WO2019026549A1

WO2019026549A1 - Active-light-sensitive or radiation-sensitive resin composition, resist film, pattern formation method, and method for manufacturing electronic device

Info

Publication number: WO2019026549A1
Application number: PCT/JP2018/025786
Authority: WO
Inventors: 大輔浅川; 研由後藤; 雅史小島; 啓太加藤; 恵士山本
Original assignee: 富士フイルム株式会社
Priority date: 2017-07-31
Filing date: 2018-07-06
Publication date: 2019-02-07
Also published as: JPWO2019026549A1; TW201910918A; JP7053625B2

Abstract

Provided are: an active-light-sensitive or radiation-sensitive resin composition with which a resist film having excellent EL performance and a pattern having excellent LWR performance can be obtained; a resist film using the active-light-sensitive or radiation-sensitive resin composition; a pattern formation method; and a method for manufacturing an electronic device. The active-light-sensitive or radiation-sensitive resin composition includes: a resin having at least one type of repeating unit selected from the group consisting of repeating unit represented by general formula (1), and the repeating unit represented by general formula (2); and a photoacid generator.

Description

Actinic radiation sensitive or radiation sensitive resin composition, resist film, pattern forming method, method of manufacturing electronic device

The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a resist film, a pattern forming method, and a method of manufacturing an electronic device.

Conventionally, in the manufacturing process of semiconductor devices such as IC (Integrated Circuit, integrated circuit) and LSI (Large Scale Integrated circuit, large scale integrated circuit), fine processing by lithography using an actinic ray-sensitive or radiation-sensitive resin composition Processing is being performed.
For example, Patent Document 1 discloses a radiation sensitive resin composition containing an acid-dissociable group-containing polymer having a predetermined repeating unit.

JP 2007-52182 A

The present inventors examined the actinic ray-sensitive or radiation-sensitive resin composition specifically described in the example section of Patent Document 1, and it was formed by the actinic ray-sensitive or radiation-sensitive resin composition. It was found that there is room for improvement with regard to the exposure latitude (EL) of the resist film and the fluctuation of the pattern line width (LWR) of the resist film.

An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of obtaining a resist film excellent in EL performance and a pattern excellent in LWR performance.
Another object of the present invention is to provide a resist film, a pattern forming method, and an electronic device manufacturing method using the actinic ray-sensitive or radiation-sensitive resin composition.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject was solvable by using resin which has a repeating unit which has a specific structure, as a result of earnestly examining in order to achieve the said subject, and completed this invention.
That is, it discovered that the said subject was solvable by the following structures.

[1] A resin having at least one repeating unit selected from the group consisting of a repeating unit represented by General Formula (1) described later and a repeating unit represented by General Formula (2) described later, and light An actinic ray-sensitive or radiation-sensitive resin composition containing an acid generator.
[2] The actinic ray-sensitive or radiation-sensitive material according to [1], wherein the content of the resin is 10% by mass or more based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. Resin composition.
[3] The actinic ray-sensitive or actinic ray-sensitive material according to [1] or [2], wherein in general formula (1) described later, in general formula (2) described later, at least one of R ₃ and R ₄ is an organic group Radiation-sensitive resin composition.
[4] In general formula (1) described later, at least one of R ₁ and R ₂ is a group represented by general formula (R) described later, and in general formula (2) described later, R ₃ and R ₄ The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein at least one of the groups is a group represented by the general formula (R) described later.
[5] The actinic ray-sensitive or radiation-sensitive resin composition as described in [4], wherein R ₅ in the general formula (1) described later represents an alkali-degradable group.
[6] In General Formula (1) to be described later, L ₁ is an alkylene group having an ether group which may have a substituent, or two groups represented by General Formula (A) to be described later L ₂ is an alkylene group having an ether group, and in general formula (2) described later, an alkylene group having an ether group which may have a substituent or a group represented by general formula (A) described later The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], which is an alkylene group having two.
[7] In General Formula (1) to be described later, R ₁ and R ₂ are a group represented by General Formula (R) to be described later, and L ₁ is a group represented by General Formula (A) to be described later The actinic ray-sensitive or radiation-sensitive resin composition as described in [4] or [6], which is a group having two.
[8] The actinic ray-sensitive or radiation-sensitive resin composition as described in any one of [1] to [7], wherein the resin has a repeating unit represented by General Formula (3) described later.
[9] The resin further has at least one repeating unit selected from the group consisting of repeating units having a lactone group, and repeating units having neither an acid-degradable group nor a polar group [1] ] The actinic-ray-sensitive or radiation-sensitive resin composition as described in any one of [8] to [8].
[10] A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition as described in any one of [1] to [9].
[11] A resist film forming step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9], and exposure for exposing the resist film A pattern forming method comprising: a process; and a development process of developing the exposed resist film using a developer.
[12] A method for producing an electronic device, comprising the pattern formation method according to [11].

According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of obtaining a resist film excellent in EL performance and a pattern excellent in LWR performance.
Further, according to the present invention, it is possible to provide a resist film, a pattern forming method, and an electronic device manufacturing method using the actinic ray-sensitive or radiation-sensitive resin composition.

Hereinafter, the present invention will be described in detail.
Although the description of the configuration requirements described below may be made based on the representative embodiments of the present invention, the present invention is not limited to such embodiments.
In the present specification, as for the notation of a group (atomic group), the notation not describing substitution and non-substitution also includes a group having a substituent together with a group having no 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).
As used herein, "organic group" refers to a group having at least one carbon atom.
In the present specification, “actinic ray” or “radiation” means, for example, the emission line spectrum of a mercury lamp, far-ultraviolet light represented by an excimer laser, extreme ultraviolet (EUV light), X-ray, and electron beam ( EB: Electron Beam) means etc.
As used herein, "light" means actinic radiation or radiation.
In the present specification, unless otherwise specified, the "exposure" means not only exposure by the bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays, X rays, EUV light, etc., but also electron beams. And, drawing by particle beam such as ion beam is also included.
In the present specification, “to” is used in the meaning including the numerical values described before and after it as the lower limit value and the upper limit value.

As used herein, "(meth) acrylate" refers to acrylate and methacrylate.
In the present specification, the weight average molecular weight (Mw), number average molecular weight (Mn) and dispersion degree (also referred to as molecular weight distribution) (Mw / Mn) of a resin are GPC (Gel Permeation Chromatography) apparatus (HLC- manufactured by Tosoh Corporation) GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40 ° C., flow rate: 1.0 mL / min, detector: differential refraction It is defined as a polystyrene conversion value by a refractive index detector (Refractive Index Detector).
The bonding direction of the divalent group (eg, -COO-) described in the present specification is not limited unless otherwise specified. For example, when M is -COO- in the compound represented by the general formula "LMN", the position bonded to the L side is * 1, the position bonded to the N side In the case of * 2, M may be * 1-O-CO- * 2 or * 1-CO-O- * 2.
In the present specification, an organic group refers to a group having a carbon atom. For example, a hydrocarbon group and a hydrocarbon group having a hetero atom can be mentioned.

Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition
The actinic ray-sensitive or radiation-sensitive resin composition (hereinafter, also simply referred to as “composition” or “composition of the present invention”) of the present invention will be described.
The composition of the present invention is a so-called resist composition, and may be a positive resist composition or a negative resist composition. Further, it may be a resist composition for alkali development or a resist composition for organic solvent development.
The composition of the present invention is typically a chemically amplified resist composition.

The characteristic point of the composition of the present invention is that it contains a resin having a repeating unit represented by the general formula (1) or (2) described later. According to the composition of the present invention containing the above-mentioned resin, a resist film excellent in EL performance and a pattern excellent in LWR performance can be formed (hereinafter, such a property of the composition of the present invention is simply referred to as “effect of the present invention It is also called ").
The details of this mechanism are not clear, but are presumed as follows.
In the repeating unit represented by the general formula (1) or (2) described later which the composition of the present invention has, the mobility of the main chain is reduced by the introduction of a ring structure to the main chain of the resin, The glass transition point (Tg) is improved. In addition, by having a certain number or more of polar groups containing heteroatoms in the main chain and side chains, the interaction between the groups is increased, and the effect of improving Tg is further increased. As a result, the solubility of the resin decreases, and the diffusion of the acid generated by the exposure from the photoacid generator can be appropriately suppressed, and as a result, the resist film made of the composition of the present invention exhibits excellent development contrast. It is presumed that the effects of the invention can be realized.

Hereinafter, the components contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention will be described in detail.

<Resin (A)>
The composition of the present invention comprises a resin having a repeating unit represented by the general formula (1) and at least one repeating unit selected from the group consisting of the repeating units represented by the general formula (2) .

(R ₁ , R ₂ , R ₃ and R ₄ )
In the general formula (1), R ₁ and R ₂ each independently represent a hydrogen atom, a group represented by the general formula (A), or an organic group other than the group represented by the above general formula (A) And at least one of R ₁ and R ₂ represents a group represented by the above general formula (A).

* -C (= O) -O-R (A)
In general formula (A), R represents a hydrocarbon group which may have a hetero atom or a hydrogen atom. * Represents a bonding position.

At least one of R ₁ and R ₂ is a group represented by the above general formula (A), and one of R ₃ and R ₄ may be a group represented by the above general formula (A) And both may be groups represented by the above general formula (A).
When only _one of R ₁ and R ₂ is a group represented by the above general formula (A), the other one represents a hydrogen atom or an organic group other than the group represented by the general formula (A).
When both of R ₁ and R ₂ are a group represented by the above general formula (A) and the group represented by L ₁ described later has one hetero atom, two general groups At least one of the two R's in the group represented by formula (A) represents a hydrocarbon group having a hetero atom.

As said hetero atom, an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom are mentioned, for example. Among them, an oxygen atom, a nitrogen atom or a sulfur atom is preferable, and an oxygen atom is more preferable.

As R ₁ and R ₂ , one is preferably a hydrogen atom and the other is a group represented by the general formula (A), or both are preferably a group represented by the general formula (A), both It is more preferable that it is a group represented by general formula (A).

In General Formula (2), R ₃ and R ₄ each independently represent a hydrogen atom or an organic group.
At least one of R ₃ and R ₄ is preferably an organic group, and either of R ₃ and R ₄ may be an organic group, and both may be an organic group.

The organic group represented by R ₃ and R ₄ is preferably a hydrocarbon group having a hetero atom.
As a hetero atom, an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom are mentioned, for example. Among them, an oxygen atom, a nitrogen atom or a sulfur atom is preferable, and an oxygen atom is more preferable.
In addition, it is preferable that the oxygen atom cooperate with the carbon atom to form an ester group, and the ester group is directly bonded to the main chain of the repeating unit represented by the general formula (2). preferable. Furthermore, it is preferable that a hydrogen atom or another organic group be bonded to the main chain via the ester group.
As another organic group bonded to the main chain via an ester group, a hydrocarbon group which may have a hetero atom is preferable. That is, the organic group represented by R ₃ and R ₄ is preferably a group represented by general formula (A).
In the case where both R ₃ and R ₄ are a group represented by the above general formula (A) and the group represented by L ₂ described later has one hetero atom, two of the above general groups It is preferable that at least one of two R in the group represented by Formula (A) represents a hydrocarbon group having a hetero atom.

As a hydrocarbon group which may have a hetero atom which is represented by R in general formula (A), for example, it may have an alkyl group which may have a hetero atom, and a hetero atom A good alkenyl group and an alkynyl group which may have a hetero atom can be mentioned.
The alkyl group, the alkenyl group and the alkynyl group may be linear or branched. The carbon number is preferably 1 to 20.
The alkyl group, the alkenyl group and the alkynyl group may or may not have a cyclic structure.
However, from the viewpoint of suppressing the decrease in Tg of the resin and further improving the effect of the present invention, when R has an alicyclic group, the above-mentioned alicyclic group constitutes a part of the acid-eliminating group Is preferred.

Among them, the group represented by General Formula (A) is preferably a group represented by General Formula (R) shown below. It is preferable that at least one of R ₁ and R ₂ is a group represented by General Formula (R), and at least one of R ₃ and R ₄ is a group represented by General Formula (R).
In other words, the composition of the present invention is a repeating unit represented by the general formula (1) in which at least one of R ₁ and R ₂ is a group represented by the general formula (R), and R ₃ and R ₄ The resin (A) has at least one repeating unit selected from the group consisting of repeating units represented by the general formula (2) in which at least one of the groups is a group represented by the general formula (R) preferable.
Among them, in the general formula (1), it is more preferable that both of R ₁ and R ₂ be a group represented by the general formula (R).

