyclooctyl are preferred.

The alkoxy group for R ₁₃ and R ₁₄ is linear or branched and preferably has 1 to 10 carbon atoms, and is preferably a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, or the like.

The alkoxycarbonyl group for R ₁₃ and R ₁₄ is linear or branched and preferably has 2 to 11 carbon atoms, and is preferably a methoxycarbonyl group, an ethoxycarbonyl group, an n-butoxycarbonyl group, or the like.

Examples of the group having a cycloalkyl group represented by R ₁₃ and R ₁₄ include a monocyclic or polycyclic cycloalkyl group (preferably a cycloalkyl group having 3 to 20 carbon atoms). Examples thereof include a cycloalkyloxy group and an alkoxy group having a monocyclic or polycyclic cycloalkyl group. These groups may further have a substituent.

The monocyclic or polycyclic cycloalkyloxy group for R ₁₃ and R ₁₄ preferably has a total carbon number of 7 or more, more preferably a total carbon number of 7 or more and 15 or less, It is preferable to have a cycloalkyl group. Monocyclic cycloalkyloxy group having 7 or more carbon atoms in total is cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, cyclododecanyloxy group, etc. Optionally substituted with an alkyl group, hydroxyl group, halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, amide group, sulfonamido group, alkoxy group, alkoxycarbonyl group, acyl group, acetoxy A monocyclic cycloalkyloxy group having a substituent such as a group, an acyloxy group such as a butyryloxy group, or a carboxy group, and having a total carbon number of 7 or more in combination with any substituents on the cycloalkyl group Represent.
Examples of the polycyclic cycloalkyloxy group having 7 or more total carbon atoms include a norbornyloxy group, a tricyclodecanyloxy group, a tetracyclodecanyloxy group, an adamantyloxy group, and the like.

The alkoxy group having a monocyclic or polycyclic cycloalkyl group of R ₁₃ and R ₁₄ preferably has a total carbon number of 7 or more, more preferably a total carbon number of 7 or more and 15 or less, An alkoxy group having a monocyclic cycloalkyl group is preferable. The alkoxy group having a total of 7 or more carbon atoms and having a monocyclic cycloalkyl group is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptoxy, octyloxy, dodecyloxy, 2-ethylhexyloxy, isopropoxy, A monocyclic cycloalkyl group which may have the above-mentioned substituent is substituted on an alkoxy group such as sec-butoxy, t-butoxy, iso-amyloxy, etc., and the total carbon number including the substituent is 7 or more. Represents things. Examples thereof include a cyclohexylmethoxy group, a cyclopentylethoxy group, a cyclohexylethoxy group, and the like, and a cyclohexylmethoxy group is preferable.

  Examples of the alkoxy group having a polycyclic cycloalkyl group having a total carbon number of 7 or more include a norbornyl methoxy group, a norbornyl ethoxy group, a tricyclodecanyl methoxy group, a tricyclodecanyl ethoxy group, a tetracyclo group. A decanyl methoxy group, a tetracyclodecanyl ethoxy group, an adamantyl methoxy group, an adamantyl ethoxy group, etc. are mentioned, A norbornyl methoxy group, a norbornyl ethoxy group, etc. are preferable.

The alkyl group of the alkyl group of R _14, include the same specific examples as the alkyl group as R ₁₃ to R ₁₅ described above.

The alkylsulfonyl group and cycloalkylsulfonyl group of R ₁₄ are linear, branched, or cyclic, and preferably those having 1 to 10 carbon atoms, such as methanesulfonyl group, ethanesulfonyl group, n-propanesulfonyl. Group, n-butanesulfonyl group, cyclopentanesulfonyl group, cyclohexanesulfonyl group and the like are preferable.

  Examples of the substituent that each of the above groups may have include a halogen atom (for example, a fluorine atom), a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group. Etc.

As a ring structure that two R ₁₅ may be bonded to each other, a 5-membered or 6-membered ring formed by two R ₁₅ together with a sulfur atom in the general formula (ZI-4), particularly preferably Includes a 5-membered ring (that is, a tetrahydrothiophene ring), and may be condensed with an aryl group or a cycloalkyl group. The divalent R ₁₅ may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxyalkyl group, an alkoxy group. Examples thereof include a carbonyl group and an alkoxycarbonyloxy group. There may be a plurality of substituents for the ring structure, and they may be bonded to each other to form a ring (aromatic or non-aromatic hydrocarbon ring, aromatic or non-aromatic heterocyclic ring, or these A polycyclic fused ring formed by combining two or more rings may be formed.
R ₁₅ in the general formula (ZI-4) is preferably a methyl group, an ethyl group, a naphthyl group, a divalent group in which two R ₁₅ are bonded to each other to form a tetrahydrothiophene ring structure together with a sulfur atom.

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

l is preferably 0 or 1, and more preferably 1.
As r, 0-2 are preferable.

  Specific examples of the cation of the compound represented by formula (ZI-4) in the present invention include the following.

Next, general formulas (ZII) and (ZIII) will be described.
In general formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.
Phenyl group and a naphthyl group are preferred as the aryl group of R ₂₀₄ to R _207, more preferably a phenyl group. Aryl group R ₂₀₄ to R ₂₀₇ represents an oxygen atom, a nitrogen atom, may be an aryl group having a heterocyclic structure having a sulfur atom and the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl group and cycloalkyl group in R _{204 to} R ₂₀₇ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups of several 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).
Aryl group, alkyl group of R ₂₀₄ to R _207, cycloalkyl groups may have a substituent. Aryl group, alkyl group of R ₂₀₄ to R _207, the cycloalkyl group substituent which may be possessed by, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms ), An aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.
Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} formula (ZI).

  Examples of the acid generator further include compounds represented by general formulas (ZIV), (ZV), and (ZVI) described in paragraphs [0227] to [0228] of JP-A-2014-232310.

Among the acid generators, compounds represented by the general formulas (ZI) to (ZIII) are more preferable.
Moreover, the compound described in paragraph [0229] of Unexamined-Japanese-Patent No. 2014-232310 can also be used suitably as an acid generator.

  Among acid generators, particularly preferable examples include, but are not limited to, the acid generators described in paragraphs [0231] to [0240] of JP2014-232310A.

The acid generator can be synthesized by a known method. For example, [0200] to [0210] of JP-A No. 2007-161707, JP-A No. 2010-100595, and International Publication No. 2011/093280 [ [0051] to [0058], [0382] to [0385] of International Publication No. 2008/153110, Japanese Patent Application Laid-Open No. 2007-161707, and the like.
An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the compound that generates an acid upon irradiation with actinic rays or radiation (excluding the case represented by the above general formula (ZI-3) or (ZI-4)) in the composition is actinic ray sensitive or 0.1-30 mass% is preferable on the basis of the total solid content of the radiation-sensitive resin composition, more preferably 0.5-25 mass%, still more preferably 3-20 mass%, and particularly preferably 3-15. % By mass.
When the acid generator is represented by the general formula (ZI-3) or (ZI-4), the content is preferably 5 to 35% by mass based on the total solid content of the composition. 6-30 mass% is more preferable, 6-30 mass% is still more preferable, and 6-25 mass% is especially preferable.

[3] Solvent (C)
The actinic ray-sensitive or radiation-sensitive resin composition used in the present invention may contain a solvent (C).
Examples of the solvent (C) that can be used in preparing the actinic ray-sensitive or radiation-sensitive resin composition include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactate alkyl ester, and alkoxypropion. Organic solvents such as alkyl acid, cyclic lactone (preferably having 4 to 10 carbon atoms), monoketone compound which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, alkyl pyruvate, etc. be able to. Solvents that can be preferably used include isoamyl acetate, butyl butanoate, methyl 2-hydroxyisobutyrate, isobutyl isobutyrate, and butyl propionate.
Specific examples of these solvents include those described in paragraphs [0441] to [0455] of US Patent Application Publication No. 2008/0187860.

In the present invention, a mixed solvent may be used as the solvent (C).
For example, alkylene glycol monoalkyl ether, alkyl lactate and the like are preferable, and propylene glycol monomethyl ether (PGME, also known as 1-methoxy-2-propanol), ethyl lactate, alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, containing a ring Two or more kinds of mixed solvents selected from monoketone compounds, cyclic lactones, alkyl acetates, etc., which may be used, are preferred, and among these, propylene glycol monomethyl ether acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane) (hereinafter, Solvent A), and selected from propylene glycol monomethyl ether, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, and butyl acetate. Species or two solvents (hereinafter also referred to as a solvent B) mixed solvent of is preferred.
The mixing ratio (solvent A / solvent B) (mass ratio) of the mixed solvent is from 1/99 to 99/1, preferably from 10/90 to 90/10, more preferably from 20/80 to 60/40.
The solvent (C) preferably contains propylene glycol monomethyl ether acetate, and is preferably a propylene glycol monomethyl ether acetate single solvent or a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.

[4] Hydrophobic resin (D)
The actinic ray-sensitive or radiation-sensitive resin composition used in the present invention is a hydrophobic resin (hereinafter referred to as “hydrophobic resin (D)” or simply “resin (D)”, particularly when applied to immersion exposure. May also be included). The hydrophobic resin (D) is preferably different from the resin (A). Moreover, it is preferable that hydrophobic resin (D) does not have an acid-decomposable group.
As a result, the hydrophobic resin (D) is unevenly distributed in the film surface layer, and when the immersion medium is water, the static / dynamic contact angle of the resist film surface with water is improved, and the immersion liquid followability is improved. be able to. In addition, since uneven distribution of the hydrophobic resin (D) can be expected to suppress so-called outgassing, the hydrophobic resin (D) may be used when the pattern forming method of the present invention is performed by EUV exposure. preferable.
The hydrophobic resin (D) is preferably designed to be unevenly distributed at the interface as described above. However, unlike the surfactant, the hydrophobic resin (D) does not necessarily need to have a hydrophilic group in the molecule. There is no need to contribute to uniform mixing.

The hydrophobic resin (D) is selected from any one of “fluorine atom”, “silicon atom”, and “CH ₃ partial structure contained in the side chain portion of the resin” from the viewpoint of uneven distribution in the film surface layer. It is preferable to have the above, and more preferable to have two or more.

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

When the hydrophobic resin (D) contains a fluorine atom, it 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 as a partial structure having a fluorine atom. Preferably there is.
The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and further a fluorine atom It may have a substituent other than.
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 of 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. .

  Preferred examples of the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, and the aryl group having a fluorine atom include groups represented by the following general formulas (F2) to (F4). The invention is not limited to this.

In general formulas (F2) to (F4),
R _{57 to} R ₆₈ each independently represent a hydrogen atom, a fluorine atom or an alkyl group (straight or branched). However, at least one of R _{57 to} R _61, at least one of R _{62 to} R ₆₄ , and at least one of R _{65 to} R ₆₈ are each independently substituted with a fluorine atom or at least one hydrogen atom. Represents an alkyl group (preferably having 1 to 4 carbon atoms).
R _{57 to} R ₆₁ and R _{65 to} R ₆₇ are preferably all fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. Further preferred. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

Specific examples of the group represented by the general formula (F2) include a p-fluorophenyl group, a pentafluorophenyl group, and a 3,5-di (trifluoromethyl) phenyl group.
Specific examples of the group represented by the general formula (F3) include trifluoromethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluorobutyl group, hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2 -Methyl) isopropyl group, nonafluorobutyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro (trimethyl) hexyl group, 2,2 , 3,3-tetrafluorocyclobutyl group, perfluorocyclohexyl group and the like. Hexafluoroisopropyl group, heptafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoroisobutyl group, nonafluoro-t-butyl group and perfluoroisopentyl group are preferable, and hexafluoroisopropyl group and heptafluoroisopropyl group are preferable. Further preferred.
Specific examples of the group represented by the general formula (F4) include, for example, —C (CF ₃ ) ₂ OH, —C (C ₂ F ₅ ) ₂ OH, —C (CF ₃ ) (CH ₃ ) OH, -CH (CF ₃₎ OH and the like, -C (CF _{3) 2} OH is preferred.

  The partial structure containing a fluorine atom may be directly bonded to the main chain, and further from the group consisting of an alkylene group, a phenylene group, an ether bond, a thioether bond, a carbonyl group, an ester bond, an amide bond, a urethane bond and a ureylene bond. You may couple | bond with a principal chain through the group selected or the group which combined these 2 or more types.

  Hereinafter, as specific examples of the repeating unit having a fluorine atom, paragraphs [0274] to [0276] of JP2012-073402A (paragraph [0398] of the corresponding US Patent Application Publication No. 2012/0777122) [0399]) can be referred to, the contents of which are incorporated herein.

