WO2019187803A1 - Active-ray-sensitive or radiation-sensitive resin composition, resist film, method for forming pattern, and method for manufacturing electronic device - Google Patents

Abstract

Provided is an active-ray-sensitive or radiation-sensitive resin composition which has high sensitivity and can be formed into a pattern having excellent collapse resistance. Also provided are: a resist film using the active-ray-sensitive or radiation-sensitive resin composition; a method for forming a pattern; and a method for manufacturing an electronic device. The active-ray-sensitive or radiation-sensitive resin composition contains a compound which can generate an acid upon the irradiation with an active ray or an radioactive ray and a resin of which the polarity can increase by the action of an acid, wherein the resin contains a repeating unit represented by general formula (B-1) and also contains at least one halogen atom selected from the group consisting of a fluorine atom and an iodine atom.

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 a semiconductor device such as an IC (Integrated Circuit) and an LSI (Large Scale Integrated circuit), a photoresist composition (hereinafter referred to as “active light sensitive or radiation sensitive resin”). Microfabrication by lithography using a “composition” is also performed. In recent years, with the high integration of integrated circuits, the formation of ultrafine patterns in the submicron region or quarter micron region has been required. Along with this, there is a tendency to shorten the exposure wavelength from g-line to i-line, and further to KrF excimer laser light. Furthermore, in addition to excimer laser light, lithography using electron beams, X-rays, or EUV (Extreme Ultra Violet) is also being developed.

As the actinic ray-sensitive or radiation-sensitive resin composition, for example, Patent Document 1 discloses a positive resist composition applicable to EUV exposure and the like.

JP 2007-094139 A

By the way, EUV light (wavelength 13.5 nm) has a short wavelength compared with, for example, ArF excimer laser light (wavelength 193 nm), and therefore has a feature that the number of incident photons is small when the resist film has the same sensitivity. . As a result, in lithography using EUV light, the influence of “photon shot noise” in which the number of photons varies stochastically is large, which is a main factor of deterioration of LER (line edge roughness).
To reduce photon shot noise, it is effective to increase the number of incident photons by increasing the exposure amount (in other words, lowering the sensitivity), but this has a trade-off relationship with the recent demand for higher sensitivity. . Although it is effective to increase the number of absorbed photons by increasing the film thickness of the resist film, the aspect ratio of the pattern to be formed becomes large, so that the fall-suppressing property deteriorates in the L / S (line / space) pattern. Is likely to occur.
Therefore, in lithography using EUV light, an actinic ray-sensitive or radiation-sensitive resin composition (in particular, high sensitivity and a tilt-inhibiting property and a high-sensitivity and a tilt-inhibiting property) can be formed. There is a need for an actinic ray-sensitive or radiation-sensitive resin composition that can form a pattern with excellent LER.

Under the background described above, the present inventors have recently introduced a large amount of elements having high EUV light absorption efficiency such as fluorine atoms and iodine atoms into a resist film (coating film of actinic ray-sensitive or radiation-sensitive resin composition). According to the method, it has been found that the resist film has excellent EUV light absorption efficiency (in other words, excellent sensitivity) even when the film thickness is small. On the other hand, it has also been confirmed that the more the element is contained in the resin, the more likely the deterioration of the pattern fall-suppressing property tends to deteriorate.

Then, this invention makes it a subject to provide the actinic-ray-sensitive or radiation-sensitive resin composition which is highly sensitive and the pattern formed falls and is excellent in inhibitory property.
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 actinic ray-sensitive or radiation-sensitive resin composition contains a repeating unit represented by the general formula (B-1) described later, a fluorine atom, and It has been found that the above problem can be solved by including an acid-decomposable resin containing at least one halogen atom selected from the group consisting of iodine atoms, and the present invention has been completed.
That is, it has been found that the above object can be achieved by the following configuration.

[1] a compound capable of generating an acid upon irradiation with actinic rays or radiation;
A resin whose polarity is increased by the action of an acid,
The actinic ray-sensitive or photosensitive material, wherein the resin contains a repeating unit represented by the general formula (B-1) described later and contains at least one halogen atom selected from the group consisting of a fluorine atom and an iodine atom. Radiation resin composition.
[2] The actinic ray-sensitive or radiation-sensitive composition according to [1], wherein the repeating unit represented by the general formula (B-1) is a repeating unit represented by the general formula (B-2) described later. Resin composition.
[3] The actinic ray-sensitive or radiation-sensitive composition according to [2], wherein the repeating unit represented by the general formula (B-2) is a repeating unit represented by the general formula (B-3) described later. Resin composition.
[4] The actinic ray-sensitive or radiation-sensitive resin composition according to [3], wherein at least one of L ³ and L ⁴ represents —CO—, —SO—, or —SO ₂ —.
[5] The actinic ray according to [3] or [4], wherein the repeating unit represented by the general formula (B-3) is a repeating unit represented by the following general formula (B-4) Or radiation sensitive resin composition.
[6] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein the resin has a weight average molecular weight of 2,000 to 30,000.
[7] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the resin contains a fluorine atom.
[8] A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7].
[9] A resist film forming step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7];
An exposure step of exposing the resist film;
A patterning method comprising: developing the exposed resist film with a developer.
[10] The pattern forming method according to [9], wherein the exposure step is a step of exposing the resist film with extreme ultraviolet light.
[11] The pattern forming method according to [9] or [10], wherein the developer is a developer containing an organic solvent.
[12] A method for manufacturing an electronic device, comprising the pattern forming method according to any one of [9] to [11].

ADVANTAGE OF THE INVENTION According to this invention, the actinic-ray-sensitive or radiation-sensitive resin composition which is highly sensitive and the pattern formed is excellent in fall-down suppression property 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 present specification, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays such as an excimer laser, extreme ultraviolet rays, X-rays, and an electron beam (EB). To do. In the present specification, “light” means actinic rays or radiation.
Unless otherwise specified, “exposure” in the present specification includes not only exposure with an emission line spectrum of a mercury lamp, far ultraviolet rays such as excimer laser, extreme ultraviolet rays, and X-rays, but also electron beams, ion beams, etc. This includes drawing with particle beams.
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 specification, (meth) acrylate represents acrylate and methacrylate.

In the present specification, regarding the notation of a group (atomic group), the notation that does not indicate substitution or unsubstituted includes a group having a substituent together with a group not having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In the present specification, the “organic group” refers to a group containing at least one carbon atom.

In the present specification, the type of substituent, the position of the substituent, and the number of substituents when “may have a substituent” are not particularly limited. The number of substituents may be, for example, 1, 2, 3, or more. Examples of the substituent include a monovalent nonmetallic atomic group excluding a hydrogen atom. For example, the substituent can be selected from the following substituent group T.
(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 An alkyl sulfanyl group such as a methylsulfanyl group and a tert-butylsulfanyl group; an arylsulfanyl group such as a phenylsulfanyl group and a p-tolylsulfanyl group; an alkyl group; a cycloalkyl group Heteroaryl group; hydroxyl group; carboxy group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; silyl group; amino group; monoalkylamino group; Arylamino groups; and combinations thereof.

In the present specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw / Mn) of the resin are GPC (Gel Permeation Chromatography) apparatus (manufactured by Tosoh Corporation). GPC measurement by HLC-8120GPC (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40 ° C., flow rate: 1.0 mL / min, detector: It is defined as a polystyrene-converted value by a differential refractive index detector (Refractive Index Detector).

[Actinic ray-sensitive or radiation-sensitive resin composition]
Features of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as “the composition of the present invention”) include a repeating unit represented by the general formula (B-1) described below. And a resin containing at least one halogen atom selected from the group consisting of a fluorine atom and an iodine atom.
The resin contained in the composition of the present invention is excellent in EUV light absorption efficiency (in other words, excellent in sensitivity) by containing at least one halogen atom selected from the group consisting of fluorine atoms and iodine atoms.
Furthermore, the above resin contains a repeating unit represented by the general formula (B-1), so that the glass transition temperature (Tg) is high, thereby being excellent in suppressing the collapse of the pattern. As will be described later, in the repeating unit represented by the general formula (B-1), depending on the types of X, Y, R ¹ , and R ^{2 in} the repeating unit, ring W ¹ is decomposed by the action of an acid. (In other words, the repeating unit represented by the general formula (B-1) can function as a repeating unit containing an acid-decomposable group), but the repeating unit represented by the general formula (B-1) is: Since it has a skeleton derived from exomethylene, it is excellent in the ability to suppress pattern collapse even after acid decomposition. In addition, since the resin contains the repeating unit represented by the general formula (B-1), the above-described deterioration of pattern collapse due to fluorine atoms and iodine atoms introduced for EUV light absorption efficiency is deteriorated. Not easily affected.
Due to the above mechanism of action, the composition of the present invention can form a pattern with high sensitivity and excellent collapse suppression. Furthermore, the pattern formed by the composition of the present invention is excellent in LER.

Hereinafter, the components contained in the composition of the present invention will be described in detail. The composition of the present invention is a so-called resist composition, and may be a positive resist composition or a negative resist composition. Further, it may be a resist composition for alkali development or a resist composition for organic solvent development.
The composition of the present invention is typically a chemically amplified resist composition.

〔resin〕
<Resin (X)>
The composition of the present invention contains a resin that satisfies the following conditions [1] and [2] and whose polarity is increased by the action of an acid (hereinafter also referred to as “resin (X)”).
Condition [1]: including a repeating unit represented by the general formula (B-1) described later.
Condition [2]: At least one halogen atom selected from the group consisting of a fluorine atom and an iodine atom is contained.
The resin (X) is a resin whose polarity increases by the action of an acid as described above. Therefore, in the pattern forming method of the present invention described later, typically, when an alkaline developer is employed as the developer, a positive pattern is suitably formed, and an organic developer is employed as the developer. A negative pattern is preferably formed.
As will be described later, the resin (X) preferably has a group (hereinafter also referred to as an “acid-decomposable group”) that is decomposed by the action of an acid to increase the polarity.

The resin (X) contains at least one halogen atom selected from the group consisting of a fluorine atom and an iodine atom (hereinafter also referred to as “specific halogen atom”) (condition [2]). The introduction position of the specific halogen atom in the resin (X) is not particularly limited.
In the resin (X), the content of the specific halogen atom is not particularly limited, but is preferably 2% by mass or more with respect to the total mass of the resin in terms of more excellent sensitivity of the resist composition. The above is more preferable, 16% by mass or more is further preferable, and 20% by mass or more is particularly preferable. The upper limit is not particularly limited, but is, for example, 70% by mass or less.

Hereinafter, the repeating unit represented by formula (B-1) contained in the resin (X) and other repeating units which may optionally be contained will be described in detail.
(Repeating unit represented by formula (B-1))

In general formula (B-1), X and Y each independently represent an oxygen atom, a sulfur atom, or —NR ³ —. R ³ represents a hydrogen atom or an organic group.
The organic group represented by R ³ is not particularly limited, and examples thereof include the groups exemplified in the substituent group T described above, and examples thereof include an alkyl group, an aryl group, an aralkyl group, and an alkenyl group. .

The alkyl group represented by R ³ is not particularly limited, but has 1 to 8 carbon atoms in that the sensitivity of the formed resist film is more excellent, and the collapse resistance and LER of the formed pattern are more excellent. Alkyl groups (which may be linear, branched or cyclic) are preferred, such as methyl, ethyl, propyl, n-butyl, sec-butyl, hexyl, and An octyl group etc. are mentioned. Of these, a linear or branched alkyl group having 1 to 4 carbon atoms is more preferable.
Note that the alkyl group represented by R ³ may further have a substituent. As a substituent, the group illustrated by the substituent group T mentioned above is mentioned, for example, Specifically, a specific halogen atom etc. are mentioned.

The aryl group represented by R ³ is not particularly limited, but has 6 to 10 carbon atoms in that the sensitivity of the formed resist film is superior, and the collapse of the pattern to be formed and the LER are more excellent. Aryl groups are preferred. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthryl group, and a phenyl group or a naphthyl group is preferable.
The aryl group may further have a substituent. As a substituent, the group illustrated by the substituent group T mentioned above is mentioned, for example, Specifically, a specific halogen atom etc. are mentioned.

