JP6992166B2 - Actinic cheilitis or radiation-sensitive resin composition, resist film, pattern forming method, manufacturing method of electronic device - Google Patents

Description

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

Conventionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integrated Circuits), photoresist compositions (hereinafter, "sensitive light-sensitive or radiation-sensitive resins" have been used. Fine processing is performed by lithography using "composition"). In recent years, with the increasing integration of integrated circuits, the formation of ultrafine patterns in the submicron region or the quartermicron region has been required. Along with this, there is a tendency for the exposure wavelength to be shortened from g-line to i-line and further to KrF excimer laser light. Furthermore, at present, in addition to excimer laser light, lithography using electron beam, X-ray, or EUV (Extreme Ultra Violet) is also being developed.

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

Japanese Unexamined Patent Publication No. 2007-094139

By the way, EUV light (wavelength 13.5 nm) has a shorter wavelength than, for example, ArF excimer laser light (wavelength 193 nm), so that the number of incident photons is small when the same sensitivity is used in the exposure of the resist film. .. As a result, in lithography using EUV light, the influence of "photon shot noise", in which the number of photons stochastically varies, is large, which is a major factor in the deterioration of LER (line edge roughness).
In order to reduce photon shot noise, it is effective to increase the exposure amount (in other words, reduce the sensitivity) and increase the number of incident photons, but this is a trade-off relationship with the recent demand for higher sensitivity. .. It is also effective to increase the film thickness of the resist film to increase the number of absorbed photons, but since the aspect ratio of the formed pattern becomes large, the L / S (line / space) pattern deteriorates the fall suppression property. Is likely to occur.
Therefore, in the lithography using EUV light, a sensitive light-sensitive or radiation-sensitive resin composition (particularly, high sensitivity and anti-tilt property) capable of forming a pattern having high sensitivity and excellent anti-tilt property. A sensitive light-sensitive or radiation-sensitive resin composition (which can form an excellent pattern for LER) is required.

Against the above background, the present inventors have recently introduced a large amount of elements having high EUV light absorption efficiency such as fluorine atom and iodine atom into a resist film (coating film of a sensitive light-sensitive or radiation-sensitive resin composition). According to the method, it has been found that the resist film is excellent in EUV light absorption efficiency (in other words, excellent in sensitivity) even if the film thickness is small. On the other hand, it has also been confirmed that the more the above-mentioned elements are contained in the resin, the more easily the collapse suppressing property of the formed pattern tends to deteriorate.

Therefore, it is an object of the present invention to provide a sensitive light-sensitive or radiation-sensitive resin composition having high sensitivity and excellent ability to suppress the formed pattern from collapsing.
Another object of the present invention is to provide a resist film, a pattern forming method, and a method for manufacturing an electronic device using the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition.

As a result of diligent studies to achieve the above problems, the present inventors have found that the sensitive light-sensitive or radiation-sensitive resin composition has a repeating unit represented by the general formula (B-1) described later, a fluorine atom and a fluorine atom. We have found that the above problems can be solved by containing an acid-degradable resin containing at least one halogen atom selected from the group consisting of iodine atoms, and completed the present invention.
That is, it was found that the above object can be achieved by the following configuration.

[1] Compounds that generate acid by irradiation with active light or radiation, and
Containing a resin whose polarity increases due to the action of acid,
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 cheilitis or radiation-sensitive radiation 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. Sex resin composition.
[3] The actinic cheilitis or radiation-sensitive radiation 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. Sex resin composition.
[4] The actinic light-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 sensitive light beam according to [3] or [4], wherein the repeating unit represented by the general formula (B-3) is a repeating unit represented by the general formula (B-4) described later. Sexual or radiation sensitive resin composition.
[6] The actinic light-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 light-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 of the sensitive light-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 sensitive light-sensitive or radiation-sensitive resin composition according to any one of [1] to [7].
The exposure process for exposing the resist film and
A pattern forming method including a developing step of developing the exposed resist film using a developing solution.
[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 developer according to [9] or [10], wherein the developer is a developer containing an organic solvent.
[12] A method for manufacturing an electronic device, which comprises the pattern forming method according to any one of [9] to [11].