* -C (= O) -O-R ₅ (R)
* Represents a bonding position.

In general formula (R), R ₅ represents a hydrogen atom, an alkali-degradable group, or an acid-leaving group. More specifically, R ₅ is a hydrogen atom, a hydrocarbon group which may have a hetero atom and which is alkali-degradable, or a hydrocarbon group which may have a hetero atom. And a group exhibiting acid releasability.
Among them, R ₅ is preferably an alkali-degradable group or an acid-eliminable group from the viewpoint that the LWR performance of the pattern is more excellent.
Further, R ₅ is preferably a hydrogen atom or an alkali-degradable group from the viewpoint of more excellent sensitivity of the resist film.
That is, R ₅ is more preferably an alkali-degradable group.

In the present specification, an alkali-degradable group is a group which is decomposed by the action of an alkaline solution to increase the solubility in the alkaline solution. For example, a group having a lactone group (for example, a hydrocarbon group having a lactone group), a group having a sultone group (for example, a hydrocarbon group having a sultone group), a group having a carbonate group (for example, a carbonate group (preferably cyclic) A hydrocarbon group having a carbonate group) and a group having an acid anhydride group (eg, a hydrocarbon group having an acid anhydride group), and a group having a lactone group, a group having a sultone group, or And groups having a carbonate group (preferably, a cyclic carbonate group) are preferable.

When R ₅ is an alkali-degradable group, the group represented by general formula (R) is preferably a group represented by the following general formula (R ′).

* -C (= O) -O-Ab-V (R ')
* Represents a bonding position.

Ab-V in the general formula (R ′) corresponds to R ₅ in the general formula (R).
Ab represents a single bond, an alkylene group, a monocyclic or polycyclic alicyclic group, an ether group, an ester group, a carbonyl group, or a divalent linking group combining these.
Among them, Ab is preferably a single bond or an alkylene group (preferably having a carbon number of 1 to 2).

V represents a lactone group, a sultone group or a cyclic carbonate group.

The lactone group is preferably a 5- to 7-membered lactone group. Among them, a group in which another ring is fused to a 5- to 7-membered lactone group in a form of forming a bicyclo ring or spiro ring is more preferable. Specific examples thereof include groups in which one hydrogen atom has been removed from the lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-21). 1) From the structure represented by General Formula (LC1-4), General Formula (LC1-5), General Formula (LC1-8), General Formula (LC1-16), or General Formula (LC1-21) The group which removed one hydrogen atom is preferable.
The sultone group is preferably a 5- to 7-membered sultone group. Among them, a group in which another ring is fused to a 5- to 7-membered ring sultone group to form a bicyclo ring or a spiro ring is more preferable. Specific examples thereof include groups in which one hydrogen atom is removed from a sultone structure represented by any one of the following general formulas (SL1-1) to (SL1-3). A group obtained by removing one hydrogen atom from the structure represented by -1) is preferable.

The lactone and sultone groups may or may not have a substituent (Rb ₂ ). As the substituent (Rb ₂ ), 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, a carboxy group, A halogen atom, a hydroxy group, a cyano group or the like is preferable, and an alkyl group having 1 to 4 carbon atoms or a cyano group is more preferable. n ₂ represents an integer of 0 to 4; When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different. Moreover, two or more substituents (Rb ₂ ) may be combined to form a ring.
In addition, the lactone group and the sultone group may have an acid-degradable group described later as a substituent (Rb ₂ ).

As a cyclic carbonate group, a group obtained by removing one hydrogen atom from the structure represented by the following general formula is preferable.

In the above general formula, n represents an integer of 0 or more.
R _A ² represents a substituent. When n is 2 or more, R _A ² independently represents a substituent.
A represents a single bond or a divalent linking group.
Z represents an atomic group forming a monocyclic or polycyclic group with a group represented by —O—C (= O) —O— in the formula. Z is preferably an alkylene group. The alkylene group may be linear or branched, and may have a cyclic structure. Among them, the above-mentioned alkylene group is preferably linear. The carbon number of the alkylene group is preferably 1 to 4, more preferably 2 to 3, and still more preferably 2.

In the present invention, it is also preferred that the group represented by the general formula (R) forms an acid decomposable group by the joint of -C (= O) -O- and R ₅ specified in the formula. It is preferable from the viewpoint of more excellent effects.
In the present specification, the acid-degradable group refers to a group which is decomposed by the action of an acid to increase the polarity.
The acid-degradable group preferably has a structure in which the polar group is protected by a group which is decomposed and eliminated by the action of an acid (acid-releasable group).
That is, from the viewpoint of more excellent effects of the present invention, it is also preferable that R ₅ is the above-mentioned acid leaving group, and in this case, the group represented by General Formula (R) forms an acid decomposable group. However, it should be noted that when the group represented by the general formula (R) forms an acid decomposable group, the sensitivity of the resist film to be formed tends to decrease.
When the group represented by the general formula (R) forms an acid-degradable group, the group represented by the general formula (R) is a group represented by the following general formula (R ′ ′) preferable.

* -C (= O) -O-R _c (R ′ ′)
* Represents a bonding position.

In the general formula (R ′ ′), R _c corresponds to R ₅ in the general formula (R).
In addition, the above-mentioned -R _c is -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), or -C (R ₀₁ ) (R ₀₂ ) Represents (OR ₃₉ ).

Each of R ₃₆ to R ₃₉ independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may combine with each other to form a ring.
Each of R ₀₁ and R ₀₂ independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

The alkyl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having a carbon number of 1 to 8, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group and a sec- A butyl group, a hexyl group, and an octyl group etc. are mentioned.
The cycloalkyl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. The monocyclic cycloalkyl group is preferably a cycloalkyl group having a carbon number of 3 to 8, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. The polycyclic cycloalkyl group is preferably a cycloalkyl group having a carbon number of 6 to 20, and examples thereof include an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an α-pinel group and a tricyclodecanyl group, Examples thereof include tetracyclododecyl group, and androstanyl group. In addition, at least one or more carbon atoms in the cycloalkyl group may be substituted by a hetero atom such as an oxygen atom.
The aryl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an aryl group having a carbon number of 6 to 10, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
The aralkyl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an aralkyl group having a carbon number of 7 to 12, and examples thereof include a benzyl group, a phenethyl group, and a naphthylmethyl group.
The alkenyl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having a carbon number of 2 to 8, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group Can be mentioned.
The ring formed by bonding R ₃₆ and R ₃₇ to each other is preferably a cycloalkyl group (monocyclic or polycyclic). The cycloalkyl group may be 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. preferable.

The specific example of group represented by general formula (R '') is shown. In the following examples, * represents a bonding position to the main chain.

(L ₁ and L ₂ )
L ₁ and L ₂ in the general formula (1) are a divalent linking group having one or more hetero atoms, and L ₁ represents an alkylene group which may have a substituent. A part of carbon atoms in the alkylene group may be substituted with a group having a hetero atom. The substituent may have a hetero atom. However, the group represented by L ₁ has one or more hetero atoms.
As described above, both of R ₁ and R _{2 in} the general formula (1) are a group represented by the above general formula (A), and the hetero atom contained in the group represented by L ₁ is 1 And at least one of two R in the two groups represented by the above general formula (A) represents a hydrocarbon group having a hetero atom. In other words, both of R ₁ and R _{2 in} the general formula (1) are a group represented by the above general formula (A), and two of the two groups represented by the above general formula (A) When one R represents a hydrocarbon group having no hetero atom, the hetero atom represented by L ₁ has 2 or more hetero atoms. L ₁ and L ₂ may be a linking group in which an alkylene group and an alkylene group are linked via a hetero atom.
L ₂ in the general formula (2) represents an alkylene group which may have a substituent. A part of carbon atoms in the alkylene group may be substituted with a group having a hetero atom. The substituent may have a hetero atom. However, the group represented by L ₂ has one or more hetero atoms.
Alkylene groups, represented by L ₁ and L ₂ , combine at each end with the two carbon atoms specified in the formula to form a cyclic group.
The group having a hetero atom may be a hetero atom itself.

L ₁ and L ₂ are preferably a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, or a divalent linking group containing a halogen atom, and among them, the hetero atom contained in L ₁ and L ₂ is an oxygen atom , A nitrogen atom, a sulfur atom or a fluorine atom is preferable.
There is no limitation on the aspect in which the group represented by L ₁ and L ₂ has a hetero atom, and a part of carbon atoms in the chain of the alkylene group may be substituted with a group having a hetero atom, and the alkylene group has The substituent may have a hetero atom.
As the group having a hetero atom, for example, ether group (-O-), sulfide group (-S-), carbonyl group (-C (= O)-), ester group (-C (= O) O-) , An amido group (-NHC (= O)-), and a sulfonyl group (-S (= O) _2- ).
When a group having a hetero atom is present in the chain of an alkylene group, the group having a hetero atom is preferably an ether group, from the viewpoint that the LWR performance of the pattern is more excellent.
When the substituent has a hetero atom, the hetero atom is preferably combined with the carbon atom to form an ester group, and more preferably to form a group represented by the above general formula (A).
The carbon number of the alkylene group is preferably 2 to 10, more preferably 2 to 6, and still more preferably 2. The number of carbon atoms does not include the number of hetero atoms that the alkylene group has in the chain and the number of carbon atoms that the substituent that the alkylene group has has.
The number of atoms constituting these rings does not include the number of atoms possessed by the substituent.

As an aspect which an alkylene group has a substituent, the case where a part of hydrogen atom in an alkylene group is substituted by a substituent is mentioned.
The type of substituent is not particularly limited, and may have a hetero atom as described above. As the type of substituent, for example, a halogen atom (-F, -Cl, -I, etc.), an alkyl group, -S (= O) ₂ -alkyl group, an alkoxy group, an aryl group, a hydroxy group, a cyano group, or And groups represented by the above-mentioned general formula (A).
Among them, as a substituent, a group represented by general formula (A) is preferable from the viewpoint that the LWR performance of the pattern is more excellent.
When the alkylene group has a group represented by General Formula (A), the alkylene group more preferably has two or more (preferably, 2 to 4) groups represented by General Formula (A), and 2 It is more preferable to have one. The groups represented by a plurality of general formulas (A) may be the same or different.
In addition, from the viewpoint that the effect of the present invention is more excellent, when the alkylene group has two groups represented by general formula (A), R ₁ and R ₂ (or R ₃ and R ₄ ) have the general formula (R) It is more preferable that it is a group represented by).
In other words, in the general formula (1), R ₁ and R ₂ are a group represented by the general formula (R), and a group in which L ₁ has two groups represented by the general formula (A) Is preferred.
In the general formula (2), R ₃ and R ₄ are groups represented by the general formula (R), and L ₂ is a group having two groups represented by the general formula (A) It is also preferable to be present.
In addition, when an alkylene group has a group represented by general formula (A), it is preferable that R in general formula (A) is a hydrocarbon group which may have a hetero atom. The preferable aspect of the hydrocarbon group which may have such a hetero atom is as above-mentioned, and an alkali degradable group or acid-releasable group as represented by R ₅ in General formula (R) May be formed.

It is preferable that the alkylene group which may be substituted represented by L ₁ and L ₂ be represented by General Formula (L) shown below.

*-(CH ₂ ) _n -Z- (CH ₂ ) _n- * (L)
* Represents a bonding position.

In the general formula (L), n each independently represents an integer of 0 or more, preferably 0 to 4, more preferably 0 to 1, and still more preferably 1.
Note that at least one of two n's represents an integer of 1 or more.