The aralkyl group represented by R ³ is not particularly limited. For example, the alkyl group in the aralkyl group preferably has 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms. Examples of the aralkyl group include a benzyl group and a phenethyl group.
The aralkyl group represented by R ³ may further have a substituent. As a substituent, the group illustrated by the substituent group T mentioned above is mentioned, for example, Specifically, a specific halogen atom etc. are mentioned.

The alkenyl group represented by R ³ is not particularly limited, but is preferably an alkenyl group having 2 to 8 carbon atoms (which may be linear, branched or cyclic), and has 2 to 4 carbon atoms. The linear or branched alkenyl group is more preferable. Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.
The alkenyl group represented by R ³ may further have a substituent. As a substituent, the group illustrated by the substituent group T mentioned above is mentioned, for example, Specifically, a specific halogen atom etc. are mentioned.

Among them, a hydrogen atom is preferable as R ³ .

In particular, as X and Y, at least one preferably represents an oxygen atom, and more preferably both represent an oxygen atom.

R ¹ and R ² each independently represents a hydrogen atom or an organic group.
The organic group represented by R ¹ and R ² is not particularly limited, and examples thereof include the groups exemplified in the substituent group T described above, and more specifically, an alkyl group, an aryl group, an aralkyl group, And an alkenyl group.
Although it does not restrict | limit especially as an alkyl group represented by R < ¹ > and R < ² >, Carbon number is 1 at the point which the sensitivity of the resist film formed is more excellent, and the fall suppression of the pattern formed and LER are more excellent. To 12 alkyl groups (which may be linear, branched or cyclic) are preferable, for example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, tert- Examples thereof include a butyl group, a hexyl group, a cyclohexyl group, and an octyl group. Among them, the number of carbon atoms of the alkyl group represented by R ¹ and R ² is more preferably 1 to 10, and further preferably 1 to 8.

The alkyl group may further have a substituent (for example, a group exemplified in the substituent group T described above). Examples of the substituent include a specific halogen atom. That is, the alkyl group may be an alkyl group substituted with at least one specific halogen atom.
The number of carbon atoms of the alkyl group substituted with at least one specific halogen atom is preferably 1 to 12, more preferably 1 to 10, still more preferably 1 to 8, particularly preferably 1 to 6, and most preferably 1 to 3. preferable.
The alkyl group substituted with at least one specific halogen atom may further have a substituent (for example, a group exemplified in the substituent group T described above). Examples of the substituent include a hydroxyl group.
As the alkyl group substituted with at least one specific halogen atom, the sensitivity of the formed resist film is more excellent, and the collapse of the formed pattern is more excellent in suppression and LER. An alkyl group (preferably a perfluoroalkyl group having 1 to 3 carbon atoms) or an alkyl group containing a hexafluoroisopropanol group is preferred.

The aryl group represented by R ¹ and R ² is not particularly limited, but has 6 carbon atoms in that the sensitivity of the resist film to be formed is more excellent, and the collapse prevention and LER of the pattern to be formed are more excellent. An aryl group having ˜14 is preferable, and an aryl group having 6 to 10 carbon atoms is more preferable. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthryl group, and a phenyl group or a naphthyl group is preferable.
The aryl group may further have a substituent (for example, a group exemplified in the substituent group T described above). Examples of the substituent include a specific halogen atom or an alkyl group substituted with at least one specific halogen atom. Among them, a specific halogen atom or a perfluoroalkyl group having 1 to 3 carbon atoms is preferable.

The aralkyl group represented by R ¹ and R ² is not particularly limited. For example, the alkyl group in the aralkyl group preferably has 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms. Examples of the aralkyl group include a benzyl group and a phenethyl group.
The aralkyl group represented by R ¹ and R ² may further have a substituent (for example, a group exemplified in the substituent group T described above). Examples of the substituent include a specific halogen atom.

The alkenyl group represented by R ¹ and R ² is not particularly limited, but is preferably an alkenyl group having 2 to 8 carbon atoms (which may be linear, branched, or cyclic). 2 to 4 linear or branched alkenyl groups are more preferred. Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.
The alkenyl group represented by R ¹ and R ² may further have a substituent (for example, a group exemplified in the substituent group T described above). Examples of the substituent include a specific halogen atom.

As R ¹ and R ² , an alkyl group or an aryl group is preferable in that the sensitivity of the formed resist film is more excellent, and the collapse of the formed pattern is more excellent in suppression and LER.

In general formula (B-1), ring W ¹ represents a ring which contains at least two carbon atoms, X and Y, and may have a substituent.
The above-mentioned two carbon atoms are carbon atoms specified in the general formula (B-1), the carbon atom at the position bonded to the main chain, and the carbon at the position connected to the above X and Y. Intended for atoms.
The number of ring members in ring W ¹ is not particularly limited, but is, for example, 6 to 10, and 6 or 7 is preferable, and 6 is more preferable in terms of more excellent ability to suppress the collapse of the formed pattern.
Ring W ¹ may have a substituent. Examples of the substituent include the groups exemplified in the substituent group T described above.

R ¹ and R ² may be bonded to each other to form a ring. R ¹ and R ² may be independently bonded to an atom contained in ring W ¹ to form a ring. When at least one of X and Y represents —NR ³ —, each R ³ independently forms a ring by bonding to R ¹ , R ² , or an atom contained in the ring W ^1. May be.
The ring is not particularly limited, and examples thereof include alicyclic rings, aromatic rings, and heterocyclic rings (including not only those having aromaticity but also those having no aromaticity).

The repeating unit represented by the general formula (B-1) is preferably a repeating unit represented by the following general formula (B-2).

In the general formula (B-2), X, Y, ^{R 1,} and ^{R 2,} the general formula (B-1) in X, Y, ^{R 1,} and ^{R 2} in the above formula, also preferred embodiments are also the same It is.
In the general formula (B-2), L ¹ represents a divalent linking group that links X specified in the formula and a carbon atom at a position bonded to the main chain, and L ² represents Represents a divalent linking group for linking Y specified in the above and the carbon atom at the position bonded to the main chain.
L ¹ and L ² are specifically a divalent group selected from the group consisting of —CO—, —C (R ⁴ ) (R ⁵ ) —, —SO—, —SO ₂ —, and combinations thereof. Represents a linking group.

R ⁴ and R ⁵ each independently represents a hydrogen atom or an organic group.
The organic group represented by R ⁴ and R ^5, those similar to the organic group represented by R ³ in the above-mentioned general formula (B-1).
As R ⁴ and R ⁵ , a hydrogen atom is preferable.

Examples of the divalent linking group represented by L ¹ and L ² include * -CO-**, * -SO-**, * -SO ₂ -**, * -C (R ⁴ ) (R ⁵ )-**, and * -C (R ⁴ ) (R ⁵ ) -C (R ⁴ ) (R ⁵ )-** and the like. In addition, * is a connection position with X or Y, and ** represents a connection position with the carbon atom of the position couple | bonded with the principal chain in general formula (B-2).
Among them, at least one of the divalent linking group represented by L ¹ and the divalent linking group represented by L ² is —CO—, in that the fall prevention property of the formed pattern is more excellent. It preferably contains —SO— or —SO ₂ —.

The number of ring members of a ring formed from two carbon atoms, X, Y, L ¹ and L ² (hereinafter also referred to as “ring W ² ”) is not particularly limited, but is, for example, 6 to 10 and formed. 6 or 7 is preferable and 6 is more preferable in that the pattern collapse suppression is more excellent.

R ¹ and R ² may be bonded to each other to form a ring. R ⁴ and R ⁵ may be bonded to each other to form a ring. In addition, when at least one of X and Y represents —NR ³ —, R ³ may be independently bonded to R ¹ , R ² , R ⁴ , or R ⁵ to form a ring. Good.

The repeating unit represented by the general formula (B-2) is preferably a repeating unit represented by the following general formula (B-3).

In the general formula (B-3), X, Y, ^{R 1,} and ^{R 2,} the general formula (B-1) in X, Y, ^{R 1,} and ^{R 2} in the above formula, also preferred embodiments are also the same It is.
In general formula (B-3), L ³ and L ⁴ each independently represent —CO—, —C (R ⁴ ) (R ⁵ ) —, —SO—, or —SO ₂ —. Among these, it is preferable that at least one of L ³ and L ⁴ represents —CO—, —SO—, or —SO ₂ — in terms of more excellent ability to suppress the collapse of the formed pattern. Note that when one of L ³ and L ⁴ represents —CO—, —SO—, or —SO ₂ —, the other preferably represents —C (R ⁴ ) (R ⁵ ) —.
R ⁴ and R ⁵ each independently represents a hydrogen atom or an organic group. The organic group represented by R ⁴ and R ^5, has the same meaning as organic groups represented by R ⁴ and R ⁵ as detailed in the above-described general formula (B-2), preferred embodiments are also the same.
R ¹ and R ² may be bonded to each other to form a ring. R ⁴ and R ⁵ may be bonded to each other to form a ring.

As the repeating unit represented by the general formula (B-3), in particular, the repeating unit represented by the following general formula (B-4) is more preferable because it is more excellent in suppressing the collapse of the pattern to be formed and LER. Is preferred.

In the general formula (B-4), ^{R 1} and ^{R 2} have the general formula (B-1) in the same meaning as ^{R 1} and ^{R 2,} also preferred embodiments are also the same. R ¹ and R ² may be bonded to each other to form a ring.

Among the repeating units represented by the general formula (B-1), the specific halogen atom is particularly preferable in that the resist film to be formed is more sensitive, and the pattern to be formed is more excellent in suppressing collapse and LER. It is preferable to contain. When the repeating unit represented by the general formula (B-1) contains a specific halogen atom, the content (hereinafter, also referred to as “specific halogen atom content”) is based on the total mass of the repeating unit. It is preferably 10% by mass or more, and more preferably 20% by mass or more. In addition, although an upper limit is not restrict | limited in particular, For example, it is 60 mass% or less.

Specific examples of the repeating unit represented by formula (B-1) are shown below, but the present invention is not limited to these specific examples. In the specific examples shown below, for example, the first compound from the upper left and the second repeating unit from the upper left can be decomposed by the action of an acid (in other words, as a repeating unit containing an acid-decomposable group). Can work).

In the resin (X), the content of the repeating unit represented by the general formula (B-1) is not particularly limited, but for example 5 to 100% by mass with respect to all the repeating units in the resin (X). Yes, 5 to 80% by mass, preferably 5 to 70% by mass, more preferably 10 to 60% by mass.
In the resin (X), when the repeating unit represented by the general formula (B-1) functions as a repeating unit containing an acid-decomposable group, the above-mentioned general formula is a repeating unit containing an acid-decomposable group. The total content of the repeating unit represented by (B-1) and the repeating unit Y1 described later is preferably 5 to 80% by mass with respect to all the repeating units in the resin (X), and preferably 5 to 70% by mass. % Is more preferable, 10 to 60% by mass is further preferable, and 20 to 60% by mass is particularly preferable.

(Other repeat units)
Resin (X) may further contain another repeating unit in addition to the repeating unit represented by formula (B-1). Below, the other repeating unit which resin (X) may contain is explained in full detail. The resin (X) is a repeating unit (homogeneous) having a higher Tg as a repeating unit that can be contained in addition to the repeating unit represented by the general formula (B-1) in that the collapse-preventing performance is better. It is preferable to include a repeating unit derived from a monomer having a higher Tg when used as a polymer.

≪Repeating unit having acid-decomposable group≫
The resin (X) preferably contains a repeating unit having an acid-decomposable group (hereinafter also referred to as “repeating unit Y1”).
The acid-decomposable group preferably has a structure in which a polar group is protected by a group (leaving group) that decomposes and leaves by the action of an acid.
Examples of polar groups include carboxy group, phenolic hydroxyl group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group Bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, etc. Acid groups (groups dissociating in an aqueous 2.38 mass% tetramethylammonium hydroxide solution), alcoholic hydroxyl groups, and the like.

The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, and means a hydroxyl group other than a hydroxyl group directly bonded on an aromatic ring (phenolic hydroxyl group). Excludes aliphatic alcohols substituted with a functional group (for example, a hexafluoroisopropanol group). The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less.