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a sensitive light-sensitive or radiation-sensitive resin composition having high sensitivity and excellent ability to suppress the formed pattern from collapsing.
Further, according to the present invention, it is possible to provide a resist film, a pattern forming method, and a method for manufacturing an electronic device using the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
As used herein, the term "active light" or "radiation" means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays, X-rays, electron beams (EB), and the like. do. As used herein, "light" means active light or radiation.
Unless otherwise specified, the term "exposure" as used herein refers to not only exposure to the emission line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, and X-rays, but also electron beams, ion beams, and the like. Also 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 the lower limit value and the upper limit value.

As used herein, (meth) acrylate represents acrylate and methacrylate.

Regarding the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes a group having a substituent as well as a group having no substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Further, the "organic group" in the present specification means a group containing at least one carbon atom.

Further, in the present specification, the type of the substituent, the position of the substituent, and the number of the substituents when "may have a substituent" are not particularly limited. The number of substituents may be, for example, one, two, three, or more. As an example of the substituent, a monovalent non-metal atomic group excluding a hydrogen atom can be mentioned, and for example, it can be selected from the following substituent group T.
(Substituent T)
The substituent T includes a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; an aryloxy group such as a phenoxy group and a 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 metoxalyl group and the like. Acrylic groups of: alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl groups; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfonyl groups; alkyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; Carboxy group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group; Can be mentioned.

Further, in the present specification, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the degree of dispersion (also referred to as molecular weight distribution) (Mw / Mn) of the resin are referred to as GPC (Gel Permeation Chromatography) apparatus (manufactured by Toso Co., Ltd.). GPC measurement by HLC-8120GPC) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Toso Co., Ltd., column temperature: 40 ° C., flow velocity: 1.0 mL / min, detector: It is defined as a polystyrene-equivalent value by a differential index detector.

[Actinic cheilitis or radiation-sensitive resin composition]
The feature of the actinic light-sensitive or radiation-sensitive resin composition of the present invention (hereinafter, also referred to as “composition of the present invention”) is a repeating unit represented by the general formula (B-1) described later. , 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.
Further, the resin contains a repeating unit represented by the general formula (B-1), so that the glass transition temperature (Tg) is high, and thus the pattern collapse inhibitory property is excellent. As will be described later, in the repeating unit represented by the general formula (B-1), the ring W ¹ is decomposed by the action of an acid depending on the types of X, Y, R ¹ and R ² in the repeating unit. (In other words, the repeating unit represented by the general formula (B-1) can function as a repeating unit containing an acid-degradable 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 suppressing pattern collapse even after acid decomposition. Further, since the resin contains a repeating unit represented by the general formula (B-1), it is due to the deterioration of the pattern collapse inhibitory property due to the fluorine atom and the iodine atom introduced for EUV light absorption efficiency described above. It is not easily affected.
By the above mechanism of action, the composition of the present invention can form a pattern having high sensitivity and excellent anti-falling property. Further, the pattern formed by the composition of the present invention is also 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 type resist composition or a negative type resist composition. Further, it may be a resist composition for alkaline 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 (hereinafter, also referred to as "resin (X)") whose polarity is increased by the action of an acid, which satisfies the following conditions [1] and [2].
Condition [1]: Contains a repeating unit represented by the general formula (B-1) described later.
Condition [2]: Contains at least one halogen atom selected from the group consisting of a fluorine atom and an iodine atom.
As described above, the resin (X) is a resin whose polarity is increased by the action of an acid. Therefore, in the pattern forming method of the present invention described later, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer. A negative pattern is preferably formed in.
As will be described later, it is preferable that the resin (X) has a group (hereinafter, also referred to as “acid-decomposable group”) which is decomposed by the action of an acid and whose polarity is increased.