  The hydrophobic resin (D) may contain a silicon atom. As a partial structure having a silicon atom, described in paragraphs [0277] to [0281] of JP2012-073402 (paragraphs [0400] to [0405] of the corresponding US Patent Application Publication No. 2012/077122) The contents of which are incorporated herein by reference.

Further, as described above, the hydrophobic resin (D) also preferably includes a “CH ₃ partial structure” in the side chain portion.
Here, the hydrophobic resins (D) CH ₃ partial structure contained in the side chain moiety in (hereinafter, simply referred to as "side chain CH ₃ partial structure") The, CH ₃ parts ethyl, and propyl groups have Includes structure.
On the other hand, the methyl group directly bonded to the main chain of the hydrophobic resin (D) (for example, the α-methyl group of the repeating unit having a methacrylic acid structure) is caused by the influence of the main chain on the surface of the hydrophobic resin (D). Since the contribution to uneven distribution is small, it is not included in the “CH ₃ partial structure”.

More specifically, the hydrophobic resin (D) is a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond, such as a repeating unit represented by the following general formula (M). In the case where R _{11 to} R ₁₄ are CH ₃ “as it is”, the CH ₃ is not included in the “CH ₃ partial structure” of the side chain moiety.
On the other hand, when CH ₃ exists from the C—C main chain through some atom, it corresponds to “CH ₃ partial structure”. For example, when R ₁₁ is an ethyl group (CH ₂ CH ₃ ), it has “one” CH ₃ partial structure.

In the general formula (M),
R _{11 to} R ₁₄ each independently represents a side chain portion.
Examples of R _{11 to} R _{14 in the} side chain portion include a hydrogen atom and a monovalent organic group.
Examples of monovalent organic groups for R _{11 to} R ₁₄ include alkyl groups, cycloalkyl groups, aryl groups, alkyloxycarbonyl groups, cycloalkyloxycarbonyl groups, aryloxycarbonyl groups, alkylaminocarbonyl groups, cycloalkylaminocarbonyls. Group, an arylaminocarbonyl group, and the like, and these groups may further have a substituent.

The hydrophobic resin (D) is preferably a resin having a repeating unit having a CH ₃ partial structure in the side chain portion, and as such a repeating unit, a repeating unit represented by the following general formula (II), and It is more preferable to have at least one repeating unit (x) among repeating units represented by the following general formula (III).

  Hereinafter, the repeating unit represented by formula (II) will be described in detail.

In the general formula (II), X _b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, R ₂ has one or more CH ₃ partial structure represents a stable organic radical to acid. Here, the organic group stable to an acid is more specifically an organic group that does not have the “group that decomposes by the action of an acid to generate a polar group” described in the resin (A). Is preferred.

The alkyl group for X _b1 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a methyl group is preferable.
X _b1 is preferably a hydrogen atom or a methyl group.

Examples of R ₂ include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and an aralkyl group having one or more CH ₃ partial structures. The above cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group and aralkyl group may further have an alkyl group as a substituent.
R ₂ is preferably an alkyl group or an alkyl-substituted cycloalkyl group having one or more CH ₃ partial structures.
The acid-stable organic group having one or more CH ₃ partial structures as R ₂ preferably has 2 or more and 10 or less CH ₃ partial structures, and more preferably 2 or more and 8 or less.

The alkyl group having one or more CH ₃ partial structures in R ₂ is preferably a branched alkyl group having 3 to 20 carbon atoms.

The cycloalkyl group having one or more CH ₃ partial structures in R ₂ may be monocyclic or polycyclic. Specific examples include groups having a monocyclo, bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms. The carbon number is preferably 6-30, and particularly preferably 7-25.
The alkenyl group having one or more CH ₃ partial structures in R ₂ is preferably a linear or branched alkenyl group having 1 to 20 carbon atoms, and more preferably a branched alkenyl group.
The aryl group having one or more CH ₃ partial structures in R ₂ is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group. is there.
The aralkyl group having one or more CH ₃ partial structures in R ₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.

  Preferred specific examples of the repeating unit represented by the general formula (II) are shown below. Note that the present invention is not limited to this.

  The repeating unit represented by the general formula (II) is preferably an acid-stable (non-acid-decomposable) repeating unit, and specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.

  Hereinafter, the repeating unit represented by formula (III) will be described in detail.

In the general formula (III), X _b2 represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom, R ₃ represents an acid-stable organic group having one or more CH ₃ partial structures, n represents an integer of 1 to 5.

The alkyl group for X _b2 is preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a hydrogen atom is preferable.
X _b2 is preferably a hydrogen atom.

Since R ₃ is an organic group that is stable to acids, more specifically, it is an organic group that does not have the “group that decomposes by the action of an acid to generate a polar group” described in the resin (A). Preferably there is.

R ₃ includes an alkyl group having one or more CH ₃ partial structures.
The acid-stable organic group having one or more CH ₃ partial structures as R ₃ preferably has 1 or more and 10 or less CH ₃ partial structures, more preferably 1 or more and 8 or less, More preferably, it is 1 or more and 4 or less.

The alkyl group having one or more CH ₃ partial structures in R ₃ is preferably a branched alkyl group having 3 to 20 carbon atoms.

  n represents an integer of 1 to 5, more preferably an integer of 1 to 3, and still more preferably 1 or 2.

  Preferred specific examples of the repeating unit represented by the general formula (III) are shown below. Note that the present invention is not limited to this.

  The repeating unit represented by the general formula (III) is preferably an acid-stable (non-acid-decomposable) repeating unit, and specifically, a group that decomposes by the action of an acid to generate a polar group. It is preferable that it is a repeating unit which does not have.

In the case where the hydrophobic resin (D) contains a CH ₃ partial structure in the side chain portion, and particularly when it does not have a fluorine atom and a silicon atom, the repeating unit represented by the general formula (II), and The content of at least one repeating unit (x) among the repeating units represented by the general formula (III) is preferably 90 mol% or more based on all repeating units of the hydrophobic resin (D). More preferably, it is 95 mol% or more. The content is usually 100 mol% or less with respect to all repeating units of the hydrophobic resin (D).

  The hydrophobic resin (D) comprises at least one repeating unit (x) among the repeating unit represented by the general formula (II) and the repeating unit represented by the general formula (III). ), The surface free energy of the hydrophobic resin (D) increases. As a result, the hydrophobic resin (D) is less likely to be unevenly distributed on the surface of the resist film, and the static / dynamic contact angle of the resist film with respect to water can be reliably improved and the immersion liquid followability can be improved. it can.

Further, the hydrophobic resin (D) includes the following (x) to (z) even when (i) contains a fluorine atom and / or silicon atom, and (ii) contains a CH ₃ partial structure in the side chain portion. It is preferable to have a repeating unit (b) having at least one group selected from the group consisting of:
(X) Alkali-soluble group (y) A group that decomposes by the action of an alkali developer and increases the solubility in an alkali developer (hereinafter also referred to as a polar conversion group).
(Z) A group that decomposes by the action of an acid to increase the solubility in an alkali developer. Examples of the repeating unit (b) include the following types.
A repeating unit (b ′) having at least one of a fluorine atom and a silicon atom and at least one group selected from the group consisting of the above (x) to (z) on one side chain
A repeating unit (b *) having at least one group selected from the group consisting of (x) to (z) and having no fluorine atom and no silicon atom
A fluorine atom and silicon on one side chain having at least one group selected from the group consisting of (x) to (z) and different from the side chain in the same repeating unit Repeating unit (b ″) having at least one of atoms
It is more preferable that the hydrophobic resin has a repeating unit (b ′) as the repeating unit (b). That is, it is more preferable that the repeating unit (b) having at least one group selected from the group consisting of the above (x) to (z) has at least one of a fluorine atom and a silicon atom.
When the hydrophobic resin has a repeating unit (b *), a repeating unit having at least one of a fluorine atom and a silicon atom (a repeating unit different from the above repeating units (b ′) and (b ″)) In addition, in the repeating unit (b ″), a side chain having at least one group selected from the group consisting of the above (x) to (z), and at least one of a fluorine atom and a silicon atom Are preferably bonded to the same carbon atom in the main chain, that is, in a positional relationship as shown in the following formula (K1).
In the formula, B1 represents a partial structure having at least one group selected from the group consisting of the above (x) to (z), and B2 represents a partial structure having at least one of a fluorine atom and a silicon atom.

The group selected from the group consisting of the above (x) to (z) is preferably (x) an alkali-soluble group or (y) a polar conversion group, and more preferably (y) a polar conversion group.
Examples of the alkali-soluble group (x) include phenolic hydroxyl group, carboxylic acid group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) ( Alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) ) And a methylene group.
Preferred alkali-soluble groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and bis (carbonyl) methylene groups.
As the repeating unit (bx) having an alkali-soluble group (x), a repeating unit in which an alkali-soluble group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a linking group is used. Examples include repeating units in which an alkali-soluble group is bonded to the main chain of the resin, and a polymerization initiator or chain transfer agent having an alkali-soluble group can also be introduced at the end of the polymer chain during polymerization. In any case, it is preferable.
When the repeating unit (bx) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, when the repeating unit (bx) corresponds to the repeating unit (b ′) or (b ″)), the repeating unit (bx) Examples of the partial structure having a fluorine atom include the same ones as mentioned in the repeating unit having at least one of the fluorine atom and the silicon atom, and preferably represented by the general formulas (F2) to (F4). In this case, the partial structure having a silicon atom in the repeating unit (bx) is the same as that described in the repeating unit having at least one of the fluorine atom and the silicon atom. Preferably, groups represented by the above general formulas (CS-1) to (CS-3) can be exemplified.
The content of the repeating unit (bx) having an alkali-soluble group (x) is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, still more preferably from 5 to 20 mol, based on all repeating units in the hydrophobic resin. %.
Specific examples of the repeating unit (bx) having an alkali-soluble group (x) include the repeating unit disclosed in paragraph 0595 of US Published Patent Application 2012/0135348, but the present invention is not limited thereto. Is not to be done.

Examples of the polar conversion group (y) include a lactone group, a carboxylic acid ester group (—COO—), an acid anhydride group (—C (O) OC (O) —), an acid imide group (—NHCONH—), A carboxylic acid thioester group (—COS—), a carbonic acid ester group (—OC (O) O—), a sulfate ester group (—OSO ₂ O—), a sulfonic acid ester group (—SO ₂ O—), and the like. A lactone group is preferred.
The polarity converting group (y) is, for example, introduced into the side chain of the resin by being included in a repeating unit of acrylic acid ester or methacrylic acid ester, or a polymerization initiator or chain having the polarity converting group (y). Any form in which a transfer agent is introduced at the end of the polymer chain using the polymerization is preferred.
Specific examples of the repeating unit (by) having a polar conversion group (y) include a repeating unit having a lactone structure represented by formulas (KA-1-1) to (KA-1-17) described later. Can do.
Further, the repeating unit (by) having the polarity converting group (y) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, the repeating unit (b ′), (b ″) corresponds to the above repeating unit (b ′)). The resin having the repeating unit (by) is hydrophobic, but is particularly preferable from the viewpoint of reducing development defects.
As the repeating unit (by), for example, a repeating unit represented by the formula (K0) can be given.

In the formula, R _k1 represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an aryl group, or a group containing a polarity converting group.
R _k2 represents an alkyl group, a cycloalkyl group, an aryl group, or a group containing a polarity converting group.
However, at least one of R _k1 and R _k2 represents a group containing a polarity converting group.
The polarity converting group represents a group that decomposes by the action of an alkali developer and increases the solubility in the alkali developer as described above. The polar conversion group is preferably a group represented by X in the partial structure represented by the general formula (KA-1) or (KB-1).

X in the general formula (KA-1) or (KB-1) is a carboxylic acid ester group: —COO—, an acid anhydride group: —C (O) OC (O) —, an acid imide group: —NHCONH—, Carboxylic acid thioester group: —COS—, carbonate ester group: —OC (O) O—, sulfate ester group: —OSO ₂ O—, sulfonate ester group: —SO ₂ O—.
Y ¹ and Y ² may be the same or different and each represents an electron-withdrawing group.
The repeating unit (by) has a group that increases the solubility in a preferable alkali developer by having a group having a partial structure represented by the general formula (KA-1) or (KB-1). Is a bond having a bond as in the case of the partial structure represented by the general formula (KA-1) and the partial structure represented by (KB-1) when Y ¹ and Y ² are monovalent. When it does not have, the group having a partial structure is a group having a monovalent or higher valent group excluding at least one arbitrary hydrogen atom in the partial structure.
The partial structure represented by the general formula (KA-1) or (KB-1) is linked to the main chain of the hydrophobic resin through a substituent at an arbitrary position.
The partial structure represented by the general formula (KA-1) is a structure that forms a ring structure (for example, an alicyclic structure) together with a group as X.