Preferred polar groups include carboxy group, phenolic hydroxyl group, fluorinated alcohol group (preferably hexafluoroisopropanol group), and sulfonic acid group.

A preferable group as the acid-decomposable group is a group in which the hydrogen atom of these groups is substituted with a group capable of leaving by the action of an acid (leaving group).
Examples of the group (leaving group) leaving by the action of an acid include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), and — C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ) and the like can be mentioned.
In the formula, R ₃₆ to R ₃₉ each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.
R ₀₁ and R ₀₂ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

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

As the repeating unit Y1, among them, a repeating unit having a structure in which a —COO— group is protected with a leaving group or a repeating unit having a structure in which a phenolic hydroxyl group is protected with a leaving group is preferable.
The structure in which the —COO— group is protected with a leaving group is preferably a cumyl ester group, an enol ester group, an acetal ester group, or a tertiary alkyl ester group, and is preferably an acetal ester group or a tertiary alkyl group. Alkyl ester groups are more preferred.

A repeating unit having a structure in which a —COO— group is protected with a leaving group —A repeating unit having a structure in which a COO— group is protected with a leaving group is a repeating unit represented by the following general formula (AI) Is preferred.

In general formula (AI):
Xa ₁ represents a hydrogen atom, a halogen 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). However, when all of Rx ₁ to Rx ₃ are alkyl groups (straight chain or branched chain), at least two of Rx ₁ to Rx ₃ are preferably methyl groups.
Two of Rx ₁ to Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).

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 (such as a fluorine atom), a hydroxyl group, or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, and 3 or less carbon atoms. An alkyl group is preferable, and a methyl group is more preferable.
Examples of the halogen atom represented by Xa ₁ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferable.
Xa ₁ is preferably a hydrogen atom, a fluorine atom, an iodine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

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

Examples of the alkyl group represented by Rx ₁ to Rx ₃ include alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group. Groups are preferred.
Examples of the cycloalkyl group represented by Rx ₁ to Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. A polycyclic cycloalkyl group such as
The cycloalkyl group formed by combining two of Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group. In addition, a norbornyl group, a tetracyclodecanyl group, Polycyclic cycloalkyl groups such as a tetracyclododecanyl group and an adamantyl group are preferred. Of these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferable.
In the cycloalkyl group formed by combining two of Rx ₁ to Rx ₃ , for example, one of the methylene groups constituting the ring is replaced with a group having a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group. It may be.

When each of the above groups has 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 an alkoxycarbonyl group ( Carbon number 2-6) and the like. The number of carbon atoms in the substituent is preferably 8 or less.

Specific examples of the repeating unit Y1 are given below, but the present invention is not limited to these specific examples.
In specific examples, Rx represents a hydrogen atom, a fluorine atom, an iodine atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each independently 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, they may be the same or different. 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 alicyclic 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 preferable.

-Repeating unit having a structure in which a phenolic hydroxyl group is protected with a leaving group In the present specification, a phenolic hydroxyl group is a group formed by substituting a hydrogen atom of an aromatic hydrocarbon group with a hydroxyl group. The aromatic ring of the aromatic hydrocarbon group is a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring and a naphthalene ring.

Examples of the leaving group that decomposes and leaves by the action of an acid include groups represented by formulas (Y1) to (Y4).
Formula (Y1): —C (Rx ₁ ) (Rx ₂ ) (Rx ₃ )
Formula (Y2): —C (═O) OC (Rx ₁ ) (Rx ₂ ) (Rx ₃ )
Formula (Y3): —C (R ₃₆ ) (R ₃₇ ) (OR ₃₈ )
Formula (Y4): —C (Rn) (H) (Ar)

In the formulas (Y1) and (Y2), Rx ₁ to Rx ₃ each independently represents an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). However, when all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), at least two of Rx ₁ to Rx ₃ are preferably methyl groups.
Among these, Rx ₁ to Rx ₃ are more preferably each independently a repeating unit representing a linear or branched alkyl group, and Rx ₁ to Rx ₃ are each independently a linear group. More preferably, it is a repeating unit representing an alkyl group.
Two of Rx ₁ to Rx ₃ may combine to form a monocycle or polycycle.
The alkyl group of Rx ₁ to Rx ₃ is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. .
Examples of the cycloalkyl group represented by Rx ₁ to Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Are preferred.
Examples of the cycloalkyl group formed by combining two of Rx ₁ to Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, or a tetracyclododecanyl group. And a polycyclic cycloalkyl group such as an adamantyl group are preferred. Among these, 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.
In the groups represented by the formulas (Y1) and (Y2), for example, Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above cycloalkyl group. preferable.

In the formula (Y3), R ₃₆ to R ₃₈ each independently represents a hydrogen atom or a monovalent organic group. R ₃₇ and R ₃₈ may be bonded to each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. R ₃₆ is preferably a hydrogen atom.

In the formula (Y4), Ar represents an aromatic hydrocarbon group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may be bonded to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

As the repeating unit having a structure in which a phenolic hydroxyl group is protected by a leaving group, those having a structure in which a hydrogen atom in the phenolic hydroxyl group is protected by a group represented by the formulas (Y1) to (Y4) are preferable.

As the repeating unit having a structure in which a phenolic hydroxyl group is protected with a leaving group, a repeating unit represented by the following general formula (AII) is preferable.

In general formula (AII),
R ₆₁ , R ₆₂ and R ₆₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. However, R ₆₂ may be bonded to Ar ₆ to form a ring, and R ₆₂ in this case represents a single bond or an alkylene group.
X ₆ represents a single bond, —COO—, or —CONR ₆₄ —. R ₆₄ represents a hydrogen atom or an alkyl group.
L ₆ represents a single bond or an alkylene group.
Ar ₆ represents an (n + 1) -valent aromatic hydrocarbon group, and when bonded to R ₆₂ to form a ring, represents an (n + 2) -valent aromatic hydrocarbon group.
Y ₂ independently represents a hydrogen atom or a group capable of leaving by the action of an acid when n ≧ 2. However, at least one of Y ₂ represents a group capable of leaving by the action of an acid. The group capable of leaving by the action of an acid as Y ₂ is preferably represented by formulas (Y1) to (Y4).
n represents an integer of 1 to 4.

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 carboxyl group, and Examples thereof include alkoxycarbonyl groups (having 2 to 6 carbon atoms), and those having 8 or less carbon atoms are preferred.

Resin (X) may contain repeating unit Y1 individually by 1 type, and may contain 2 or more types together.

When the resin (X) includes the repeating unit Y1 (the total when there are a plurality of repeating units Y1), the content of the repeating unit Y1 is 5 to 60% by mass with respect to all the repeating units in the resin (X). Is preferably 10 to 60% by mass, more preferably 10 to 50% by mass.

≪Repeating unit having phenolic hydroxyl group≫
The resin (X) may contain a repeating unit having a phenolic hydroxyl group (hereinafter also referred to as “repeating unit Y2”).
Examples of the repeating unit Y2 include repeating units represented by the following general formula (I).

In formula (I),
R ₄₁ , R ₄₂ and R ₄₃ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. However, R ₄₂ may form a ring with Ar _4, R ₄₂ in this case represents a single bond or an alkylene group.
X ₄ represents a single bond, —COO—, or —CONR ₆₄ —, and R ₆₄ represents a hydrogen atom or an alkyl group.
L ₄ represents a single bond or a divalent linking group.
Ar ₄ represents an (n + 1) -valent aromatic group, and represents an (n + 2) -valent aromatic group when bonded to R ₄₂ to form a ring.
n represents an integer of 1 to 5.
For the purpose of making the repeating unit represented by formula (I) highly polar, it is also preferable that n is an integer of 2 or more, or X ₄ is —COO— or —CONR ₆₄ —.

Examples of the alkyl group represented by R ₄₁ , R ₄₂ , and R ₄₃ in the general formula (I) include a methyl group, an ethyl group, a propyl group, an isopropyl group, and an n-butyl group, which may have a substituent. , Sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group and the like, preferably an alkyl group having 20 or less carbon atoms, more preferably an alkyl group having 8 or less carbon atoms, and an alkyl group having 3 or less carbon atoms. Is more preferable.

The cycloalkyl group represented by R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I) may be monocyclic or polycyclic. A monocyclic cycloalkyl group having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent, is preferable.
Examples of the halogen atom represented by R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
As the alkyl group contained in the alkoxycarbonyl group represented by R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I), the same alkyl groups as those described above for R ₄₁ , R ₄₂ and R ₄₃ are preferable.

Preferred substituents in each of the above groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyls. Group, acyloxy group, alkoxycarbonyl group, cyano group, nitro group and the like, and the number of carbon atoms of the substituent is preferably 8 or less.

Ar ₄ represents an (n + 1) -valent aromatic group. The divalent aromatic hydrocarbon group in the case where n is 1 may have a substituent, for example, an arylene having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, and an anthracenylene group. An aromatic hydrocarbon group containing a heterocyclic group such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole is preferable.

Specific examples of the (n + 1) -valent aromatic group in the case where n is an integer of 2 or more include (n-1) arbitrary hydrogen atoms removed from the above-described specific examples of the divalent aromatic group. The group formed can be preferably mentioned.
The (n + 1) -valent aromatic group may further have a substituent.
Preferable substituents in the (n + 1) -valent aromatic group include, for example, a halogen atom (a fluorine atom or an iodine atom is preferable) and a halogenated alkyl group (a perfluoroalkyl group is preferable).

_-CONR 64 represented by X ₄ - _{(R 64} represents a hydrogen atom or an alkyl group) The alkyl group for _{R 64} in, which may have a substituent, a methyl group, an ethyl group, a propyl group An alkyl group having 20 or less carbon atoms such as isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group is preferable, and an alkyl group having 8 or less carbon atoms is more preferable. .
X ₄ is preferably a single bond, —COO— or —CONH—, more preferably a single bond or —COO—, and still more preferably a single bond.

The divalent linking group as L ₄ is preferably an alkylene group, and as the alkylene group, a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, which may have a substituent, And an alkylene group having 1 to 8 carbon atoms, such as an octylene group.
L ₄ is particularly preferably a single bond.

Ar ₄ is preferably an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, more preferably a benzene ring group, a naphthalene ring group, or a biphenylene ring group, and even more preferably a benzene ring group. .
n is preferably 1 or 2.

The repeating unit represented by the general formula (I) is preferably a repeating unit derived from hydroxystyrene or a hydroxystyrene derivative. That is, Ar ₄ preferably represents a benzene ring group, and X ₄ and L ₄ preferably represent a single bond.

Specific examples of the repeating unit Y2 will be given below, but the present invention is not limited to these specific examples. In the formula, a represents 1 or 2.

Resin (X) may have 1 type of repeating unit Y2, and may contain it in combination of 2 or more types.
When the resin (X) contains the repeating unit Y2 (when there are a plurality of repeating units Y2), the content of the repeating unit Y2 is 5 to 60 masses with respect to all the repeating units in the resin (X). %, Preferably 10 to 50% by mass, more preferably 10 to 30% by mass.

≪Repeating unit containing fluorine atom or iodine atom and containing acid group≫
The resin (X) preferably contains a repeating unit containing a fluorine atom or an iodine atom and containing an acid group (hereinafter also referred to as “repeating unit Y3”). The repeating unit Y3 does not correspond to the repeating unit represented by the general formula (B-1) and the repeating unit Y2.
The acid group contained in the repeating unit Y3 includes a fluorinated alcohol group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, an (alkylsulfonyl) (alkylcarbonyl) imide group, and a bis (alkylcarbonyl). Examples include a methylene group, a bis (alkylcarbonyl) imide group, a bis (alkylsulfonyl) methylene group, a bis (alkylsulfonyl) imide group, a tris (alkylcarbonyl) methylene group, and a tris (alkylsulfonyl) methylene group. Moreover, it is preferable that the hydrogen atom contained in these acid groups is substituted with the fluorine atom.

Specific examples of the repeating unit Y3 are shown below, but the present invention is not limited to these specific examples. In the formula, Rx represents a hydrogen atom, CH ₃ , CF ₃ , or CH ₂ OH.