Further, the resin (X) contains at least one halogen atom (hereinafter, also referred to as “specific halogen atom”) selected from the group consisting of a fluorine atom and an iodine atom (condition [2]). The introduction position of the specific halogen atom in the resin (X) is not particularly limited.
The content of the specific halogen atom in the resin (X) is not particularly limited, but is preferably 2% by mass or more, preferably 4% by mass, based on the total mass of the resin, in that the sensitivity of the resist composition is more excellent. 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 the general formula (B-1) contained in the resin (X) and other repeating units which may be optionally contained will be described in detail.
(Repeating unit represented by the general formula (B-1))

In the general formula (B-1), X and Y each independently represent an oxygen atom, a sulfur atom, or -NR ^3- . Further, 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 above-mentioned substituent group T, 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 resist film to be formed is more excellent, the pattern collapse inhibitory property to be formed, and the LER is more excellent. Alkyl groups (which may be linear, branched or cyclic) are preferred, for example methyl, ethyl, propyl, n-butyl, sec-butyl, hexyl and hexyl groups. Examples include octyl groups. Of these, a linear or branched alkyl group having 1 to 4 carbon atoms is more preferable.
The alkyl group represented by R ³ may further have a substituent. Examples of the substituent include the groups exemplified in the above-mentioned substituent group T, and specific examples thereof include a specific halogen atom and the like.

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

The aralkyl group represented by R ³ is not particularly limited, but 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. Examples of the substituent include the groups exemplified in the above-mentioned substituent group T, and specific examples thereof include a specific halogen atom and the like.

The alkenyl group represented by R ³ is not particularly limited, but an alkenyl group having 2 to 8 carbon atoms (which may be linear, branched or cyclic) is preferable, and 2 to 4 carbon atoms are preferable. Linear or branched alkenyl groups are more preferred. Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a cyclohexenyl group and the like.
The alkenyl group represented by ^R3 may further have a substituent. Examples of the substituent include the groups exemplified in the above-mentioned substituent group T, and specific examples thereof include a specific halogen atom and the like.

As R3 ^, a hydrogen atom is particularly preferable.

As X and Y, it is preferable that at least one of them represents an oxygen atom, and it is more preferable that both of them represent an oxygen atom.

R ¹ and R ² each independently represent 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 above-mentioned substituent group T, and more specifically, an alkyl group, an aryl group, an aralkyl group, and the like. And an alkenyl group and the like.
The alkyl group represented by R ¹ and R ² is not particularly limited, but the number of carbon atoms is 1 in that the sensitivity of the resist film to be formed is more excellent, the collapse inhibitory property of the formed pattern is more excellent, and the LER is more excellent. Alkyl groups of up to 12 (which may be linear, branched, or cyclic) are preferred, 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. The number of carbon atoms of the alkyl group represented by R ¹ and R ² is more preferably 1 to 10, and even more preferably 1 to 8.

The alkyl group may further have a substituent (for example, the group exemplified in the above-mentioned substituent group T). 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, further preferably 1 to 8, particularly preferably 1 to 6, and most preferably 1 to 3. preferable.
Further, the alkyl group substituted with at least one specific halogen atom may further have a substituent (for example, the group exemplified in the above-mentioned substituent group T). Examples of the substituent include a hydroxyl group and the like.
As the alkyl group substituted with at least one specific halogen atom, the sensitivity of the resist film formed is more excellent, and the pattern collapse inhibitory property and LER of the formed pattern are more excellent. An alkyl group (preferably a perfluoroalkyl group having 1 to 3 carbon atoms) or an alkyl group containing a hexafluoroisopropanol group is preferable.

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 formed is more excellent, the pattern collapse inhibitory property to be formed, and the LER is more excellent. An aryl group of about 14 to 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, an anthryl group and the like, and a phenyl group or a naphthyl group is preferable.
The aryl group may further have a substituent (for example, the group exemplified in the above-mentioned substituent group T). Examples of the substituent include a specific halogen atom or an alkyl group substituted with at least one specific halogen atom, and 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, but 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 groups represented by R ¹ and R ² may further have a substituent (for example, the group exemplified in the above-mentioned substituent group T). Examples of the substituent include a specific halogen atom and the like.

