WO2018043122A1

WO2018043122A1 - Actinic ray-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, and method for producing electronic device

Info

Publication number: WO2018043122A1
Application number: PCT/JP2017/029398
Authority: WO
Inventors: 惠瑜王; 研由後藤; 啓太加藤; 享平崎田
Original assignee: 富士フイルム株式会社
Priority date: 2016-08-31
Filing date: 2017-08-15
Publication date: 2018-03-08
Also published as: JP6892864B2; TW201831997A; JPWO2018043122A1

Abstract

The present invention addresses the problem of providing an actinic ray-sensitive or radiation-sensitive resin composition having excellent depth of focus (DOF). The present invention addresses the problem of also providing a resist film that uses the actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method, and a method for producing an electronic device. This actinic ray-sensitive or radiation-sensitive resin composition comprises: a resin containing repeating units having a lactone structure or repeating units having a sultone structure; a photoacid generator for acid generation by exposure to actinic rays or radiation; and a compound represented by formula (1).

Description

Actinic ray-sensitive or radiation-sensitive resin composition, resist film, pattern formation method, and electronic device manufacturing method

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

Conventionally, in the manufacturing process of semiconductor devices such as IC (Integrated Circuit) and LSI (Large Scale Integrated circuit), fine processing by lithography using a chemically amplified resist composition has been performed. Yes.
In particular, in the chemically amplified resist composition, a quencher is often used for the purpose of improving the contrast by controlling the diffusion of the acid into the unexposed portion.

Various amine quenchers have been proposed as the quencher.
For example, Patent Document 1 discloses a chemically amplified resist material containing an oxime compound having a specific structure as a quencher, a base polymer, and an acid generator.

Japanese Unexamined Patent Publication No. 2016-42171

When the present inventors examined and prepared an actinic ray-sensitive or radiation-sensitive resin composition using the oxime compound described in Patent Document 1, the focus tolerance (DOF: Depth of Focus) is not necessarily limited. It was clarified that there was room for further improvement.

Then, this invention makes it a subject to provide the actinic-ray-sensitive or radiation-sensitive resin composition excellent in focus tolerance (DOF).
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.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using an oxime derivative having a specific structure as a quencher, and have completed the present invention.
That is, it has been found that the above object can be achieved by the following configuration.

(1) a resin containing a repeating unit having a lactone structure or a repeating unit having a sultone structure;
A photoacid generator that generates acid upon irradiation with actinic rays or radiation; and
An actinic ray-sensitive or radiation-sensitive resin composition containing a compound represented by the formula (1) described later.
However, the compound represented by the above formula (1) does not include a compound represented by the following structure.

(2) The above-mentioned R ¹ , R ² , and R ³ each independently represents an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. Resin composition.
(3) The compound represented by the formula (1) is represented by the compound represented by the formula (2) described later, the compound represented by the formula (3) described later, and the formula (4) described later. The actinic ray-sensitive or radiation-sensitive resin composition according to (1) or (2), which is at least one selected from the group consisting of:
(4) The compound represented by the above formula (1) is at least one selected from the group consisting of a compound represented by the following formula (2) and a compound represented by the following formula (3). The actinic ray-sensitive or radiation-sensitive resin composition according to (3).
(5) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (4), wherein the resin is a resin that is decomposed by the action of an acid to increase polarity.
(6) A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (5).
(7) 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 (5);
An exposure step of exposing the resist film;
A patterning method comprising: developing the exposed resist film with a developer.
(8) The pattern forming method according to (7), wherein the developer contains an organic solvent.
(9) A method for manufacturing an electronic device, comprising the pattern forming method according to (7) or (8).

According to the present invention, an actinic ray-sensitive or radiation-sensitive resin composition excellent in focus tolerance (DOF) can be provided.
Moreover, according to this invention, the resist film using the said actinic-ray-sensitive or radiation-sensitive resin composition, the pattern formation method, and the manufacturing method of an electronic device can be provided.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the description of the group (atomic group) in this specification, the notation which does not describe substitution and non-substitution includes the thing which has a substituent with the thing which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
“Actinic rays” or “radiation” in the present specification refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB), etc. Means. In the present invention, light means actinic rays or radiation.
In addition, unless otherwise specified, “exposure” in the present specification is not limited to exposure with a far ultraviolet ray, an extreme ultraviolet ray, an X-ray, an EUV light or the like represented by a mercury lamp or an excimer laser, but an electron beam, and In addition, drawing with a particle beam such as an ion beam is included in the exposure.
In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

In the present invention, the weight average molecular weight (Mw) and number average molecular weight (Mn) are polystyrene conversion values determined by gel permeation chromatography (GPC) method using tetrahydrofuran (THF) as a developing solvent. .

[Actinic ray-sensitive or radiation-sensitive resin composition]
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention includes a resin containing a repeating unit having a lactone structure or a repeating unit having a sultone structure, and a photoacid generator that generates an acid upon irradiation with an actinic ray or radiation. And a compound represented by the formula (1) described later.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention has excellent focus tolerance (DOF) by adopting the above-described configuration.
Although this is not clear in detail, it is estimated as follows.
The compound represented by the above formula (1) (basic compound) is converted into the compound (1A) by trapping the acid generated by cleavage of the photoacid generator with actinic rays or radiation. Compound (1A) is in equilibrium with compound (1B). This compound (1B) is further converted to the compound (1C) due to the presence of excess acid, and then converted to the compound (1D) by elimination of the substituent R ³ .
The compound represented by the formula (1) has sufficient basicity to function as a quencher in an unexposed area where little acid is generated.
On the other hand, in the exposed region where a large amount of acid is generated, a large amount of compound (1D) is formed due to the presence of the acid. Since this compound (1D) functions as an acid, the acid concentration gradient between the exposed region and the unexposed region is increased. Therefore, it is presumed that the acid diffusion from the exposed area to the unexposed area is promoted and the focus tolerance (DOF) is excellent. In addition, since the acid concentration in the exposure region is high, it is possible to reduce fluctuations in the pattern line width (LWR (line width roughness)) of the resist film.

Hereinafter, components contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as “the composition of the present invention”) will be described in detail.

Hereinafter, the compound represented by Formula (1) is demonstrated.
<Compound represented by Formula (1)>

In formula (1),
R ¹ , R ² , and R ³ each independently represents a monovalent organic group. R ¹ , R ² , and R ³ may be bonded to each other to form a ring.
However, the compound represented by the above formula (1) does not include a compound represented by the following structure.

The monovalent organic group represented by R ¹ , R ² , and R ³ is not particularly limited, but is preferably an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. These groups may further have a substituent (preferably a substituent T described later).

Examples of the alkyl group include an alkyl group having 1 to 30 carbon atoms (which may be linear or branched), specifically, a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, sec-butyl, t-butyl, 1-ethylpentyl Group, 2-ethylhexyl group and the like.
Among these, from the viewpoint of further improving DOF, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.

The cycloalkyl group may be monocyclic or polycyclic.
Examples of the monocyclic cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic cycloalkyl group include an adamantyl group, a norbornyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, and a dicyclohexyl group.
Among these, from the viewpoint of further improving DOF, a cycloalkyl group having 1 to 15 carbon atoms is preferable, a cycloalkyl group having 1 to 10 carbon atoms is more preferable, and a cyclohexyl group is further preferable.

Specific examples of the aryl group and the heteroaryl group include a benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptalene ring, indecene ring, perylene ring, pentacene ring, acetaphthalene ring, phenanthrene ring, anthracene ring, Naphthacene ring, chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indolizine ring, indole Ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine Ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiin ring, phenothiazine ring, and one group formed by removing a hydrogen atom from the phenazine ring and the like. Of these, a group in which one hydrogen atom has been removed from a benzene ring or naphthalene ring is preferred from the viewpoint of further improving DOF.

R ¹ , R ² , and R ³ may combine with each other to form a ring. The ring may be either an alicyclic ring (non-aromatic hydrocarbon ring) or an aromatic ring.

One preferred embodiment of the compound represented by the formula (1) includes compounds represented by the formulas (2) to (4). The compounds represented by the formulas (2) to (4) are compounds formed by combining R ¹ , R ² , and R ³ with each other ( ^{two of} R ¹ , R ² , and R ³ are A compound formed by bonding to each other). Especially, the compound represented by Formula (2) and the compound represented by Formula (3) are preferable.