Resin (X) may have repeating unit Y3 individually by 1 type, and may contain 2 or more types together.
When the resin (X) contains the repeating unit Y3 (the total when there are a plurality of repeating units Y3), the content of the repeating unit Y3 is 5 to 60 mass with respect to all the repeating units in the resin (A). %, More preferably 15 to 50% by mass, and still more preferably 15 to 40% by mass.

≪Repeating unit having a polar group≫
Resin (X) preferably contains a repeating unit containing a polar group (hereinafter also referred to as “repeating unit Y4”). The repeating unit Y4 does not correspond to the repeating unit represented by the general formula (B-1), the repeating unit Y2, and the repeating unit Y3.
As the repeating unit Y4, among them, a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure (hereinafter also referred to as “repeating unit Y4-1”), or the above repeating unit A repeating unit having another polar group other than the unit Y4-1 (hereinafter also referred to as “repeating unit Y4-2”) is preferable.

.Repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure (repeating unit Y4-1)
The lactone structure or sultone structure only needs to have a lactone structure or sultone structure, and a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure is preferable. Among them, a 5- to 7-membered ring lactone structure that is condensed with another ring structure to form a bicyclo structure or a spiro structure, or a 5- to 7-membered ring that forms a bicyclo structure or a spiro structure. Those having other ring structures condensed to the sultone structure are more preferable.
Resin (X) is a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21), or any of the following general formulas (SL1-1) to (SL1-3): More preferably, it contains a repeating unit having a sultone structure. A lactone structure or a sultone structure may be directly bonded to the main chain. As a preferable structure, general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-8), general formula (LC1-16), or general formula (LC1 -21), or a sultone structure represented by the general formula (SL1-1).

The lactone structure portion or the sultone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxy group. A halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group. An alkyl group having 1 to 4 carbon atoms, a cyano group, or an acid-decomposable group is preferable. n ₂ represents an integer of 0 to 4. When n ₂ is 2 or more, the plurality of substituents (Rb ₂ ) may be the same or different. A plurality of substituents (Rb ₂ ) may be bonded to form a ring.

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

In the general formula (III),
A represents an ester bond (a group represented by —COO—) or an amide bond (a group represented by —CONH—).
n is the number of repetitions of the structure represented by —R ₀ —Z—, and represents an integer of 0 to 5, preferably 0 or 1, and more preferably 0. When n is 0, —R ₀ —Z— does not exist and becomes a single bond.
R ₀ represents an alkylene group, a cycloalkylene group, or a combination thereof. If R ₀ is plural, R ₀ each independently represents a alkylene group, a cycloalkylene group, or a combination thereof.
Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond. When there are a plurality of Z, each Z independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
R ₈ represents a monovalent organic group having a lactone structure or a sultone structure.
R ₇ represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).

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

Resin (X) may have a repeating unit having a carbonate structure. The carbonate structure is preferably a cyclic carbonate structure.
The repeating unit having a cyclic carbonate structure is preferably a repeating unit represented by the following general formula (A-1).

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

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

Further, as the repeating unit Y4-1, in addition to the above monomers, the following monomers are also preferably used.

The resin (X) preferably contains the repeating unit described in paragraphs <0370> to <0414> of US Patent Application Publication No. 2016 / 0070167A1 as the repeating unit Y4-1.

Resin (X) may have one type of repeating unit Y4-1, or may contain two or more types in combination.
When the resin (X) includes the repeating unit Y4-1, the content of the repeating unit Y4-1 is preferably 5 to 40% by mass, and preferably 5 to 30% by mass with respect to all the repeating units in the resin (X). More preferred is 5 to 25% by mass.

・ Repeating units having other polar groups other than the above repeating unit Y4-1 (repeating unit Y4-2)
The resin (X) preferably contains a repeating unit Y4-2.
Examples of polar groups include hydroxyl group, cyano group, amide group, carboxylic acid group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group Bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, etc. Is mentioned.
Examples of the repeating unit Y4-2 include a repeating unit having an alicyclic hydrocarbon structure (specifically, a cyclohexyl group, an adamantyl group, or a norbornane group) substituted with a polar group such as a hydroxyl group and a cyano group. It is done.

Specific examples of the monomer corresponding to the repeating unit Y4-2 are given below, but the present invention is not limited to these specific examples.

Other specific examples of the repeating unit Y4-2 include the repeating units disclosed in paragraphs <0415> to <0433> of US Patent Application Publication No. 2016 / 0070167A1.

Resin (X) may have one type of repeating unit Y4-2, or may contain two or more types in combination.
When the resin (X) includes the repeating unit Y4-2, the content of the repeating unit Y4-2 is preferably 5 to 40% by mass, and preferably 5 to 30% by mass with respect to all the repeating units in the resin (X). More preferred is 5 to 25% by mass.

Resin (X) may have other repeating units in addition to the repeating units Y1 to Y4 described above.

Resin (X) can be synthesized according to a conventional method (for example, radical polymerization).

The weight average molecular weight of the resin (X) is preferably from 2,000 to 30,000, more preferably from 3,500 to 15,000, more preferably from 5,000 to 12, from the viewpoint that the fall prevention property of the formed pattern is more excellent. Is more preferable. The degree of dispersion (Mw / Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and even more preferably 1.1 to 2.0. preferable.

Resin (X) may be used individually by 1 type, and may use 2 or more types together.
In the composition of the present invention, the content of the resin (X) (the total when there are a plurality of types) is generally 20.0% by mass or more with respect to the total solid content of the composition, 30.0 mass% or more is preferable, 40.0 mass% or more is more preferable, and 50.0 mass% or more is still more preferable. Although an upper limit in particular is not restrict | limited, 99.9 mass% or less is preferable, 99.5 mass% or less is more preferable, and 99.0 mass% or less is still more preferable.

[Compound that generates acid upon irradiation with actinic ray or radiation]
The composition of the present invention includes a compound that generates an acid upon irradiation with actinic rays or radiation (hereinafter, also referred to as “photo acid generator”).
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 still 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 (X) or in a resin different from the resin (X).
Among these, the photoacid generator is preferably in the form of a low molecular compound.
The photoacid generator is not particularly limited as long as it is a known one, but a compound that generates an organic acid upon irradiation with actinic rays or radiation (preferably an electron beam or extreme ultraviolet rays) is preferable.
As the organic acid, for example, at least one of sulfonic acid, bis (alkylsulfonyl) imide, and tris (alkylsulfonyl) methide is preferable.
As a photo-acid generator, the compound represented by the following general formula (ZI), the following general formula (ZII), or the following general formula (ZIII) is preferable.

In the general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The organic group represented by R ₂₀₁ , R ₂₀₂ and R ₂₀₃ generally has 1 to 30 carbon atoms, and 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, a pentylene group, and the like).
Z ⁻ represents a non-nucleophilic anion (an anion having an extremely low ability to cause a nucleophilic reaction).

_Examples of the organic group for R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include an aryl group, an alkyl group, and a cycloalkyl group.
Of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , at least one is preferably an aryl group, more preferably all three are aryl groups. As an aryl group, in addition to a phenyl group and a naphthyl group, a heteroaryl group such as an indole residue and a pyrrole residue can be used.
The alkyl group for R ₂₀₁ to R ₂₀₃ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and is a methyl group, an ethyl group, an n-propyl group, an i-propyl group, or an n-butyl group. Is more preferable.
The cycloalkyl group of R ₂₀₁ to R ₂₀₃ is preferably a cycloalkyl group having 3 to 10 carbon atoms, more preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, or a cycloheptyl group.
The substituents that these groups may have include nitro groups, halogen atoms such as fluorine atoms, carboxy groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), alkyl groups ( Preferably 1 to 15 carbon atoms), a fluoroalkyl group substituted with a fluorine atom (preferably 1 to 15 carbon atoms, preferably a perfluoroalkyl group), a cycloalkyl group (preferably 3 to 15 carbon atoms) An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), and an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7) and the like.

Examples of the non-nucleophilic anion include a sulfonate anion (such as an aliphatic sulfonate anion, an aromatic sulfonate anion, and a camphor sulfonate anion), a carboxylate anion (an aliphatic carboxylate anion, an aromatic carboxylate anion, And aralkylcarboxylate anions), sulfonylimide anions, bis (alkylsulfonyl) imide anions, tris (alkylsulfonyl) methide anions, and the like.

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

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

The alkyl group, cycloalkyl group, and aryl group mentioned above may have a substituent. The substituent is not particularly limited, and specific examples thereof include nitro groups, halogen atoms such as fluorine atoms, carboxy groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), alkyl groups ( Preferably 1 to 10 carbon atoms, a cycloalkyl group (preferably 3 to 15 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group ( Preferably 2 to 12 carbon atoms, alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), alkylthio group (preferably 1 to 15 carbon atoms), alkylsulfonyl group (preferably 1 to 15 carbon atoms), alkylimino Examples include sulfonyl groups (preferably having 1 to 15 carbon atoms), aryloxysulfonyl groups (preferably having 6 to 20 carbon atoms), and the like.

The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 14 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

Examples of the sulfonylimide anion include saccharin anion.

The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of the substituent of these alkyl groups include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, and a cycloalkylaryloxysulfonyl group. Alkyl groups substituted with atoms or fluorine atoms are preferred.
The alkyl groups in the bis (alkylsulfonyl) imide anion may be bonded to each other to form a ring structure. This increases the acid strength.

Examples of other non-nucleophilic anions include fluorinated phosphorus (eg, PF ₆ ⁻ ), fluorinated boron (eg, BF ₄ ⁻ ), and fluorinated antimony (eg, SbF ₆ ⁻ ).

Examples of the non-nucleophilic anion include an aliphatic sulfonate anion in which at least α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group having a fluorine atom A bis (alkylsulfonyl) imide anion substituted with a tris (alkylsulfonyl) methide anion in which an alkyl group is substituted with a fluorine atom is preferred. Of these, a perfluoroaliphatic sulfonate anion (preferably having 4 to 8 carbon atoms) or a benzenesulfonate anion having a fluorine atom is more preferred. Nonafluorobutanesulfonate anion, perfluorooctanesulfonate anion, pentafluorobenzene A sulfonate anion or a 3,5-bis (trifluoromethyl) benzenesulfonate anion is more preferable.

From the viewpoint of acid strength, the pKa of the generated acid is preferably −1 or less in order to improve sensitivity.

Further, as the non-nucleophilic anion, anions represented by the following general formula (AN1) are also preferable.

Where
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ¹ and R ² each independently represent a hydrogen atom, a fluorine atom, or an alkyl group, and when there are a plurality of R ¹ and R ² , R ¹ and R ² may be the same or different.
L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
A represents a cyclic organic group.
x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

The general formula (AN1) will be described in more detail.
The carbon number of the alkyl group in the alkyl group substituted with the fluorine atom of Xf is preferably 1 to 10, and more preferably 1 to 4. Further, the alkyl group substituted with the fluorine atom of Xf is preferably a perfluoroalkyl group.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of Xf include a fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ , and CH ₂ CH ₂ C ₄ F ₉ , among others, a fluorine atom, or CF ₃ is preferred. In particular, it is preferable that both Xf are fluorine atoms.

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

x is preferably from 1 to 10, and more preferably from 1 to 5.
y is preferably 0 to 4, more preferably 0.
z is preferably 0 to 5, and more preferably 0 to 3.
The divalent linking group for L is not particularly limited, and is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group, a cycloalkylene group, Examples include alkenylene groups and linking groups in which a plurality of these groups are linked, and linking groups having a total carbon number of 12 or less are preferred. Of these, —COO—, —OCO—, —CO—, or —O— is preferable, and —COO— or —OCO— is more preferable.

The cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and has an alicyclic group, an aromatic ring group, and a heterocyclic group (not only those having aromaticity but also aromaticity). And the like).
The alicyclic group may be monocyclic or polycyclic, and is preferably a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. In addition, a norbornyl group, a tricyclodecanyl group, a tetracyclo group, and the like are preferable. A polycyclic cycloalkyl group such as a decanyl group, a tetracyclododecanyl group, and an adamantyl group is preferred. 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 used in the post-exposure heating step. It is preferable from the viewpoint of improving MEEF (Mask Error Enhancement Factor) because diffusibility in the film can be suppressed.
Examples of the aromatic ring group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.
Examples of the heterocyclic group include those derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Of these, those derived from a furan ring, a thiophene ring, or a pyridine ring are preferable.