Z represents a group having a hetero atom.
Examples of Z include an ether group (-O-), a sulfide group (-S-), a carbonyl group (-C (= O)-), an ester group (-C (= O) O-), an amido group ( -NHC (= O)-), sulfonyl group (-S (= O) _2- ), -C (Y ₁ ) (Y ₂ )-, and -N (Y ₃ )-.
Y ₁ , Y ₂ and Y ₃ each independently represent a hydrogen atom or a substituent.
At least one of Y ₁ and Y ₂ represents a substituent having a hetero atom.
The substituents represented by Y ₁ , Y ₂ and Y ₃ are each independently a halogen atom (-F, -Cl, -I or the like), an alkyl group or -S (= O) ₂ -alkyl group Alternatively, a group represented by formula (A) is preferable, and a group represented by —S (SO) ₂ -alkyl group or a group represented by formula (A) is more preferable. The alkyl group that Y ₁ , Y ₂ , and Y ₃ may have (including the case where Y ₁ , Y ₂ , and Y ₃ are alkyl groups themselves) preferably has 1 to 2 carbon atoms, and more preferably It may have a substituent (preferably a halogen atom, more preferably -F).
Z is preferably an ether group or —C (Y ₁ ) (Y ₂ ) — in which Y ₁ and Y ₂ are each represented by general formula (A), and —C (Y ₁ ) (Y ₂ ) And Y ₁ and Y ₂ are more preferably a group represented by formula (A).
In addition, when Z is -C (Y ₁ ) (Y ₂ )-and Y ₁ and Y ₂ are a group represented by general formula (A), a plurality of general formulas (A) are present. The groups represented may be the same or different.
In addition, R in the general formula (A) which can be represented by Y ₁ , Y ₂ and Y ₃ is preferably a hydrocarbon group which may have a hetero atom. The preferable aspect of the hydrocarbon group which may have such a hetero atom is as above-mentioned, and an alkali degradable group or acid-releasable group as represented by R ₅ in General formula (R) May be formed.

Resin (A) may have the repeating unit represented by General formula (1) or (2) individually by 1 type, and may have it in combination of 2 or more types.
The content of the repeating unit represented by the general formula (1) or (2) is not particularly limited, but from the viewpoint of more excellent effects of the present invention, 5 to 70 with respect to all repeating units in the resin (A). The mole% is preferable, 5 to 60 mole% is more preferable, and 10 to 50 mole% is more preferable.
In addition, when resin (A) contains both the repeating unit represented by General formula (1), and the repeating unit represented by General formula (2), the said content is total amount of these. is there.

The repeating unit represented by the general formula (1) or (2) is preferably, for example, a repeating unit derived from a cyclopolymerizable monomer. More specifically, it is obtained, for example, by cyclopolymerization of a diene monomer.
Moreover, resin (A) may have other repeating units other than the repeating unit represented by General formula (1) or (2).

(Repeating unit having an acid decomposable group represented by the general formula (3))
It is also preferable that the resin (A) further has a repeating unit having an acid decomposable group represented by the following general formula (3).

In the general formula (3), R ₆ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
The alkyl group may have a substituent, and examples of the substituent include a hydroxy group and a halogen atom (preferably a fluorine atom).
Among them, the alkyl group is preferably an alkyl group having a carbon number of 1 to 4, more preferably a methyl group, an ethyl group, a propyl group, a hydroxymethyl group or a trifluoromethyl group, still more preferably a methyl group.

In General Formula (3), L ₃ represents a divalent linking group which may have a substituent.
L ₃ is preferably an alkylene group, an arylene group, a carbonyl group, an ester group, or a divalent linking group combining these, and a carbonyl group, an -alkylene group, a -carbonyl group, an -arylene group, a -carbonyl group,- An ester group-alkylene group-carbonyl group- is more preferable, and a carbonyl group is more preferable.
In addition, the said alkylene group and arylene group may have a substituent, and a halogen atom is preferable as a substituent.

X represents an acid leaving group and has the same meaning as R _c described in the general formula (R ′ ′) described above, and the preferred range is also the same.

In the general formula (3), examples of -L ₃ -OX include the groups shown as specific examples of the group represented by the above-mentioned general formula (R ′ ′).

The following groups are also mentioned as an example of -L ₃ -O-X.

Resin (A) may have the repeating unit represented by General formula (3) individually by 1 type, and may use it in combination of 2 or more types.

The content of the repeating unit having an acid decomposable group represented by the general formula (3) is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, based on all repeating units of the resin (A). And 30 to 80 mol% are more preferable.

(Repeating unit having a lactone group, a sultone group, or a carbonate group)
The resin (A) preferably has a repeating unit having at least one group selected from the group consisting of lactone groups, sultone groups, and carbonate groups.
However, unless otherwise specified, the repeating unit having a lactone group referred to herein is a repeating unit represented by the above-mentioned general formula (1) or (2) and having a lactone group (in particular, Repeating units other than the repeating unit having a group represented by ') are intended.

The lactone group and the sultone group are the same as the lactone group and the sultone group which can be V described in the general formula (R ′), and the preferred ranges are also the same.

As a repeating unit having a lactone group or a sultone group, a repeating unit represented by the following general formula (III) is preferable.

In the above general formula (III),
A represents an ester group (-COO-) or an amido group (-CONH-).
n represents an integer of 0 to 5, preferably 0 or 1, and more preferably 0.
R ₀ represents an alkylene group or a cycloalkylene group which may have a substituent, or a combination thereof. When a plurality of R ₀ exist, R ₀ may be the same or different.
Z represents a single bond, an ether group, an ester group, an amido group, a urethane group or a urea group. When a plurality of Z are present, Z may be the same or different. As Z, an ether group or an ester group is preferable, and an ester group is more preferable.
R ₈ represents a lactone group or a sultone group.
R ₇ represents a hydrogen atom, a halogen atom, or an organic group (preferably a methyl group).

The resin (A) may have a repeating unit having a carbonate group. As a carbonate group, a cyclic carbonate group is preferable.
As a repeating unit having a cyclic carbonate group, a repeating unit represented by the following general formula (A-1) is preferable.

In formula (A-1), R _A ¹ represents a hydrogen atom, a halogen atom, or an organic group (preferably a methyl group).
n represents an integer of 0 or more.
R _A ² represents a substituent. When n is 2 or more, R _A ² independently represents a substituent.
A represents a single bond or a divalent linking group.
Z represents an atomic group forming a monocyclic or polycyclic group with a group represented by —O—C (= O) —O— in the formula.

Resin (A) is a repeating unit having at least one group selected from the group consisting of a lactone group, a sultone group, and a carbonate group, as described in paragraph <0370> of US Patent Application Publication No. 2016 / 0070167A1. It is also preferable to have the repeating unit described in <0414>.

The resin (A) may have a repeating unit having at least one group selected from the group consisting of a lactone group, a sultone group, and a carbonate group by one type alone, and two or more types may be used in combination You may have.

Specific examples of the monomer corresponding to the repeating unit represented by the general formula (III) and specific examples of the monomer corresponding to the repeating unit represented by the general formula (A-1) will be given below. It is not limited to these specific examples. The following specific examples correspond to the case where R ₇ in the general formula (III) and R _A ¹ in the general formula (A-1) are a methyl group, but R ₇ and R _A ¹ are a hydrogen atom, a halogen atom Or, it can be optionally substituted by an organic group.

In addition to the above monomers, the following monomers are also suitably used as a raw material of the resin (A).

The content of the repeating unit having at least one group selected from the group consisting of a lactone group, a sultone group, and a carbonate group is 5 to 70% by mole based on all repeating units in the resin (A). Preferably, it is 10 to 65 mol%, more preferably 20 to 60 mol%.
In addition, said content is the quantity which totaled each, when multiple repeating units which have at least 1 sort (s) of groups selected from the group which consists of a lactone group, a sultone group, and a carbonate group exist.

(Repeating unit having polar group)
In addition to the repeating units represented by the general formula (1) or (2), the resin (A) may have a repeating unit having a polar group.
As a polar group, a hydroxy group, a cyano group, a carboxy group, or a fluorinated alcohol group etc. are mentioned.
The repeating unit having a polar group is preferably a repeating unit having an alicyclic group substituted by a polar group.
Especially, it is preferable that resin (A) is a repeating unit which has a polar group, Comprising: It is preferable to have a repeating unit which does not have an acid degradable group.
As an alicyclic group in the alicyclic group substituted by the polar group, an adamantyl group or a norbornane group is preferable.

Although the specific example of the monomer corresponded to the repeating unit which has a polar group below is given, this invention is not limited to these specific examples.

Other specific examples of the repeating unit having a polar group include the repeating units disclosed in paragraphs <0415> to <0433> of US Patent Application Publication 2016/0070167 A1.
The resin (A) may have a repeating unit having a polar group singly or in combination of two or more.
The content of the repeating unit having a polar group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, still more preferably 10 to 25 mol%, based on all the repeating units in the resin (A).

(A repeating unit having neither an acid-degradable group nor a polar group)
The resin (A) also preferably has a repeating unit having neither an acid-degradable group nor a polar group. It is preferable that the repeating unit which has neither an acid-degradable group nor a polar group has an alicyclic group. Examples of the repeating unit having neither an acid degradable group nor a polar group include the repeating units described in paragraphs <0236> to <0237> of US Patent Application Publication No. 2016 / 0026083A1. Preferred examples of monomers corresponding to repeating units having neither an acid-degradable group nor a polar group are shown below.

Other specific examples of the repeating unit having neither an acid degradable group nor a polar group include the repeating units disclosed in paragraph <0433> of US Patent Application Publication No. 2016/0070167 A1. .
The resin (A) may have a single type of repeating unit having neither an acid degradable group nor a polar group, and may have two or more types in combination.
The content of the repeating unit having neither an acid decomposable group nor a polar group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, based on all repeating units in the resin (A). 5 to 25 mol% is more preferable.

The resin (A) has dry etching resistance, standard developer suitability, substrate adhesion, resist profile, or, in addition to the above-mentioned repeating unit, resolution, heat resistance, or sensitivity which are generally necessary characteristics of resists. You may have various repeating units for the purpose of adjusting etc.
Such repeating units include, but are not limited to, repeating units corresponding to a predetermined monomer.

As the predetermined monomer, for example, an addition-polymerizable unsaturated bond selected from acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. The compound etc. which have individual are mentioned.
In addition, addition polymerizable unsaturated compounds copolymerizable with the monomers corresponding to the above-mentioned various repeating structural units may be used.
In the resin (A), the content molar ratio of each repeating structural unit is appropriately set to adjust various performances.

When the composition of the present invention is for ArF exposure, it is preferable that the resin (A) substantially does not have an aromatic group from the viewpoint of ArF light transmittance. More specifically, the repeating unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, based on all repeating units in the resin (A), and ideally Is more preferably 0 mol%, that is, it does not have a repeating unit having an aromatic group. In addition, the resin (A) preferably has a monocyclic or polycyclic alicyclic group.

In the resin (A), the acrylate-based repeating unit is preferably 50 mol% or less based on all repeating units of the resin (A).

When the composition of the present invention is for KrF exposure, EB exposure or EUV exposure, the resin (A) preferably has a repeating unit having an aromatic hydrocarbon group. More preferably, the resin (A) has a repeating unit having a phenolic hydroxy group. As a repeating unit which has a phenolic hydroxy group, a hydroxystyrene repeating unit or a hydroxystyrene (meth) acrylate repeating unit is mentioned.
When the composition of the present invention is for KrF exposure, EB exposure or EUV exposure, the resin (A) is a group from which the hydrogen atom of the phenolic hydroxy group is decomposed and eliminated by the action of acid (acid releasability It is preferable to have a structure protected by (group).
The content of the repeating unit having an aromatic hydrocarbon group contained in the resin (A) is preferably 30 to 100 mol%, more preferably 40 to 100 mol%, with respect to all the repeating units in the resin (A). And 50 to 100 mol% are more preferable.

The weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, still more preferably 3,000 to 15,000, and 3,000 to 11,000. Particularly preferred. The dispersion degree (Mw / Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and still more preferably 1.1 to 2.0. preferable.

Resin (A) may be used individually by 1 type, and may use 2 or more types together.
The content of the resin (A) in the total solid content of the composition of the present invention is not particularly limited, but 10% by mass or more is preferable, 20% by mass or more is more preferable, 40 to 99.5% by mass is preferable, -99% by mass is more preferable, and 80-97% by mass is more preferable.

<Photo acid generator (C)>
The composition of the present invention contains a photoacid generator (hereinafter also referred to as "photoacid generator (C)").
The photoacid generator is a compound that generates an acid upon irradiation with an actinic ray or radiation.
As the photoacid generator, a compound capable of generating an organic acid upon irradiation with an actinic ray or radiation is preferable. Examples include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imidosulfonate compounds, oxime sulfonate compounds, diazodisulfone compounds, disulfone compounds, and o-nitrobenzyl sulfonate compounds.

As the photoacid generator, known compounds which generate an acid upon irradiation with an actinic ray or radiation can be appropriately selected and used alone or as a mixture thereof. For example, paragraphs <0125> to <0319> of U.S. Patent Application Publication 2016/0070167 A1; paragraphs <0086> to <0094> of U.S. Patent Application Publication 2015/0004544 A1, and U.S. Patent Application Publication 2016 / The known compounds disclosed in paragraphs <0323> to <0402> of the specification can be suitably used as the photoacid generator (C).