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

Among R ¹ and R ² , an alkyl group or an aryl group is preferable because the sensitivity of the resist film to be formed is more excellent, the pattern collapse inhibitory property to be formed, and the LER are more excellent.

In the general formula (B-1), the ring W ¹ represents a ring containing 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 where the main chain is bonded, and the carbon at the position where the above X and the above Y are connected. Intended to be an atom.
The ^number of ring members of the ring W1 is not particularly limited, but is, for example, 6 to 10, and 6 or 7 is preferable, and 6 is more preferable in that the formed pattern is more excellent in the collapse suppressing property.
Further, the ring W ¹ may have a substituent. Examples of the substituent include the groups exemplified in the above-mentioned substituent group T.

In addition, R ¹ and R ² may be bonded to each other to form a ring. Further, R ¹ and R ² may independently bond with the atoms contained in the ring W ¹ to form a ring. Further, when at least one of X and Y represents -NR ^3- , each of R ³ independently bonds with an atom contained in R ¹ , R ² , or ring W ¹ to form a ring. You may.
The ring is not particularly limited, and examples thereof include an alicyclic ring, an aromatic ring, and a heterocycle (including not only those having aromaticity but also those having no aromaticity).

As the repeating unit represented by the general formula (B-1), the repeating unit represented by the following general formula (B-2) is preferable.

In the general formula (B-2), X, Y, R ¹ and R ² are synonymous with X, Y, R ¹ and R ² in the general formula (B-1), and the preferred embodiments are also the same. Is.
In the general formula (B-2), L ¹ represents a divalent linking group that connects X specified in the formula and a carbon atom at a position bonded to the main chain, and L ² is represented in the formula. Represents a divalent linking group that links Y specified in 1 and a carbon atom at a position bonded to the main chain.
L ¹ and L ² are specifically divalent 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 represent a hydrogen atom or an organic group.
Examples of the organic group represented by R ⁴ and R ⁵ include the same organic groups represented by R ³ in the above-mentioned general formula (B-1).
Of these, hydrogen atoms are preferable as R ⁴ and R ⁵ .

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 can be mentioned. Note that * indicates a connection position with X or Y, and ** represents a connection position with a carbon atom at a position bonded to the main chain in the general formula (B-2).
Among them, at least ^one of the divalent linking group represented by L1 and the ^divalent linking group represented by L2 is -CO-, in that the collapse inhibitory property of the formed pattern is more excellent. It preferably contains -SO- or -SO _2- .

The number of ring members of the ring formed from the 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 is formed. 6 or 7 is preferable, and 6 is more preferable, in that the pattern collapse inhibitory property is more excellent.

In addition, R ¹ and R ² may be bonded to each other to form a ring. R ⁴ and R ⁵ may be coupled to each other to form a ring. Further, when at least one of X and Y represents −NR ³ −, R ³ may independently combine with R ¹ , R ² , R ⁴ or R ⁵ to form a ring. good.

As the repeating unit represented by the general formula (B-2), the repeating unit represented by the following general formula (B-3) is preferable.

In the general formula (B-3), X, Y, R ¹ and R ² are synonymous with X, Y, R ¹ and R ² in the general formula (B-1), and the preferred embodiments are also the same. Is.
In the general formula (B-3), L ³ and L ⁴ independently represent -CO-, -C (R ⁴ ) (R ⁵ )-, -SO-, or -SO _2- . Among them, it is preferable that at least one of L ³ and L ⁴ represents -CO-, -SO-, or -SO _2-- because the formed pattern is more excellent in the collapse suppressing property. 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 represent a hydrogen atom or an organic group. The organic group represented by R ⁴ and R ⁵ has the same meaning as the organic group represented by R ⁴ and R ⁵ described in detail in the above-mentioned general formula (B-2), and the preferred embodiment is also the same.
In addition, R ¹ and R ² may be bonded to each other to form a ring. R ⁴ and R ⁵ may be coupled to each other to form a ring.

As the repeating unit represented by the above general formula (B-3), the repeating unit represented by the following general formula (B-4) is particularly excellent in that the formed pattern is more excellent in the collapse suppressing property and the LER. Is preferable.