In addition, examples of the cyclic organic group include lactone structures, and specific examples include lactone structures represented by the general formulas (LC1-1) to (LC1-17) described above.

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

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

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R ₂₀₇ are the same as the groups described as the aryl group, alkyl group, and cycloalkyl group of R ₂₀₁ to R ₂₀₃ in the general formula (ZI). is there.
_Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have include the aryl group, alkyl group, and cycloalkyl of R ₂₀₁ to R ₂₀₃ in the above compound (ZI). It is the same as the substituent that the group may have, and the preferred embodiment is also the same.

Z ⁻ represents a non-nucleophilic anion, which is synonymous with the non-nucleophilic anion of Z ⁻ in formula (ZI), and the preferred embodiment is also the same.

In addition, as a photoacid generator, in terms of improving the resolution by suppressing the diffusion of the acid generated by exposure to the non-exposed portion, the volume of 130 to ³ or more by irradiation with an electron beam or extreme ultraviolet rays. A compound capable of generating an acid having a size (more preferably, sulfonic acid) is preferred. As the photoacid generator, among others, volume 190 Å ³ or more the size of the acid (more preferably sulfonic acid) more preferably a compound capable of generating a volume 270 Å ³ or more the size of the acid (more preferably sulfonic acid) Are more preferable, and compounds that generate an acid having a volume of 400 ³ or more (more preferably sulfonic acid) are particularly preferable. However, from the viewpoint of sensitivity or coating solvent solubility, the volume is preferably 2000 to ³ or less, and more preferably 1500 to ³ or less. The volume value is obtained using “WinMOPAC” manufactured by Fujitsu Limited.
In calculating the volume value, first, the chemical structure of the acid according to each example is input, and then the molecular structure of each acid is calculated by molecular force field calculation using the MM (Molecular Mechanics) 3 method with this structure as the initial structure. By determining the most stable conformation and then performing molecular orbital calculation using the PM3 method for these most stable conformations, the “accessible volume” of each acid can be calculated.

Specific examples of the acid generated by the photoacid generator (acid having a proton bonded to the anion moiety) and the volume thereof are shown below, but the present invention is not limited thereto. In addition, the volume shown in the following illustration is a calculated value (unit ^{３ 3} ). One foot is 1 × 10 ⁻¹⁰ m.

Examples of the photoacid generator include paragraphs <0368> to <0377> of JP-A-2014-41328 and paragraphs <0240> to <0262 of JP-A-2013-228881 (corresponding US Patent Application Publication No. 2015). No./004533 <0339>), which is incorporated herein by reference. Moreover, although the following compounds are mentioned as a preferable specific example, it is not restrict | limited to these.

A photo-acid generator may be used individually by 1 type, and may use 2 or more types together.
In the composition of the present invention, the content of the photoacid generator (when there are a plurality of types) is preferably 0.1 to 50.0% by mass relative to the total solid content of the composition. 0 to 40.0 mass% is more preferable, and 5.0 to 35.0 mass% is still more preferable.

[Acid diffusion control agent]
The composition of the present invention may contain an acid diffusion controller as long as the effects of the present invention are not hindered.
The acid diffusion controller acts as a quencher that traps the acid generated from the acid generator or the like during exposure and suppresses the reaction of the acid-decomposable resin in the unexposed area due to excess generated acid. Examples of the acid diffusion controller include a basic compound (DA), a basic compound (DB) whose basicity is reduced or disappeared by irradiation with actinic rays or radiation, and an onium that is a weak acid relative to the acid generator. A salt (DC), a low molecular compound (DD) having a nitrogen atom and a group capable of leaving by the action of an acid, or an onium salt compound (DE) having a nitrogen atom in the cation moiety is used as an acid diffusion controller. it can.
In the composition of the present invention, a known acid diffusion controller can be used as appropriate. For example, paragraphs <0627> to <0664> of U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs <0095> to <0187> of Publication No. 2015 / 0004544A1 of U.S. Patent Application Publication No. 2016 / 0237190A1. Known compounds disclosed in paragraphs <0403> to [0423] of the specification and paragraphs <0259> to <0328> of U.S. Patent Application Publication No. 2016 / 0274458A1 can be suitably used as the acid diffusion controller. .

As the basic compound (DA), compounds having structures represented by the following formulas (A) to (E) are preferable.

In general formula (A), R ²⁰⁰ , R ²⁰¹ and R ²⁰² each independently represent a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), Or an aryl group (preferably having 6 to 20 carbon atoms). R ²⁰¹ and R ²⁰² may combine with each other to form a ring.
In general formula (E), R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ each independently represents an alkyl group having 1 to 20 carbon atoms.

The alkyl group in the general formulas (A) and (E) may have a substituent or may be unsubstituted.
Regarding the alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.
The alkyl groups in general formulas (A) and (E) are more preferably unsubstituted.

As the basic compound (DA), guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like are preferable, imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, A compound having a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, an aniline derivative having a hydroxyl group and / or an ether bond, or the like is more preferable.

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, and benzimidazole.
Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, and 1,8-diazabicyclo [5,4 , 0] undec-7-ene and the like.
Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxide having a 2-oxoalkyl group (specifically, triphenylsulfonium hydroxide, tris (t-butyl). Phenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, and the like.
Examples of the compound having an onium carboxylate structure are compounds in which the anion moiety of the compound having an onium hydroxide structure is a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate. .
Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine.
Examples of the compound having an aniline structure or a pyridine structure include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline, and the like.
Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, and tris (methoxyethoxyethyl) amine.
Examples of aniline derivatives having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline.

Moreover, a super organic base can also be used as a basic compound (DA).
Examples of the super organic base include guanidine bases such as tetramethylguanidine and polyguanidine (including substituted guanidine derivatives and polyguanides as guanidine and guanidine derivatives), diazabicyclononene (DBN), diazabicycloundecene ( DBU), triazabicyclodecene (TBD), N-methyl-triazabicyclodecene (MTBD), and other amidine and guanidine polynitrogen polyheterocyclic compounds and their polymer-supported strong bases, schweisser ) Bases, as well as proazaphosphatran (Verkade) bases.

Also, as the basic compound (DA), amine compounds and ammonium salt compounds can also be used.

Examples of the amine compound include primary, secondary, and tertiary amine compounds, and amine compounds in which one or more alkyl groups (preferably having 1 to 20 carbon atoms) are bonded to a nitrogen atom are preferable. However, tertiary amine compounds are more preferred.
When the amine compound is a secondary or tertiary amine compound, the group bonded to the nitrogen atom in the amine compound includes, for example, a cycloalkyl group (preferably having a carbon number of 3 to 20), and aryl groups (preferably having 6 to 12 carbon atoms).
Moreover, it is preferable that the amine compound contains the oxyalkylene group. The number of oxyalkylene groups in the molecule is preferably 1 or more, more preferably 3 to 9, and still more preferably 4 to 6. Among the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or CH ₂ CH ₂ CH ₂ O—) is preferable, and the oxyethylene group Is more preferable.

Examples of the ammonium salt compound include primary, secondary, tertiary, and quaternary ammonium salt compounds, and an ammonium salt compound in which one or more alkyl groups are bonded to a nitrogen atom is preferable.
In addition, when the ammonium salt compound is a secondary, tertiary, or quaternary ammonium salt compound, the group bonded to the nitrogen atom in the ammonium salt compound includes, for example, a cycloalkyl group ( Preferred are C 3-20) and aryl groups (preferably C 6-12).
The ammonium salt compound preferably contains an oxyalkylene group. The number of oxyalkylene groups in the molecule is preferably 1 or more, more preferably 3 to 9, and still more preferably 4 to 6. Of the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—), an oxypropylene group (—CH (CH ₃ ) CH ₂ O—, or —CH ₂ CH ₂ CH ₂ O—) is preferable, An ethylene group is more preferable.

Examples of the anion of the ammonium salt compound include a halogen atom, a sulfonate, a borate, and a phosphate. Among them, a halogen atom or a sulfonate is preferable.
As a halogen atom, a chlorine atom, a bromine atom, or an iodine atom is preferable.
As the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is preferable, and specific examples thereof include an alkyl sulfonate having 1 to 20 carbon atoms and an aryl sulfonate. The alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group, an acyl group, and an aromatic ring group. Examples of the alkyl sulfonate include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate. In addition, examples of the aryl group of the aryl sulfonate include a benzene ring group, a naphthalene ring group, and an anthracene ring group. The substituent that the benzene ring group, naphthalene ring group, and anthracene ring group may have is an alkyl group having 1 to 6 carbon atoms (which may be linear or branched), or the number of carbon atoms. 3-6 cycloalkyl groups are preferred. Specific examples of the alkyl group and the cycloalkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an i-butyl group, a t-butyl group, and an n-hexyl group. And a cyclohexyl group.
The alkyl group and the cycloalkyl group may further have other substituents such as an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, an acyl group, and an acyloxy group. Groups and the like.

As the basic compound (DA), an amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group can also be used.

The amine compound having a phenoxy group and the ammonium salt compound having a phenoxy group are those having a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound or the ammonium salt compound described above.
Examples of the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxy group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. Groups and the like. The substitution position of the substituent may be any of the 2-6 positions. The number of substituents may be 1 to 5.

The amine compound having a phenoxy group and the ammonium salt compound having a phenoxy group preferably include at least one oxyalkylene group between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups in the molecule is preferably 1 or more, more preferably 3 to 9, and still more preferably 4 to 6. Of the oxyalkylene groups, an oxyethylene group (—CH ₂ CH ₂ O—) or an oxypropylene group (—CH (CH ₃ ) CH ₂ O— or —CH ₂ CH ₂ CH ₂ O—) is preferable. Groups are more preferred.

The amine compound having a phenoxy group is prepared by reacting a primary or secondary amine having a phenoxy group and a haloalkyl ether by heating and then reacting with a strong base (for example, sodium hydroxide, potassium hydroxide, tetraalkylammonium, etc. ) And an extraction of the reaction product with an organic solvent (for example, ethyl acetate and chloroform). Alternatively, it is obtained by heating and reacting a primary or secondary amine with a haloalkyl ether having a phenoxy group at the end, adding an aqueous solution of a strong base to the reaction system, and further extracting the reaction product with an organic solvent. It is done.

A compound (DB) whose basicity decreases or disappears upon irradiation with actinic rays or radiation (hereinafter also referred to as “compound (DB)”) has a proton acceptor functional group, and has a function of actinic rays or radiation. It is a compound that decomposes by irradiation and whose proton acceptor property is lowered, disappears, or changes from proton acceptor property to acidity.

The proton acceptor functional group is a group capable of electrostatically interacting with a proton or a functional group having an electron, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a π conjugate. It means a functional group having a nitrogen atom with an unshared electron pair that does not contribute to. The nitrogen atom having an unshared electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure represented by the following general formula.

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

The compound (DB) is decomposed by irradiation with actinic rays or radiation to generate a compound in which the proton acceptor property is lowered or eliminated, or the proton acceptor property is changed to acidic. Here, the decrease or disappearance of the proton acceptor property, or the change from the proton acceptor property to the acid property is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group. Specifically, when a proton adduct is produced from a compound (DB) having a proton acceptor functional group and a proton, the equilibrium constant in the chemical equilibrium is reduced.
Proton acceptor property can be confirmed by measuring pH.

Specific examples of the compound (DB) are described, for example, in paragraphs <0421> to <0428> of JP 2014-41328 A and paragraphs <0108> to <0116> of JP 2014-134686 A. Can be incorporated, the contents of which are incorporated herein.

In the composition of the present invention, an onium salt (DC) that is a weak acid relative to the acid generator can be used as an acid diffusion controller.
When an acid generator and an onium salt that generates an acid that is a relatively weak acid with respect to the acid generated from the acid generator are mixed and used, it is generated from the acid generator by irradiation with actinic rays or radiation. When the acid collides with an onium salt having an unreacted weak acid anion, a weak acid is released by salt exchange to yield an onium salt having a strong acid anion. In this process, the strong acid is exchanged with a weak acid having a lower catalytic ability, so that the acid is apparently deactivated and the acid diffusion can be controlled.