As a photo-acid generator (C), the compound represented by the following general formula (ZI), general formula (ZII), or general formula (ZIII) is preferable, for example.

In the above general formula (ZI),
Each of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ independently represents an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.
In addition, two of R ₂₀₁ to R ₂₀₃ may be combined 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. Examples of the group formed by bonding of two of R ₂₀₁ to R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group) and CH ₂ -CH ₂ -O-CH ₂ -CH _2- .
Z ^- represents an anion.

Preferred embodiments of the cation in the general formula (ZI) include the compounds (ZI-1), the compound (ZI-2), the compound (ZI-3) and the corresponding groups in the compound (ZI-4) described later. It can be mentioned.
The photoacid generator (C) may be a compound having a plurality of structures represented by general formula (ZI). For example, at least one of _R 201 _{~ R 203} of the compound represented by formula (ZI), the another compound represented by formula (ZI) of _R 201 _{~ R 203} at least one and is, It may be a compound having a structure linked via a single bond or a linking group.

First, the compound (ZI-1) will be described.
The compound (ZI-1) is an arylsulfonium compound in which at least one of R ₂₀₁ to R _{203 in} the general formula (ZI) is an aryl group, that is, a compound having an arylsulfonium as a cation.
In the arylsulfonium compound, all of R ₂₀₁ to R ₂₀₃ may be aryl groups, or a part of R ₂₀₁ to R ₂₀₃ may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group.
Examples of arylsulfonium compounds include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

The aryl group contained in the arylsulfonium compound is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, or a sulfur atom or the like. Examples of the heterocyclic structure include pyrrole residue, furan residue, thiophene residue, indole residue, benzofuran residue, and 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 which the arylsulfonium compound optionally has is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or 3 to 6 carbon atoms. The cycloalkyl group of 15 is preferable, and examples thereof include a methyl group, 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.

The aryl group, alkyl group and cycloalkyl group of _R201 to _R203 are each independently 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, It may have 6 to 14 carbon atoms, an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxy group or a phenylthio group as a substituent.

Next, the compound (ZI-2) will be described.
The compound (ZI-2) is a compound in which each of R ₂₀₁ to R ₂₀₃ in formula (ZI) independently represents an organic group having no aromatic ring. Here, the aromatic ring also includes an aromatic ring having a hetero atom.
The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, and preferably 1 to 20 carbon atoms.
Each of _R201 to _R203 independently is preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, and is a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group or An alkoxycarbonylmethyl group is more preferable, and a linear or branched 2-oxoalkyl group is more preferable.

As the alkyl group and cycloalkyl group of R ₂₀₁ to R _203, a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (eg, methyl group, ethyl group, propyl group, A butyl group, and a pentyl group and the like, and a cycloalkyl group having a carbon number of 3 to 10 (for example, a cyclopentyl group, a cyclohexyl group, and a norbornyl group) are preferable.
R ₂₀₁ to R ₂₀₃ may be further substituted by a halogen atom, an alkoxy group (for example, 1 to 5 carbon atoms), a hydroxy 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 having a phenacylsulfonium salt structure.

In the general formula (ZI-3),
R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxy Represents a group, a nitro group, an alkylthio group or an arylthio group.
R _6c and R _7c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
Each of R _x and R _y 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 respectively combine to form a ring structure Each ring structure may independently 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, and a polycyclic fused ring in which two or more of these rings are combined. The ring structure is usually a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

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. Examples of the alkylene group include a methylene group and an ethylene group.
Zc ^- represents an anion.

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

In the general formula (ZI-4),
l represents an integer of 0 to 2;
r represents an integer of 0 to 8;
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxy 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.
R ₁₄ represents a group having a hydroxy 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. These groups may have a substituent. When a plurality of R ₁₄ are present, they may be the same or different.
Each R ₁₅ independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have a substituent. Two R ₁₅ may bond to each other to form a ring. When two R ₁₅ bonds to each other to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. In one aspect, it is preferred that two R ₁₅ be an alkylene group and combine with each other to form a ring structure.
Z ^- represents an anion.

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

Next, general formulas (ZII) and (ZIII) will be described.
In formulas (ZII) and (ZIII), each of R ₂₀₄ to R ₂₀₇ independently represents an aryl group, an alkyl group or a cycloalkyl group.
The aryl group of R ₂₀₄ to R ₂₀₇ is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group of R ₂₀₄ to R ₂₀₇ 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 skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
As the alkyl group and cycloalkyl group of R ₂₀₄ to R _207, a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (eg, methyl group, ethyl group, propyl group, A butyl group or a pentyl group) or a cycloalkyl group having 3 to 10 carbon atoms (eg, a cyclopentyl group, a cyclohexyl group or a norbornyl group) is preferable.

The aryl group, alkyl group and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may each independently have a substituent. Examples of the substituent which the aryl group, alkyl group and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have include, for example, an alkyl group (for example, 1 to 15 carbon atoms) and a cycloalkyl group (for example, 3 carbon atoms) And 15), an aryl group (for example, 6 to 15 carbon atoms), an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxy group, and a phenylthio group.
Z ^- represents an anion.

Formula Z in (ZI) ^-, the formula Z in (ZII) ^-, Zc in formula (ZI-3) ^-, and, Z in formula (ZI-4) ^- as represented by the following general formula (3) The anion represented by is preferable.

In general formula (3),
o represents an integer of 1 to 3; p represents an integer of 0 to 10. q represents an integer of 0 to 10;

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The carbon number of this alkyl group is preferably 1 to 10, and more preferably 1 to 4. As the alkyl group substituted by at least one fluorine atom, a perfluoroalkyl group is preferable.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF ₃ . In particular, it is more preferable that both Xf be a fluorine atom.

R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When a plurality of R ₄ and R ₅ are present, R ₄ and R ₅ may be the same or different.
The alkyl group represented by R ₄ and R ₅ may have a substituent, and preferably has 1 to 4 carbon atoms. R ₄ and R ₅ are preferably hydrogen atoms.
Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as specific examples and preferred embodiments of Xf in the general formula (3).

L represents a divalent linking group. When a plurality of L are present, L may be the same or different.
Examples of the divalent linking group include, for example, -COO-(-C (= O) -O-), -CONH-, -CO-, -O-, -S-, -SO-, -SO _2- , An alkylene group (preferably having a carbon number of 1 to 6), a cycloalkylene group (preferably having a carbon number of 3 to 15), an alkenylene group (preferably having a carbon number of 2 to 6), and a divalent linking group combining a plurality of these Etc. Among them, -COO -, - CONH -, - 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.

W represents an organic group having a cyclic structure. Among these, cyclic organic groups are preferable.
As a cyclic organic group, an alicyclic group, an aryl group, and a heterocyclic group are mentioned, for example.
The alicyclic group may be monocyclic or polycyclic. As a monocyclic alicyclic group, monocyclic cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group, are mentioned, for example. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as norbornyl group, tricyclodecanyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. Among them, an alicyclic group having a bulky structure having 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group is preferable.

The aryl group may be monocyclic or polycyclic. Examples of this aryl group include phenyl group, naphthyl group, phenanthryl group, and anthryl group.
The heterocyclic group may be monocyclic or polycyclic. The polycycle can suppress the diffusion of acid more. 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. The hetero ring having no aromaticity includes, for example, tetrahydropyran ring, lactone ring, sultone ring, and decahydroisoquinoline ring. Examples of lactone ring and sultone ring include lactone group and sultone group exemplified in the above-mentioned resin. The heterocyclic ring in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring or a decahydroisoquinoline ring.

The cyclic organic group may have a substituent. As this substituent, for example, an alkyl group (which may be linear or branched and preferably has 1 to 12 carbon atoms), a cycloalkyl group (including, for example, single ring and multiple ring (eg, spiro ring) is also included. And C 3-20 are preferable), an aryl group (preferably having a carbon number of 6 14), a hydroxy group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, and a thioether group. , A sulfonamide group, and a sulfonic acid ester group. In addition, the carbon atom (carbon atom which contributes to ring formation) which comprises cyclic organic group may be a carbon atom which forms a carbonyl group.

As the anion represented by the general formula (3), SO ₃ ^-- CF ₂ -CH ₂ -OCO- (L) q'-W, SO ₃ ^-- CF ₂ -CHF-CH ₂ -OCO- (L) _{^{_{q'-W, SO 3 - -CF}}} 2 -COO- (L) q'-W, SO 3 - -CF 2 -CF 2 -CH 2 -CH 2 - (L) q-W or,, SO ₃ ^- -CF ₂ -CH (CF ₃ ) -OCO- (L) q'-W is preferred. Here, L, q, and W are the same as in the general formula (3). q 'represents an integer of 0 to 10;

In one embodiment, Z in formula (ZI) ^-, Z in the general formula (ZII) ^-, Zc in formula (ZI-3) ^-, and, Z in formula (ZI-4) ^- as the following The anion represented by formula (4) is also preferred.

In general formula (4),
Each of X ^B1 and X ^B2 independently represents a hydrogen atom or an organic group having no fluorine atom. X ^B1 and X ^B2 are preferably hydrogen atoms.
Each of X ^B3 and X ^B4 independently represents a hydrogen atom or an organic group. Is preferably at least one of X ^B3 and X ^B4 are an organic group having a fluorine atom or a fluorine atom, and more preferably both X ^B3 and X ^B4 are an organic group having a fluorine atom or a fluorine atom. More preferably, both X ^B3 and X ^B4 are an alkyl group substituted with a fluorine atom.
L, q and W are the same as in the general formula (3).

Z in the general formula (ZI) ^-, Z in the general formula (ZII) ^-, Zc in formula (ZI-3) ^-, and, Z in formula (ZI-4) ^- is a benzenesulfonate anion It is also preferable that it is a benzenesulfonic acid anion substituted by a branched alkyl group or a cycloalkyl group.

Z in the general formula (ZI) ^-, Z in the general formula (ZII) ^-, Zc in formula (ZI-3) ^-, and, Z in formula (ZI-4) ^- The following general formula (SA1 The aromatic sulfonate anion represented by) is also preferable.

In the formula (SA1),
Ar represents an aryl group, and may further have a substituent other than a sulfonate anion and a (D-B) group. Examples of the substituent which may further have a fluorine atom and a hydroxy group.

N represents an integer of 0 or more. As n, 1 to 4 is preferable, 2 to 3 is more preferable, and 3 is more preferable.

D represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfonic acid group, a sulfonic acid ester group, an ester group, and a group composed of a combination of two or more of these.

B represents a hydrocarbon group.

Preferably, D is a single bond and B is an aliphatic hydrocarbon structure. B is more preferably isopropyl or cyclohexyl.

Preferred examples of the sulfonium cation in the general formula (ZI) and the iodonium cation in the general formula (ZII) are shown below.

Preferred examples of the anion Z ⁻ in the general formula (ZI) and the general formula (ZII), Zc ⁻ in the general formula (ZI-3), and Z ^{− in} the general formula (ZI-4) are shown below.

The above-mentioned cations and anions can be optionally combined and used as a photoacid generator.

The photoacid generator may be in the form of a low molecular weight compound, or may be in the form of being incorporated into a part of a polymer. Also, the form of the low molecular weight compound and the form incorporated into a part of the polymer may be used in combination.
The photoacid generator is preferably in the form of a low molecular weight compound.
When the photoacid generator is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,000 or less.
When the photoacid generator is in a form incorporated into a part of a polymer, it may be incorporated into a part of the resin (A) described above, or may be incorporated into a resin different from the resin (A) .
A photo-acid generator may be used individually by 1 type, and may use 2 or more types together.
The content of the photoacid generator in the composition (the total amount of the multiple types, if any) is preferably 0.1 to 35% by mass, based on the total solid content of the composition, 0.5 to 25% by mass Is more preferable, 3 to 20% by mass is further preferable, and 3 to 17% by mass is particularly preferable.
When the photoacid generator contains a compound represented by the above general formula (ZI-3) or (ZI-4), the content of the photoacid generator contained in the composition The total amount is preferably 5 to 35% by mass, and more preferably 7 to 30% by mass, based on the total solid content of the composition.

<Resin (B)>
When the composition of the present invention contains a crosslinking agent (G) described later, the composition of the present invention contains an alkali-soluble resin (B) having a phenolic hydroxy group (hereinafter also referred to as “resin (B)”) Is preferred. The resin (B) preferably has a repeating unit having a phenolic hydroxy group.
In this case, typically, a negative pattern is suitably formed.
The crosslinking agent (G) may be in a form supported by the resin (B).
The resin (B) may have the acid-degradable group described above.