X in the general formula (KA-1) is preferably a carboxylic acid ester group (that is, when a lactone ring structure is formed as KA-1), an acid anhydride group, or a carbonic acid ester group. More preferably, it is a carboxylic acid ester group.
The ring structure represented by the general formula (KA-1) may have a substituent, for example, may have nka substituents Z _ka1 .
Z _ka1 represents a halogen atom, an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group, or an electron withdrawing group. If Z _ka1 there are a plurality, each _{Z ka1} may or may not be the same.
Z _ka1 may be linked to form a ring. Examples of the ring formed by connecting Z _{ka1 to} each other include a cycloalkyl ring and a hetero ring (a cyclic ether ring, a lactone ring, etc.).
nka represents an integer of 0 to 10. Preferably it is an integer of 0 to 8, more preferably an integer of 0 to 5, more preferably an integer of 1 to 4, and most preferably an integer of 1 to 3.
The electron withdrawing group as Z _{ka1 is the same} as the electron withdrawing group as Y ¹ and Y ² described later. The electron withdrawing group may be substituted with another electron withdrawing group.
Z _ka1 is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, or an electron withdrawing group, and more preferably an alkyl group, a cycloalkyl group, or an electron withdrawing group. The ether group is preferably an ether group substituted with an alkyl group or a cycloalkyl group, that is, an alkyl ether group. The electron withdrawing group is as defined above.
Examples of the halogen atom as Z _ka1 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

The alkyl group as Z _ka1 may have a substituent and may be linear or branched. The linear alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. The branched alkyl group preferably has 3 to 30 carbon atoms, and more preferably 3 to 20 carbon atoms. C1-C4 things, such as a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, t-butyl group, are preferable.
The cycloalkyl group as Z _ka1 may have a substituent, and may be monocyclic or polycyclic. In the case of a polycyclic type, the cycloalkyl group may be a bridged type. That is, in this case, the cycloalkyl group may have a bridged structure. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group. Examples of the polycyclic type include groups having a bicyclo, tricyclo, tetracyclo structure or the like having 5 or more carbon atoms, and a cycloalkyl group having 6 to 20 carbon atoms is preferable. For example, an adamantyl group, norbornyl group, isobornyl group, Examples thereof include a camphanyl group, a dicyclopentyl group, an α-pinel group, a tricyclodecanyl group, a tetocyclododecyl group, and an androstanyl group. As the cycloalkyl group, structural formulas (1) to (50) disclosed in paragraph 0619 of US Patent Publication No. 2012/0135348 are also preferable. Note that at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.
Preferred examples of the alicyclic moiety include an adamantyl group, a noradamantyl group, a decalin group, a tricyclodecanyl group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclodecanyl group. And cyclododecanyl group. More preferred are an adamantyl group, a decalin group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, a cyclododecanyl group, and a tricyclodecanyl group.
Examples of the substituent of these alicyclic structures include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group.

Moreover, the said group may have a substituent further.
X in the general formula (KA-1) is a carboxylic acid ester group, and the partial structure represented by the general formula (KA-1) is preferably a lactone ring, and more preferably a 5- to 7-membered lactone ring.
In addition, as in the following (KA-1-1) to (KA-1-17), a 5- to 7-membered lactone ring as a partial structure represented by the general formula (KA-1) has a bicyclo structure, a spiro It is preferred that other ring structures are condensed in a form that forms the structure.
As for the peripheral ring structure to which the ring structure represented by the general formula (KA-1) may be bonded, for example, those in the following (KA-1-1) to (KA-1-17), or The thing according to can be mentioned.

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

The structure containing the lactone ring structure may or may not have a substituent. Preferable substituents include those similar to the substituent Z _ka1 that the ring structure represented by the general formula (KA-1) may have.
Preferred examples of X in the general formula (KB-1) include a carboxylic acid ester group (—COO—).
Y ¹ and Y ² in formula (KB-1) each independently represent an electron-withdrawing group.
The electron withdrawing group is a partial structure represented by the following formula (EW). * In the formula (EW) represents a bond directly connected to (KA-1) or a bond directly connected to X in (KB-1).

In formula (EW),
R _ew1 and R _ew2 each independently represent an arbitrary substituent, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
n _ew is the repeating number of the linking group represented by —C (R _ew1 ) (R _ew2 ) — and represents an integer of 0 or 1. When n _ew is 0, it represents a single bond, indicating that Y _ew1 is directly bonded.
Y _ew1 is a halogen atom, a cyano group, a nitrile group, a nitro group, a halo (cyclo) alkyl group or a haloaryl group represented by —C (R _f1 ) (R _f2 ) —R _f3 , an oxy group, a carbonyl group, a sulfonyl group Examples thereof include a group, a sulfinyl group, and a combination thereof. The electron-withdrawing group may have the following structure, for example. The “halo (cyclo) alkyl group” represents an alkyl group and a cycloalkyl group that are at least partially halogenated, and the “haloaryl group” represents an aryl group that is at least partially halogenated. In the following structural formula, R _ew3 and R _ew4 each independently represent an arbitrary structure. R _ew3 and R _ew4 may have any structure, and the partial structure represented by the formula (EW) may have an electron withdrawing property, and may be linked to, for example, the main chain of the resin. An alkyl group and a fluorinated alkyl group;

When Y _ew1 is a divalent or higher group, the remaining bond forms a bond with an arbitrary atom or substituent. At least one group of Y _ew1 , R _ew1 , and R _ew2 may be connected to the main chain of the hydrophobic resin through a further substituent.
Y _ew1 is preferably a halogen atom, or a halo (cyclo) alkyl group or haloaryl group represented by —C (R _f1 ) (R _f2 ) —R _f3 .
At least two of R _ew1 , R _ew2 and Y _ew1 may be connected to each other to form a ring.
Here, R _f1 represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group, or a perhaloaryl group, more preferably a fluorine atom, a perfluoroalkyl group, or a perfluorocycloalkyl group, still more preferably a fluorine atom or a trialkyl group. Represents a fluoromethyl group.
R _f2 and R _f3 each independently represent a hydrogen atom, a halogen atom or an organic group, and R _f2 and R _f3 may be linked to form a ring. Examples of the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group. More preferably, R _f2 represents the same group as R _f1 or is linked to R _f3 to form a ring.
R _{f1 to} R _f3 may be linked to form a ring, and examples of the ring formed include a (halo) cycloalkyl ring and a (halo) aryl ring.
Examples of the (halo) alkyl group in R _{f1 to} R _f3 include the alkyl group in Z _ka1 described above and a structure in which this is halogenated.
Examples of the (per) halocycloalkyl group and the (per) haloaryl group in R _{f1 to} R _f3 or in the ring formed by linking R _f2 and R _f3 include, for example, the aforementioned cycloalkyl group in Z _ka1 is a halogen atom. And a perfluoroaryl group represented by -C _(n) F _(n-1) and more preferably a fluorocycloalkyl group represented by -C _(n) F _(2n-2) H Can be mentioned. Although carbon number n is not specifically limited here, the thing of 5-13 is preferable and 6 is more preferable.
The ring that may be formed by linking at least two of R _ew1 , R _ew2 and Y _ew1 preferably includes a cycloalkyl group or a heterocyclic group, and the heterocyclic group is preferably a lactone ring group. Examples of the lactone ring include structures represented by the above formulas (KA-1-1) to (KA-1-17).
In the repeating unit (by), a plurality of partial structures represented by the general formula (KA-1), a plurality of partial structures represented by the general formula (KB-1), or a general formula (KA) It may have both a partial structure represented by -1) and a partial structure represented by the general formula (KB-1).

Note that part or all of the partial structure of the general formula (KA-1) may also serve as an electron withdrawing group as Y ¹ or Y ² in the general formula (KB-1). For example, when X in the general formula (KA-1) is a carboxylic acid ester group, the carboxylic acid ester group functions as an electron withdrawing group as Y ¹ or Y ² in the general formula (KB-1). There is also a possibility.
In addition, when the repeating unit (by) corresponds to the repeating unit (b *) or the repeating unit (b ″) and has a partial structure represented by the general formula (KA-1), the general formula (KA) As for the partial structure represented by -1), it is more preferable that the polarity conversion group is a partial structure represented by -COO- in the structure represented by the general formula (KA-1).

  The repeating unit (by) can be a repeating unit having a partial structure represented by the general formula (KY-0).

In the general formula (KY-0),
R ₂ represents a chain or cyclic alkylene group, and when there are a plurality of R ₂ groups, they may be the same or different.
R ₃ represents a linear, branched or cyclic hydrocarbon group in which part or all of the hydrogen atoms on the constituent carbons are substituted with fluorine atoms.
R ₄ is a halogen atom, cyano group, hydroxy group, amide group, alkyl group, cycloalkyl group, alkoxy group, phenyl group, acyl group, alkoxycarbonyl group, or R—C (═O) — or R—C ( = O) A group represented by O- (R represents an alkyl group or a cycloalkyl group). When there are a plurality of R _{4 s} , they may be the same or different, and two or more R ₄ may be bonded to form a ring.
X represents an alkylene group, an oxygen atom, or a sulfur atom.
Z and Za represent a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond, and when there are a plurality of them, they may be the same or different.
* Represents a bond to the main chain or side chain of the resin.
o is the number of substituents and represents an integer of 1 to 7.
m is the number of substituents and represents an integer of 0 to 7.
n represents the number of repetitions and represents an integer of 0 to 5.

The structure represented by —R ₂ —Z— is preferably a structure represented by — (CH ₂ ) ₁ —COO— (l represents an integer of 1 to 5).
The preferred carbon number range and specific examples of the chain or cyclic alkylene group as R ₂ are the same as those described for the chain alkylene group and cyclic alkylene group in Z ₂ of the general formula (bb).
The linear, branched or cyclic hydrocarbon group as R ₃ has preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and preferably 3 carbon atoms when branched. -30, more preferably 3-20, and in the case of a ring, it is 6-20. Specific examples of R ₃ include specific examples of the alkyl group and cycloalkyl group as Z _ka1 described above.
Preferred carbon numbers and specific examples of the alkyl group and cycloalkyl group as R ₄ and R are the same as those described in the alkyl group and cycloalkyl group as Z _ka1 described above.
The acyl group as R ₄ is preferably one having 1 to 6 carbon atoms, and examples thereof include a formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, and pivaloyl group.
Examples of the alkyl moiety in the alkoxy group and alkoxycarbonyl group as R ₄ include a linear, branched or cyclic alkyl moiety, and the preferred carbon number of the alkyl moiety and specific examples thereof are those described above for Z _ka1. The same as those described in the alkyl group and cycloalkyl group.
Examples of the alkylene group as X include a chain or cyclic alkylene group, and preferred carbon numbers and specific examples thereof are the same as those described for the chain alkylene group and cyclic alkylene group as R ₂ .
Moreover, the repeating unit which has a partial structure shown below as a specific structure of a repeating unit (by) is mentioned.

In general formulas (rf-1) and (rf-2),
X ′ represents an electron-attracting substituent, preferably a carbonyloxy group, an oxycarbonyl group, an alkylene group substituted with a fluorine atom, or a cycloalkylene group substituted with a fluorine atom.
A represents a single bond or a divalent linking group represented by -C (Rx) (Ry)-. Here, Rx and Ry are each independently a hydrogen atom, a fluorine atom, an alkyl group (preferably having 1 to 6 carbon atoms and optionally substituted with a fluorine atom or the like), or a cycloalkyl group (preferably a carbon atom). And may be substituted with a fluorine atom or the like. Rx and Ry are preferably a hydrogen atom, an alkyl group, or an alkyl group substituted with a fluorine atom.

X represents an electron withdrawing group, and specific examples thereof include the above-mentioned electron withdrawing groups as Y ¹ and Y ² , preferably a fluorinated alkyl group or a fluorinated cycloalkyl group. An aryl group substituted with a fluorine or fluorinated alkyl group, an aralkyl group substituted with a fluorine or fluorinated alkyl group, a cyano group, or a nitro group.
* Represents a bond to the main chain or side chain of the resin. That is, it represents a bond that is bonded to the main chain of the resin through a single bond or a linking group.
In addition, when X 'is a carbonyloxy group or an oxycarbonyl group, A is not a single bond.
When the polarity conversion group is decomposed by the action of the alkali developer and the polarity is changed, the receding contact angle with water of the resist film after alkali development can be lowered. It is preferable from the viewpoint of suppressing development defects that the receding contact angle with water of the film after alkali development is lowered.
The receding contact angle with water of the resist film after alkali development is preferably 50 ° or less at a temperature of 23 ± 3 ° C. and a humidity of 45 ± 5%, more preferably 40 ° or less, still more preferably 35 ° or less. Most preferably, it is 30 ° or less.