As the onium salt that becomes a weak acid relative to the acid generator, compounds represented by the following general formulas (d1-1) to (d1-3) are preferable.

In the formula, R ⁵¹ represents a hydrocarbon group which may have a substituent, and Z ^2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (however, a carbon adjacent to S). R ⁵² is an organic group, Y ³ is a linear, branched or cyclic alkylene group or an arylene group, and Rf is a fluorine atom. Each of the M ⁺ is independently an ammonium cation, a sulfonium cation or an iodonium cation.

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

An onium salt (DC) that is a weak acid relative to an acid generator has a cation moiety and an anion moiety in the same molecule, and the cation moiety and the anion moiety are linked by a covalent bond ( (Hereinafter also referred to as “compound (DCA)”).
The compound (DCA) is preferably a compound represented by any one of the following general formulas (C-1) to (C-3).

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

Examples of the substituent having 1 or more carbon atoms in R ₁ to R ₃ include alkyl group, cycloalkyl group, aryl group, alkyloxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, alkylaminocarbonyl group, cycloalkylamino A carbonyl group, an arylaminocarbonyl group, etc. are mentioned. Of these, an alkyl group, a cycloalkyl group, or an aryl group is preferable.

L ₁ as the divalent linking group is a linear or branched alkylene group, cycloalkylene group, arylene group, carbonyl group, ether bond, ester bond, amide bond, urethane bond, urea bond, and two types thereof. Examples include groups formed by combining the above. L ₁ is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more thereof.

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

In general formula (d-1),
Rb each independently represents a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably 3 to 30 carbon atoms), an aralkyl group ( Preferably, it represents 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably 1 to 10 carbon atoms). Rb may be connected to each other to form a ring.
The alkyl group, cycloalkyl group, aryl group and aralkyl group represented by Rb are each independently a functional group such as a hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, oxo group, alkoxy group, or halogen. It may be substituted with an atom. The same applies to the alkoxyalkyl group represented by Rb.

Rb is preferably a linear or branched alkyl group, a cycloalkyl group, or an aryl group, and more preferably a linear or branched alkyl group or a cycloalkyl group.
Examples of the ring formed by connecting two Rb to each other include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, and derivatives thereof.
Specific examples of the structure represented by the general formula (d-1) include, but are not limited to, the structure disclosed in paragraph <0466> of US Patent Publication US2012 / 0135348A1.

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

In general formula (6),
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l + m = 3.
Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, two Ras may be the same or different, and two Ras may be connected to each other to form a heterocyclic ring together with the nitrogen atom in the formula. This heterocycle may contain a heteroatom other than the nitrogen atom in the formula.
Rb has the same meaning as Rb in formula (d-1), and preferred examples are also the same.
In the general formula (6), the alkyl group, cycloalkyl group, aryl group and aralkyl group as Ra are each independently substituted with the alkyl group, cycloalkyl group, aryl group and aralkyl group as Rb. A good group may be substituted with the same group as described above.

Specific examples of the Ra alkyl group, cycloalkyl group, aryl group, and aralkyl group (these groups may be substituted with the above groups) include the same groups as those described above for Rb. It is done.
Specific examples of the particularly preferred compound (DD) in the present invention include, but are not limited to, compounds disclosed in paragraph <0475> of US Patent Application Publication No. 2012 / 0135348A1.

The onium salt compound (DE) having a nitrogen atom in the cation part (hereinafter also referred to as “compound (DE)”) is preferably a compound having a basic site containing a nitrogen atom in the cation part. The basic moiety is preferably an amino group, and more preferably an aliphatic amino group. More preferably, all of the atoms adjacent to the nitrogen atom in the basic moiety are hydrogen atoms or carbon atoms. From the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, and a halogen atom) is not directly connected to the nitrogen atom.
Preferable specific examples of the compound (DE) include, but are not limited to, compounds disclosed in paragraph <0203> of US Patent Application Publication No. 2015 / 03009408A1.

Preferred examples of the acid diffusion controller are shown below.

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

In the composition of the present invention, the content of the acid diffusion controller (the total when there are a plurality of types) is preferably 0.001 to 10% by mass, based on the total solid content of the composition, 0.01 to 7.0 mass% is more preferable.

Examples of the acid diffusion control agent include compounds described in paragraphs <0140> to <0144> of JP2013-11833A (amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, etc.). ) Can also be used.

[Surfactant]
The composition of the present invention may contain a surfactant. By including a surfactant, when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less is used, it is possible to form a resist pattern with good sensitivity and resolution, excellent adhesion, and fewer development defects. It becomes possible.
As the surfactant, fluorine-based and / or silicon-based surfactants are preferable.
Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in paragraph <0276> of US Patent Application Publication No. 2008/0248425. Also, F-top EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Florard FC 430, 431 and 4430 (manufactured by Sumitomo 3M Co., Ltd.); Megafac F171, F173, F176, F189, F113, F110, F177, F120 and R08 (manufactured by DIC Corporation); Surflon S-382, SC101, 102, 103, 104, 105 and 106 (manufactured by Asahi Glass Co., Ltd.); Troisol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 and GF-150 (manufactured by Toa Gosei Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.); F-top EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801 , EF802, and EF601 ((shares PF636, PF656, PF6320, and PF6520 (manufactured by OMNOVA); KH-20 (manufactured by Asahi Kasei Corporation); FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D, and 222D (manufactured by Gemco); (Neos Co., Ltd.) may be used. Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon surfactant.

The surfactant is a fluoroaliphatic compound produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method) in addition to the known surfactants as described above. You may synthesize using. Specifically, a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as a surfactant. This fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-90991.
Further, surfactants other than 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 combination of two or more.

In the composition of the present invention, the content of the surfactant is preferably 0.0001 to 2.0 mass%, more preferably 0.0005 to 1.0 mass%, based on the total solid content of the composition.

[Hydrophobic resin]
The composition of the present invention may contain a hydrophobic resin. The hydrophobic resin is a resin different from the resin (X).
When the composition of the present invention contains a hydrophobic resin, the static / dynamic contact angle on the surface of the actinic ray-sensitive or radiation-sensitive film can be controlled. This makes it possible to improve development characteristics, suppress outgassing, improve immersion liquid follow-up in immersion exposure, reduce immersion defects, and the like.
The hydrophobic resin is preferably designed to be unevenly distributed on the surface of the resist film, but unlike a surfactant, it does not necessarily have a hydrophilic group in the molecule, and a polar / nonpolar substance is mixed uniformly. You don't have to contribute to

The hydrophobic resin is at least one selected from the group consisting of “fluorine atom”, “silicon atom”, and “CH ₃ partial structure contained in the side chain portion of the resin” from the viewpoint of uneven distribution in the film surface layer. A resin having a repeating unit having a seed is preferable.
When the hydrophobic resin contains a fluorine atom and / or a silicon atom, the fluorine atom and / or silicon atom in the hydrophobic resin may be contained in the main chain of the resin or in the side chain. May be.

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

The hydrophobic resin preferably has at least one group selected from the following groups (x) to (z).
(X) Acid group (y) A group that is decomposed by the action of an alkali developer to increase the solubility in the alkali developer (hereinafter also referred to as a polar conversion group).
(Z) a group decomposable by the action of an acid

Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, and an (alkylsulfonyl) (alkyl Carbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, and tris (alkylsulfonyl) ) And a methylene group.
The acid group is preferably a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonimide group, or a bis (alkylcarbonyl) methylene group.

Examples of the group (y) which is decomposed by the action of the alkali developer and increases the solubility in the alkali developer include a lactone group, a carboxylic acid ester group (—COO—), and an acid anhydride group (—C (O) OC. (O)-), acid imide group (—NHCONH—), carboxylic acid thioester group (—COS—), carbonate ester group (—OC (O) O—), sulfate ester group (—OSO ₂ O—), and Examples thereof include a sulfonic acid ester group (—SO ₂ O—), and a lactone group or a carboxylic acid ester group (—COO—) is preferable.
The repeating unit containing these groups is, for example, a repeating unit in which these groups are directly bonded to the main chain of the resin, and examples thereof include a repeating unit of an acrylate ester and a methacrylate ester. In this repeating unit, these groups may be bonded to the main chain of the resin via a linking group. Or this repeating unit may be introduce | transduced into the terminal of resin using the polymerization initiator or chain transfer agent which has these groups at the time of superposition | polymerization.
Examples of the repeating unit having a lactone group include those similar to the repeating unit having a lactone structure described above in the section of the resin (X).

The content of the repeating unit having a group (y) that is decomposed by the action of the alkaline developer and increases the solubility in the alkaline developer is preferably 1 to 100 mol% with respect to all the repeating units in the hydrophobic resin. 3 to 98 mol% is more preferable, and 5 to 95 mol% is still more preferable.

Examples of the repeating unit having a group (z) capable of decomposing by the action of an acid in the hydrophobic resin include the same repeating units having an acid-decomposable group as mentioned for the resin (X). The repeating unit having a group (z) that decomposes by the action of an acid may have at least one of a fluorine atom and a silicon atom. The content of the repeating unit having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, more preferably 20 to 20 mol%, based on all repeating units in the hydrophobic resin. 60 mol% is more preferable.
The hydrophobic resin may further have a repeating unit different from the above-described repeating unit.

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

On the other hand, particularly when the hydrophobic resin contains a CH ₃ partial structure in the side chain portion, it is also preferable that the hydrophobic resin does not substantially contain a fluorine atom and a silicon atom. Moreover, it is preferable that hydrophobic resin 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 weight average molecular weight of the hydrophobic resin in terms of standard polystyrene is preferably 1,000 to 100,000, and more preferably 1,000 to 50,000.

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

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

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

A hydrophobic resin may be used individually by 1 type, and may use 2 or more types together.
It is preferable to use a mixture of two or more types of hydrophobic resins having different surface energies from the viewpoint of achieving both immersion liquid followability and development characteristics in immersion exposure.
The content of the hydrophobic resin in the composition (when there are a plurality of types) is preferably 0.01 to 10.0% by mass, and preferably 0.05 to 8.% by mass with respect to the total solid content in the composition. 0 mass% is more preferable.

〔solvent〕
The composition of the present invention may contain a solvent.
The solvent preferably includes at least one of the following component (M1) and the following component (M2), and more preferably includes the following component (M1).
When a solvent contains the following component (M1), it is preferable that a solvent consists only of a component (M1) or is a mixed solvent containing at least a component (M1) and a component (M2).

Below, a component (M1) and a component (M2) are shown.
Component (M1): Propylene glycol monoalkyl ether carboxylate Component (M2): Solvent selected from the following component (M2-1) or Solvent selected from the following component (M2-2) Component (M2-1): Propylene glycol monoalkyl ether, lactate ester, acetate ester, butyl butyrate, alkoxypropionate ester, chain ketone, cyclic ketone, lactone, or alkylene carbonate Component (M2-2): Flash point (hereinafter also referred to as fp) is 37 Solvent that is above ℃

When the solvent and the resin (X) are used in combination, the coating property of the composition is improved and a pattern with a small number of development defects is obtained. The reason for this is not necessarily clear, but the solvent has a good balance of the solubility, boiling point and viscosity of the resin (X) described above. It is thought that it originates in being able to suppress.

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

As the component (M2-1), the following are preferable.
As propylene glycol monoalkyl ether, propylene glycol monomethyl ether (PGME) or propylene glycol monoethyl ether is preferable.
As the lactic acid ester, ethyl lactate, butyl lactate or propyl lactate is preferable.
As the acetate ester, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate is preferable.
As the alkoxypropionate, methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferable.
Examples of chain ketones include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, phenylacetone, methyl ethyl ketone, methyl isobutyl. Ketones, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methyl naphthyl ketone, or methyl amyl ketone are preferred.
As the cyclic ketone, methylcyclohexanone, isophorone, or cyclohexanone is preferable.
As the lactone, γ-butyrolactone is preferable.
As the alkylene carbonate, propylene carbonate is preferable.