As a repeating unit which has a phenolic hydroxy group which resin (B) has, the repeating unit represented by the following general formula (II) is preferable.

In general formula (II),
R ₂ represents a hydrogen atom, an alkyl group (preferably a methyl group), or a halogen atom (preferably a fluorine atom).
B 'represents a single bond or a divalent linking group.
Ar 'represents an aromatic ring group.
m represents an integer of 1 or more.
Resin (B) may be used individually by 1 type, and may use 2 or more types together.
The content of the resin (B) in the total solid content of the composition of the present invention is not particularly limited, but generally 30% by mass or more in many cases, preferably 40 to 99% by mass, and 50 to 90% by mass Is more preferable, and 50 to 85% by mass is more preferable.
As the resin (B), resins disclosed in paragraphs <0142> to <0347> of US Patent Application Publication No. 2016/0282720 A1 can be suitably mentioned.

<Acid diffusion control agent (D)>
The composition of the present invention preferably contains an acid diffusion control agent (D). The acid diffusion control agent (D) traps an acid generated from a photoacid generator or the like at the time of exposure, and acts as a quencher to suppress the reaction of the acid decomposable resin in the unexposed area by the extra generated acid. For example, a basic compound (DA), a basic compound (DB) whose basicity is reduced or disappears upon irradiation with an actinic ray or radiation, an onium salt (DC) which becomes a relatively weak acid to an acid generator, a nitrogen atom And an onium salt compound (DE) having a nitrogen atom in the cation part can be used as an acid diffusion control agent. In the composition of the present invention, known acid diffusion control agents can be suitably used. For example, paragraphs <0627> to <0664> of U.S. Patent Application Publication 2016/0070167 A1; paragraphs <0095> to <0187> of U.S. Patent Application Publication 2015/0004544 A1, U.S. Patent Application Publication 2016/0237190 A1 The known compounds disclosed in paragraphs <0403> to <0423> of the specification and paragraphs <0259> to <0328> of US Patent Application Publication No. 2016 / 0274458A1 are suitable as the acid diffusion control agent (D) It can be used for

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

In the general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ^{202, which} may be the same or different, each independently represent a hydrogen atom, an alkyl group (preferably 1 to 20 carbon atoms), a cycloalkyl group (preferably 3 to 20 carbon atoms), or And an aryl group (having 6 to 20 carbon atoms). R ²⁰¹ and R ²⁰² may bond to each other to form a ring.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ^{206, which} may be the same or different, each independently represent an alkyl group having 1 to 20 carbon atoms.

The alkyl group in the general formulas (A) and (E) may have a substituent or may not be substituted.
As the alkyl group having a substituent, as the alkyl group having a substituent, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms is preferable.
The alkyl group in the general formulas (A) and (E) is more preferably unsubstituted.

The basic compound (DA) is preferably guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkyl morpholine or piperidine, and the like, and has an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure. More preferred are a compound having a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxy group and / or an ether bond, or an aniline derivative having a hydroxy group and / or an ether bond.

Basic compound (DB) whose basicity decreases or disappears upon irradiation with actinic rays or radiation
(Hereafter, it is also referred to as “compound (DB)”) has a proton acceptor functional group and decomposes upon irradiation with an actinic ray or radiation to reduce the proton acceptor property, to disappear, or to protonic acid. It is a compound that changes from septic to acidic.

The proton acceptor functional group is a functional group having a group or an electron capable of electrostatically interacting with a proton, and is, for example, a functional group having a macrocyclic structure such as cyclic polyether or π conjugated Means a functional group having a nitrogen atom having a non-covalent electron pair that does not contribute to The nitrogen atom having a noncovalent electron pair not contributing to the π conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula.

Preferred partial structures of the proton acceptor functional group include, for example, a crown ether structure, an azacrown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure.

The compound (DB) decomposes upon irradiation with an actinic ray or radiation to reduce or eliminate the proton acceptor property, or generates a compound which has been changed from the proton acceptor property to the acidity. Here, the reduction or disappearance of the proton acceptor property or the change from the proton acceptor property to the acidity is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group, specifically Means that, when a proton adduct is formed from a compound (DB) having a proton acceptor functional group and a proton, the equilibrium constant in its chemical equilibrium is reduced.
The proton acceptor property can be confirmed by performing pH measurement.

The acid dissociation constant pKa of the compound generated by decomposition of the compound (DB) upon irradiation with an actinic ray or radiation preferably satisfies pKa <−1, more preferably −13 <pKa <−1, It is more preferable to satisfy 13 <pKa <-3.

The acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, and is defined, for example, in Chemical Handbook (II) (revised 4th edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.). The lower the value of the acid dissociation constant pKa, the greater the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured by measuring the acid dissociation constant at 25 ° C. using an infinite dilution aqueous solution. Alternatively, a value based on Hammett's substituent constant and a database of known literature values can also be obtained by calculation using the following software package 1. All the pKa values described in the present specification indicate values calculated by using this software package.

Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V 8.14 for Solaris (1994-2007 ACD / Labs).

In the composition of the present invention, an onium salt (DC) that is relatively weak to the photoacid generator can be used as an acid diffusion control agent.
When a photoacid generator and an onium salt that generates an acid that is a relatively weak acid with respect to the acid generated from the photoacid generator are mixed and used, the photoacid generator is irradiated with an actinic ray or radiation. When the acid generated from the acid collides with the onium salt having an unreacted weak acid anion, the weak acid is released by salt exchange to form an onium salt having a strong acid anion. In this process, since the strong acid is exchanged to a weak acid having a lower catalytic ability, the acid is apparently inactivated to control the acid diffusion.

As the onium salt which is relatively weak with respect to the photoacid generator, compounds represented by the following general formulas (d1-1) to (d1-3) are preferable.

In the formula, R ⁵¹ is a hydrocarbon group which may have a substituent, and Z ^2c is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (but carbon adjacent to S) Is a fluorine atom is not substituted), R ⁵² is an organic group, Y ³ is a linear, branched or cyclic alkylene group or an arylene group, R f Is a hydrocarbon group having a fluorine atom, and each M ⁺ is independently an ammonium cation, a sulfonium cation or an iodonium cation.

Preferred examples of the sulfonium cation or iodonium cation represented as M ⁺ include the sulfonium cation exemplified in the general formula (ZI) and the iodonium cation exemplified in the general formula (ZII).

A compound having a cation site and an anion site in the same molecule and a cation site and an anion site linked by a covalent bond (the onium salt (DC) to be a relatively weak acid with respect to the photoacid generator Hereinafter, it may be referred to as “compound (DCA)”.
The compound (DCA) is preferably a compound represented by any one of the following formulas (C-1) to (C-3).

In the general formulas (C-1) to (C-3),
R ₁ , R ₂ and R ₃ each independently represent a substituent having 1 or more carbon atoms.
L ₁ represents a divalent linking group or a single bond linking a cation site and an anion site.
-X ^- it ^{_{^{is, -COO -, -SO 3 -,}}} -SO 2 -, ^{and, N} - represents the anion moiety selected from -R _4. R ₄ represents a carbonyl group (-C (= O)-), a sulfonyl group (-S (= O) _2- ), and a sulfinyl group (-S (= O) at the linking site to the adjacent N atom Represents a substituent having at least one of —).
R ₁ , R ₂ , R ₃ , R ₄ and L ₁ may be combined with each other to form a ring structure. In General Formula (C-3), two of R ₁ to R ₃ may be combined to represent one divalent substituent, which may be bonded to an N atom by a double bond.

As a substituent having 1 or more carbon atoms in R ₁ to R ₃ , an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, a cycloalkylamino group A carbonyl group, and an arylamino carbonyl group etc. are mentioned. Preferably, it is an alkyl group, a cycloalkyl group or an aryl group.

L ₁ as a divalent linking group is a linear or branched alkylene group, a cycloalkylene group, an arylene group, a carbonyl group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, and the like The group etc. which combine 2 or more types are mentioned, An alkylene group, an arylene group, an ether bond, an ester bond, or the group formed by combining 2 or more types of these is preferable.

The low molecular weight compound (DD) having a nitrogen atom and having a group capable of leaving by the action of an acid (hereinafter also referred to as “compound (DD)”) has a group leaving by the action of an acid on the nitrogen atom It is preferable that it is an amine derivative which it has.
As a group leaving by the action of an acid, an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxy group or a hemiaminal ether group is preferable, and a carbamate group or a hemiaminal ether group is more preferable. preferable.
The molecular weight of the compound (DD) is preferably 100 to 1000, more preferably 100 to 700, and still more preferably 100 to 500.
The compound (DD) may have a carbamate group having a protecting group on the nitrogen atom. The protective group constituting the carbamate group is represented by the following general formula (d-1).

In the general formula (d-1),
Each R _b independently represents a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 10), a cycloalkyl group (preferably having a carbon number of 3 to 30), an aryl group (preferably having a carbon number of 3 to 30), and an aralkyl group (Preferably 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably 1 to 10 carbon atoms). R _b may be linked to each other to form a ring.
The alkyl group, cycloalkyl group, aryl group and aralkyl group represented by R _b are each independently functional groups such as hydroxy group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, oxo group and the like, and alkoxy groups Or may be substituted by a halogen atom. The same applies to the alkoxyalkyl group represented by R _b .

As R _b , a linear or branched alkyl group, a cycloalkyl group or an aryl group is preferable, and a linear or branched alkyl group or a cycloalkyl group is more preferable.
Alicyclic hydrocarbon, aromatic hydrocarbon, heterocyclic hydrocarbon, and its derivative etc. are mentioned as a ring which two R _b mutually connects and forms.
Specific examples of the structure of the group represented by Formula (d-1) include, but are not limited to, the structures disclosed in paragraph <0466> of US Patent Publication No. US 2012/0135348 A1.

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

In the general formula (6),
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and l + m = 3 is satisfied.
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 s} may be the same or different, and two R _{a s} may be mutually linked to form a heterocyclic ring with the nitrogen atom in the formula. The hetero 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.
In the general formula (6), the alkyl group as R _a, a cycloalkyl group, an aryl group, and aralkyl group, each independently, alkyl groups as R _b, cycloalkyl group, aryl group, and, an aralkyl group It may be substituted by the same group as the group described above as the group which may be substituted.

Specific examples of the above-mentioned alkyl group of R _a , cycloalkyl group, aryl group and aralkyl group (these groups may be substituted by the above group) are the same as the specific examples described above for R _b Groups are mentioned.
Specific examples of particularly preferred compound (DD) in the present invention include, but are not limited to, the compounds disclosed in paragraph <0475> of US Patent Application Publication 2012/0135348 A1.

The onium salt compound (DE) having a nitrogen atom in the cation part (hereinafter also referred to as “compound (DE)”) is preferably a compound having a basic site having a nitrogen atom in the cation part. The basic moiety is preferably an amino group, more preferably an aliphatic amino group. More preferably, all atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. Further, from the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, and a halogen atom) is not directly linked to the nitrogen atom.
Preferred specific examples of the compound (DE) include, but are not limited to, the compounds disclosed in paragraph <0203> of US Patent Application Publication No. 2015/0309408 A1.

Preferred examples of the acid diffusion control agent (D) are shown below.

In the composition of this invention, an acid diffusion control agent (D) may be used individually by 1 type, and may use 2 or more types together.
The content of the acid diffusion control agent (D) in the composition (the total amount of the multiple species, if any) is preferably 0.1 to 10% by mass based on the total solid content of the composition, 0.1 to 10 5 mass% is more preferable.

<Hydrophobic resin (E)>
The composition of the present invention may contain a hydrophobic resin (E). The hydrophobic resin (E) is preferably a resin different from the resins (A) and (B).
By containing the hydrophobic resin (E), the composition of the present invention can control the static and / or dynamic contact angle on the surface of the resist film. This makes it possible to improve development characteristics, suppress outgassing, improve immersion liquid followability in immersion exposure, and reduce immersion defects.
The hydrophobic resin (E) is preferably designed to be localized on the surface of the resist film, but unlike a surfactant, it does not necessarily have to have a hydrophilic group in the molecule, and polar substances and nonpolar substances It does not have to contribute to uniformly mixing.