In the above formula ^{(2) ~ (4),} R 1, R 2, and ^{R 3,} ^R 1, ^{R 2} in the above-mentioned formula (1), and has the same meaning as ^{R 3,} preferable embodiments thereof are also the same .
In formula (2), Z ¹ represents a ring which contains at least one carbon atom and one nitrogen atom and may have a substituent. In addition, the said one carbon atom and one nitrogen atom intend the carbon atom and nitrogen atom which are contained in the group represented by N = C in Formula (2).
In Formula (3), Z ² represents a ring that contains at least one oxygen atom, one carbon atom, and one nitrogen atom and may have a substituent. Note that the one oxygen atom, one carbon atom, and one nitrogen atom mean a nitrogen atom, a carbon atom, and an oxygen atom contained in the group represented by N = CO in formula (3). .
In formula (4), Z ³ represents a ring which contains at least one carbon atom and one oxygen atom and may have a substituent. Note that the one carbon atom and one oxygen atom are carbon atoms and oxygen atoms contained in the group represented by C—O in the formula (2).

The compound represented by the above formula (2) is a compound in which R ¹ and R ² in the formula (1) are bonded to each other to form a ring, and the carbon contained in the ring represented by Z ¹ The number is preferably 4-8. The ring may further have a substituent (preferably a substituent T described later).
In particular, the compound represented by the formula (2) is preferably a compound represented by the following formula (2-A).

In the above formula (2-A), ^{R 3} has the same meaning as ^{R 3} in the formula (1) described above, preferable embodiments thereof are also the same.
R ⁴ , R ⁵ , and R ⁶ each independently represent a hydrogen atom or a monovalent organic group. R ⁴ , R ⁵ , and R ⁶ may be bonded to each other to form a ring.

The monovalent organic group represented by R ⁴ , R ⁵ , and R ⁶ is not particularly limited, and examples thereof include a substituent T described later. Among them, an alkyl group, a cycloalkyl group, an aryl group, or hetero Aryl groups are preferred.
The alkyl group, cycloalkyl group, aryl group, and heteroaryl group represented by R ⁴ , R ⁵ , and R ⁶ are represented by R ¹ , R ² , and R ³ in the above-described formula (1). It is synonymous with an alkyl group, a cycloalkyl group, an aryl group, and a heteroaryl group, and a preferable aspect is also the same.

R ⁴ and R ⁵ , and R ⁵ and R ⁶ may be bonded to each other to form a ring. The ring formed by combining R ⁴ and R ⁵ , and R ⁵ and R ⁶ may be either an alicyclic ring or an aromatic ring, for example, a ring having 5 to 10 carbon atoms. It is preferable. In addition, the said ring may have a substituent (preferably the substituent T mentioned later).

The compound represented by the formula (3) is a compound in which R ¹ and R ³ in the formula (1) are bonded to each other to form a ring, and the number of carbon atoms in the ring represented by Z ² is 3 to 6 are preferred. The ring may further have a substituent (preferably a substituent T described later).
In particular, the compound represented by the formula (3) is preferably a compound represented by the following formula (3-A).

In the formula (3-A), ^{R 2} has the same meaning as ^{R 2} in the formula (1) described above, preferable embodiments thereof are also the same.
R ⁷ and R ⁸ each independently represent a hydrogen atom or a monovalent organic group. R ⁷ and R ⁸ may combine with each other to form a ring. However, R ⁷ and R ⁸ are not bonded to each other to form a benzene ring.

The monovalent organic group represented by R ⁷ and R ^8, is not particularly limited, and a substituted group T which will be described later, among others, alkyl groups, cycloalkyl group, aryl group, or heteroaryl group is preferably .
The alkyl group, cycloalkyl group, aryl group, and heteroaryl group represented by R ⁷ and R ⁸ are the alkyl group represented by R ¹ , R ² , and R ³ in the above formula (1), cyclo It is synonymous with an alkyl group, an aryl group, and a heteroaryl group, and its preferable aspect is also the same.

R ⁷ and R ⁸ may be bonded to each other to form a ring. As the ring formed by combining R ⁷ and R ⁸ , for example, an alicyclic ring having 5 to 10 carbon atoms is preferable. The ring may further have a substituent (preferably a substituent T described later). From the viewpoint of efficiently converting the compound (1D) (acid) and improving DOF, it is preferable that R ⁷ and R ⁸ are not bonded to each other to form a ring.

The compound represented by the above formula (4) is a compound in which R ² and R ³ in the formula (1) are bonded to each other to form a ring, and the number of carbon atoms in the ring represented by Z ³ is 5-9 are preferred. The ring may further have a substituent (preferably a substituent T described later).

(Substituent T)
Examples of the substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group; Alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group Table by R ^{1, R} ^2, and R ^3; an acyl group; methylsulfanyl group and tert- butylsulfanyl alkylsulfinyl such as Le group sulfanyl group; phenylsulfanyl arylsulfanyl group such as Le group and p- tolylsulfanyl group Monovalent alkyl group such as an alkyl group described above as the organic group; cycloalkyl groups the cycloalkyl group described above as R ^{1, R} ^2, and a monovalent organic group represented by R ^3; R ^1, R An aryl group such as the aryl group described above as a monovalent organic group represented by ² and R ³ ; a heteroaryl group described above as a monovalent organic group represented by R ¹ , R ² and R ³ ; Heteroaryl group; hydroxyl group; carboxy group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamido group; silyl group; amino group; monoalkylamino group; As well as combinations thereof.

Hereinafter, although the specific example of a compound represented by Formula (1) is illustrated, this invention is not limited to this.

The compound represented by the above formula (1) can be synthesized according to an ordinary method such as borate action using an amide compound as a raw material.

The content of the compound represented by the formula (1) is preferably 0.1 to 15% by mass, more preferably 0.5 to 0.5% based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. It is 8% by mass, more preferably 0.5-6% by mass. If the content of the compound represented by the formula (1) is within this range, the DOF can be further improved.
In addition, the compound represented by Formula (1) may be used individually by 1 type, or may use 2 or more types together. When using together the compound represented by 2 or more types of Formula (1), it is preferable that total content is in the said range.

<Resin>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a resin containing a repeating unit having a lactone structure or a repeating unit having a sultone (cyclic sulfonic acid ester) structure.
As the resin, a known resin capable of forming a resist pattern can be used as long as it contains a repeating unit having a lactone structure or a repeating unit having a sultone structure. A changing resin (hereinafter referred to as “resin (A)”) is preferred.
Among them, the resin (A) is more preferably a resin (A1) that is decomposed by the action of an acid to increase the polarity. That is, a resin whose solubility in an alkaline developer is increased by the action of an acid, or in which the solubility in a developer containing an organic solvent as a main component is reduced by the action of an acid. Specifically, the main chain of the resin And a resin having a group capable of decomposing by the action of an acid to generate an alkali-soluble group (hereinafter also referred to as “acid-decomposable group”) in at least one of the side chains.
Examples of the alkali-soluble group include a carboxy group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), and a sulfonic acid group.
Hereinafter, the resin (A) will be described in detail.

(Repeating unit having lactone structure, repeating unit having sultone structure)
The resin (A) contains a repeating unit having a lactone structure or a repeating unit having a sultone (cyclic sulfonate ester) structure.

The repeating unit having a lactone structure preferably has a lactone structure in the side chain, and more preferably, for example, is a repeating unit derived from a (meth) acrylic acid derivative monomer. Moreover, it is preferable that the repeating unit which has a sultone structure has a sultone structure in a side chain, for example, it is more preferable that it is a repeating unit derived from a (meth) acrylic acid derivative monomer.

As the lactone structure, a 5- to 7-membered lactone structure is preferable, and a structure in which another ring structure is condensed to form a bicyclo structure or a spiro structure on the 5- to 7-membered lactone structure is more preferable.
The lactone structure preferably has a repeating unit having a lactone structure represented by any of the following formulas (LC1-1) to (LC1-17). As the lactone structure, a lactone structure represented by formula (LC1-1), formula (LC1-4), formula (LC1-5), or formula (LC1-8) is preferable, and represented by formula (LC1-4). The lactone structure is more preferable.

The lactone structure portion may have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxy group. , A halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group. 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, and a plurality of substituents (Rb ₂ ) may be bonded to form a ring. .

The sultone structure is preferably a 5- to 7-membered sultone structure, and more preferably a structure in which another ring structure is condensed to form a bicyclo structure or a spiro structure in the 5- to 7-membered sultone structure.
The sultone structure preferably has a repeating unit having a sultone structure represented by any of the following formulas (SL1-1) and (SL1-2). Further, the sultone structure may be directly bonded to the main chain.