In the general formula (B-4), R ¹ and R ² are synonymous with R ¹ and R ² in the general formula (B-1), and the preferred embodiments are also the same. In addition, R ¹ and R ² may be bonded to each other to form a ring.

The repeating unit represented by the above general formula (B-1) is a specific halogen atom in that the resist film formed is more excellent in sensitivity, and the pattern collapse inhibitory property and LER of the formed pattern are more excellent. It is preferable to include. When the repeating unit represented by the above general formula (B-1) contains a specific halogen atom, the content thereof (hereinafter, also referred to as “specific halogen atom content”) is the total mass of the repeating unit. It is preferably 10% by mass or more, and more preferably 20% by mass or more. The upper limit is not particularly limited, but is, for example, 60% by mass or less.

Specific examples of the repeating unit represented by the general formula (B-1) will be given 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-degradable group). Can work).

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

(Other repeating units)
The resin (X) may contain still another repeating unit in addition to the repeating unit represented by the above general formula (B-1). The other repeating units that the resin (X) may contain are described in detail below. The resin (X) is a repeating unit having a higher Tg (homogeneous) in that it has better fall suppressing performance as other repeating units that can be contained in addition to the repeating unit represented by the above general formula (B-1). It is preferable to include a repeating unit derived from a monomer having a higher Tg when made into a polymer).

≪Repeating unit with acid-degradable group≫
The resin (X) preferably contains a repeating unit having an acid-decomposable group (hereinafter, also referred to as “repeating unit Y1”).
The acid-degradable group preferably has a structure in which a polar group is protected by a group (leaving group) that is decomposed and desorbed by the action of an acid.
The polar group includes a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, and a (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. Examples thereof include an acidic group (a group that dissociates in a 2.38 mass% tetramethylammonium hydroxide aqueous solution) and an alcoholic hydroxyl group.

The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group and refers to a hydroxyl group other than the hydroxyl group directly bonded on the aromatic ring (phenolic hydroxyl group), and the α-position of the hydroxyl group is electron attraction such as a fluorine atom. Excludes aliphatic alcohols substituted with sex groups (eg, hexafluoroisopropanol groups, etc.). 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 a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), and a sulfonic acid group.

A preferable group as an acid-degradable group is a group in which the hydrogen atom of these groups is replaced with a group (leaving group) that is eliminated by the action of an acid.
Examples of the group desorbed by the action of an acid (leaving group) include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), and-. Examples thereof include C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ).
In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be coupled to each other to form a ring.
R ₀₁ and R ₀₂ independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

As the alkyl group represented by R ₃₆ to R ₃₉ , R ₀₁ , and R ₀₂ , an alkyl group having 1 to 8 carbon atoms is preferable, and for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, or sec- Examples thereof include a butyl group, a hexyl group, and an octyl group.
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, for example, an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an α-pinene group, a tricyclodecanyl group, Examples thereof include a tetracyclododecyl group and an androstanyl group. In addition, at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.
As the aryl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ , an aryl group having 6 to 10 carbon atoms is preferable, 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 bonding R ₃₆ and R ₃₇ to 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, a repeating unit having a structure in which the -COO- group is protected by a leaving group or a repeating unit having a structure in which a phenolic hydroxyl group is protected by a leaving group is preferable.
As the structure in which the -COO- group is protected by the desorption group, a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like is preferable, and an acetal ester group or a tertiary group is preferable. Alkyl ester groups are more preferred.

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

In the general formula (AI)
Xa ₁ represents an alkyl group which may have a hydrogen atom, a halogen atom, or a substituent.
T represents a single bond or a divalent linking group.
Rx ₁ to Rx ₃ independently represent an alkyl group (linear or branched chain) or a cycloalkyl group (monocyclic or polycyclic). However, when all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), it is preferable that at least two of Rx ₁ to Rx ₃ are methyl groups.
Two of Rx ₁ to Rx ₃ may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the alkyl group represented by Xa ₁ which may have a substituent include a methyl group and a group represented by _−CH2 - _R11 . R ₁₁ represents a halogen atom (fluorine atom or the like), 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 having 3 or less carbon atoms. Alkyl groups are preferred, and methyl groups are more preferred.
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.
As Xa ₁ , a hydrogen atom, a fluorine atom, an iodine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group is preferable.