The hydrophobic resin (E) is selected from the group consisting of "fluorine atom", "silicon atom", and "CH ₃ partial structure contained in the side chain portion of the resin" from the viewpoint of localization to the film surface. It is preferable that it is resin which has a repeating unit which has at least 1 sort.
When the hydrophobic resin (E) has a fluorine atom and / or a silicon atom, the fluorine atom and / or the silicon atom in the hydrophobic resin (E) may be contained in the main chain of the resin, It may be contained in the chain.

When the hydrophobic resin (E) has 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 Is preferred.

The hydrophobic resin (E) preferably has at least one group selected from the following groups (x) to (z).
(X) Acid group (y) Alkali decomposable group (z) Group to be decomposed by the action of acid

Examples of the acid group (x) include phenolic hydroxy group, carboxylic acid group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) ( (Alkylcarbonyl) imide group, bis (alkyl carbonyl) methylene group, bis (alkyl carbonyl) imide group, bis (alkyl sulfonyl) methylene group, bis (alkyl sulfonyl) imide group, tris (alkyl carbonyl) methylene group, And alkylsulfonyl) methylene groups and the like.
As the acid group, a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfoneimide group or a bis (alkylcarbonyl) methylene group is preferable.

Examples of the alkali degradable group (y) that the hydrophobic resin may have include lactone group, carboxylic acid ester group (-COO-), acid anhydride group (-C (O) OC (O)-), acid Imido group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate group (-OC (O) O-), sulfate group (-OSO ₂ O-), and sulfonate group (- SO ₂ O-) and the like can be mentioned, and a lactone group or a carboxylic acid ester group (-COO-) is preferable.
As a repeating unit containing these groups, it is a repeating unit which these groups are directly couple | bonded with the principal chain of resin, for example, the repeating unit etc. by acrylic acid ester and methacrylic acid ester are mentioned, for example. In this repeating unit, these groups may be bonded to the main chain of the resin via a linking group. Alternatively, this repeating unit may be introduced at the end of the resin by using a polymerization initiator or a chain transfer agent having these groups at the time of polymerization.
As a repeating unit which has a lactone group, the repeating unit similar to the repeating unit which has the lactone structure previously demonstrated by the term of resin (A) is mentioned, for example.

The content of the repeating unit having an alkali-degradable group (y) is preferably 1 to 100 mol%, more preferably 3 to 98 mol%, with respect to all the repeating units in the hydrophobic resin (E). 95 mol% is more preferred.

The repeating unit which has group (z) which decomposes | disassembles by the effect | action of an acid in hydrophobic resin (E) includes the repeating unit similar to the repeating unit which has an acid degradable group mentioned by resin (A). The repeating unit having a group (z) capable of decomposing under the action of an acid may have at least one of a fluorine atom and a silicon atom. The content of the repeating unit having a group (z) capable of decomposing by the action of an acid is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, based on all the repeating units in the hydrophobic resin (E). And 20 to 60 mol% is more preferable.
The hydrophobic resin (E) may further have another repeating unit other than the above-described repeating unit.

The repeating unit having a fluorine atom is preferably 10 to 100% by mole, and more preferably 30 to 100% by mole, based on all repeating units in the hydrophobic resin (E). Further, the repeating unit having a silicon atom is preferably 10 to 100% by mole, and more preferably 20 to 100% by mole, relative to all repeating units in the hydrophobic resin (E).

On the other hand, it is also preferable that the hydrophobic resin (E) does not substantially contain a fluorine atom and a silicon atom, particularly when the hydrophobic resin (E) has a CH ₃ partial structure in the side chain portion. In addition, it is preferable that the hydrophobic resin (E) is substantially constituted only by a repeating unit constituted only by an atom selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom.

The weight average molecular weight of the hydrophobic resin (E) in terms of standard polystyrene is preferably 1,000 to 100,000, and more preferably 1,000 to 50,000.

The total content of the remaining monomer and / or oligomer components contained in the hydrophobic resin (E) is preferably 0.01 to 5% by mass, and more preferably 0.01 to 3% by mass. The degree of dispersion (Mw / Mn) is preferably in the range of 1 to 5, and more preferably in the range of 1 to 3.

As hydrophobic resin (E), well-known resin can be suitably selected and used as an individual or a mixture thereof. For example, known resins disclosed in paragraphs <0451> to <0704> of US Patent Application Publication No. 2015/0168830 A1 and in paragraphs <0340> to <0356> of US Patent Application Publication No. 2016/0274458 A1. Can be suitably used as the hydrophobic resin (E). In addition, repeating units disclosed in paragraphs <0177> to <0258> of US Patent Application Publication No. 2016/0237190 A1 are also preferable as repeating units constituting the hydrophobic resin (E).

Preferred examples of the monomer corresponding to the repeating unit constituting the hydrophobic resin (E) are shown below.

Hydrophobic resin (E) may be used individually by 1 type, and may use 2 or more types together.
It is preferable to use a mixture of two or more types of hydrophobic resins (E) having different surface energy, from the viewpoint of achieving both the immersion liquid followability and the development characteristics in immersion exposure.
The content of the hydrophobic resin (E) in the composition is preferably 0.01 to 10% by mass, and more preferably 0.05 to 8% by mass, with respect to the total solid content in the composition of the present invention.

<Solvent (F)>
The composition of the present invention may contain a solvent.
In the composition of the present invention, known resist solvents can be appropriately used. For example, paragraphs <0665> to <0670> of U.S. Patent Application Publication 2016 / 0070167A1; paragraphs <0210> to <0235> of U.S. Patent Application Publication 2015 / 0004544A1, U.S. Patent Application Publication 2016 / 0237190A1 Known solvents disclosed in paragraphs <0424> to <0426> of the specification and paragraphs <0357> to <0366> of US Patent Application Publication 2016/0274458 A1 can be suitably used.
Examples of solvents that can be used when preparing the composition include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactic acid alkyl ester, alkyl alkoxypropionate, cyclic lactone (preferably having a carbon number of 4 to 10), Examples thereof include organic solvents such as monoketone compounds (preferably having a carbon number of 4 to 10) which may have a ring, alkylene carbonates, alkyl alkoxyacetates and alkyl pyruvates.

As the organic solvent, a mixed solvent obtained by mixing a solvent having a hydroxyl group in the structure and a solvent having no hydroxyl group may be used.
As the solvent having a hydroxy group and the solvent having no hydroxy group, the above-mentioned exemplified compounds can be appropriately selected. As a solvent having a hydroxy group, alkylene glycol monoalkyl ether, alkyl lactate and the like are preferable, and propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate is preferable. More preferable. Further, as the solvent having no hydroxy group, alkylene glycol monoalkyl ether acetate, alkyl alkoxy propionate, monoketone compound which may have a ring, cyclic lactone, alkyl acetate and the like are preferable, and propylene glycol monomethyl Ether acetate (PGMEA), ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate is more preferable, and propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxy propionate, More preferred is cyclohexanone, cyclopentanone or 2-heptanone. Propylene carbonate is also preferable as the solvent having no hydroxy group.
The mixing ratio (mass ratio) of the solvent having a hydroxy group to the solvent having no hydroxy group is usually 1/99 to 99/1, preferably 10/90 to 90/10, and 20/80 to 60 / 40 is more preferred. A mixed solvent containing 50% by mass or more of a solvent having no hydroxy group is preferred in view of coating uniformity.
The solvent preferably contains propylene glycol monomethyl ether acetate, and may be propylene glycol monomethyl ether acetate alone or a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate.

<Crosslinking agent (G)>
The composition of the present invention may contain a compound which crosslinks the resin by the action of an acid (hereinafter, also referred to as a crosslinking agent (G)). A well-known compound can be used suitably as a crosslinking agent (G). For example, known compounds disclosed in paragraphs <0379> to <0431> of US Patent Application Publication No. 2016/0147154 A1 and in paragraphs <0064> to <0141> of US Patent Application Publication No. 2016/0282720 A1. Can be suitably used as the crosslinking agent (G).
The crosslinking agent (G) is a compound having a crosslinkable group capable of crosslinking the resin, and as the crosslinkable group, a hydroxymethyl group, an alkoxymethyl group, an acyloxymethyl group, an alkoxymethyl ether group, an oxirane ring group And oxetane ring groups and the like.
The crosslinkable group is preferably a hydroxymethyl group, an alkoxymethyl group, an oxirane ring group, or an oxetane ring group.
The crosslinking agent (G) is preferably a compound (including a resin) having two or more crosslinkable groups.
The crosslinking agent (G) is more preferably a phenol derivative having a hydroxymethyl group or an alkoxymethyl group, a urea compound (a compound having a urea structure), or a melamine compound (a compound having a melamine structure).
A crosslinking agent may be used individually by 1 type, and may use 2 or more types together.
The content of the crosslinking agent (G) is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, and still more preferably 5 to 30% by mass, with respect to the total solid content of the resist composition.

<Surfactant (H)>
The composition of the present invention may contain a surfactant. When the surfactant is contained, a fluorine-based and / or silicon-based surfactant (specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both a fluorine atom and a silicon atom) Is preferred.

When the composition of the present invention contains a surfactant, when an exposure light source of 250 nm or less, particularly 220 nm or less is used, a pattern with less adhesion and development defects can be obtained with good sensitivity and resolution.
The fluorine-based and / or silicon-based surfactants include the surfactants described in paragraph <0276> of US Patent Application Publication No. 2008/0248425.
In addition, other surfactants other than fluorine-based and / or silicon-based surfactants described in paragraph <0280> of US Patent Application Publication No. 2008/0248425 can also be used.

These surfactants may be used alone or in combination of two or more.
When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, with respect to the total solid content of the composition. preferable.
On the other hand, when the content of the surfactant is 10 ppm or more based on the total solid content of the composition, the surface uneven distribution of the hydrophobic resin (E) is increased. As a result, the surface of the resist film can be made more hydrophobic, and the ability to follow water during immersion exposure is improved.

(Other additives)
The composition of the present invention may further contain an acid multiplier, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali soluble resin, a dissolution inhibitor, a dissolution accelerator, and the like.

<Preparation method>
The solid content concentration of the composition of the present invention is preferably 1.0 to 10% by mass, more preferably 2.0 to 5.7% by mass, and still more preferably 2.0 to 5.3% by mass. The solid content concentration is a mass percentage of the mass of the other components excluding the solvent with respect to the total mass of the composition.

The thickness of the resist film made of the composition of the present invention is preferably 20 μm or less, more preferably 15 μm or less, from the viewpoint of improving resolution. 20 nm or more is preferable and, as for the minimum of the film thickness of a resist film, 40 nm or more is more preferable. 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 adjusting the coating property or the film forming property.

The composition of the present invention is used by dissolving the above-mentioned components in a predetermined organic solvent, preferably the above-mentioned mixed solvent, filtering it, and then applying it on a predetermined support (substrate). 0.1 micrometer or less is preferable, as for the pore size of the filter used for filter filtration, 0.05 micrometer or less is more preferable, and 0.03 micrometer or less is more preferable. The filter is preferably made of polytetrafluoroethylene, polyethylene or nylon. In the filter filtration, for example, as disclosed in JP-A-2002-62667, cyclic filtration may be performed, or filtration may be performed by connecting a plurality of types of filters in series or in parallel. The composition may also be filtered multiple times. Furthermore, the composition may be subjected to a degassing treatment and the like before and after the filter filtration.

<Use>
The composition of the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition which changes its property in response to irradiation with actinic rays or radiation. More specifically, the composition of the present invention can be used in semiconductor manufacturing processes such as IC, manufacture of circuit substrates such as liquid crystals or thermal heads, preparation of imprint mold structures, other photofabrication processes, or lithographic printing plates About. The pattern formed using the composition of the present invention can be used in an etching process, an ion implantation process, a bump electrode formation process, a rewiring formation process, or MEMS (Micro Electro Mechanical Systems).

[Pattern formation method]
The present invention also relates to a method of forming a pattern using the above actinic ray sensitive or radiation sensitive resin composition. Hereinafter, the pattern formation method of the present invention will be described. In addition to the description of the pattern formation method, the resist film (the actinic ray-sensitive or radiation-sensitive film) of the present invention is also described.

The pattern formation method of the present invention is
(I) forming a resist film on a support using the actinic ray-sensitive or radiation-sensitive resin composition described above (film forming step (resist film forming step)),
(Ii) exposing the resist film (irradiating with an actinic ray or radiation) (exposure step), and
(Iii) developing the exposed resist film with a developer (developing step).