As the component (M2-1), propylene glycol monomethyl ether (PGME), ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, pentyl acetate, γ-butyrolactone, or propylene carbonate is more preferable. .

Specific examples of the component (M2-2) include propylene glycol monomethyl ether (fp: 47 ° C.), ethyl lactate (fp: 53 ° C.), ethyl 3-ethoxypropionate (fp: 49 ° C.), methyl amyl ketone. (Fp: 42 ° C.), cyclohexanone (fp: 44 ° C.), pentyl acetate (fp: 45 ° C.), methyl 2-hydroxyisobutyrate (fp: 45 ° C.), γ-butyrolactone (fp: 101 ° C.), or propylene carbonate (Fp: 132 ° C.). Among these, propylene glycol monoethyl ether, ethyl lactate, pentyl acetate, or cyclohexanone is preferable, and propylene glycol monoethyl ether or ethyl lactate is more preferable.
Here, “flash point” means a value described in a reagent catalog of Tokyo Chemical Industry Co., Ltd. or Sigma Aldrich.

The mixing ratio (mass ratio: M1 / M2) of the component (M1) and the component (M2) is preferably 100/0 to 15/85, more preferably 100/0 to 40/60 in that the number of development defects is further reduced. Is more preferable, and 100/0 to 60/40 is still more preferable.

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

Examples of the other solvent include ester solvents having 7 or more carbon atoms (preferably 7 to 14, preferably 7 to 12, more preferably 7 to 10), and a hetero atom number of 2 or less. . The ester solvent having 7 or more carbon atoms and 2 or less hetero atoms does not include the solvent corresponding to the component (M2) described above.

Examples of ester solvents having 7 or more carbon atoms and 2 or less heteroatoms include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, butyl propionate, Isobutyl butyrate, heptyl propionate, butyl butanoate and the like are preferable, and isoamyl acetate is preferable.

[Other additives]
The composition of the present invention comprises a dissolution inhibiting compound (a compound that decomposes by the action of an acid to reduce the solubility in an organic developer, preferably having a molecular weight of 3000 or less), a dye, a plasticizer, and a photosensitizer. , A light absorber, and / or a compound that promotes solubility in a developer (for example, a phenol compound having a molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxy group).

[Preparation method]
In the composition of the present invention, the solid content concentration is preferably 0.5 to 30% by mass, more preferably 1.0 to 20.0% by mass, and more preferably 1.0 to 10.0 in terms of better coatability. % By mass is more preferable, and 1.0 to 5.0% by mass is particularly preferable. 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.

The film thickness of the resist film (actinic ray-sensitive or radiation-sensitive film) made of the composition of the present invention is generally 200 nm or less, and preferably 100 nm or less, from the viewpoint of improving resolution. For example, in order to resolve a 1: 1 line and space pattern having a line width of 20 nm or less, the thickness of the resist film to be formed is preferably 90 nm or less. If the film thickness is 90 nm or less, pattern collapse is less likely to occur when a development process described later is applied, and a better resolution performance can be obtained.
In the case of EUV exposure or electron beam exposure, the range of film thickness is preferably 15 to 90 nm. 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 composition of the present invention is used by dissolving the above components in a predetermined organic solvent, preferably the above mixed solvent, filtering the solution, and applying the solution on 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 further preferably 0.03 μm or less. This filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. In the filter filtration, for example, as disclosed in Japanese Patent Application Publication No. 2002-62667 (Japanese Patent Laid-Open No. 2002-62667), a cyclic filtration may be performed, and a plurality of types of filters may be connected in series or in parallel. It may be connected to and filtered. 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.

[Use]
The composition of the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition that changes its properties upon reaction with irradiation with actinic rays or radiation. More specifically, the composition of the present invention is a semiconductor manufacturing process such as an IC (Integrated Circuit), a circuit board such as a liquid crystal or a thermal head, a mold structure for imprinting, other photofabrication processes, or The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition used for producing a lithographic printing plate or an acid-curable composition. The pattern formed in the present invention can be used in an etching process, an ion implantation process, a bump electrode forming process, a rewiring forming process, MEMS (Micro Electro Mechanical Systems), and the like.

[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 step of forming a resist film (actinic light sensitive or radiation sensitive film) on a support with the above-mentioned actinic ray sensitive or radiation sensitive resin composition (resist film forming step);
(Ii) exposing the resist film (irradiating actinic rays or radiation) (exposure step); and
(Iii) a step of developing the exposed resist film using a developer (development step),
Have

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 may be immersion exposure.
The pattern forming method of the present invention preferably includes (ii) a preheating (PB) step before the exposure step.
The pattern forming method of the present invention preferably includes (v) a post exposure bake (PEB) step after (ii) the exposure step and before (iii) the development 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.

In the pattern forming method of the present invention, the above-described (i) film formation step, (ii) exposure step, and (iii) development step can be performed by a generally known method.
If necessary, a resist underlayer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon), and antireflection film) may be formed between the resist film and the support.
As a material constituting the resist underlayer film, a known organic or inorganic material can be appropriately used.
A protective film (top coat) may be formed on the upper layer of the resist film. As the protective film, a known material can be appropriately used. For example, U.S. Patent Application Publication No. 2007/0178407, U.S. Patent Application Publication No. 2008/0085466, U.S. Patent Application Publication No. 2007/0275326, U.S. Patent Application Publication No. 2016/0299432, The composition for forming a protective film disclosed in US Patent Application Publication No. 2013/0244438 and International Patent Application Publication No. 2016 / 157988A can be suitably used. As a composition for protective film formation, what contains the acid diffusion control agent mentioned above is preferable.
The thickness of the protective film is preferably 10 to 200 nm, more preferably 20 to 100 nm, and still more preferably 40 to 80 nm.

The support is not particularly limited, and is generally used in a manufacturing process of a semiconductor such as an IC, or a manufacturing process of a circuit board such as a liquid crystal or a thermal head, and other photofabrication lithography processes. A substrate can be used. Specific examples of the support include inorganic substrates such as silicon, SiO ₂ , and SiN.

The heating temperature is preferably 80 to 150 ° C., more preferably 80 to 140 ° C., and still more preferably 80 to 130 ° C. in both (iv) the preheating step and (v) the post-exposure heating step.
The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and still more preferably 60 to 600 seconds in both (iv) the preheating step and (v) the post-exposure heating step.
The heating can be performed by means provided in the exposure apparatus and the developing apparatus, and may be performed using a hot plate or the like.

Although there is no restriction | limiting in the light source wavelength used for an exposure process, For example, infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-ray | X_line, an electron beam, etc. are mentioned. Of these, the light source wavelength is preferably 250 nm or less, more preferably 220 nm or less, and even 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), electron beam, etc., KrF excimer laser, ArF excimer laser, EUV or electron beam is preferable, EUV or electron beam is more preferable, and EUV is still more preferable.

(Iii) In the development step, an alkaline developer may be used, or a developer containing an organic solvent (hereinafter also referred to as an organic developer) may be used.

As the alkali component contained in the alkali developer, a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used. In addition, an aqueous alkali solution containing an alkali component such as an inorganic alkali, a primary to tertiary amine, an alcohol amine, and a cyclic amine can also be used.
Furthermore, the alkaline developer may contain an appropriate amount of alcohols and / or surfactant. The alkali concentration of the alkali developer is usually from 0.1 to 20% by mass. The pH of the alkaline developer is usually 10-15.
The development time using an alkali developer is usually 10 to 300 seconds.
The alkali concentration, pH, and development time of the alkali developer can be appropriately adjusted according to the pattern to be formed.

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

Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, acetonyl acetone, ionone, diacetyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, and propylene carbonate.

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

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

A plurality of the above solvents may be mixed, or may be mixed with a solvent other than the above or water. The water content of the entire developer is preferably less than 50% by mass, more preferably less than 20% by mass, still more preferably less than 10% by mass, and particularly preferably substantially free of moisture.
The content of the organic solvent in the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and 95 to 100% by mass with respect to the total amount of the developer. % Is particularly preferred.

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

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

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

As a developing method, for example, a method 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 left stationary for a certain time (paddle method), a substrate Examples include a method of spraying developer on the surface (spray method) or a method of continuously discharging developer while scanning a developer discharge nozzle on a substrate rotating at a constant speed (dynamic dispensing method). It is done.

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

(Iii) It is preferable to include a step of washing with a rinsing liquid (rinsing step) after the developing step.

For example, pure water can be used as the rinsing solution used in the rinsing step after the developing step using the alkaline developer. The pure water may contain an appropriate amount of a surfactant. In this case, after the developing process or the rinsing process, a process for removing the developing solution or the rinsing liquid adhering to the pattern with a supercritical fluid may be added. Further, after the rinse treatment or the treatment with the supercritical fluid, a heat treatment may be performed in order to remove moisture remaining in the pattern.

There is no particular limitation on the rinsing solution used in the rinsing step after the developing step using the developing solution containing an organic solvent, as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. As the rinse liquid, use a rinse 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 preferred.
Specific examples of the hydrocarbon solvent, ketone solvent, ester solvent, alcohol solvent, amide solvent, and ether solvent are the same as those described in the developer containing an organic solvent.
As the rinse liquid used in the rinse step in this case, a rinse liquid containing a monohydric alcohol is more preferable.

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

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.

The rinse solution may contain an appropriate amount of a surfactant.
In the rinsing step, the substrate that has been developed using the organic developer is washed with a rinse containing an 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. Examples thereof include a method (dip method) and a method (spray method) of spraying a rinsing liquid on the substrate surface. 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 2,000 to 4,000 rpm to remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. By this heating process, the developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed. In the heating step after the rinsing step, the heating temperature is usually 40 to 160 ° C., preferably 70 to 95 ° C., and the heating time is usually 10 seconds to 3 minutes, preferably 30 to 90 seconds.

The 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 The topcoat-forming composition or the like) preferably does not contain impurities such as metal components, isomers, and residual monomers. The content of these impurities contained in the above various materials is preferably 1 ppm or less, more preferably 100 ppt or less, still more preferably 10 ppt or less, and substantially not (less than the detection limit of the measuring device). Is particularly preferred.

Examples of a method for removing impurities such as metals from the various materials include filtration using a filter. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. 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. The filter is preferably a filter with reduced eluate as disclosed in Japanese Patent Application Publication No. 2016-201426 (Japanese Patent Laid-Open No. 2016-201426).
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. Examples of the metal adsorbent include those disclosed in Japanese Patent Application Publication No. 2016-206500 (Japanese Patent Laid-Open No. 2016-206500).
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.

The various materials described above are described in U.S. Patent Application Publication No. 2015/0227049, Japanese Patent Application Publication No. 2015-123351 (Japanese Patent Laid-Open No. 2015-123351), etc., in order to prevent contamination by impurities. Preferably, it is stored in a separate container.

A method for improving the surface roughness of the pattern may be applied to the pattern formed by the pattern forming method of the present invention. As a method for improving the surface roughness of the pattern, for example, a method of processing a pattern by a plasma of a gas containing hydrogen disclosed in US Patent Application Publication No. 2015/0104957 is cited. In addition, Japanese Patent Application Publication No. 2004-235468 (JP 2004-235468), US Patent Application Publication No. 2010/0020297, Proc. of SPIE Vol. 8328 83280N-1 “EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement” may be applied.
In addition, the pattern formed by the above method is, for example, a spacer process disclosed in Japanese Patent Application Publication No. 1991-270227 (Japanese Patent Laid-Open No. 3-270227) and US Patent Application Publication No. 2013/0209941. It can be used as a core material (Core).

[Electronic device manufacturing method]
The present invention also relates to an electronic device manufacturing method including the pattern forming method described above. The electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitably mounted on an electric / electronic device (for example, home appliances, OA (Office Automation) -related devices, media-related devices, optical devices, communication devices, etc.). Is done.

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.

[Actinic ray-sensitive or radiation-sensitive resin composition]
First, various components contained in the actinic ray-sensitive or radiation-sensitive resin composition (hereinafter referred to as “resist composition”) having the composition shown in Table 2 are shown below.