The receding contact angle is a contact angle measured when the contact line at the droplet-substrate interface recedes, and is useful for simulating the ease of movement of the droplet in a dynamic state. It is generally known. In simple terms, it can be defined as the contact angle when the droplet interface recedes when the droplet discharged from the needle tip is deposited on the substrate and then sucked into the needle again. It can be measured by using a contact angle measuring method generally called an expansion / contraction method.
The hydrolysis rate of the hydrophobic resin with respect to the alkaline developer is preferably 0.001 nm / second or more, more preferably 0.01 nm / second or more, still more preferably 0.1 nm / second or more, Most preferably, it is 1 nm / second or more.
Here, the hydrolysis rate of the hydrophobic resin with respect to the alkaline developer was 23 ° C. when TMAH (tetramethylammonium hydroxide aqueous solution) (2.38 mass%) was used to form the resin film with only the hydrophobic resin. This is the rate at which the film thickness decreases.
The repeating unit (by) is more preferably a repeating unit having at least two or more polar conversion groups.
When the repeating unit (by) has at least two polar conversion groups, the repeating unit (by) preferably has a group having a partial structure having two polar conversion groups represented by the following general formula (KY-1). In addition, when the structure represented by general formula (KY-1) does not have a bond, it is a group having a monovalent or higher valent group in which at least one arbitrary hydrogen atom in this structure is removed.

In general formula (KY-1),
R _ky1 and R _ky4 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, carbonyl group, carbonyloxy group, oxycarbonyl group, ether group, hydroxyl group, cyano group, amide group, or aryl group Represents. Alternatively, R _ky1 and R _ky4 may be bonded to the same atom to form a double bond. For example, R _ky1 and R _ky4 are bonded to the same oxygen atom to form a part of a carbonyl group (═O). May be formed.
R _ky2 and R _ky3 are each independently an electron withdrawing group, or R _ky1 and R _ky2 are linked to form a lactone ring and R _ky3 is an electron withdrawing group. As the lactone ring to be formed, the structures (KA-1-1) to (KA-1-17) are preferable. Examples of the electron withdrawing group include those similar to Y ₁ and Y ₂ in the above formula (KB-1), and preferably a halogen atom or the above —C (R _f1 ) (R _f2 ) —R _f3. A halo (cyclo) alkyl group or a haloaryl group represented by the formula: Preferably _{R ky3} halogen atom, or, the _{-C (R f1)} (R f2) halo (cyclo) alkyl groups or haloaryl groups represented by _{-R f3,} lactone _{R ky2} is linked to _{R ky1} An electron withdrawing group that forms a ring or has no halogen atom.
R _ky1 , R _ky2 , and R _ky4 may be connected to each other to form a monocyclic or polycyclic structure.
Specific examples of R _ky1 and R _ky4 include the same groups as Z _ka1 in formula (KA-1).
As the lactone ring formed by linking R _ky1 and R _ky2 , the structures (KA-1-1) to (KA-1-17) are preferable. Examples of the electron withdrawing group include those similar to Y ₁ and Y ₂ in the above formula (KB-1).
The structure represented by the general formula (KY-1) is more preferably a structure represented by the following general formula (KY-2). Note that the structure represented by the general formula (KY-2) is a group having a monovalent or higher group obtained by removing at least one arbitrary hydrogen atom in the structure.

In formula (KY-2),
R _{ky6 to} R _ky10 are each independently a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, carbonyl group, carbonyloxy group, oxycarbonyl group, ether group, hydroxyl group, cyano group, amide group, or aryl. Represents a group.
Two or more of R _{ky6 to} R _ky10 may be linked to each other to form a monocyclic or polycyclic structure.
R _ky5 represents an electron withdrawing group. Examples of the electron withdrawing group include the same groups as those described above for Y ₁ and Y ₂ , preferably a halogen atom or a halo (cyclo (cyclo) represented by —C (R _f1 ) (R _f2 ) —R _f3 above. ) An alkyl group or a haloaryl group.
Specific examples of R _{ky5 to} R _ky10 include the same groups as Z _ka1 in formula (KA-1).
The structure represented by the formula (KY-2) is more preferably a partial structure represented by the following general formula (KY-3).

In the formula (KY-3), Z _ka1 and nka are each synonymous with the general formula (KA-1). R _ky5 is synonymous with the above formula (KY-2).
L _ky represents an alkylene group, an oxygen atom or a sulfur atom. _Examples of the alkylene group for L _ky include a methylene group and an ethylene group. L _ky is preferably an oxygen atom or a methylene group, and more preferably a methylene group.
The repeating unit (b) is not limited as long as it is a repeating unit obtained by polymerization such as addition polymerization, condensation polymerization, addition condensation, etc., but is a repeating unit obtained by addition polymerization of a carbon-carbon double bond. Preferably there is. Examples include acrylate-based repeating units (including those having substituents at the α-position and β-position), styrene-based repeating units (including those having substituents at the α-position and β-position), vinyl ether-based repeating units, norbornene-based Repeating units, maleic acid derivatives (maleic anhydride and derivatives thereof, maleimides, etc.), and the like, acrylate-based repeating units, styrene-based repeating units, vinyl ether-based repeating units, norbornene-based repeating units Preferred are acrylate repeat units, vinyl ether repeat units, and norbornene repeat units, with acrylate repeat units being most preferred.

When the repeating unit (by) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, when the repeating unit (by) corresponds to the above repeating unit (b ′) or (b ″)), the repeating unit (by) Examples of the partial structure having a fluorine atom include the same ones as mentioned in the repeating unit having at least one of the fluorine atom and the silicon atom, and preferably represented by the general formulas (F2) to (F4). In this case, the partial structure having a silicon atom in the repeating unit (by) has the same structure as that described in the repeating unit having at least one of the fluorine atom and the silicon atom. Preferably, groups represented by the above general formulas (CS-1) to (CS-3) can be exemplified.
The content of the repeating unit (by) in the hydrophobic resin is preferably from 10 to 100 mol%, more preferably from 20 to 99 mol%, still more preferably from 30 to 97 mol%, based on all repeating units in the hydrophobic resin. Most preferably, it is 40-95 mol%.
Specific examples of the repeating unit (by) having a group that increases the solubility in an alkali developer include the repeating unit disclosed in paragraph 0725 of US Patent Publication No. 2012/0135348. It is not limited.

  As the monomer having a polar conversion group (y) (a monomer serving as a repeating unit having a polar conversion group (y)), a monomer represented by the following general formula (D-1) is also preferable.

Wherein M is a polymerizable functional group including vinyl and acrylic, R is an alkyl spacer group with or without a carboxyl linkage (eg, C1-20 linear, branched or cyclic), and Rf Is a fluoro or perfluoroalkyl group (e.g. C1-20 alkyl having 1 to 8 fluorine atoms) in which at least the alpha carbon (the carbon next to the carbonyl carbon) is fluorinated, and n is an integer greater than or equal to 1 It is.
Specific examples of the monomer represented by formula (D-1) include the following monomers.

  As the repeating unit having a polar conversion group (y), a repeating unit represented by the following general formula (S-1) is also preferable.

In the formula, R ^f1 represents a hydrogen atom or a methyl group. A ^f1 represents an alkanediyl group having 1 to 6 carbon atoms. R ^f2 represents a C 1-10 hydrocarbon group having a fluorine atom.
Specific examples of the repeating unit represented by the general formula (S-1) include the following repeating units.

Examples of the method for synthesizing the monomer corresponding to the repeating unit (by) having the polar conversion group (y) as described above include the method described in International Publication No. 2010/069705, International Publication No. 2010/069705, or the like. Can be synthesized with reference to
Examples of the repeating unit (bz) having a group (z) capable of decomposing by the action of an acid in the hydrophobic resin include the same repeating units having an acid-decomposable group as mentioned for the resin A.
When the repeating unit (bz) is a repeating unit having at least one of a fluorine atom and a silicon atom (that is, when the repeating unit corresponds to the above repeating unit (b ′) or (b ″)), the repeating unit (bz) Examples of the partial structure having a fluorine atom include the same ones as mentioned in the repeating unit having at least one of the fluorine atom and the silicon atom, and preferably represented by the general formulas (F2) to (F4). In this case, the partial structure having a silicon atom in the repeating unit (by) has the same structure as that described in the repeating unit having at least one of the fluorine atom and the silicon atom. Preferably, groups represented by the above general formulas (CS-1) to (CS-3) can be exemplified.

In the hydrophobic resin, the content of the repeating unit (bz) having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol%, more preferably based on all repeating units in the hydrophobic resin. It is 10-80 mol%, More preferably, it is 20-60 mol%.
Hereinabove, the repeating unit (b) having at least one group selected from the group consisting of the above (x) to (z) has been described, but the content of the repeating unit (b) in the hydrophobic resin is hydrophobic. It is preferably 1 to 98 mol%, more preferably 3 to 98 mol%, still more preferably 5 to 97 mol%, and most preferably 10 to 95 mol% with respect to all repeating units in the conductive resin.
The content of the repeating unit (b ′) is preferably 1 to 100 mol%, more preferably 3 to 99 mol%, still more preferably 5 to 97 mol%, and most preferably 10 to 10 mol% with respect to all repeating units in the hydrophobic resin. 95 mol%.
The content of the repeating unit (b *) is preferably from 1 to 90 mol%, more preferably from 3 to 80 mol%, still more preferably from 5 to 70 mol%, most preferably from 10 to 10%, based on all repeating units in the hydrophobic resin. 60 mol%. The content of the repeating unit having at least one of a fluorine atom and a silicon atom used together with the repeating unit (b *) is preferably 10 to 99 mol%, more preferably 20 with respect to all repeating units in the hydrophobic resin. It is -97 mol%, More preferably, it is 30-95 mol%, Most preferably, it is 40-90 mol%.
The content of the repeating unit (b ″) is preferably 1 to 100 mol%, more preferably 3 to 99 mol%, still more preferably 5 to 97 mol%, and most preferably 10 to 10 mol% based on all repeating units in the hydrophobic resin. 95 mol%.

The hydrophobic resin (D) may further have a repeating unit represented by the general formula (III) described in paragraphs [0292] to [0294] of JP-A-2014-232310.
The hydrophobic resin (D) preferably further has a repeating unit represented by the general formula (CII-AB) described in paragraphs [0296] to [0299] of JP 2014-232310. .

When the hydrophobic resin (D) has a fluorine atom, the content of the fluorine atom is preferably 5 to 80% by mass with respect to the weight average molecular weight of the hydrophobic resin (D), and is 10 to 80% by mass. More preferably. Moreover, it is preferable that it is 10-100 mol% in all the repeating units contained in hydrophobic resin (D), and, as for the repeating unit containing a fluorine atom, it is more preferable that it is 30-100 mol%.
When the hydrophobic resin (D) has a silicon atom, the content of the silicon atom is preferably 2 to 50% by mass, and 2 to 30% by mass with respect to the weight average molecular weight of the hydrophobic resin (D). More preferably. Moreover, it is preferable that the repeating unit containing a silicon atom is 10-100 mol% in all the repeating units contained in hydrophobic resin (D), and it is more preferable that it is 20-100 mol%.

On the other hand, particularly when the hydrophobic resin (D) contains a CH ₃ partial structure in the side chain portion, it is also preferable that the resin (D) contains substantially no fluorine atom or silicon atom. The content of the repeating unit having a fluorine atom or a silicon atom is preferably 5 mol% or less, more preferably 3 mol% or less, based on all repeating units in the hydrophobic resin (D). It is preferably 1 mol% or less, ideally 0 mol%, that is, it does not contain a fluorine atom and a silicon atom. Moreover, it is preferable that hydrophobic resin (D) is substantially comprised only by the repeating unit comprised only by the atom chosen from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom, and a sulfur atom. More specifically, the repeating unit composed only of atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom is 95 mol% or more in all the repeating units of the hydrophobic resin (D). It is preferably 97 mol% or more, more preferably 99 mol% or more, and ideally 100 mol%.