The sultone structure part may have a substituent (Rb ₂ ). In the above formula, the substituent (Rb ₂₎ and _{n 2} have the same meanings as substituent of the lactone structure moiety as described above (Rb ₂₎ and _{n 2.}

As the repeating unit having a lactone structure and the repeating unit having a sultone structure, a repeating unit represented by the following formula (III) is preferable. That is, when the repeating unit represented by the following formula (III) represents a repeating unit having a lactone structure, R ₈ represents a monovalent organic group having a lactone structure, and is represented by the following formula (III). When the repeating unit represents a repeating unit having a sultone structure, R ₈ represents a monovalent organic group having a sultone structure.

In formula (III),
R ₇ represents a hydrogen atom, a halogen atom or an alkyl group.
A represents an ester bond (a group represented by —COO—) or an amide bond (a group represented by —CONH—).
R ₈ represents a monovalent organic group having a lactone structure or a sultone structure.
n is the number of repetitions of the structure represented by —R ₀ —Z—, and represents an integer of 0-2.
R ₀ represents a chain alkylene group, a cycloalkylene group, or a combination thereof. In the case where R ₀ there is a plurality, the plurality of R ₀ is may each be the same or different.
Z is a single bond, ether bond, ester bond, amide bond, urethane bond

Or urea bond

Represents. Here, each R independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. When there are a plurality of Zs, the plurality of Zs may be the same or different.

The chain alkylene group or cycloalkylene group represented by R ₀ may have a substituent.
Z is preferably an ether bond or an ester bond, and more preferably an ester bond.

The alkyl group for R ₇ is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a methyl group. Each of the chain alkylene group and the cycloalkylene group represented by R ₀ and the alkyl group represented by R ₇ may be substituted. R ₇ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

The chain alkylene group represented by R ₀ is preferably a chain alkylene having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. A preferred cycloalkylene group is a cycloalkylene group having 3 to 20 carbon atoms. Among these, a chain alkylene group is more preferable, and a methylene group is still more preferable.

The monovalent organic group having a lactone structure or sultone structure represented by R ₈ is not limited as long as it has a lactone structure or sultone structure.
When R ₈ is a monovalent organic group having a lactone structure, specific examples of the monovalent organic group having a lactone structure are represented by the above formulas (LC1-1) to (LC1-17). Lactone structure. Among these, a structure represented by formula (LC1-4) is preferable. In formulas (LC1-1) to (LC1-17), n ₂ is preferably 2 or less.
Examples of the monovalent organic group having a lactone structure represented by R ₈ include a monovalent organic group having an unsubstituted lactone structure, a methyl group, a cyano group, an N-alkoxyamide group, or an alkoxycarbonyl group. A monovalent organic group having a lactone structure as a substituent is preferable, and a monovalent organic group having a lactone structure (cyanolactone) having a cyano group as a substituent is more preferable.

When R ₈ is a monovalent organic group having a sultone structure, specific examples of the monovalent organic group having a sultone structure include those represented by the above formulas (SL1-1) and (SL1-2). Sultone structure. In the formula (SL1-1) and the formula (SL1-2), n ₂ is preferably 2 or less.
The monovalent organic group having a sultone structure represented by R _{8 includes} a monovalent organic group having an unsubstituted sultone structure, or a methyl group, a cyano group, an N-alkoxyamide group, or an alkoxycarbonyl group. A monovalent organic group having a sultone structure as a substituent is preferable, and a monovalent organic group having a sultone structure having a cyano group as a substituent (cyanosultone) is more preferable.

In the formula (III), n is preferably 1 or 2.

Resin (A) may contain the repeating unit which has a lactone structure individually by 1 type, and may contain 2 or more types, However, It is preferable to contain individually by 1 type. Moreover, resin (A) may contain the repeating unit which has a sultone structure individually by 1 type, and may contain 2 or more types, However, It is preferable to contain individually by 1 type. In particular, the resin (A) preferably has a repeating unit having a lactone structure, and more preferably has a repeating unit having a structure represented by the formula (LC1-4).
The resin (A) may contain both a repeating unit having a lactone structure and a repeating unit having a sultone structure.
The total amount of the repeating unit having a lactone structure and the repeating unit having a sultone structure with respect to all the repeating units of the resin (A) is, for example, 3 to 80 mol%, and preferably 3 to 60 mol%.

(Repeating unit having an acid-decomposable group)
Moreover, it is preferable that resin (A) has a repeating unit which has the acid-decomposable group mentioned above. The repeating unit having an acid-decomposable group is preferably a repeating unit represented by the following formula (AI).

In the formula (AI),
Xa ₁ represents a hydrogen atom or an alkyl group which may have a substituent.
T represents a single bond or a divalent linking group.
Rx ₁ to Rx ₃ each independently represents an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic).
Two of Rx ₁ to Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the alkyl group that may have a substituent represented by Xa ₁ include a methyl group and a group represented by —CH ₂ —R ₁₁ . R ₁₁ represents a halogen atom (fluorine atom or the like), a hydroxyl group, or a monovalent organic group.
In one embodiment, Xa ₁ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, a hydroxymethyl group, or the like.

Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a —COO—Rt— group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH ₂ — group, a — (CH ₂ ) ₂ — group, or a — (CH ₂ ) ₃ — group.

The alkyl group of Rx ₁ to Rx ₃ is preferably one having 1 to 4 carbon atoms.

Examples of the cycloalkyl group represented by Rx ₁ to Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a multicyclic group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. A cyclic cycloalkyl group is preferred.
The cycloalkyl group formed by combining two of Rx ₁ to Rx ₃ includes a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, or a tetracyclododecanyl group. Or a polycyclic cycloalkyl group such as an adamantyl group is preferred. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.

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

The repeating unit represented by the formula (AI) preferably has, for example, an embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-described cycloalkyl group.

Each of the above groups may have a substituent. Examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxy group, And alkoxycarbonyl groups (having 2 to 6 carbon atoms) and the like, and those having 8 or less carbon atoms are preferred.

The total content of the repeating units having an acid-decomposable group is preferably 20 to 90 mol%, more preferably 25 to 85 mol%, based on all repeating units in the resin (A). 30 to 80 mol% is more preferable.

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

In specific examples, Rx and Xa ₁ each independently represent a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms. Z represents a substituent containing a polar group, and when there are a plurality of them, each is independent. p represents 0 or a positive integer. Examples of the substituent containing a polar group represented by Z include a linear or branched alkyl group or cycloalkyl group having a hydroxyl group, a cyano group, an amino group, an alkylamide group, or a sulfonamide group. And an alkyl group having a hydroxyl group is preferable. As the branched alkyl group, an isopropyl group is more preferable.

(Repeating unit having carbonate structure)
The resin (A) may have a repeating unit having a carbonate structure.
The carbonate structure (cyclic carbonate structure) is a structure having a ring including a bond represented by —O—C (═O) —O— as an atomic group constituting the ring. The ring containing a bond represented by —O—C (═O) —O— as an atomic group constituting the ring is preferably a 5- to 7-membered ring, and more preferably a 5-membered ring. Such a ring may be condensed with another ring to form a condensed ring.
The resin (A) preferably contains a repeating unit represented by the following formula (A-1) as a repeating unit having a carbonate structure (cyclic carbonate structure).

In formula (A-1), R _A ¹ represents a hydrogen atom or an alkyl group.
R _A ¹⁹ each independently represents a hydrogen atom or a chain hydrocarbon group.
A represents a single bond, a divalent or trivalent chain hydrocarbon group, a divalent or trivalent alicyclic hydrocarbon group, or a divalent or trivalent aromatic hydrocarbon group, and A represents a trivalent In this case, the carbon atom contained in A and the carbon atom constituting the cyclic carbonate are combined to form a ring structure.
n _A represents an integer of 2 to 4.

In formula (A-1), R _A ¹ represents a hydrogen atom or an alkyl group. The alkyl group represented by R _A ¹ may have a substituent such as a fluorine atom. R _A ¹ preferably represents a hydrogen atom, a methyl group or a trifluoromethyl group, and more preferably represents a methyl group.
R _A ¹⁹ each independently represents a hydrogen atom or a chain hydrocarbon group. The chain hydrocarbon group represented by R _A ¹⁹ is preferably a chain hydrocarbon group having 1 to 5 carbon atoms. As the “chain hydrocarbon group having 1 to 5 carbon atoms”, for example, a linear alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group; an isopropyl group, an isobutyl group, And a branched alkyl group having 3 to 5 carbon atoms such as t-butyl group. The chain hydrocarbon group may have a substituent such as a hydroxyl group.
R _A ¹⁹ more preferably represents a hydrogen atom.