The pattern formation method of the present invention is not particularly limited as long as it includes the above steps (i) to (iii), and may further have the following steps.
In the pattern formation method of the present invention, (ii) the exposure method in the exposure step may be immersion exposure.
The pattern formation method of the present invention preferably includes (iv) a preheating (PB: PreBake) step before (ii) the exposure step.
The pattern formation method of the present invention preferably includes (v) a post exposure baking (PEB) step after (ii) the exposure step and (iii) before the development step.
The pattern formation method of the present invention may include (ii) multiple exposure steps.
The pattern formation method of the present invention may include (iv) a preheating step a plurality of times.
The pattern formation method of the present invention may include (v) a post-exposure heating step a plurality of times.

In the pattern formation method of the present invention, the above-described (i) film formation step, (ii) exposure step, and (iii) development step can be performed by generally known methods.
In addition, if necessary, a resist underlayer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon), and antireflective film) may be formed between the resist film and the support. As a material which comprises a resist underlayer film, a well-known organic type or inorganic type material is used suitably.
A protective film (top coat) may be formed on the upper layer of the resist film. A well-known material is suitably used as a protective film. For example, U.S. Patent Application Publication No. 2007/0178407, U.S. Patent Application Publication No. 2008/0085466, U.S. Patent Application Publication No. 2007/0275326, U.S. Patent Application Publication No. 2016/0299432, The composition for protective film formation disclosed by US Patent Application Publication No. 2013/0244438 and International Patent Application Publication No. 2016 / 157988A can be suitably used. As a composition for protective film formation, the composition for protective film formation containing the acid diffusion control agent mentioned above is preferable.
A protective film may be formed on the upper layer of the resist film containing the hydrophobic resin described above.

The support is not particularly limited, and a substrate generally used in other photofabrication lithography processes or the like can be used in addition to the process of manufacturing semiconductors such as ICs or the process of manufacturing circuit substrates such as liquid crystals or thermal heads. . Specific examples of the support include silicon, SiO ₂ , and inorganic substrates such as SiN.

The heating temperature is preferably 70 to 130 ° C. and more preferably 80 to 120 ° C. in any of the (iv) pre-heating step and the (v) post-exposure heating step.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds in any of the (iv) pre-heating step and (v) post-exposure heating step.
The heating can be performed by means provided in the exposure device and the developing device, and may be performed using a hot plate or the like.

The light source wavelength used in the exposure step is not limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams. Among these, far ultraviolet light is preferable, and its wavelength is preferably 250 nm or less, more preferably 220 nm or less, and still more preferably 1 to 200 nm. Specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), _{F 2} excimer laser (157 nm), X-ray, EUV (13 nm), or, preferably electron beams, KrF excimer laser, ArF excimer laser , EUV or electron beam is more preferable.

(Iii) In the developing step, the developing solution may be either an alkaline developing solution or a developing solution containing an organic solvent (hereinafter also referred to as an organic developing solution).

Usually, quaternary ammonium salts represented by tetramethyl ammonium hydroxide are used as the alkaline developer, but in addition to this, alkaline aqueous solutions such as inorganic alkalis, primary to tertiary amines, alcohol amines and cyclic amines are also used. It is usable.
Furthermore, the above alkaline developer may contain an appropriate amount of alcohol and / or surfactant. The alkali concentration of the alkali developer is usually 0.1 to 20% by mass. The pH of the alkaline developer is usually 10-15.
The time for developing using an alkaline developer is usually 10 to 300 seconds.
The alkali concentration, pH, and development time of the alkali developer can be appropriately adjusted according to the pattern to be formed.

The organic developer is a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. Preferably there.

Examples of ketone solvents 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, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone, isophorone, propylene carbonate and the like.

As ester solvents, for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl 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-ethoxy propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, butyl lactate, butane And butyl acid, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.

As the alcohol solvent, the amide solvent, the ether solvent, and the hydrocarbon solvent, the solvents disclosed in paragraphs <0715> to <0718> of US Patent Application Publication No. 2016/0070167 A1 can be used.

A plurality of the above solvents may be mixed, or may be mixed with a solvent other than the above or water. The water content of the developer as a whole is preferably less than 50% by weight, more preferably less than 20% by weight, still more preferably less than 10% by weight, and particularly preferably substantially free of water.
The content of the organic solvent to the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, with respect to the total amount of the developer. % Is particularly preferred.

The developer may contain an appropriate amount of a known surfactant as needed.

The content 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.

The organic developer may contain the acid diffusion control agent described above.

As a developing method, for example, a method of immersing the substrate in a bath filled with a developer for a certain time (dip method), a method of raising the developer on the substrate surface by surface tension and standing still for a certain time (paddle method) Method of spraying the developer on the surface (spray method) or method of continuing to discharge the developer while scanning the developer discharge nozzle at a constant speed on the substrate rotating at a constant speed (dynamic dispense method) It can be mentioned.

The step of developing using an aqueous alkali solution (alkali developing step) and the step of developing using a developer containing an organic solvent (organic solvent developing step) may be combined. As a result, since pattern formation can be performed without dissolving only the region of intermediate exposure intensity, a finer pattern can be formed.

(Iii) It is preferable to include the process (rinse process) wash | cleaned using a rinse agent after the image development process.

The rinse liquid used for the rinse process after the image development process using an alkaline developing solution can use a pure water, for example. The pure water may contain an appropriate amount of surfactant. In addition, after the development step or the rinse step, a process of removing the developer or rinse solution adhering on the pattern with a supercritical fluid may be added. Furthermore, after the rinsing process or the process with the supercritical fluid, a heat treatment may be performed to remove moisture remaining in the pattern.

The rinse liquid used for the rinse process after the development process using the developing solution containing an organic solvent does not have a restriction | limiting in particular, if the pattern is not melt | dissolved, The solution containing a common organic solvent can be used. As the rinse solution, a rinse solution 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 is used. Is preferred.
Specific examples of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents include the same examples as those described for the developer containing an organic solvent.
As the rinse solution used in the rinse step in this case, a rinse solution containing a monohydric alcohol is more preferable.

Examples of the monohydric alcohol used in the rinsing step include linear, branched or cyclic monohydric alcohol. Specifically, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1 Heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and methyl isobutyl carbinol. Examples of monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and methyl isobutyl carbinol. Be

A plurality of each component may be mixed, or may be mixed with an organic solvent other than the above.
10 mass% or less is preferable, as for the water content in the rinse liquid at the time of using the solution containing an organic solvent as a rinse liquid, 5 mass% or less is more preferable, and 3 mass% or less is more preferable. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

When using a solution containing an organic solvent as a rinse liquid, the rinse liquid may contain an appropriate amount of surfactant.
In the rinse step in this case, the substrate which has been developed using the organic developer is washed using a rinse solution containing an organic solvent. Although the method of the cleaning process is not particularly limited, for example, a method of continuously discharging the rinse liquid onto the substrate rotating at a constant speed (rotation coating method), and immersing the substrate in a bath filled with the rinse liquid for a fixed time Examples include a method (dip method) or a method of spraying a rinse liquid on the substrate surface (spray method). Among them, it is preferable to carry out cleaning treatment by spin coating, and after cleaning, rotate the substrate at a rotational speed of 2,000 to 4,000 rpm to remove the rinse solution from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. This heating step removes the developer and rinse solution remaining between the patterns and within the patterns. In the heating step after the rinsing step, the heating temperature is usually 40 to 160 ° C., preferably 70 to 95 ° C., and the heating time is usually 10 seconds to 3 minutes, preferably 30 to 90 seconds.

The composition of the present invention, and various materials used in the pattern forming method of the present invention (for example, a developer, a rinse solution, a composition for forming an antireflective film, a composition for forming a top coat, etc.) It is preferable not to contain impurities such as components, isomers, and residual monomers. The content of these impurities contained in the above-mentioned various materials is preferably 1 ppm or less, more preferably 100 ppt or less, still more preferably 10 ppt or less, and substantially not including it (the detection limit of the measuring device or less) Is particularly preferred.

As a method of removing impurities, such as a metal, from said various materials, the filtration using a filter is mentioned, for example. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, 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 used by washing in advance with an organic solvent. In the filter filtration step, plural types of filters may be connected in series or in parallel. When multiple types of filters are used, filters with different pore sizes and / or different materials may be used in combination. Also, the various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulation filtration step. As the filter, a filter with reduced eluate as disclosed in JP-A-2016-201426 is preferable.
In addition to filter filtration, removal of impurities by adsorbent may be performed, and filter filtration and adsorbent may be used in combination. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel or zeolite, or organic adsorbents such as activated carbon can be used. As a metal adsorption material, the metal adsorption material indicated by JP, 2016-206500, A is mentioned, for example.
In addition, as a method of reducing impurities such as metals contained in the above-mentioned various materials, filter filtration is performed on the materials constituting the various materials, in which the material having a small metal content is selected as the materials constituting the various materials. Alternatively, there may be mentioned a method such as distilling under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark) or the like. The preferable conditions in the filter filtration performed with respect to the raw material which comprises various materials are the same as the conditions mentioned above.

The above-mentioned various materials are preferably stored in the container described in US Patent Application Publication 2015/0227049 or Japanese Patent Application Laid-Open No. 2015-123351 etc. in order to prevent the contamination of impurities.

A method of improving the surface roughness of the pattern may be applied to the pattern formed by the pattern forming method of the present invention. As a method of improving the surface roughness of the pattern, for example, a method of processing the pattern by plasma of a gas containing hydrogen disclosed in US Patent Application Publication No. 2015/0104957 can be mentioned. In addition, JP-A-2004-235468, US Patent Application Publication No. 2010/0020297, or Proc. of SPIE Vol. A known method may be applied as described in 8328 83280 N-1 “EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement”.
Also, the pattern formed by the above method can be used as a core of a spacer process disclosed in, for example, JP-A-3-270227 and US Patent Application Publication No. 2013/0209941.

[Method of Manufacturing Electronic Device]
The present invention also relates to a method of manufacturing an electronic device, including the pattern forming method described above. The electronic device manufactured by the method of manufacturing an electronic device according to the present invention is preferably used in electric and electronic devices (for example, home appliances, office automation (OA) related devices, media related devices, optical devices, communication devices, etc.). Will be mounted.

Hereinafter, the present invention will be described in more detail based on examples. Materials, amounts used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention is not limitedly interpreted by the examples shown below. Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition

Below, the component used for manufacture of the actinic-ray-sensitive or radiation-sensitive resin composition tested by the Example and the comparative example is described.

<Resin (A)>
(Example of synthesis of resin (A-2))
Resin (A-2) was synthesized based on the scheme shown below.

The aqueous solution consisting of sodium hydroxide (14.1 g) and water (127 g) was cooled to 0 ° C., and Compound A (manufactured by Nippon Shokubai Co., Ltd.) (50 g) was added while stirring. The aqueous solution was heated to room temperature (23 ° C.) and then stirred for 4 hours. The aqueous solution was then cooled to 0 ° C. and 1N aqueous HCl (500 mL) was added dropwise. The resulting aqueous solution was extracted twice with dichloromethane (300 mL) and the extracted organic phase was dried over sodium sulfate. The dried organic phase was filtered and concentrated to obtain a crude product containing compound B as a main component.

While stirring a mixed solution consisting of dimethylacetamide (460 mL), 2,6-ditert-butyl-4-methylphenol (50 mg), and potassium carbonate (48.6 g), compound B is the main component The crude product was added dropwise. Thereafter, α-bromo-γ-butyrolactone (52.8 g) was added dropwise to the mixed solution, and after completion of the dropwise addition, the mixed solution was heated to 40 ° C. and reacted for stirring for 5 hours. After completion of the reaction, ethyl acetate (400 mL) and water (100 mL) were added to the mixed solution. After washing the mixed solution with saturated aqueous sodium hydrogen carbonate solution (200 mL), the organic phase was extracted. The remaining aqueous phase was extracted twice with ethyl acetate (200 mL), and the organic phase was further collected. The resulting organic phase was washed twice with saturated aqueous ammonium chloride solution (100 mL), and the organic phase was dried over sodium sulfate. The dried organic phase was filtered and further concentrated to obtain a crude product containing monomer A. The crude product containing monomer A was purified with a silica gel column to obtain a high purity product (36.6 g) of monomer A (2 steps, yield: 51%).