The weight average molecular weight of the hydrophobic resin (D) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and still more preferably 2,000 to 15,000. is there.
In addition, the hydrophobic resin (D) may be used alone or in combination.
The content of the hydrophobic resin (D) in the composition is preferably 0.01 to 10% by mass, and 0.05 to 8% by mass with respect to the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition. % Is more preferable, and 0.1-7 mass% is still more preferable.

  As for the hydrophobic resin (D), as in the resin (A), it is natural that the residual monomer and oligomer components are preferably 0.01 to 5% by mass, and more preferably less impurities such as metals. Is more preferably 0.01 to 3% by mass and 0.05 to 1% by mass. As a result, an actinic ray-sensitive or radiation-sensitive resin composition that does not change over time such as foreign matter in liquid or sensitivity can be obtained. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, more preferably 1 to 3, and still more preferably from the viewpoints of resolution, resist shape, resist pattern sidewall, roughness, and the like. It is the range of 1-2.

As the hydrophobic resin (D), various commercially available products can be used, and the hydrophobic resin (D) can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and heating is performed, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours. The dropping polymerization method is added, and the dropping polymerization method is preferable.
The reaction solvent, the polymerization initiator, the reaction conditions (temperature, concentration, etc.) and the purification method after the reaction are the same as those described for the resin (A), but in the synthesis of the hydrophobic resin (D), The reaction concentration is preferably 30 to 50% by mass.

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

[5] Basic compound The actinic ray-sensitive or radiation-sensitive resin composition used in the present invention may contain a basic compound in order to reduce a change in performance over time from exposure to heating. Although the basic compound which can be used is not specifically limited, For example, the compound classified into the following (1)-(5) can be used.

(1) Basic compound (N)
Preferred examples of the basic compound include compounds (N) having a structure represented by the following formulas (A) to (E).

In general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and are a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (having a carbon number). 6-20), wherein R ²⁰¹ and R ²⁰² may combine with each other to form a ring.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.

About the said alkyl group, as an alkyl group which has a substituent, a C1-C20 aminoalkyl group, a C1-C20 hydroxyalkyl group, or a C1-C20 cyanoalkyl group is preferable.
The alkyl groups in these general formulas (A) and (E) are more preferably unsubstituted.
Preferable compound (N) includes guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, and more preferable compound (N) includes imidazole structure, diazabicyclo structure, onium hydroxy group. Compound (N) having an alkyl group 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. Specific examples thereof include the compounds described in paragraph [0321] of JP 2014-232310.

  Preferred examples of the basic compound (N) further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group. Examples of these compounds include compounds (C1-1) to (C3-3) exemplified in paragraph [0066] of US Patent Application Publication No. 2007 / 0224539A1.

  The following compounds are also preferable as the basic compound (N).

As the basic compound (N), in addition to the above-mentioned compounds, paragraphs [0180] to [0225] of JP2011-22560A, paragraphs [0218] to [0219] of JP2012-137735A, The compounds described in paragraphs [0416] to [0438] of International Publication No. 2011/158687 can also be used. The basic compound (N) may be a basic compound or an ammonium salt compound whose basicity is lowered by irradiation with actinic rays or radiation.
These basic compounds (N) may be used alone or in combination of two or more.

The actinic ray-sensitive or radiation-sensitive resin composition may or may not contain the basic compound (N), but when it is contained, the content of the basic compound (N) is actinic ray-sensitive or The amount is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the solid content of the radiation-sensitive resin composition.
The use ratio of the acid generator and the basic compound (N) in the composition is preferably acid generator / basic compound (molar ratio) = 2.5 to 300. That is, the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing resolution from being reduced due to the thickening of the resist pattern over time until post-exposure heat treatment. The acid generator / basic compound (N) (molar ratio) is more preferably 5.0 to 200, still more preferably 7.0 to 150.

(2) Basic compound or ammonium salt compound (E) whose basicity is reduced by irradiation with actinic rays or radiation
The actinic ray-sensitive or radiation-sensitive resin composition may contain a basic compound or an ammonium salt compound (hereinafter also referred to as “compound (E)”) whose basicity is lowered by irradiation with actinic rays or radiation. preferable.
The compound (E) is preferably a compound (E-1) having a basic functional group or an ammonium group and a group that generates an acidic functional group upon irradiation with actinic rays or radiation. That is, the compound (E) is a basic compound having a basic functional group and a group capable of generating an acidic functional group upon irradiation with active light or radiation, or an acidic functional group upon irradiation with an ammonium group and active light or radiation. An ammonium salt compound having a group to be generated is preferable.
The compound (E) or (E-1) is decomposed by irradiation with actinic rays or radiation, and the compound with reduced basicity is represented by the following general formula (PA-I), (PA-II) or (PA -III) can be mentioned. In particular, from the viewpoint of achieving excellent effects on LWR (Line Width Roughness), local pattern dimension uniformity, and DOF (Depth of Focus) at a high level, the general formula (PA-II) or ( Compounds represented by PA-III) are preferred.
First, the compound represented by general formula (PA-I) is demonstrated.
_{Q-A 1 - (X)} n -B-R (PA-I)
In general formula (PA-I),
A ₁ represents a single bond or a divalent linking group.
Q represents -SO ₃ H, or -CO ₂ H. Q corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.
X represents —SO ₂ — or —CO—.
n represents 0 or 1.
B represents a single bond, an oxygen atom or -N (Rx)-.
Rx represents a hydrogen atom or a monovalent organic group.
R represents a monovalent organic group having a basic functional group or a monovalent organic group having an ammonium group.
Next, the compound represented by general formula (PA-II) is demonstrated.
_{Q 1 -X 1 -NH-X 2} -Q 2 (PA-II)
In general formula (PA-II),
Q ₁ and Q ₂ each independently represents a monovalent organic group. However, either Q ₁ or Q ₂ has a basic functional group. Q ₁ and Q ₂ may combine to form a ring, and the formed ring may have a basic functional group.
X ₁ and X ₂ each independently represent —CO— or —SO ₂ —.
Note that —NH— corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.
Next, the compound represented by general formula (PA-III) is demonstrated.
_{Q 1 -X 1 -NH-X 2} -A 2 - (X 3) m -B-Q 3 (PA-III)
In general formula (PA-III),
Q ₁ and Q ₃ each independently represents a monovalent organic group. However, either Q ₁ or Q ₃ has a basic functional group. Q ₁ and Q ₃ may combine to form a ring, and the formed ring may have a basic functional group.
X ₁ , X ₂ and X ₃ each independently represent —CO— or —SO ₂ —.
A ₂ represents a divalent linking group.
B represents a single bond, an oxygen atom, or —N (Qx) —.
Qx represents a hydrogen atom or a monovalent organic group.
When B is —N (Qx) —, Q ₃ and Qx may combine to form a ring.
m represents 0 or 1.
Note that —NH— corresponds to an acidic functional group generated by irradiation with actinic rays or radiation.

  Hereinafter, although the specific example of a compound (E) is given, it is not limited to these. In addition to the exemplified compounds, preferred specific examples of the compound (E) include compounds (A-1) to (A-44) of US Patent Application Publication No. 2010/0233629, and US Patent Application Publication No. (A-1)-(A-23) of 2012/0156617 specification, etc. are mentioned.

It is preferable that the molecular weight of a compound (E) is 500-1000.
The actinic ray-sensitive or radiation-sensitive resin composition may or may not contain the compound (E), but when it is contained, the content of the compound (E) is the actinic ray-sensitive or radiation-sensitive resin. 0.1-20 mass% is preferable on the basis of solid content of the composition, more preferably 0.1-10 mass%.
Further, as one aspect of the compound (E), a compound (E-2) that generates an acid (weak acid) having a strength that does not decompose the acid-decomposable group of the resin (A) by acid irradiation or radiation irradiation. Can also be mentioned.
Examples of the compound include an onium salt of a carboxylic acid having no fluorine atom (preferably a sulfonium salt) and an onium salt of a sulfonic acid having no fluorine atom (preferably a sulfonium salt). More specifically, for example, among onium salts represented by the following general formula (6A), those in which the carboxylic acid anion does not have a fluorine atom, among onium salts represented by the following general formula (6B) Examples include those in which the sulfonate anion does not have a fluorine atom. As a cation structure of a sulfonium salt, the sulfonium cation structure mentioned by the acid generator (B) can be mentioned preferably.
More specifically, as compound (E-2), compounds listed in paragraph [0170] of International Publication No. 2012/053527, paragraphs [0268] to [0269] of JP2012-173419A, Compound etc. are mentioned.
A compound (E) may be used individually by 1 type, and may be used in combination of 2 or more type.

(3) Low molecular weight compound (F) having a nitrogen atom and a group capable of leaving by the action of an acid
The actinic ray-sensitive or radiation-sensitive resin composition may contain a compound having a nitrogen atom and a group capable of leaving by the action of an acid (hereinafter also referred to as “compound (F)”).
The group capable of leaving by the action of an acid is not particularly limited, but is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, and a carbamate group or a hemiaminal ether group. It is particularly preferred.
The molecular weight of the compound (N ″) having a group capable of leaving by the action of an acid is preferably 100 to 1000, more preferably 100 to 700, and particularly preferably 100 to 500.
As the compound (F), an amine derivative having a group capable of leaving by the action of an acid on the nitrogen atom is preferable.

  Compound (F) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group can be represented by the following general formula (d-1).

In general formula (d-1),
R _b is independently a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), or an aralkyl group. (Preferably having 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably having 1 to 10 carbon atoms). R _b may be connected to each other to form a ring.

The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by R _b are substituted with a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, and an oxo group, an alkoxy group, and a halogen atom. May be. The same applies to the alkoxyalkyl group represented by R _b .
R _b is preferably a linear or branched alkyl group, cycloalkyl group, or aryl group. More preferably, it is a linear or branched alkyl group or cycloalkyl group.

Examples of the ring formed by connecting two R _b to each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group, or a derivative thereof.
Specific examples of the structure represented by the general formula (d-1) include the structure disclosed in paragraph [0466] of US Patent Application Publication No. 2012/0135348. It is not limited.

  The compound (F) particularly preferably has a structure represented by the following general formula (6).

In the general formula (6), R _a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When l is 2, two R _a may be the same or different, and two R _a may be connected to each other to form a heterocyclic ring together with the nitrogen atom in the formula. The heterocyclic ring may contain a hetero atom other than the nitrogen atom in the formula.
R _b has the same meaning as R _b in formula (d-1), and preferred examples are also the same.
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l + m = 3.

In the general formula (6), an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group as R _a are groups in which the alkyl group, cycloalkyl group, aryl group, and aralkyl group as R _b may be substituted. It may be substituted with a group similar to the group described above.
Preferred examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by R _a (these alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with the above groups) The same group as the preferable example mentioned above about _Rb is mentioned.
Further, the heterocyclic ring formed by connecting R _a to each other preferably has 20 or less carbon atoms. For example, pyrrolidine, piperidine, morpholine, 1,4,5,6-tetrahydropyrimidine, 1,2,3 , 4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, 1H-1,2,3-triazole, 1,4,7 -Triazacyclononane, tetrazole, 7-azaindole, indazole, benzimidazole, imidazo [1,2-a] pyridine, (1S, 4S)-(+)-2,5-diazabicyclo [2.2.1] Heptane, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, indole, indoline, 1,2,3 -Groups derived from heterocyclic compounds such as tetrahydroquinoxaline, perhydroquinoline, 1,5,9-triazacyclododecane, and groups derived from these heterocyclic compounds derived from linear and branched alkanes Groups derived from cycloalkanes, groups derived from aromatic compounds, groups derived from heterocyclic compounds, hydroxyl groups, cyano groups, amino groups, pyrrolidino groups, piperidino groups, morpholino groups, oxo groups Or a group substituted with one or more of the above.

  Specific examples of the preferred compound (F) include, but are not limited to, compounds disclosed in paragraph [0475] of US Patent Application Publication No. 2012/0135348.

The compound represented by the general formula (6) can be synthesized based on JP2007-298869A, JP2009-199021A, and the like.
In the present invention, the low molecular compound (F) can be used singly or in combination of two or more.
The content of the compound (F) in the actinic ray-sensitive or radiation-sensitive resin composition is preferably 0.001 to 20% by mass, more preferably 0.001 based on the total solid content of the composition. -10 mass%, More preferably, it is 0.01-5 mass%.

(4) Onium salt Moreover, as a basic compound, you may include the onium salt represented by the following general formula (6A) or (6B). This onium salt is expected to control the diffusion of the generated acid in the resist system in relation to the acid strength of the photoacid generator usually used in the resist composition.