In formula (A-1), n _A represents an integer of 2 to 4. That is, the cyclic carbonate is a 5-membered ring structure when n = 2 (ethylene group), a 6-membered ring structure when n = 3 (propylene group), and a 7-membered ring when n = 4 (butylene group). It becomes a structure. For example, the repeating unit (A-1a) described below is an example of a 5-membered ring structure, and (A-1j) is an example of a 6-membered ring structure.
n _A is preferably 2 or 3, and more preferably 2.

In formula (A-1), A represents a single bond, a divalent or trivalent chain hydrocarbon group, a divalent or trivalent alicyclic hydrocarbon group, or a divalent or trivalent aromatic hydrocarbon group. Represents.
The divalent or trivalent chain hydrocarbon group is preferably a divalent or trivalent chain hydrocarbon group having 1 to 30 carbon atoms.
The divalent or trivalent alicyclic hydrocarbon group is preferably a divalent or trivalent alicyclic hydrocarbon group having 3 to 30 carbon atoms.
The divalent or trivalent aromatic hydrocarbon group is preferably a divalent or trivalent aromatic hydrocarbon group having 6 to 30 carbon atoms.

When A is a single bond, the oxygen atom of (alkyl) acrylic acid (typically (meth) acrylic acid) in which R _A ¹ is bonded to the α-position constituting the polymer, and carbon constituting the cyclic carbonate Atoms are directly bonded. In addition, (meth) acrylic acid in this specification is the meaning which includes both acrylic acid and methacrylic acid.

A preferably represents a divalent or trivalent chain hydrocarbon group or a divalent or trivalent alicyclic hydrocarbon group, and more preferably represents a divalent or trivalent chain hydrocarbon group. More preferably, it represents a linear alkylene group having 1 to 5 carbon atoms.

The above monomers are described in, for example, Tetrahedron Letters, Vol. 27, no. 32 p. 3741 (1986), Organic Letters, Vol. 4, no. 15 p. 2561 (2002) and the like, and can be synthesized by a conventionally known method.

Specific examples of the repeating unit represented by the formula (A-1) (repeating units (A-1a) to (A-1w)) are shown below, but the present invention is not limited thereto.
Incidentally, _R ^{A 1} in the following specific examples are the same meaning as _R ^{A 1} in the formula (A-1).

In the resin (A), one type of repeating units represented by the formula (A-1) may be contained alone, or two or more types may be contained.
In the resin (A), the content of the repeating unit having a carbonate structure (cyclic carbonate structure) (preferably the repeating unit represented by the formula (A-1)) is the total repeating unit constituting the resin (A). The content is preferably 3 to 80 mol%, more preferably 3 to 60 mol%, still more preferably 3 to 30 mol%.

(Other repeat units)
The resin (A) may contain other repeating units.
For example, the resin (A) may contain a repeating unit having a hydroxyl group or a cyano group. Examples of such a repeating unit include the repeating units described in paragraphs [0081] to [0084] of JP-A No. 2014-098921.
Further, the resin (A) may have a repeating unit having an alkali-soluble group. Examples of the alkali-soluble group include a carboxy group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol (for example, hexafluoroisopropanol group) in which the α-position is substituted with an electron withdrawing group. Examples of the repeating unit having an alkali-soluble group include the repeating units described in paragraphs [0085] to [0086] of JP-A No. 2014-098921.
Further, the resin (A) can further have a repeating unit that has an alicyclic hydrocarbon structure that does not have a polar group (for example, an alkali-soluble group, a hydroxyl group, a cyano group, etc.) and does not exhibit acid decomposability. . Examples of such a repeating unit include the repeating units described in paragraphs [0114] to [0123] of JP-A-2014-106299.
Further, the resin (A) may contain, for example, repeating units described in paragraphs [0045] to [0065] of JP2009-258586A.
Resin (A) used for the composition of this invention can have various repeating units other than said repeating unit. Examples of such a repeating unit include, but are not limited to, repeating units corresponding to the following monomers.
As such a monomer, for example, it has one addition polymerizable unsaturated bond selected from acrylic esters, methacrylic esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like. Compounds and the like.
In addition, any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.
In the resin (A) used in the composition of the present invention, the content molar ratio of each repeating structural unit is appropriately set.

When the composition of the present invention is for ArF exposure, it is preferable that the resin (A) used in the composition of the present invention has substantially no aromatic group from the viewpoint of transparency to ArF light. . More specifically, the repeating unit having an aromatic group is preferably 5% by mole or less, more preferably 3% by mole or less, and more ideally, during the entire repetition of the resin (A). More preferably, it is 0 mol%, that is, it does not have a repeating unit having an aromatic group. The resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

The weight average molecular weight (Mw) 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, particularly preferably. 3,000 to 11,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and developability is deteriorated, and the film forming property is deteriorated due to increased viscosity. Can be prevented.
The degree of dispersion (molecular weight distribution), which is the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in the resin (A), is usually 1.0 to 3.0, preferably 1 The range is from 0.0 to 2.6, more preferably from 1.0 to 2.0, and still more preferably from 1.1 to 2.0. The smaller the molecular weight distribution, the better the resolution and the resist shape, and the smoother the sidewall of the resist pattern, the better the roughness.

The content of the resin (preferably the resin (A)) in the entire composition is preferably 30 to 99% by mass, more preferably 50 to 95% by mass, based on the total solid content.
In addition, resin (preferably resin (A)) may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types of resin (preferably resin (A)) together, it is preferable that total content is in the said range.

<Photo acid generator>
The composition of the present invention contains a photoacid generator.
The photoacid generator corresponds to a compound that generates an acid upon irradiation with actinic rays or radiation.
Although it does not specifically limit as a photo-acid generator, It is preferable that it is a compound which generate | occur | produces an organic acid by irradiation of actinic light or a radiation.
The photoacid generator is not particularly limited, and is used for photoresist of photocationic polymerization, photoinitiator of radical photopolymerization, photodecoloring agent of dyes, photochromic agent, microresist, etc. Known compounds that generate an acid upon irradiation with actinic rays or radiation and mixtures thereof can be appropriately selected and used. For example, paragraphs [0039] to [0103] of JP2010-61043A And the compounds described in paragraphs [0284] to [0389] of JP2013-4820A, and the like.
Specific examples include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.

As a photo-acid generator which the composition of this invention contains, the photo-acid generator represented by following formula (3) can be mentioned suitably.
(Photoacid generator represented by Formula (3))

≪Anion≫
In formula (3),
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one 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, and when there are a plurality of R ₄ and R ₅ , R ₄ and R ₅ are the same But it can be different.
L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
W represents an organic group containing a cyclic structure.
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 alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Xf is more preferably a fluorine atom or CF ₃ . In particular, it is preferable that both Xf are fluorine atoms.

R 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, and when there are a plurality of R ₄ and R ₅ , R ₄ and R ₅ are the same But it can be different.
The alkyl group as R ₄ and R ₅ may have a substituent, and preferably has 1 to 4 carbon atoms. R ₄ and R ₅ are more preferably a hydrogen atom.
Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in formula (3).

L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
Examples of the divalent linking group include —COO—, —OCO—, —CONH—, —NHCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group ( Preferable examples include 1 to 6 carbon atoms, a cycloalkylene group (preferably 3 to 10 carbon atoms), an alkenylene group (preferably 2 to 6 carbon atoms), and a divalent linking group obtained by combining a plurality of these. Among these, —COO—, —OCO—, —CONH—, —NHCO—, —CO—, —O—, —SO ₂ —, —COO-alkylene group—, —OCO-alkylene group—, —CONH— alkylene group -, or -NHCO- alkylene group - are preferred, -COO -, - OCO -, - CONH -, - SO 2 -, - COO- alkylene group -, or -OCO- alkylene group - is more preferable.

W represents an organic group containing a cyclic structure. Of these, a cyclic organic group is preferable.
Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.
The alicyclic group may be monocyclic or polycyclic. Further, it may contain a hetero atom such as a nitrogen atom.
Examples of the monocyclic alicyclic group include a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and the like. Examples of the polycyclic alicyclic group include a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, a bicyclodecanyl group, an azabicyclodecanyl group, and an adamantyl group. And a cycloalkyl group of a ring. 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 a PEB (post-exposure heating) step. From the viewpoints of suppressing diffusibility in the film and improving MEEF (Mask Error Enhancement Factor).

The aryl group may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. Among these, a naphthyl group having a relatively low light absorbance at 193 nm is preferable.
The heterocyclic group may be monocyclic or polycyclic, but the polycyclic group can suppress acid diffusion more. Moreover, the heterocyclic group may have aromaticity or may not have aromaticity. Examples of the heterocyclic ring having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring not having aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is preferable. Examples of the lactone ring and sultone ring include the lactone structure and sultone structure exemplified in the above <Resin>.