The results of measurement of the obtained monomer A by ¹ H-NMR (Nuclear Magnetic Resonance) are as follows.
¹ H-NMR, 400 MHz, δ ((CDCl ₃ ) ppm: 2.30-2.40 (1H, m), 2.71-2.73 (1H, m), 4.01-4.10 (2H) , M), 4.22 (2H, s), 4.33 (1H, q), 4.50 (1H, t), 5.21 (1H, d), 5.31 (1H, d), 5 50 (1 H, t), 5.85-6.00 (1 H, m), 6.02 (1 H, s), 6.42 (1 H, s).

Cyclohexanone (4.95 parts by weight) was heated to 85 ° C. under a nitrogen stream. In this liquid, monomer A (2.26 parts by mass), monomer B (1.96 parts by mass) shown in the above scheme, cyclohexanone (9.19 parts by mass), and polymerization initiator AIBN (azobisisobutyro) A mixed solution of nitrile) (0.046 parts by mass) was added dropwise over 4 hours while stirring. After completion of the dropwise addition, the mixture was further stirred at 85 ° C. for 2 hours. The reaction solution was allowed to cool and then reprecipitated using a large amount of methanol / water (mass ratio 9: 1). The precipitated solid was collected by filtration and further vacuum dried to obtain a resin (A-2) (2.62 parts by mass).

Similarly, other resins (A-1) (A-3) to (A-13) and (A-15) to (A-20) shown below were synthesized.
In addition, resin (A-14) was synthesized according to a conventional method.
In the following tests, resins (A-1) to (A-13) and (A-18) to (A-20) were used in the examples, and resins (A-14) to (A-17) were used. Was used in the comparative example.

The repeating unit which resin (A) used by the Example and the comparative example has is shown below.
In addition, the numerical value described to the side of each repeating unit shows content (mol%) of each repeating unit in each resin.

The values of weight average molecular weight (Mw) and degree of dispersion (Mw / Mn) of the resins (A-1) to (A-20) are shown below.

<Photo acid generator>
The structures of the photoacid generators (C) used in Examples and Comparative Examples are shown below.

<Acid diffusion control agent>
The structures of the acid diffusion control agents (D) used in the examples and comparative examples are shown below.

<Hydrophobic resin>
The structures of the hydrophobic resin (E) used in Examples and Comparative Examples are shown below.

The weight average molecular weight (Mw) of the hydrophobic resin (1b) is 7,000, the degree of dispersion (Mw / Mn) is 1.30, and the molar ratio of each repeating unit is 50/45/5 from the left.
The weight average molecular weight (Mw) of the hydrophobic resin (2b) is 18,600, the degree of dispersion (Mw / Mn) is 1.57, and the molar ratio of each repeating unit is 40/40/20 from the left.

<Solvent>
The solvents (F) used in Examples and Comparative Examples are shown below.
SL-1: Propylene glycol monomethyl ether acetate (PGMEA)
SL-2: Propylene glycol monomethyl ether (PGME)
SL-3: cyclohexanone SL-4: γ-butyrolactone

<Surfactant>
The surfactants (H) used in Examples and Comparative Examples are shown below.
W-1: PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc .; fluorosurfactant)

[Preparation of actinic ray-sensitive or radiation-sensitive resin composition]
A mixed solution was prepared so that the solid content concentration of each component shown in the following Table 2 would be 3.8% by mass. Under the present circumstances, solid content was mix | blended so that it might become a mass part ratio shown in Table 2.
In addition, solid content here means all the components other than a solvent (F).
The prepared mixture was filtered through a polyethylene filter with a pore size of 0.1 μm. The obtained filtrate was evaluated in Examples and Comparative Examples as actinic ray-sensitive or radiation-sensitive resin compositions.

[Evaluation]
<Formation of pattern>
A composition ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) for forming an organic antireflective film was coated on a silicon wafer and heated at 205 ° C. for 60 seconds to form an antireflective film with a film thickness of 95 nm. The actinic ray-sensitive or radiation-sensitive resin compositions of Examples and Comparative Examples are coated on the obtained antireflective film, heated at 100 ° C. for 60 seconds (PB: Prebake), and a resist film having a thickness of 85 nm. Formed.
Using the ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA 1.20, C-Quad, outer sigma 0.900, inner sigma 0.812, XY deflection), the resist film on the obtained silicon wafer It was exposed through a 6% halftone mask of 1: 1 line and space pattern of 44 nm line width. Ultrapure water was used as the immersion liquid.
Thereafter, the resist film after exposure is heated at 105 ° C. for 60 seconds (PEB: Post Exposure Bake), and then developed by a paddle method for 30 seconds using a negative developing solution (organic developing solution, butyl acetate). A rinse solution (methyl isobutyl carbinol (MIBC)) was used to rinse by a paddle method for 30 seconds. Subsequently, the silicon wafer was spin-dried at a rotational speed of 4000 rpm for 30 seconds to form a 1: 1 line-and-space pattern with a line width of 44 nm.

<Line width roughness (LWR, nm)>
The obtained 44 nm 1: 1 line-and-space pattern was observed from the top of the pattern using a scanning electron microscope (S-8840, manufactured by Hitachi, Ltd.). Under the present circumstances, 50 points of line widths were measured about the range of edge 2 micrometer of the longitudinal direction of a line pattern, and the standard deviation (3 (sigma)) was calculated about the measurement dispersion of the measured line widths.
The smaller the value, the better the LWR performance.
The results are shown in Table 2 below.

<Exposure latitude (EL,%)>
An exposure dose for reproducing a 1: 1 line-and-space mask pattern having a line width of 44 nm was determined, and this was taken as the optimum exposure dose Eopt.
Next, the exposure dose was determined such that the line width of the line became the target value of ± 10% of 44 nm (that is, 39.6 nm and 48.4 nm).
The exposure latitude (EL) defined by the following equation was calculated using the obtained exposure value.
The larger the EL value, the smaller the change in line width due to the change in exposure amount, and the better the EL performance of the resist film.
EL (%) = [[(exposure at which the line width of the line becomes 48.4 nm) − (exposure at which the line width of the line becomes 39.6 nm)] / Eopt] × 100
The results are shown in Table 2 below.

<Sensitivity (mJ / cm ² )>
The optimum exposure amount Eopt obtained in the evaluation of the exposure latitude was taken as the sensitivity (mJ / cm ² ) of each resist film. The smaller this value is, the better the sensitivity of the resist film is.
The results are shown in Table 2 below.

Table 2 below shows the formulation of the actinic ray-sensitive or radiation-sensitive resin composition and the evaluation results of LWR and EL in each Example and Comparative Example.
In Table 2, the value in the parenthesis of each solid content column represents the ratio (parts by mass) of the blending amount of the solid content.
The value in the parenthesis of the column of solvent represents the ratio of the blending amount of each solvent (mass ratio). As described above, the total amount of the solvent added is such that the solid content concentration of each actinic ray-sensitive or radiation-sensitive resin composition is 3.8% by mass.
In Table 2, the column of “general formula (R)” is a repeating unit in which the resin (A) contained in the actinic ray sensitive or radiation sensitive resin composition is represented by the general formula (1) or (2) And the presence or absence of a group represented by General Formula (R) in the repeating unit.
In Table 2, in the column of “acid-eliminating group”, the repeating unit represented by the general formula (1) or (2) in the resin (A) is a group represented by the above general formula (R) When present, it indicates the presence or absence of an acid leaving group in the group corresponding to R ₅ .
In Table 2, in the column of “ether group”, when the resin (A) contained in the actinic ray-sensitive or radiation-sensitive resin composition has a repeating unit represented by the general formula (1) or (2) And the presence or absence of the ether group in the alkylene group in the group represented by L ₁ or L ₂ in the above-mentioned repeating unit.
In Table 2, in the column “general formula (A) × 2”, the resin (A) contained in the actinic ray sensitive or radiation sensitive resin composition is represented by the general formula (1) or (2) In the case of having a repeating unit, it indicates whether or not two groups represented by General Formula (A) are present in the alkylene group of the group represented by L ₁ or L ₂ in the above repeating unit.

From Table 2, it was confirmed that a resist film excellent in EL performance and a pattern excellent in LWR performance can be obtained by using the actinic ray sensitive or radiation sensitive resin composition of the present invention.
Further, the repeating unit represented by the general formula (1) or (2) which the resin (A) contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention has is represented by the general formula (R) It was confirmed that the effect of the present invention which is superior to that of the present invention can be obtained in the case of having a group (comparison of Examples 2 and 6 to 17 with other examples).
When the repeating unit represented by the general formula (1) or (2) is further an alkylene group having L ₁ or L ₂ having an ether group, it is confirmed that the LWR performance of the pattern tends to be more excellent (Example 2, 7-8 and 11-14)).
In addition, also when the repeating unit represented by the general formula (1) or (2) is an alkylene group having a group represented by two general formulas (A), L ₁ or L ₂ may be The tendency for more excellent LWR performance was confirmed (results of Examples 15 to 17).
When the group corresponding to R ₅ of the group represented by General Formula (R) in the repeating unit represented by General Formula (1) or (2) is a group other than an acid leaving group, the sensitivity of the resist film Were superior (Examples 14 and 17 and comparison with other examples).

Even when the resist film formed in the above example is subjected to ArF exposure and the film after exposure is subjected to alkali development, a resist film excellent in EL performance and a pattern excellent in LWR performance are obtained. Confirmed that Similarly, the resist film formed in the above example is subjected to KrF exposure, electron beam exposure, or EUV exposure, and the film after exposure is subjected to alkali development or organic solvent development. It was also confirmed that a resist film excellent in EL performance and a pattern excellent in LWR performance can be obtained.

Claims

A resin comprising a resin having at least one repeating unit selected from the group consisting of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2), and a photoacid generator Actinic radiation sensitive or radiation sensitive resin composition.

In the general formula (1), R 1 and R 2 each independently represent a hydrogen atom, a group represented by the general formula (A), or an organic group other than the group represented by the general formula (A) And at least one of R 1 and R 2 represents a group represented by the above general formula (A). L 1 represents an alkylene group which may have a substituent. A part of carbon atoms in the alkylene group represented by L 1 may be substituted by a group having a hetero atom. The substituent may have a hetero atom. However, the group represented by L 1 has one or more hetero atoms.
When both of R 1 and R 2 are a group represented by the above general formula (A), and the group represented by L 1 has one hetero atom, two of the above general formulas ( At least one of two R in the group represented by A) represents a hydrocarbon group having a hetero atom.
* -C (= O) -O-R (A)
In general formula (A), R represents a hydrocarbon group which may have a hetero atom or a hydrogen atom. * Represents a bonding position.
In General Formula (2), R 3 and R 4 each independently represent a hydrogen atom or an organic group. L 2 represents an alkylene group which may have a substituent. A part of carbon atoms in the alkylene group represented by L 2 may be substituted by a group having a hetero atom. The substituent may have a hetero atom. However, the group represented by L 2 has one or more hetero atoms.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the content of the resin is 10% by mass or more based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. object.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein at least one of R 3 and R 4 is an organic group.
4. The method according to claim 1, wherein at least one of R 1 and R 2 is a group represented by general formula (R), and at least one of R 3 and R 4 is a group represented by general formula (R). The actinic ray-sensitive or radiation-sensitive resin composition according to any one of the above.
* -C (= O) -O-R 5 (R)
In general formula (R), R 5 represents a hydrogen atom, an alkali-degradable group, or an acid-leaving group. * Represents a bonding position.
R 5 is representative of the alkali-decomposable group, actinic ray-sensitive or radiation-sensitive resin composition of claim 4.
L 1 is an alkylene group having an ether group which may have a substituent, or an alkylene group having two groups represented by the general formula (A),
The L 2 is an alkylene group having an ether group which may have a substituent, or an alkylene group having two groups represented by the general formula (A). The actinic ray-sensitive or radiation-sensitive resin composition according to any one of the preceding items.
The group according to claim 4, wherein R 1 and R 2 are a group represented by the general formula (R), and L 1 is a group having two groups represented by the general formula (A). Actinic ray sensitive or radiation sensitive resin composition.
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7, wherein the resin further has a repeating unit represented by the general formula (3).

In the general formula (3), R 6 represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. L 3 represents a divalent linking group which may have a substituent. X represents an acid leaving group.
9. The resin according to claim 1, further comprising at least one repeating unit selected from the group consisting of repeating units having a lactone group, and repeating units having neither an acid-degradable group nor a polar group. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of the above.
A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 9.
A resist film forming step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 9;
An exposure step of exposing the resist film;
And developing the exposed resist film with a developer.
A method of manufacturing an electronic device, comprising the pattern formation method according to claim 11.