In general formula (6A),
Ra represents an organic group. However, those in which a fluorine atom is substituted for a carbon atom directly bonded to a carboxylic acid group in the formula are excluded. X ⁺ represents an onium cation.
In General Formula (6B), Rb represents an organic group. However, those in which a fluorine atom is substituted for a carbon atom directly bonded to the sulfonic acid group in the formula are excluded. X ⁺ represents an onium cation.

In the organic group represented by Ra and Rb, the atom directly bonded to the carboxylic acid group or sulfonic acid group in the formula is preferably a carbon atom. However, in this case, in order to make the acid relatively weaker than the acid generated from the above-mentioned photoacid generator, the fluorine atom does not substitute for the carbon atom directly bonded to the sulfonic acid group or carboxylic acid group.
Examples of the organic group represented by Ra and Rb include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and an aralkyl group having 7 to 30 carbon atoms. Or a C3-C30 heterocyclic group etc. are mentioned. In these groups, some or all of the hydrogen atoms may be substituted.
Examples of the substituent that the alkyl group, cycloalkyl group, aryl group, aralkyl group and heterocyclic group may have include a hydroxyl group, a halogen atom, an alkoxy group, a lactone group, and an alkylcarbonyl group.

Examples of the onium cation represented by X ⁺ in the general formulas (6A) and (6B) include a sulfonium cation, an ammonium cation, an iodonium cation, a phosphonium cation, and a diazonium cation. Of these, a sulfonium cation is more preferable.
As the sulfonium cation, for example, an arylsulfonium cation having at least one aryl group is preferable, and a triarylsulfonium cation is more preferable. The aryl group may have a substituent, and the aryl group is preferably a phenyl group.
As examples of the sulfonium cation and the iodonium cation, the aforementioned sulfonium cation structure of the general formula (ZI) and the iodonium structure of the general formula (ZII) in the compound (B) can also be preferably exemplified.

A specific structure of the onium salt represented by the general formula (6A) or (6B) is shown below.
In addition, onium salt may be used individually by 1 type, and may be used in combination of 2 or more types.

(5) Betaine compound Furthermore, the composition includes a compound contained in formula (I) of JP2012-189777A, a compound represented by formula (I) of JP2013-6827A, and JP2013- Both an onium salt structure and an acid anion structure in one molecule, such as a compound represented by the formula (I) of No. 8020 and a compound represented by the formula (I) of JP 2012-252124 A A compound having the same (hereinafter also referred to as betaine compound) can be preferably used. Examples of the onium salt structure include a sulfonium, iodonium, and ammonium structure, and a sulfonium or iodonium salt structure is preferable. Moreover, as an acid anion structure, a sulfonate anion or a carboxylate anion is preferable. Examples of this compound include the following.
In addition, a betaine compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  The actinic ray-sensitive or radiation-sensitive resin composition used in the present invention is composed of (1) a basic compound (N), (2) a basic compound or ammonium whose basicity is reduced by irradiation with an actinic ray or radiation. Selected from the group consisting of a salt compound (E), (3) a low molecular compound (F) having a nitrogen atom and a group capable of leaving by the action of an acid, (4) an onium salt, and (5) a betaine compound. Two or more compounds may be contained.

[6] Surfactant (F)
The actinic ray-sensitive or radiation-sensitive resin composition used in the present invention may further contain a surfactant. In the case of containing a surfactant, either fluorine and / or silicon surfactant (fluorine surfactant, silicon surfactant, surfactant having both fluorine atom and silicon atom), or two kinds It is more preferable to contain the above.

When the actinic ray-sensitive or radiation-sensitive resin composition contains a surfactant, a resist pattern with good sensitivity and resolution and less adhesion and development defects when using an exposure light source of 250 nm or less, particularly 220 nm or less. Can be given.
As surfactants such as fluorine-based and / or silicon-based surfactants, for example, surfactants described in paragraphs [0353] to [0355] of JP 2014-232310 A can be used.

  These surfactants may be used alone or in several combinations.

When the actinic ray-sensitive or radiation-sensitive resin composition contains a surfactant, the amount of the surfactant used is based on the total amount of the actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent). Preferably it is 0.0001-2 mass%, More preferably, it is 0.0005-1 mass%.
On the other hand, when the amount of the surfactant added is 10 ppm or less with respect to the total amount of the actinic ray-sensitive or radiation-sensitive resin composition (excluding the solvent), the surface unevenness of the hydrophobic resin is increased. As a result, the surface of the resist film can be made more hydrophobic, and the water followability during immersion exposure can be improved.

[7] Other additives (G)
The actinic ray-sensitive or radiation-sensitive resin composition includes an acid proliferator, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, and a compound that promotes solubility in a developer ( For example, a phenol compound having a molecular weight of 1000 or less, an alicyclic compound having a carboxyl group, or an aliphatic compound) may be contained.

Such a phenol compound having a molecular weight of 1000 or less is disclosed in, for example, JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294, and the like. It can be easily synthesized by those skilled in the art with reference to the method described.
Specific examples of alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, cyclohexane Examples thereof include, but are not limited to, dicarboxylic acids.

The actinic ray-sensitive or radiation-sensitive resin composition is preferably used at a film thickness of 30 to 250 nm, more preferably at a film thickness of 30 to 200 nm, from the viewpoint of improving resolution. Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coating property and film forming property.
The solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition is usually 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, and more preferably 2.0 to 5. 3% by mass. By setting the solid content concentration within the above range, the resist solution can be uniformly coated on the support, and further, a resist pattern having excellent line width roughness can be formed. The reason for this is not clear, but perhaps the solid content concentration is 10% by mass or less, preferably 5.7% by mass or less, whereby aggregation of the material in the resist solution, particularly the acid generator, is suppressed, As a result, it is considered that a uniform resist film was formed.
The solid content concentration is a weight percentage of the weight of other resist components excluding the solvent with respect to the total weight of the actinic ray-sensitive or radiation-sensitive resin composition.

The actinic ray-sensitive or radiation-sensitive resin composition is preferably prepared by dissolving the above components in a predetermined organic solvent, preferably the above mixed solvent.
During the preparation, a process of reducing metal impurities in the composition to the ppb level using an ion exchange membrane, a process of filtering impurities such as various particles using an appropriate filter, a deaeration process, etc. Good. Specifics of these steps are described in JP 2012-88574 A, JP 2010-189563 A, JP 2001-12529 A, JP 2001-350266 A, and JP 2002-99076 A. JP-A-5-307263, JP-A 2010-164980, WO 2006/121162, JP-A 2010-243866, JP-A 2010-020297, and the like.
In particular, with respect to a suitable filter used in the filtering step, a pore size of 0.1 μm or less, more preferably 0.05 μm or less, and further preferably 0.03 μm or less made of polytetrafluoroethylene, polyethylene, or nylon is used. preferable.
The actinic ray-sensitive or radiation-sensitive resin composition preferably has a low water content. Specifically, the water content is preferably 2.5% by mass or less, more preferably 1.0% by mass or less, and still more preferably 0.3% by mass or less in the total weight of the composition.

[Procedure of step (1)]
The method for forming a film on the support using the actinic ray-sensitive or radiation-sensitive resin composition is not particularly limited, and a known method can be adopted. Especially, the method of apply | coating the said actinic-light sensitive or radiation sensitive resin composition on a support body from the point that adjustment of the thickness of a film | membrane is easier is mentioned.
The application method is not particularly limited, and a known method can be adopted. Among these, spin coating is preferably used in the semiconductor manufacturing field.
Moreover, you may implement the drying process for removing a solvent as needed after apply | coating actinic-ray-sensitive or radiation-sensitive resin composition. The method for the drying treatment is not particularly limited, and examples thereof include heat treatment and air drying treatment.

〔film〕
The receding contact angle of a film (resist film) formed using the actinic ray-sensitive or radiation-sensitive resin composition in the present invention is preferably 70 ° or more at a temperature of 23 ± 3 ° C. and a humidity of 45 ± 5%. , 75 ° or more, more preferably 75 to 85 °. When the receding contact angle of the resist film is in the above range, it is suitable for exposure through an immersion medium.
If the receding contact angle is too small, it cannot be suitably used for exposure through an immersion medium, and the effect of reducing water residue (watermark) defects cannot be sufficiently exhibited. In order to realize a preferable receding contact angle, it is preferable to include the hydrophobic resin in the actinic ray-sensitive or radiation-sensitive composition. Alternatively, the receding contact angle may be improved by forming a coating layer (so-called “topcoat”) of a hydrophobic resin composition on the resist film.

  The thickness of the resist film is not particularly limited, but is preferably 1 to 500 nm and more preferably 1 to 100 nm because a fine pattern with higher accuracy can be formed.

[Step (2): Exposure step]
Step (2) is a step of exposing the film formed in step (1). More specifically, it is a step of selectively exposing the film so that a desired pattern is formed. As a result, the film is exposed in a pattern, and the solubility of the resist film changes only in the exposed part.
“Exposing” intends to irradiate actinic rays or radiation.

The light used for the exposure is not particularly limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams. Preferably, it is far ultraviolet light having a wavelength of 250 nm or less, more preferably 220 nm or less, and still more preferably 1 to 200 nm.
More specifically, a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F ₂ excimer laser (157 nm), an X-ray, an EUV (13 nm), an electron beam, and the like can be mentioned. ArF excimer laser, EUV or electron beam is preferable, and ArF excimer laser is more preferable.

The method for selectively exposing the film is not particularly limited, and a known method can be used. For example, a binary mask (Binary-Mask) in which the light transmittance of the light shielding portion is 0% or a halftone phase shift mask (HT-Mask) in which the light transmittance of the light shielding portion is 6% can be used.
In general, a binary mask is used in which a chromium film, a chromium oxide film, or the like is formed on a quartz glass substrate as a light shielding portion.
As the halftone phase shift mask, generally, a quartz glass substrate on which a MoSi (molybdenum silicide) film, a chromium film, a chromium oxide film, a silicon oxynitride film, or the like is formed as a light shielding portion is used.
In the present invention, the exposure is not limited to exposure through a photomask, and selective exposure (pattern exposure) may be performed by exposure without using a photomask, for example, drawing with an electron beam or the like.
This step may include multiple exposures.

(Heat treatment)
Prior to this step, heat treatment (PB: Prebake) may be performed on the film. Heat treatment (PB) may be performed a plurality of times.
Moreover, you may perform a heat processing (PEB: Post Exposure Bake) with respect to a resist film after this process. The heat treatment (PEB) may be performed a plurality of times.
The reaction of the exposed part is promoted by the heat treatment, and the sensitivity and pattern profile are further improved.
In both PB and PEB, the temperature of the heat treatment is preferably 70 to 130 ° C, more preferably 80 to 120 ° C.
For both PB and PEB, the heat treatment time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and even more preferably 30 to 90 seconds.
For both PB and PEB, the heat treatment can be performed by means provided in a normal exposure / development machine, and may be performed using a hot plate or the like.

(Preferred embodiment: immersion exposure)
As a suitable aspect of exposure, for example, liquid immersion exposure can be mentioned. By using immersion exposure, a finer pattern can be formed. Note that immersion exposure can be combined with super-resolution techniques such as a phase shift method and a modified illumination method.

The immersion liquid used for immersion exposure is transparent to the exposure wavelength and has a refractive index temperature coefficient as much as possible so as to minimize distortion of the optical image projected onto the resist film. Small liquids are preferred. In particular, when the exposure light source is an ArF excimer laser (wavelength: 193 nm), it is preferable to use water from the viewpoints of availability and ease of handling in addition to the above-described viewpoints.
When water is used as the immersion liquid, an additive (liquid) that decreases the surface tension of water and increases the surface activity may be added in a small proportion. This additive is preferably one that does not dissolve the resist film and can ignore the influence on the optical coating on the lower surface of the lens element.
As such an additive, for example, an aliphatic alcohol having a refractive index substantially equal to that of water is preferable, and specific examples include methyl alcohol, ethyl alcohol, isopropyl alcohol and the like. By adding an alcohol having a refractive index substantially equal to that of water, even if the alcohol component in water evaporates and the content concentration changes, an advantage that the change in the refractive index of the entire liquid can be made extremely small can be obtained.
On the other hand, when an opaque material or impurities whose refractive index is significantly different from water are mixed with respect to 193 nm light, the optical image projected on the resist is distorted. For this reason, distilled water is preferable as the water to be used. Further, pure water filtered through an ion exchange filter or the like may be used.
The water used as the immersion liquid preferably has an electric resistance of 18.3 MΩcm or more, a TOC (organic substance concentration) of 20 ppb or less, and is preferably deaerated.
Moreover, it is possible to improve lithography performance by increasing the refractive index of the immersion liquid. From such a viewpoint, an additive for increasing the refractive index may be added to water, or heavy water (D ₂ O) may be used instead of water.