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

o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.
In one embodiment, o in Formula (3) is an integer of 1 to 3, p is an integer of 1 to 10, and q is preferably 0. Xf is preferably a fluorine atom, R ₄ and R ₅ are preferably both hydrogen atoms, and W is preferably a polycyclic hydrocarbon group. o is more preferably 1 or 2, and still more preferably 1. p is preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1. W is more preferably a polycyclic cycloalkyl group, and further preferably an adamantyl group or a diamantyl group.

≪Cation≫
In the formula (3), X ⁺ represents a cation.
X ⁺ is not particularly limited as long as it is a cation, and suitable embodiments include, for example, cations (parts other than Z ⁻ ) in formulas (ZI) and (ZII) described later.

<< Preferred Aspect >>
As a suitable aspect of the photo-acid generator represented by the said Formula (3), the compound represented by the following formula (ZI) and (ZII) is mentioned, for example.

In the above formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
Two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R ₂₀₁ to R ₂₀₃ include an alkylene group (for example, a butylene group and a pentylene group).
Z ⁻ represents an anion in the formula (3), specifically, as described above.

Examples of the organic group represented by R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include a corresponding group in the compound (ZI-4) described later.
A compound having a plurality of structures represented by the formula (ZI) may be used. For example, at least one of R ₂₀₁ to R ₂₀₃ of the compound represented by the formula (ZI) is a single bond or linking group with at least one of R ₂₀₁ to R ₂₀₃ of another compound represented by the formula (ZI). It may be a compound having a structure bonded via

More preferable (ZI) component includes, for example, compound (ZI-4) described below.
The compound (ZI-4) is represented by the following formula (ZI-4).

In the formula (ZI-4),
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group. These groups may have a substituent.
R ₁₄ is independently a group having a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group, when a plurality of R ₁₄ are present. Represents. These groups may have a substituent.
R ₁₅ each independently represents an alkyl group, a cycloalkyl group, a phenyl group, or an aryl group. These groups may have a substituent. Two R ₁₅ may be bonded to each other to form a ring. When two R ₁₅ 's are bonded to each other to form a ring, the ring skeleton may contain a hetero atom such as an oxygen atom or a nitrogen atom. In one embodiment, it is preferred that two R ₁₅ are alkylene groups and are bonded to each other to form a ring structure.
l represents an integer of 0-2.
r represents an integer of 0 to 8.
Z ⁻ represents an anion in the formula (3), specifically, as described above.

In the formula (ZI-4), the alkyl group of R ₁₃ , R ₁₄ and R ₁₅ is linear or branched and preferably has 1 to 10 carbon atoms, and is preferably a methyl group, an ethyl group, n- A butyl group or a t-butyl group is preferred.
Examples of the cation of the compound represented by the formula (ZI-4) in the present invention include paragraphs [0121], [0123], [0124] of JP2010-256842A and JP2011-76056A. Cations described in paragraphs [0127], [0129], [0130] and the like can be mentioned.

Next, the formula (ZII) will be described.
In formula (ZII), R ₂₀₄ to R ₂₀₅ each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
The aryl group for R ₂₀₄ to R ₂₀₅ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group represented by R ₂₀₄ to R ₂₀₅ may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, or a sulfur atom. 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 in R ₂₀₄ to R _{205, a} linear or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group), Alternatively, a cycloalkyl group having 3 to 10 carbon atoms (cyclopentyl group, cyclohexyl group, or norbornyl group) is preferable.

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R ₂₀₅ may have a substituent. Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R ₂₀₅ may have include, for example, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 3 carbon atoms). 15), an aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.
Z ⁻ represents an anion in the formula (3), specifically, as described above.

The photoacid generator may be in the form of a low molecular compound or may be incorporated in a part of the polymer. Moreover, you may use together the form incorporated in a part of polymer and the form of a low molecular compound.
When the photoacid generator is in the form of a low molecular compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.
When the photoacid generator is in a form incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) described above.
The photoacid generator can be synthesized by a known method, for example, according to the method described in Japanese Patent Application Laid-Open No. 2007-161707.
A photo-acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the photoacid generator in the composition (when there are a plurality of types) is preferably 0.1 to 30% by mass, and preferably 0.5 to 25% by mass based on the total solid content of the composition Is more preferred,
More preferably, it is 1 to 20% by mass.

<Hydrophobic resin>
The composition of the present invention may contain a hydrophobic resin (HR). The hydrophobic resin (HR) is preferably different from the above-described resin (preferably the resin (A)).
Hydrophobic resin (HR) is preferably designed to be unevenly distributed at the interface, but unlike surfactants, it does not necessarily have a hydrophilic group in the molecule, and polar / nonpolar substances are mixed uniformly. You don't have to contribute to
Examples of the effect of adding the hydrophobic resin include control of the static / dynamic contact angle of the resist film surface with respect to water, improvement of immersion liquid followability, or suppression of outgas.

Hydrophobic resin (HR) is any one of “fluorine atom”, “silicon atom”, and “CH ₃ partial structure contained in side chain portion of resin” from the viewpoint of uneven distribution in the surface layer of the film It is preferable to have the above, and it is more preferable to have two or more.
When the hydrophobic resin (HR) contains a fluorine atom and / or a silicon atom, the fluorine atom and / or silicon atom in the hydrophobic resin (HR) may be contained in the main chain of the resin. , May be contained in the side chain.

When the hydrophobic resin (HR) contains a fluorine atom, the partial structure having a fluorine atom 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. Preferably there is.
The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, Furthermore, you may have substituents other than a fluorine atom.
A cycloalkyl group having a fluorine atom and an aryl group having a fluorine atom are a cycloalkyl group in which one hydrogen atom is substituted with a fluorine atom and an aryl group having a fluorine atom, respectively, and further a substituent other than a fluorine atom is substituted. You may have.

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

In formulas (F2) to (F4),
R ₅₇ to R ₆₈ each independently represents a hydrogen atom, a fluorine atom or an alkyl group (straight or branched). Provided that at least one of R ₅₇ to R ₆₁ , at least one of R ₆₂ to R ₆₄ , and at least one of R ₆₅ to R ₆₈ are each independently a fluorine atom or at least one hydrogen atom is a fluorine atom. It represents a substituted alkyl group (preferably having 1 to 4 carbon atoms).
All of R ₅₇ to R ₆₁ and R ₆₅ to R ₆₇ are preferably fluorine atoms. R ₆₂ , R ₆₃ and R ₆₈ are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and preferably a perfluoroalkyl group having 1 to 4 carbon atoms. More preferred. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

The hydrophobic resin (HR) may contain a silicon atom. The partial structure having a silicon atom is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure.
Examples of the repeating unit having a fluorine atom or a silicon atom include those exemplified in US2012 / 0251948A1 [0519].

The repeating unit containing a fluorine atom is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, based on all repeating units contained in the hydrophobic resin (HR). The repeating unit containing a silicon atom is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, based on all repeating units contained in the hydrophobic resin (HR).

On the other hand, particularly when the hydrophobic resin (HR) contains a CH ₃ partial structure in the side chain portion, a mode in which the hydrophobic resin (HR) does not substantially contain a fluorine atom and a silicon atom is also preferable. Moreover, it is preferable that hydrophobic resin (HR) is substantially comprised only by the repeating unit comprised only by the atom chosen from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom, and a sulfur atom.

The standard polystyrene equivalent weight average molecular weight of the hydrophobic resin (HR) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000.
The content of the hydrophobic resin (HR) 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.
In addition, hydrophobic resin (HR) may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of hydrophobic resin (HR) together, it is preferable that total content is in the said range.

In the hydrophobic resin (HR), the content of residual monomers and oligomer components is preferably 0.01 to 5% by mass, and more preferably 0.01 to 3% by mass. The molecular weight distribution (Mw / Mn, also referred to as dispersity) is preferably in the range of 1 to 5, and more preferably in the range of 1 to 3.

As the hydrophobic resin (HR), various commercially available products can be used, or they can be synthesized according to a conventional method (for example, radical polymerization).

<Solvent>
The composition of the present invention usually contains a solvent.
Solvents that can be used in preparing the composition include, for example, alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactate esters, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 4 carbon atoms). 10), an organic solvent such as a monoketone compound (preferably having 4 to 10 carbon atoms) which may have a ring, alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.
Specific examples of these solvents include those described in US Patent Application Publication No. 2008/0187860 [0441] to [0455].