[Various ingredients]
<Resin>
Table 1 below shows the composition ratio (mass ratio), weight average molecular weight (Mw), and dispersity (Mw / Mn) of each resin shown in Table 2. Table 1 below also shows the content (% by mass) of fluorine atoms or iodine atoms in the resin.

The specific structures of the monomers used in the resins P-1 to P-59 shown in Table 1 and the comparative resins A-1 and A-2 are shown below. In the monomers shown below, the repeating units derived from M-1 to M-9 and M-63 to M-66 correspond to the repeating units represented by formula (B-1).

The resin synthesis examples shown in Table 1 are shown below.
(Synthesis Example 1: Synthesis of Resin P-1)
Monomers corresponding to each repeating unit (M-1 / M-11 / M-12) of the resin P-1 were 50.0 g, 15.0 g, 35.0 g in order from the left, and a polymerization initiator V-601 ( Wako Pure Chemical Industries, Ltd. (12.72 g) was dissolved in cyclohexanone (358 g). The solution thus obtained was used as a monomer solution.
Cyclohexanone (198 g) was placed in the reaction vessel, and the monomer solution was dropped into the reaction vessel adjusted to 85 ° C. over 4 hours in a nitrogen gas atmosphere. The resulting reaction solution was stirred at 85 ° C. for 2 hours in a reaction vessel, and then allowed to cool to room temperature.
The reaction solution after standing to cool was dropped into a mixed solution of methanol and water (methanol / water = 5/5 (mass ratio)) over 20 minutes, and the precipitated powder was collected by filtration. The obtained powder was dried to obtain Resin P-1 (31.6 g).
The composition ratio (mass ratio) of each repeating unit determined by the NMR (nuclear magnetic resonance) method was 50/15/35. The weight average molecular weight of the resin P-1 by GPC method was 6200 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.6.

(Synthesis of Resins P-2 to P-59 and Resin A-1 and A-2 for Comparative Example)
The same operations as in Synthesis Example 1 were performed to synthesize Resins P-2 to P-59 and Comparative Resins A-1 and A-2. In the resins P-2 to P-59 and the comparative resins A-1 and A-2, the composition (mass ratio), weight average molecular weight (Mw), and dispersity (Mw / Mn) of each repeating unit Was determined by the same method as for the above-mentioned resin P-1.

<Photo acid generator>
The structure of the photoacid generator shown in Table 2 is shown below.
In the following, the cation part and the anion part of the photoacid generator are individually shown. That is, the photoacid generator shown in Table 2 consists of a combination of a cation part and an anion part. However, PAG-Cation 10 shown below is an amphoteric ion having a cation portion and an anion portion in one molecule, and acts alone as a photoacid generator.
(Cation part of photoacid generator)

(Anion part of photoacid generator)

<Acid diffusion control agent>
The structure of the acid diffusion controller shown in Table 2 is shown below.

<Additive polymer (hydrophobic resin)>
The structure of the additive polymer (hydrophobic resin) shown in Table 2 is shown below.
In addition, the numerical value in the following formula | equation represents the mass ratio (mass%) of each repeating unit.

<Surfactant>
The surfactants shown in Table 2 are shown below.
W-1: Megafuck F176 (DIC Corporation; Fluorine)
W-2: Megafuck R08 (DIC Corporation; fluorine and silicon)

<Solvent>
The solvents shown in Table 2 are shown below.
SL-1: Propylene glycol monomethyl ether acetate (PGMEA)
SL-2: Propylene glycol monomethyl ether (PGME)
SL-3: ethyl lactate SL-4: γ-butyrolactone SL-5: cyclohexanone

(Preparation of resist composition)
Each component shown in Table 2 was mixed so as to have the solid content concentration and composition shown in Table 2. Subsequently, the obtained liquid mixture was filtered through a polyethylene filter having a pore size of 0.03 μm to prepare a resist composition. In the resist composition, the solid content means all components other than the solvent. The obtained resist composition was used in Examples and Comparative Examples.
The contents (mass%) of each component described in the columns of “resin”, “photoacid generator”, “acid diffusion controller”, “added polymer”, and “surfactant” below are all The ratio of each component with respect to solid content is represented. The description in the “Solvent” column represents the mass ratio of the content of each solvent.

[Pattern formation and evaluation]
A pattern was formed using the resist composition. In forming the pattern, the following developer and rinse solution and lower layer film were used.

<Developer and rinse solution>
D-1: 3.00 mass% tetramethylammonium hydroxide aqueous solution D-2: 2.38 mass% tetramethylammonium hydroxide aqueous solution D-3: 1.50 mass% tetramethylammonium hydroxide aqueous solution D-4: 1 .00 mass% tetramethylammonium hydroxide aqueous solution D-5: 0.80 mass% tetramethylammonium hydroxide aqueous solution D-6: pure water D-7: FIRM Extreme 10 (manufactured by AZEM)
E-1: Butyl acetate E-2: 2-Heptanone E-3: Diisobutyl ketone E-4: Isoamyl acetate E-5: Dibutyl ether E-6: Undecane

<Underlayer>
UL-1: AL412 (manufactured by Brewer Science)
UL-2: SHB-A940 (manufactured by Shin-Etsu Chemical Co., Ltd.)

<Pattern formation>
The resist composition described in Table 3 was applied to a silicon wafer (12 inches) on which the lower layer film described in Table 3 was formed to form a coating film. The obtained coating film is heated under the bake conditions described in the column “Resist application conditions” in Table 3 to form a resist film having the film thickness described in Table 3 to obtain a silicon wafer having the resist film. It was.
Pattern irradiation is performed on a silicon wafer having a resist film obtained using an EUV exposure apparatus (manufactured by Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). It was. As the reticle, a mask having a line size = 20 nm and a line: space = 1: 1 was used.
Thereafter, the film was baked (Post Exposure Bake; PEB) under the conditions shown in the “PEB / development conditions” column of Table 3 below, and then developed by pudging with the developer shown in Table 3 for 30 seconds. The paddle was rinsed with the rinse solution shown in FIG. Thereafter, the silicon wafer was rotated at 4000 rpm for 30 seconds and further baked at 90 ° C. for 60 seconds to obtain a line and space pattern having a pitch of 40 nm and a line width of 20 nm (space width of 20 nm).

<Evaluation>
The evaluation shown below was performed using the resist film and pattern obtained by the above method. The results are summarized in Table 3.

(sensitivity)
The line width of the formed line and space pattern was measured while changing the exposure amount, the exposure amount (optimal exposure amount) when the line width was 20 nm was determined, and this was defined as sensitivity (mJ / cm ² ). The smaller this value, the higher the sensitivity of the resist film and the better the performance.

(Falling suppression (pattern collapse suppression))
The line width of the formed line and space pattern was measured while changing the exposure amount. At this time, the minimum line width that resolved without the pattern falling over 10 μm square was defined as the falling line width. A smaller value indicates a wider pattern collapse margin and better pattern collapse suppression.

(LER performance)
When observing a resist pattern of line and space resolved at the optimum exposure for sensitivity evaluation, observe from the top of the pattern with a scanning electron microscope (SEM: Scanning Electron Microscope (CG-4100, Hitachi High-Technologies Corporation)) In this case, the distance from the center of the pattern to the edge was observed at an arbitrary point (100 points), and the measurement variation was evaluated at 3σ. A smaller value indicates better LER performance.

The results are shown in Table 3 below.

From the results in Table 3, it was confirmed that the resist composition of the example (and the resist film formed from the resist composition of the example) had excellent sensitivity. Moreover, it was confirmed that the pattern formed with the resist composition of an Example is excellent in collapse suppression and LER.
From the comparison between Example 1 and Example 8 and Example 9, when the content of the specific halogen atom in the resin (X) is 16% by mass or more with respect to the total mass of the resin (X), the resist composition It was confirmed that the sensitivity of was better.
From the comparison between Example 1 and Examples 10 to 13, it was confirmed that when the weight average molecular weight of the resin (X) is 3,500 to 15,000, the collapse resistance of the formed pattern is more excellent. .
From the comparison between Example 1 and Example 14, it was confirmed that when two kinds of photoacid generators were used in combination, the collapse suppression of the formed pattern was more excellent.
From comparison between Example 1 and Examples 20 to 23, the resin (X) contains a repeating unit represented by the general formula (B-3), and at least one of L ³ and L ⁴ is —CO—. In the case of-, -SO-, or -SO _2-, it was confirmed that the pattern formed was more excellent in suppressing the collapse. In particular, when the resin (X) contains a repeating unit represented by the general formula (B-4), it was confirmed that the pattern formed was superior in terms of LER.
From the comparison of Example 60 to Example 65, it was confirmed that the same effect can be obtained regardless of whether the development method is alkali development or organic solvent development.

Claims (12)

1. A compound that generates an acid upon irradiation with actinic rays or radiation; and
   A resin whose polarity is increased by the action of an acid,
   The actinic ray-sensitive or radiation-sensitive resin wherein the resin contains a repeating unit represented by the following general formula (B-1) and contains at least one halogen atom selected from the group consisting of a fluorine atom and an iodine atom Resin composition.
   

   

   In the above formula, X and Y each independently represent an oxygen atom, a sulfur atom, or —NR ³ —. R ¹ , R ² , and R ³ each independently represent a hydrogen atom or an organic group. Ring W ¹ represents a ring containing two carbon atoms, X and Y, and optionally having a substituent.
   R ¹ and R ² may be bonded to each other to form a ring. R ¹ and R ² may each independently bond to an atom contained in ring W ¹ to form a ring. When at least one of X and Y represents —NR ³ —, each R ³ is independently bonded to R ¹ , R ² , or an atom contained in the ring W ¹ to form a ring. Also good.
2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit represented by the general formula (B-1) is a repeating unit represented by the following general formula (B-2). .
   

   

   In the above formula, X and Y each independently represent an oxygen atom, a sulfur atom, or —NR ³ —. L ¹ and L ² are each independently a divalent linkage selected from the group consisting of —CO—, —C (R ⁴ ) (R ⁵ ) —, —SO—, —SO ₂ —, and combinations thereof. Represents a group. R ¹ , R ² , R ³ , R ⁴ , and R ⁵ each independently represent a hydrogen atom or an organic group.
   R ¹ and R ² may be bonded to each other to form a ring. R ⁴ and R ⁵ may be bonded to each other to form a ring. When at least one of X and Y represents —NR ³ —, R ³ may be independently bonded to R ¹ , R ² , R ⁴ , or R ⁵ to form a ring.
3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 2, wherein the repeating unit represented by the general formula (B-2) is a repeating unit represented by the following general formula (B-3). .
   

   

   In the above formula, X and Y each independently represent an oxygen atom, a sulfur atom, or —NR ³ —. L ³ and L ⁴ each independently represents —CO—, —C (R ⁴ ) (R ⁵ ) —, —SO—, or —SO ₂ —. R ¹ , R ² , R ³ , R ⁴ , and R ⁵ each independently represent a hydrogen atom or an organic group.
   R ¹ and R ² may be bonded to each other to form a ring. R ⁴ and R ⁵ may be bonded to each other to form a ring.
4. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 3, wherein at least one of L ³ and L ⁴ represents -CO-, -SO-, or -SO _2- .
5. The actinic ray-sensitive or radiation-sensitive resin according to claim 3 or 4, wherein the repeating unit represented by the general formula (B-3) is a repeating unit represented by the following general formula (B-4). Composition.
   

   

   In the above formula, R ¹ and R ² each independently represent a hydrogen atom or an organic group.
   R ¹ and R ² may be bonded to each other to form a ring.
6. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein the resin has a weight average molecular weight of 2,000 to 30,000.
7. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 6, wherein the resin contains a fluorine atom.
8. A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7.
9. A resist film forming step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7;
   An exposure step of exposing the resist film;
   A patterning method comprising: developing the exposed resist film using a developer.
10. The pattern forming method according to claim 9, wherein the exposure step is a step of exposing the resist film with extreme ultraviolet light.
11. The pattern forming method according to claim 9 or 10, wherein the developer is a developer containing an organic solvent.
12. An electronic device manufacturing method comprising the pattern forming method according to any one of claims 9 to 11.