  In immersion exposure, the surface of the resist film may be washed with an aqueous chemical before exposure and / or after exposure (before heat treatment).

[Step (3): Development step]
Step (3) is a step of developing the film exposed in step (2) to form a resist pattern and exposing at least a part of the above-described underlayer.
In this step, an alkali development step of developing with an alkaline developer (hereinafter also referred to as “step A”) and an organic solvent development step of developing with a developer containing an organic solvent (hereinafter also referred to as “step B”) One of the steps (hereinafter also referred to as “first development step”) is performed, and then the other step (hereinafter also referred to as “second development step”) is performed. That is, step A and step B are performed in no particular order. More specifically, the process B may be performed after the process A is performed, or the process A may be performed after the process B is performed. Among these, it is preferable to perform step B after performing step A because the CDU of the pattern is more excellent (hereinafter also referred to simply as “the point where the effect of the present invention is more excellent”).
In step A, the “region with a large amount of exposure” in step (2) is dissolved by the developer to form a so-called positive pattern. On the other hand, in the step B, the “region with a small amount of exposure” in the step (2) is dissolved by the developer, and a so-called negative pattern is formed. That is, the process A is a process of selectively dissolving / removing a region where the exposure amount is greater than or equal to the threshold value (a), and the process B is a process of selectively dissolving / removing a region where the exposure amount is less than the threshold value (b). It is a process of removing. Note that the threshold (a) is larger than the threshold (b) in terms of the magnitude relationship between the threshold (a) and the threshold (b).

[Developer]
In step A, an alkaline developer is used. As the alkali developer, an alkali aqueous solution containing an alkali is preferably used.
The type of the aqueous alkali solution is not particularly limited. For example, tetramethylammonium hydroxide, quaternary ammonium salts represented by dimethylbis (2-hydroxyethyl) ammonium hydroxide, inorganic alkali, primary amine, secondary amine, Examples include alkaline aqueous solutions containing tertiary amines, alcohol amines, cyclic amines, and the like. Among these, an aqueous solution of a quaternary ammonium salt typified by tetramethylammonium hydroxide (TMAH) is preferable.

Appropriate amounts of alcohols and surfactants can be added to the alkaline aqueous solution. Specific examples and usage amounts of the surfactant are the same as those of the organic developer described later.
The alkali concentration of the aqueous alkali solution is usually 0.1 to 20% by mass.
The pH of the alkaline aqueous solution is usually 10.0 to 15.0.

In step B, a developer containing a soluble solvent (hereinafter also referred to as “organic developer” as appropriate) is used.
The developer used in Step B contains an organic solvent as a main component. The main component means that the content of the organic solvent is more than 50% by mass with respect to the total amount of the developer.
The organic solvent contained in the organic developer is not particularly limited, and examples thereof include polar solvents such as ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. . Moreover, these mixed solvents may be sufficient.

  Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.

  Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate (isoamyl acetate), amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate. , Diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, lactic acid Examples include propyl, butyl butanoate, methyl 2-hydroxyisobutyrate, isobutyl isobutyrate, and butyl propionate.

  Examples of the alcohol solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, alcohols such as n-octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, Diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butano It can be mentioned glycol ether solvents such as Le.

  Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.

  Examples of the amide solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.

  Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.

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

A plurality of organic solvents may be mixed, or may be used by mixing with other solvents or water. However, in order to fully exhibit the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture.
That is, the amount of the organic solvent used in the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less, with respect to the total amount of the developer.

  The vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the organic developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, and temperature uniformity in the wafer surface is improved. As a result, dimensional uniformity in the wafer surface. Improves.

An appropriate amount of a surfactant can be added to the organic developer as required.
The surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP 63-34540 A, JP 7-230165 A, JP 8-62834 A, JP 9-54432 A, JP 9-5988 A, US Pat. No. 5,405,720, etc. The surfactants described in the specifications of US Pat. Preferably, it is a nonionic surfactant. Although it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.
The addition amount of the surfactant is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass with respect to the total amount of the developer.

[Development method]
As the developing method in the process A and the process B, for example, a method of immersing the substrate in a tank filled with the developer for a certain time (dip method), and raising the developer on the surface of the substrate by the surface tension and leaving it stationary for a certain time. The developing method (paddle method), the method of spraying the developer on the substrate surface (spray method), the developer is continuously discharged while scanning the developer discharge nozzle at a constant speed on the substrate rotating at a constant speed. A method (dynamic dispensing method) or the like can be applied.
When the various development methods described above include a step of discharging the developer from the developing nozzle of the developing device toward the resist film, the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is As an example, it is preferably 2 mL / sec / mm ² or less, more preferably 1.5 mL / sec / mm ² or less, and still more preferably 1 mL / sec / mm ² or less. Although there is no particular lower limit of the flow rate, 0.2 mL / sec / mm ² or more is preferable in consideration of throughput. Details thereof are described in paragraphs [0022] to [0029] of JP 2010-232550 A in particular.
Moreover, you may implement the process of stopping image development, after substituting with another solvent after the process developed using the developing solution containing an organic solvent.

(Rinse treatment)
After the development step, it is preferable to use a rinse solution as necessary.
The rinsing liquid is not particularly limited as long as the resist film is not dissolved, and a solution containing a general organic solvent can be used.

  The rinsing liquid is a rinsing liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. More preferably, it is a rinsing liquid containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, alcohol solvents or ester solvents. More preferably, it is a rinsing liquid containing a monohydric alcohol, and most preferably a rinsing liquid containing a monohydric alcohol with 5 or more carbon atoms.

Specific examples of the hydrocarbon solvent, ketone solvent, ester solvent, alcohol solvent, amide solvent and ether solvent are the same as those of the organic developer described above, but decane, undecane, butyl acetate / OK73 ( Tokyo Ohka Kogyo Co., Ltd.) is preferable.
Examples of the monohydric alcohol include linear, branched, and cyclic monohydric alcohols. More specifically, 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1 -Pentanol, 3-methyl-1-butanol and the like.
When an ester solvent is used as the rinsing liquid, a glycol ether solvent may be used in addition to the ester solvent (one or more). Specific examples in this case include using an ester solvent (preferably butyl acetate) as a main component and a glycol ether solvent (preferably propylene glycol monomethyl ether (PGME)) as a subcomponent. Thereby, residue defects are suppressed.
The rinse liquid may contain a plurality of solvents. Moreover, the rinse liquid may contain an organic solvent other than the above.

  The water content of the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, better development characteristics can be obtained.

  The vapor pressure of the rinse liquid is preferably 0.05 kPa or more and 5 kPa or less at 20 ° C., more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa or more and 3 kPa or less. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling due to the penetration of the rinse solution is suppressed, and the dimensional uniformity in the wafer surface. Improves.

  An appropriate amount of a surfactant can be added to the rinse solution. Specific examples and usage amounts of the surfactant are the same as those of the organic developer described above.

  In the rinsing process, the wafer subjected to the organic solvent development is cleaned using the rinsing liquid. The cleaning method is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), and the like can be applied. Among these, a method of performing a cleaning process by a spin coating method, rotating the substrate at a rotational speed of 2000 rpm to 4000 rpm after cleaning, and removing the rinse liquid from the substrate is preferable. Moreover, it is preferable to perform a heat treatment (Post Bake) after the rinsing treatment. The developer and the rinsing liquid remaining between the patterns and inside the patterns are removed by heat treatment. The heat treatment after the rinsing treatment is usually performed at 40 to 160 ° C., preferably 70 to 95 ° C., and usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

  The organic processing solution (developer, rinse solution, etc.) used in the present invention is free from failures in chemical piping and various parts (filters, O-rings, tubes, etc.) due to electrostatic charging and subsequent electrostatic discharge. In order to prevent this, a conductive compound may be added. Although it does not restrict | limit especially as an electroconductive compound, For example, methanol is mentioned. The addition amount is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less from the viewpoint of maintaining preferable development characteristics. Regarding chemical solution piping members, SUS (stainless steel) or various pipes coated with antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) should be used. it can. Similarly, polyethylene, polypropylene, or fluorine resin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) subjected to antistatic treatment can be used for the filter and O-ring.

〔Additive〕
In the developer, especially the organic developer used in Step B, the resin (A) described above as an additive further includes a polar group generated by the action of an acid, an ionic bond, a hydrogen bond, a chemical bond, and a dipole mutual bond. Compounds that can form at least one of the interactions may be added.
When the resin (A) and this additive form a predetermined interaction, the solubility of the resin (A) is changed, and film slippage is unlikely to occur. In addition, an ionic bond means the electrostatic interaction of a cation and an anion, and salt formation etc. are also included.
Examples of such additives include at least one selected from the group consisting of an onium salt compound, a nitrogen-containing compound, and a phosphorus compound, and more specifically, for example, JP-A-2014-232310. Examples thereof include the additives described in paragraphs [0380] to [0474] of the publication.
When the additive is used, the total mass of the additive in the developer is not particularly limited, but is preferably 0.1 to 5% by mass, more preferably 1 to 5% by mass with respect to the total amount of the developer. 1-3 mass% is further more preferable.
In addition, as said additive, only 1 type of compounds may be used and 2 or more types of compounds from which chemical structures differ may be used.

[Step (4): Etching step]
Step (4) is a step of etching the underlying layer exposed in step (3) using plasma generated from a processing gas containing a deposition gas and depositing a deposit on the side surface of the resist pattern.

A specific example of this step is shown below.
The support on which the resist pattern after step (3) described above is formed is placed in the chamber, CHF ₃ gas, which is a deposition gas, is supplied into the chamber at a flow rate of 100 to 300 sccm, preferably 200 sccm, and HBr gas is supplied at a flow rate. It is supplied to the chamber 22 at 300 sccm or less, preferably 100 sccm. Then, high frequency power is supplied. At this time, plasma is generated by the high frequency power applied with CHF ₃ gas and HBr gas, and ions and radicals are generated. These ions and radicals collide and react with the exposed underlayer, and etch the portions. Furthermore, since CHF ₃ gas is a deposition gas, deposits are deposited on the side surfaces of the resist pattern, and the width of the opening is reduced. More specifically, the method described in paragraphs [0050] to [0051] of JP 2011-82577 A can be mentioned.

The deposition gas may be any deposition gas that can etch the underlayer such as the antireflection film, and specifically, a CF deposition gas is preferable. The CF-based deposit _gas, CHF 3, _CH 2 _{F 2} gas, CH ₃ F _gas, C 5 _{F 8} gas _may be C 4 _{F 6} gas.

  By the step (4), a laminate (pattern) of a patterned base layer (base pattern) and a patterned resist film (resist pattern) is formed on the substrate. As described above, in the present invention, since a resin having a high molecular weight is used for the resist composition, deposits are selectively deposited on a resist pattern having a wide opening. As a result, the variation in the width of the opening is reduced, and the critical dimension uniformity (CDU) of the formed pattern is extremely high.

Since the pattern formed by the pattern forming method of the present invention has an excellent CDU as described above, patterning with excellent uniformity can be performed on the substrate by using the pattern as an etching mask.
As described above, the pattern formed by the pattern forming method of the present invention is suitably used as an etching mask for a semiconductor device or the like, but can also be used for other purposes. As other applications, for example, guide pattern formation in DSA (Directed Self-Assembly) (see, for example, ACS Nano Vol. 4 No. 8 Pages 4815-4823), use as a core material (core) of a so-called spacer process (for example, JP-A-3-270227, JP-A-2013-164509, etc.).
In addition, you may apply the method of improving the surface roughness of a pattern with respect to the pattern formed by the pattern formation method of this invention. As a method for improving the surface roughness of the pattern, for example, a method of treating a resist pattern with a plasma of a hydrogen-containing gas disclosed in WO2014 / 002808A1 can be mentioned. In addition, JP 2004-235468 A, US 2010/0020297 A, JP 2008-83384 A, Proc. of SPIE Vol. 8328 83280N-1 “EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement” may be applied.
Actinic ray-sensitive or radiation-sensitive resin composition used in the present invention, and various materials used in the pattern forming method of the present invention (for example, a resist solvent, a developer, a rinsing liquid, an antireflection film-forming composition) Products, topcoat forming compositions, etc.) preferably do not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 ppm or less, more preferably 10 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, and substantially free (below the detection limit of the measuring device). Is most preferable.
Examples of a method for removing impurities such as metals from the various materials include filtration using a filter. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. As a 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 and ion exchange media. A filter that has been washed in advance with an organic solvent may be used. In the filter filtration 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 pore diameters and / or materials may be used in combination. Moreover, various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.
Moreover, as a method for reducing impurities such as metals contained in the various materials, a raw material having a low metal content is selected as a raw material constituting the various materials, and filter filtration is performed on the raw materials constituting the various materials. For example, the inside of the apparatus may be lined with Teflon (registered trademark), and distillation may be performed under a condition in which contamination is suppressed as much as possible. The preferable conditions for filter filtration performed on the raw materials constituting the various materials are the same as those described above.
In addition to filter filtration, impurities may be removed by an 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.