In this invention, you may use the mixed solvent which mixed the solvent which contains a hydroxyl group in a structure, and the solvent which does not contain a hydroxyl group as an organic solvent.
As the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, the above-mentioned exemplary compounds can be appropriately selected. As the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate or the like is preferable, and propylene glycol monomethyl Ether (PGME, also known as 1-methoxy-2-propanol), methyl 2-hydroxyisobutyrate, or ethyl lactate is more preferred. As the solvent not containing a hydroxyl group, an alkylene glycol monoalkyl ether acetate, an alkyl alkoxypropionate, a monoketone compound which may contain a ring, a cyclic lactone, an alkyl acetate or the like is preferable, and among these, propylene glycol monomethyl Ether acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, or butyl acetate is more preferable, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate Or 2-heptanone is more preferred.
The mixing ratio (mass ratio) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. is there. A mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.
The solvent preferably contains propylene glycol monomethyl ether acetate, and is preferably a propylene glycol monomethyl ether acetate single solvent or a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.

<Other additives>
(Surfactant)
The composition of the present invention may or may not further contain a surfactant. When it is contained, the fluorine-based and / or silicon-based surfactant (fluorinated surfactant, silicon-based surfactant, or fluorine Surfactants having both atoms and silicon atoms) are preferred.

When the composition of the present invention contains a surfactant, when using an exposure light source of 250 nm or less, particularly 220 nm or less, it is possible to provide a resist pattern with less adhesion and development defects with good sensitivity and resolution. Become.
Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in paragraph [0276] of US Patent Application Publication No. 2008/0248425.
In the present invention, surfactants other than the fluorine-based and / or silicon-based surfactants described in paragraph [0280] of US Patent Application Publication No. 2008/0248425 may be used.

These surfactants may be used alone or in several combinations.
When the composition of the present invention contains a surfactant, the amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1%, based on the total solid content of the composition. % By mass.
On the other hand, by making the addition amount of the surfactant 10 ppm or less with respect to the total amount of the composition (excluding the solvent), the surface unevenness of the hydrophobic resin is increased, thereby making the resist film surface more hydrophobic. It is possible to improve water followability at the time of immersion exposure.

(Carboxylic acid onium salt)
The composition of the present invention may or may not contain a carboxylic acid onium salt. Examples of such carboxylic acid onium salts include those described in US Patent Application Publication No. 2008/0187860 [0605] to [0606].
These carboxylic acid onium salts can be synthesized by reacting sulfonium hydroxide, iodonium hydroxide, ammonium hydroxide and carboxylic acid with silver oxide in a suitable solvent.

When the composition of the present invention contains a carboxylic acid onium salt, the content thereof is generally 0.1 to 20% by mass, preferably 0.5 to 10% by mass, based on the total solid content of the composition. More preferably, it is 1 to 7% by mass.

(Other additives)
The composition of the present invention may further comprise an acid proliferating agent, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, or a compound that promotes solubility in a developer as necessary. (For example, a phenol compound having a molecular weight of 1000 or less, an alicyclic compound having a carboxy group, or an aliphatic compound) may be contained.

Such phenol compounds having a molecular weight of 1000 or less include, for example, JP-A-4-122938, JP-A-2-28531, U.S. Pat. No. 4,916,210, or European Patent 219294. It can be easily synthesized by those skilled in the art with reference to the method described in 1).
Specific examples of the alicyclic or aliphatic compound having a carboxy group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, or lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, and cyclohexane carboxylic acid. And cyclohexanedicarboxylic acid.

<Preparation method>
The composition of the present invention is preferably a resist film having a film thickness of 90 nm or less, preferably 85 nm or less, from the viewpoint of improving resolution. Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coating property or film forming property.
The solid content concentration of the composition in the present invention is usually 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, and more preferably 2.0 to 5.3% by mass. By setting the solid content concentration in the above range, the resist solution can be uniformly applied on the substrate, and further, an excellent resist pattern can be formed by LWR. The reason for this is not clear, but perhaps the solid content concentration is 10% by mass or less, preferably 5.7% by mass or less, which suppresses aggregation of the material in the resist solution, particularly the photoacid generator. As a result, it is considered that a uniform resist film can be formed.
The solid content concentration is a mass percentage of the mass of other resist components excluding the solvent with respect to the total mass of the composition.

In the composition of the present invention, the above components are dissolved in a predetermined organic solvent, preferably the above mixed solvent, filtered, and then applied onto a predetermined support (substrate). The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and still more preferably 0.03 μm or less made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as in JP-A-2002-62667, circulation 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 be filtered multiple times. Furthermore, you may perform a deaeration process etc. with respect to a composition before and after filter filtration.

<Application>
The composition of the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition whose properties change upon irradiation with actinic rays or radiation. More specifically, the present invention relates to a semiconductor manufacturing process such as an IC, a circuit board such as a liquid crystal or a thermal head, a mold structure for imprinting, a further photofabrication process, a lithographic printing plate, or an acid. The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition used for a curable composition.

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

The pattern forming method of the present invention comprises:
(I) a resist film forming step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition described above;
(Ii) an exposure step of exposing the resist film;
(Iii) a developing step of developing the exposed resist film using a developer;
including.

The pattern forming method of the present invention is not particularly limited as long as it includes the steps (i) to (iii), and may further include the following steps.
In the pattern forming method of the present invention, (ii) the exposure method in the exposure step is preferably immersion exposure.
The pattern forming method of the present invention preferably includes (iv) a preheating step before (ii) the exposure step.
The pattern forming method of the present invention preferably includes (v) a post-exposure heating step after (ii) the exposure step.
The pattern forming method of the present invention may include (ii) an exposure step a plurality of times.
The pattern forming method of the present invention may include (iv) a preheating step a plurality of times.
The pattern forming method of the present invention may include (v) a post-exposure heating step a plurality of times.

The resist film in the present invention is a film formed from the actinic ray-sensitive or radiation-sensitive resin composition described above, and more specifically, a film formed by applying the above composition on a substrate. Preferably there is.
In the pattern forming method of the present invention, the above-described (i) resist film forming step, (ii) exposure step, and (iii) development step can be performed by a generally known method.
Further, if necessary, an antireflection film may be formed between the resist film and the substrate. As the antireflection film, a known organic or inorganic antireflection film can be appropriately used.

The substrate is not particularly limited, and is generally used in a manufacturing process of a semiconductor such as an IC, a manufacturing process of a circuit board such as a liquid crystal or a thermal head, and other photo-fabrication lithography processes. A substrate can be used, and specific examples thereof include inorganic substrates such as silicon, SiO ₂ , and SiN, and coating-based inorganic substrates such as SOG (Spin On Glass).

As described above, the pattern forming method of the present invention preferably includes (iv) a pre-heating step (PB; Prebake) after (i) the resist film forming step and (ii) before the exposure step.
It is also preferable to include (v) a post-exposure heating step (PEB) after the (ii) exposure step and before the (iii) development step.
By baking as described above, the reaction of the exposed portion is promoted, and the sensitivity and / or pattern profile is improved.

The heating temperature is preferably 70 to 130 ° C. and more preferably 80 to 120 ° C. for both PB and PEB.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds for both PB and PEB.
The heating can be performed by means provided in a normal exposure machine and developing machine, and may be performed using a hot plate or the like.

There is no limitation on the light source wavelength used in the exposure apparatus, but examples include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably 250 nm or less, more Far ultraviolet light with a wavelength of preferably 220 nm or less, 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), and an electron beam, KrF excimer laser, ArF excimer laser, EUV or electron beam is preferable, and ArF excimer laser is more preferable.

In the pattern forming method of the present invention, (ii) an immersion exposure method can be applied to the exposure step. The immersion exposure method can be combined with a super-resolution technique such as a phase shift method or a modified illumination method. The immersion exposure can be performed, for example, according to the method described in paragraphs [0594] to [0601] of JP2013-242397A.