The present invention also relates to an electronic device manufacturing method including the pattern forming method of the present invention described above, and an electronic device manufactured by this manufacturing method.
The electronic device of the present invention is suitably mounted on electrical and electronic equipment (home appliances, OA / media related equipment, optical equipment, communication equipment, etc.).

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

[Preparation of resist composition]
Resist compositions were prepared by dissolving the components shown in Table 2 below in the solvents shown in the table so that the solid content concentration shown in the table was obtained. In Table 2, the ratio of the solvent represents a mass ratio.

In Table 2, the acid-decomposable resin is as follows.
Table 3 below shows the composition ratio, weight average molecular weight (Mw), and dispersity (Pd) of each acid-decomposable resin. Here, the composition ratio represents the molar ratio of repeating units in the chemical formula in order from the left. The evaluation methods of the weight average molecular weight and the degree of dispersion are as described above.
As shown in Table 3 below, P-1 to P-36 correspond to the resin (A) described above because the weight average molecular weight is 5,000 or more, and Comparative P-1 and Comparative P-2 are Since the weight average molecular weight is less than 5,000, it does not correspond to the resin (A) described above.

  In Table 2, the photoacid generator is as follows.

  In Table 2, the acid diffusion control agent is as follows.

In Table 2, the hydrophobic resin is as follows.
Table 4 below shows the composition ratio, weight average molecular weight (Mw), and dispersity (Pd) of each hydrophobic resin. Here, the composition ratio represents the molar ratio of repeating units in the chemical formula in order from the left. The evaluation methods of the weight average molecular weight and the degree of dispersion are as described above.

In Table 2, the solvents are as follows.
SL-1: Propylene glycol monomethyl ether acetate (PGMEA)
SL-2: Propylene glycol monomethyl ether (PGME)
SL-3: cyclohexanone SL-4: γ-butyrolactone SL-5: propion carbonate

[Preparation of upper layer film composition]
The upper layer film composition was prepared by dissolving the components shown in Table 5 below in the solvent shown in the same table so as to have a solid content concentration shown in the same table. In Table 5, the ratio of the solvent represents a mass ratio.

In Table 5, the upper layer film resin is as follows.
Table 6 below shows the composition ratio, weight average molecular weight (Mw), and dispersity (Pd) of each upper layer resin. Here, the composition ratio represents the molar ratio of repeating units in the chemical formula in order from the left. The evaluation methods of the weight average molecular weight and the degree of dispersion are as described above.

  In the table, the additives are as follows.

In Table 5, the solvents are as follows.
MIBC: methyl isobutyl carbinol (4-methyl-2-pentanol)
-BuOH: n-butanol-IAE: Isoamyl ether-IBIB: Isobutyl isobutyrate

[Examples 1-39 and Comparative Examples 1-2]
<Contact hole>
(Film formation process)
First, the base layer described in Table 7 was formed in order from the left on the silicon wafer. Note that SOC, SOG, BARC-A, and BARC-B were formed by baking at 205 ° C. for 60 seconds after coating by a spin coating method.
Next, the resist composition described in Table 7 is applied on the formed underlayer, and then baked (Prebake; PB) under the conditions described in the column “PB” in Table 7, and the resist is formed on the underlayer. A film was formed. Table 7 shows the thickness of the formed resist film.
In addition, about what has description, the upper layer film | membrane composition was apply | coated further, and it baked on the conditions as described in "Baking after application | coating" of Table 7, and formed the upper layer film | membrane (topcoat).

(Exposure process)
The resulting resist film was subjected to pattern exposure using an ArF excimer laser immersion scanner (XT1700i, NA1.20, Annular, outer sigma 0.95, inner sigma 0.7, manufactured by ASML). In Table 7, “BF” in the “reticle” column uses the reticle shown in FIG. 2A, and “DF” shows in FIG. 2B. The indicated reticle was used. Here, black is a light shielding portion, and the dimensions are based on an optical image at the time of projection. Moreover, ultrapure water was used as the immersion liquid.
Thereafter, the substrate was baked under the conditions described in the column “PEB” in Table 7 (Post Exposure Bake; PEB), and then cooled to room temperature. About what was described, the upper layer film | membrane was peeled using the upper layer film | membrane peeling solvent.

(Development process)
Next, the first development process was performed.
Specifically, development was performed with the developer and the development time described in the column of “First development step” in Table 7, and those described were rinsed with a rinse solution for 30 seconds. Thereafter, baking was performed under the conditions described in the column “Bake after development” in Table 7. In Example 38, baking was not performed.
Further, a second development process was performed.
Specifically, development was performed with the developer and the development time described in the column of “Second development step” in Table 7, and those described were rinsed with a rinse solution for 30 seconds. Then, it baked on the conditions as described in the column of "Post-baking" of Table 7.
In this way, a resist pattern of contact holes with a pitch of 64 nm was formed, and a part of the underlayer was exposed.
In Examples 35 to 39, alkali development and rinsing were performed by the same method as that described in the third embodiment described in JP2013-162040A.

(Etching process)
Next, the exposed underlayer was etched using plasma generated from CHF ₃ gas, which is a CF-based deposition gas, and deposits were deposited on the side surfaces of the formed resist pattern. Specifically, it was performed according to the method described in paragraph [0051] of JP2011-82577A.
In this way, a pattern (contact hole) was formed.

<Line and space>
Using an ArF excimer laser immersion scanner (SMTL XT1700i, NA 1.20, Dipole, outer sigma 0.9, inner sigma 0.8), a reticle having a half pitch of 64 nm and a line and space of 1: 1 was used. Except for the above, a pattern (line and space) having a half pitch of 32 nm was formed according to the same procedure as that for forming the pattern (contact hole) described above.

[Evaluation of CDU]
The CDU before and after the etching process was evaluated for the contact hole (CH) and line and space (LS) patterns formed in each example and comparative example. The results are shown in Table 7. The improvement rate (= (1−CDU after etching process / CDU before etching process) × 100 (%)) is also shown. It can be said that the smaller the CDU after the etching step, the better the CDU of the pattern. The CDU evaluation method is as follows.

  The exposure amount at which the average diameter of the holes formed by the first development step is the same as the average diameter of the holes formed by the second development step is defined as the optimum exposure amount (Eop), and the hole is formed by the above Eop. A total of 30 hole pattern diameters were measured, the standard deviation of the length measurement values of the total 30 diameters was calculated, and a value obtained by multiplying the diameter by 3 was calculated as CDU (unit: nm). A scanning electron microscope (“CG-4100”, manufactured by Hitachi High-Technologies Corporation) was used for length measurement.

  In Table 7, “C” intends “° C.” and “s” means “seconds” for baking. For example, “90C60s” represents baking at 90 ° C. for 60 seconds.

In Table 7, the foundation layer is as follows.
・ SOC: Brewer spin-on carbon material (thickness: 120 nm)
SOG: Brewer spin-on-glass material (thickness: 30 nm)
-BARC-A: Brewer's organic antireflection film (thickness: 80 nm)
BARC-B: Nissan Chemical's organic antireflection film (thickness: 30 nm)
・ SiON: Silicon nitride oxide deposited film (thickness: 15 nm)

  In Table 7, the resist composition is as described above.

  In Table 7, the upper layer film composition is as described above.

In Table 7, the upper layer film peeling solvent is as follows. “MIBC / IAE” represents a mixed solvent of methyl isobutyl carbinol and isoamyl ether.
MIBC: methyl isobutyl carbinol (4-methyl-2-pentanol)
-IAE: Isoamyl ether-Decane: Decane

In Table 7, the developer is as follows.
・ TMAH: Tetramethylammonium hydroxide ・ Butyl acetate: Butyl acetate ・ Isoamyl acetate: Isoamyl acetate

In Table 7, the rinse solution is as follows.
・ Pure water: Pure water ・ MIBC: Methyl isobutyl carbinol (4-methyl-2-pentanol)
・ Undecane: Undecane

As can be seen from Table 7, the CDU was excellent in the pattern formed by the present example using the resin having the acid-decomposable group (resin (A)) having a weight average molecular weight of 5,000 or more. The improvement rate was also high.
From the comparison of Examples 1 to 6, Examples 2 to 6, in which the weight average molecular weight of the resin (A) is 7,000 or more, were more excellent in CDU (contact hole). Especially, Examples 3-6 whose weight average molecular weights of resin (A) are 12,000 or more were more excellent in CDU (contact hole). Among them, in Examples 4 to 6 in which the weight average molecular weight of the resin (A) is 17,000 or more, CDU (contact hole) was more excellent.
From the comparison of Examples 4 to 6, the resin (A) contains a repeating unit having an acid-decomposable group, and the content of the repeating unit having an acid-decomposable group contained in the resin (A) is the resin (A). Examples 4-5 which are 55 mol% or more with respect to all the repeating units of these were more excellent in CDU. Among them, in Example 5 in which the content of the repeating unit having an acid-decomposable group contained in the resin (A) is 65 mol% or more with respect to all the repeating units of the resin (A), the CDU is more It was excellent.
From the comparison between Examples 2 and 16 (the weight average molecular weight of the resin (A) is 10,000) and the comparison between Examples 4 to 6 and 15 (the weight average molecular weight of the resin (A) is 20,000) In Examples 2 and 4 to 6, in which the alkali concentration of the alkali developer was 2.0% by mass or more, CDU (contact hole) was more excellent.
From the comparison of Examples 4 to 6, 17 and 18, the weight average molecular weight of the resin (A) is 20,000, Examples 4 to 6 and 18 in which the development time in the alkali development step is 40 seconds or less are CDUs. Was better.
From the comparison between Examples 2 and 21 (resin (A) has a weight average molecular weight of 10,000), Example 2 in which the baking time after alkali development is 100 seconds or less was superior in CDU.
From the comparison of Examples 3 to 6 and 22 to 23 (the weight average molecular weight of the resin (A) is 12,000 or more), the baking temperature after organic development is 130 ° C. or less. It was excellent.
From the comparison of Examples 1-2 and 32-33 (the weight average molecular weight of the resin (A) is less than 12,000), Examples 1-2 in which the temperature of PEB is 80-90 ° C. are CDUs (contact holes). ) Was better.

  On the other hand, Comparative Examples 1-2 using resins having a weight average molecular weight of less than 5,000 had insufficient CDU.

DESCRIPTION OF SYMBOLS 1 Substrate 5 Underlayer 6 Underground pattern 7 Exposed underlayer 8 Opening 10 Support 12, 14 Resist pattern 16 Depot 20 Pattern

Claims (5)

A film forming step of forming a film using the actinic ray-sensitive or radiation-sensitive resin composition on the base layer of the support having the base layer and the substrate;
An exposure step of exposing the film;
Developing the film after the exposure step to form a resist pattern and exposing at least a portion of the underlayer; and
An etching step of etching the exposed underlayer using plasma generated from a processing gas containing a deposition gas and depositing a deposit on a side surface of the resist pattern,
The actinic ray-sensitive or radiation-sensitive resin composition contains a resin having an acid-decomposable group having a weight average molecular weight of 5,000 or more,
The development step is carried out by performing any one of an alkali development step for developing with an alkali developer and an organic solvent development step for developing with a developer containing an organic solvent, and then performing the other step. A pattern forming method as a process.   The pattern forming method according to claim 1, wherein the acid-decomposable group is a group that is decomposed by the action of an acid to generate a carboxy group. The resin includes a repeating unit having an acid-decomposable group,
The pattern formation method of Claim 1 or 2 whose content of the repeating unit which has the said acid-decomposable group contained in the said resin is 50 mol% or more with respect to all the repeating units of the said resin.   The pattern formation method of any one of Claims 1-3 in which the said resin contains the repeating unit which has a lactone structure, a sultone structure, a cyclic ketone structure, or a cyclic sulfone structure.   The manufacturing method of an electronic device containing the pattern formation method of any one of Claims 1-4.