In addition, if the receding contact angle of the resist film formed using the composition of the present invention is too small, it cannot be suitably used for exposure through an immersion medium, and water residue defects can be reduced. The effect of can not be fully demonstrated. In order to achieve a preferable receding contact angle, it is preferable to include the hydrophobic resin (HR) in the composition. Alternatively, an immersion liquid hardly soluble film (hereinafter also referred to as “top coat”) formed of the above-described hydrophobic resin (HR) may be provided on the upper layer of the resist film. Examples of functions necessary for the top coat include suitability for application to the upper layer portion of the resist film and poor solubility in immersion liquid. The composition for forming the top coat is preferably not mixed with the composition film of the composition of the present invention and can be uniformly applied to the upper layer of the composition film of the composition of the present invention.
The preparation of the composition for forming the top coat and the method for forming the top coat are not particularly limited, and conventionally known methods such as those described in paragraphs [0072] to [0082] of JP-A No. 2014-059543 are disclosed. Can be implemented on the basis of
In the later-described (iii) development step, when a developer containing an organic solvent is used, a topcoat containing a basic compound described in JP2013-61648A may be formed on the resist film. preferable.
Further, even when the exposure is performed by a method other than the immersion exposure method, a top coat may be formed on the resist film.

In the immersion exposure process, the immersion liquid needs to move on the wafer following the movement of the exposure head scanning the wafer at high speed to form an exposure pattern. For this reason, the contact angle of the immersion liquid with respect to the resist film in a dynamic state becomes important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.
The receding contact angle of water (temperature: 23 ° C., relative humidity: 45%) on the actinic ray-sensitive or radiation-sensitive film (in other words, on the resist film) and the top coat is preferably 75 ° or more. 80 ° or more, more preferably 85 ° or more. For example, even when the scanning speed during exposure is set to 800 mm / s, the immersion defect is sufficiently reduced by setting the receding contact angle to 85 ° or more.

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

As the organic developer, a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, or an ether solvent, or a hydrocarbon solvent can be used.

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

In particular, 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 and ether solvents. preferable.

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

An appropriate amount of a surfactant can be added to the organic developer as necessary.

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

The organic developer may contain a basic compound. Examples of basic compounds include amine compounds, amide group-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds.

As a development method, for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying a developer on the substrate surface (spray method), and a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispensing). Law) etc. can be applied. The preferred range of the discharge pressure of the discharged developer and the method for adjusting the discharge pressure of the developer are not particularly limited. For example, paragraphs [0631] to [0631] to [0631] 0636] can be used.

In the pattern forming method of the present invention, a step of developing using a developer containing an organic solvent (organic solvent developing step) and a step of developing using an alkaline aqueous solution (alkali developing step) are used in combination. May be. Thereby, a finer pattern can be formed.
In the present invention, a portion with low exposure intensity is removed by the organic solvent development step, but a portion with high exposure strength is also removed by further performing the alkali development step. In this way, by the multiple development process in which development is performed a plurality of times, a pattern can be formed without dissolving only the intermediate exposure intensity region, so that a finer pattern than usual can be formed (Japanese Patent Laid-Open No. 2008-292975 [0077]. ] And the same mechanism).

(Iii) It is preferable to include the process (rinsing process) wash | cleaned using the rinse liquid after the image development process.
The rinsing solution used in the rinsing step after the step of developing with a developer containing an organic solvent is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a general organic solvent should be used. Can do. As the rinsing liquid, a rinsing liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. It is more preferable.
Specific examples of the hydrocarbon solvent, ketone solvent, ester solvent, alcohol solvent, amide solvent, and ether solvent are the same as those described for the developer containing an organic solvent.

More preferably, after the step of developing using a developer containing an organic solvent, at least selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, and hydrocarbon solvents. A step of washing with a rinsing liquid containing one kind of organic solvent is performed, more preferably a step of washing with a rinsing liquid containing an alcohol solvent or an ester solvent, and particularly preferably monovalent. A cleaning step is performed using a rinse solution containing alcohol, and most preferably, a cleaning step is performed using a rinse solution containing a monohydric alcohol having 5 or more carbon atoms.

A plurality of each component may be mixed, or may be used by mixing with an organic solvent other than the above.
The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

An appropriate amount of a surfactant can be added to the rinse solution.
In the rinsing step, the wafer that has been developed using the developer containing the organic solvent is washed using the rinse solution containing the organic solvent. The method of the cleaning process is not particularly limited. For example, a method of continuing to discharge the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), and immersing the substrate in a bath filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), and the like can be applied. In particular, it is preferable to perform a cleaning process by a spin coating method, and after the cleaning, rotate the substrate at a rotational speed of 2000 rpm to 4000 rpm to remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. The developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking. The heating step after the rinsing step is usually performed at 40 to 160 ° C., preferably 70 to 95 ° C., usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention and various materials used in the pattern forming method of the present invention (for example, a resist solvent, a developer, a rinse solution, an antireflection film-forming composition, or It is preferable that the topcoat-forming composition or the like does not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 ppm or less, more preferably 100 ppt or less, still more preferably 10 ppt or less, and particularly preferably (not more than the detection limit of the measuring device).
Examples of a method for removing impurities such as metals from the various materials include filtration using a filter. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. The filter material is preferably a polytetrafluoroethylene, polyethylene, or nylon filter. A filter that has been washed in advance with an organic solvent may be used. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters and / or materials may be used in combination. Moreover, various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.
Moreover, as a method for reducing impurities such as metals contained in the various materials, a raw material having a low metal content is selected as a raw material constituting the various materials, and filter filtration is performed on the raw materials constituting the various materials. Alternatively, a method of performing distillation under a condition in which contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark) or the like can be mentioned. The preferable conditions for filter filtration performed on the raw materials constituting the various materials are the same as those described above.
In addition to filter filtration, impurities may be removed with an adsorbent, or a combination of filter filtration and adsorbent may be used. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used.

[Method of manufacturing electronic device]
The present invention also relates to a method for manufacturing an electronic device including the pattern forming method of the present invention described above. The electronic device manufactured by the electronic device manufacturing method of the present invention is suitable for electrical and electronic equipment (for example, home appliances, OA (Office Automation) related equipment, media related equipment, optical equipment, and communication equipment). It is to be installed.

Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[Preparation of actinic ray-sensitive or radiation-sensitive resin composition]
The various components contained in the actinic ray-sensitive or radiation-sensitive resin composition are shown below.
<Resin>
The structures of the resins (A-1 to A-6) shown in Table 3 are shown below.
The weight average molecular weights (Mw) and dispersities (Mw / Mn) of the resins A-1 to A-6 were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene). The composition ratio (mol% ratio) of the resin was measured by ¹³ C-NMR (nuclear magnetic resonance). The weight average molecular weight (Mw) and dispersity (Mw / Mn) of resins A-1 to A-6 are shown in Table 1 below.

<Photo acid generator>
The structures of the photoacid generators (B-1 to B-7) shown in Table 3 are shown below.

<Compound represented by formula (1) (basic compound)>
The structures of the compounds (basic compounds) (C-1 to C-6) represented by the formula (1) shown in Table 3 are shown below. In addition, a synthesis example of compound C-1 is also shown as an example.

(Synthesis Example: Synthesis of Compound C-1)
The 1000 mL flask was purged with nitrogen, and 100 mL of 1 mol / L triethyloxonium tetrafluoroborate (dichloromethane solution) was added and cooled to 0 ° C. To the obtained solution, 13 g of the following compound (a) was added dropwise, and after completion of the addition, the solution was returned to room temperature and further stirred for 2 hours. After stirring, the flask was cooled again to 0 ° C., and 300 mL of a mixed solvent of triethylamine / hexane was added to the solution to stop the reaction. The organic layer was taken out by liquid separation, and the organic layer was washed with water. The organic layer after washing with water was distilled to obtain 5.6 g of Compound C-1.

In addition, the same operations as in the above synthesis example were performed to synthesize compounds C-2 to C-6 described later.
The compounds C-1 to C-6 are shown below.

<Basic compounds other than the compound represented by the above formula (1)>
The structures of basic compounds (D-1 to D-5) other than the compound represented by the above formula (1) shown in Table 3 are shown below.

<Hydrophobic resin>
The structures of the hydrophobic resins (HR-1 to HR-7) shown in Table 3 are shown below. Table 2 below shows the weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) of the hydrophobic resins HR-1 to HR-7.

<Solvent>
The solvents shown in Table 3 are as follows.

SL-1: Propylene glycol monomethyl ether acetate (PGMEA)
SL-2: Cyclohexanone SL-3: Propylene glycol monomethyl ether (PGME)
SL-4: γ-butyrolactone SL-5: propylene carbonate SL-6: 2-ethylbutanol SL-7: perfluorobutyltetrahydrofuran SL-8: ethyl lactate

<Preparation of actinic ray-sensitive or radiation-sensitive resin composition>
The components shown in Table 3 below are dissolved in the solvent shown in Table 3, and a solution with a solid content of 4% by mass is prepared for each, and this is filtered through a polyethylene filter having a pore size of 0.05 μm. An actinic ray-sensitive or radiation-sensitive resin composition was prepared.
Next, the obtained actinic ray-sensitive or radiation-sensitive resin composition was evaluated by the following method. The results are shown in Table 3.

[Evaluation]
<Evaluation of resist using negative developer>
(Formation of resist pattern)
≪ArF immersion exposure≫
An organic antireflection film-forming composition ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 95 nm. An actinic ray-sensitive or radiation-sensitive resin composition was applied onto the obtained antireflection film, and baked (PB: Prebake) at 100 ° C. for 60 seconds to form a resist film having a film thickness of 85 nm.
The obtained wafer was used with an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA 1.20, C-Quad, outer sigma 0.900, inner sigma 0.812, XY deflection) 1: Exposure was through a 6% halftone mask with a one line and space pattern. Ultra pure water was used as the immersion liquid. Then, it heated at 105 degreeC for 60 second (PEB: Post Exposure Bake). Next, the film was developed by paddle with a negative developer (butyl acetate) for 30 seconds, and paddled with a rinse solution [methyl isobutyl carbinol (MIBC)] for 30 seconds for rinsing. Subsequently, the wafer was rotated at a rotational speed of 4000 rpm for 30 seconds to form a 1: 1 line and space pattern with a line width of 48 nm.

(DOF evaluation)
Under the exposure and development conditions described above (resist pattern formation), exposure and development were performed by changing the exposure focus conditions in increments of 10 nm in the focus direction at the exposure amount for forming a line pattern with a line width of 48 nm. The space line width (CD) of each pattern obtained was measured using a line width measurement scanning electron microscope SEM (Hitachi, Ltd. S-9380), and the curve obtained by plotting each of the above CDs The focus corresponding to the local minimum value or local maximum value was taken as the best focus. When the focus was changed around the best focus, a focus fluctuation range allowing a line width of 48 nm ± 10%, that is, a focus tolerance (nm) was calculated. A larger focus tolerance value is preferable.

(LWR evaluation)
The obtained line / space = 1/1 line pattern (ArF immersion exposure: line width 48 nm) was observed with a scanning microscope (S9380, manufactured by Hitachi, Ltd.). The width was measured at 50 points, the standard deviation was calculated for the measurement variation, and 3σ was calculated. A smaller value indicates better performance.

(Evaluation results)
The results of the above evaluation tests are shown in Table 3 below.
In addition, in the table | surface, it prepares so that the sum total of the density | concentration of solid content (each component except a solvent) may be 100 mass%.
Resin A-6 corresponds to a resin having neither a repeating unit having a lactone structure nor a repeating unit having a sultone structure.

From the results in Table 3, it is confirmed that the resist pattern produced using the actinic ray-sensitive or radiation-sensitive resin composition of Examples containing the compound represented by the formula (1) is excellent in DOF. It was done.
Moreover, it was confirmed that the resist pattern produced using the actinic ray sensitive or radiation sensitive resin composition of the Example containing the compound represented by Formula (1) has small LWR.
From the comparison of Examples 1 to 8, it was confirmed that the compound represented by the formula (1) is superior to the DOF when the compound represented by the formula (2) or the formula (3) described above.

On the other hand, it is clear that the actinic ray-sensitive or radiation-sensitive resin composition of the comparative example does not satisfy the desired requirements.

[Preparation of composition for forming top coat]
Each component shown in Table 4 was dissolved in the solvent shown in the same table, and a solution having a solid content concentration of 2.7% by mass was prepared. Next, in the same procedure as the preparation of the actinic ray-sensitive or radiation-sensitive resin composition described above, this was filtered through a polyethylene filter having a pore size of 0.03 μm, and a topcoat-forming composition (Y-1 to Y -10) was prepared.
Table 4 shows the composition for forming the top coat. In Table 4, the composition for forming the top coat is prepared so that the total concentration of solids (each component excluding the solvent) is 100% by mass. That is, the content of the resin (X) corresponds to a value obtained by subtracting the content (% by mass) of the compound (A) from the total amount (% by mass) of the solid content. In Table 4, in the solvent column, the composition ratio of the mixed solvent is based on mass.

Hereinafter, each component shown in Table 4 will be described.

<Compound (A)>
As the compound (A) shown in Table 4, the following compounds TQ-1 to TQ-10 were used.

<Resin (X)>
Each repeating unit contained in the resins X1 to X10 shown in Table 4 is as follows.
The composition ratio (molar ratio), weight average molecular weight (Mw), and dispersity (Mw / Mn) of each repeating unit in the resins X1 to X10 are the same as those of the resins (A-1) to (A-6) described above. It calculated | required by the same method.

[Evaluation]
<Evaluation of resist using negative developer>
(Formation of resist pattern)
≪ArF immersion exposure≫
An organic antireflection film-forming composition ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a thickness of 95 nm. An actinic ray-sensitive or radiation-sensitive resin composition was applied onto the obtained antireflection film, and baked (PB: Prebake) at 100 ° C. for 60 seconds to form a resist film having a film thickness of 85 nm. Furthermore, the composition for topcoat formation was apply | coated on the obtained resist film, and it baked at 90 degreeC for 60 second, and formed the topcoat with a film thickness of 70 nm.
The obtained wafer was used with an ArF excimer laser immersion scanner (manufactured by ASML: XT1700i, NA 1.20, C-Quad, outer sigma 0.900, inner sigma 0.812, XY polarized light) 1: Exposure was through a 6% halftone mask with a one line and space pattern. Ultra pure water was used as the immersion liquid. Then, it heated at 105 degreeC for 60 second (PEB: PostExposure Bake). Subsequently, the film was developed by paddle with a negative developer (butyl acetate) for 30 seconds, and rinsed by paddle with a rinse solution [methyl isobutyl carbinol (MIBC)] for 30 seconds. Subsequently, the wafer was rotated at a rotational speed of 4000 rpm for 30 seconds to form a 1: 1 line and space pattern having a line width of 48 nm.

(Evaluation results)
The DOF evaluation and the LWR evaluation were performed in the same manner as in Example 1 above. The results are shown in Table 5.
The actinic ray-sensitive or radiation-sensitive resin composition used in Table 5 was prepared by the same method as in Examples 1 to 8 described above. Also, each component used is the same as described above. Furthermore, in Table 5, the actinic ray-sensitive or radiation-sensitive resin composition is prepared so that the total concentration of solids (each component excluding the solvent) is 100% by mass.

From the results of Examples 9 to 18 in Table 5, the resist pattern produced using the actinic ray-sensitive or radiation-sensitive resin composition containing the compound represented by formula (1) is excellent in DOF and LWR. This was also confirmed in an evaluation system using a top coat.
On the other hand, it is clear that the actinic ray-sensitive or radiation-sensitive resin composition of the comparative example does not satisfy the desired requirements even in an evaluation system using a top coat.

Claims

A resin containing a repeating unit having a lactone structure or a repeating unit having a sultone structure;
A photoacid generator that generates acid upon irradiation with actinic rays or radiation; and
The actinic-ray-sensitive or radiation-sensitive resin composition containing the compound represented by following formula (1).

In formula (1),
R 1 , R 2 , and R 3 each independently represents a monovalent organic group. R 1 , R 2 , and R 3 may be bonded to each other to form a ring.
However, the compound represented by the above formula (1) does not include a compound represented by the following structure.
2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 , wherein R 1 , R 2 , and R 3 each independently represents an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. .
The compound represented by the formula (1) is selected from the group consisting of a compound represented by the following formula (2), a compound represented by the following formula (3), and a compound represented by the following formula (4). The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, which is at least one selected.

In the formula (2) ~ (4), R 1, R 2, and R 3 have the same meaning as R 1, R 2, and R 3 in the formula (1).
In formula (2), Z 1 represents a ring which contains at least one carbon atom and one nitrogen atom and may have a substituent.
In Formula (3), Z 2 represents a ring that contains at least one oxygen atom, one carbon atom, and one nitrogen atom and may have a substituent.
In formula (4), Z 3 represents a ring which contains at least one carbon atom and one oxygen atom and may have a substituent.
The compound represented by the formula (1) is at least one selected from the group consisting of the compound represented by the formula (2) and the compound represented by the formula (3). 3. The actinic ray-sensitive or radiation-sensitive resin composition according to 3.
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4, wherein the resin is a resin that is decomposed by the action of an acid to increase polarity.
A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5.
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 5;
An exposure step of exposing the resist film;
And a developing step of developing the exposed resist film using a developer.
The pattern forming method according to claim 7, wherein the developer contains an organic solvent.
An electronic device manufacturing method including the pattern forming method according to claim 7.