Examples of the divalent linking group represented by T include an alkylene group, an arylene group, an -COO-Rt- group, an -O-Rt- group and the like. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, preferably a -CH _2- group, a- (CH ₂ ) _2- group, or a- (CH ₂ ) _3- group. Is more preferable.

The alkyl group represented by Rx ₁ to Rx ₃ includes an alkyl 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. 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. Etc., a polycyclic cycloalkyl group is preferable.
As the cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ , a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group is preferable, and in addition, a norbornyl group, a tetracyclodecanyl group, and the like. 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 bonding two of Rx ₁ to Rx ₃ , for example, one of the methylene groups constituting the ring is replaced with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group. May be.

When each of the above groups has a substituent, the substituents include, for example, 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 (1 to 4 carbon atoms). Examples thereof include 2 to 6) carbon atoms. The number of carbon atoms in the substituent is preferably 8 or less.

Specific examples of the repeating unit Y1 will be given below, but the present invention is not limited to these specific examples.
In the specific example, Rx represents a hydrogen atom, a fluorine atom, an iodine atom, CH ₃ , CF ₃ , or CH ₂ OH. Rxa and Rxb each independently represent an alkyl group having 1 to 4 carbon atoms. Z represents a substituent including a polar group, and when a plurality of substituents are present, they may be the same or different from each other. 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 an alicyclic group having a hydroxyl group, a cyano group, an amino group, an alkylamide group, or a sulfonamide group. Alkyl groups having a hydroxyl group are preferred. As the branched chain alkyl group, an isopropyl group is preferable.

-A repeating unit in which a phenolic hydroxyl group has a structure protected by a desorbing 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 is eliminated by the action of an acid include groups represented by the formulas (Y1) to (Y4).
Equation (Y1): -C (Rx ₁ ) (Rx ₂ ) (Rx ₃ )
Equation (Y2): -C (= O) OC (Rx ₁ ) (Rx ₂ ) (Rx ₃ )
Equation (Y3): -C (R ₃₆ ) (R ₃₇ ) (OR ₃₈ )
Equation (Y4): -C (Rn) (H) (Ar)

In the formulas (Y1) and (Y2), Rx ₁ to Rx ₃ independently represent an alkyl group (linear or branched chain) or a cycloalkyl group (monocyclic or polycyclic). However, when all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), it is preferable that at least two of Rx ₁ to Rx ₃ are methyl groups.
Among them, Rx ₁ to Rx ₃ are more preferably repeating units each independently representing a linear or branched alkyl group, and Rx ₁ to Rx ₃ are each independently linear. It is more preferably a repeating unit representing an alkyl group.
Two of Rx ₁ to Rx ₃ may be combined to form a monocyclic or polycyclic ring.
As the alkyl group of Rx ₁ to Rx ₃ , 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 is preferable. ..
Examples of the cycloalkyl group of 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. Cycloalkyl group is preferred.
Examples of the cycloalkyl group formed by bonding 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, and a tetracyclododecanyl. Polycyclic cycloalkyl groups such as groups and adamantyl groups are preferred. Of these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
The cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group. It may be replaced.
The group represented by the formulas (Y1) and (Y2) is, for example, an embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-mentioned cycloalkyl group. preferable.

In formula (Y3), R ₃₆ to R ₃₈ each independently represent a hydrogen atom or a monovalent organic group. R ₃₇ and R ₃₈ may be coupled 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, an alkenyl group and the like. R ₃₆ is preferably a hydrogen atom.

In 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 combined with each other to form a non-aromatic ring. Ar is more preferably an aryl group.

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

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

In the general formula (AII),
R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. However, R ₆₂ may be bonded to Ar ₆ to form a ring, in which case R ₆₂ 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 a (n + 1) -valent aromatic hydrocarbon group, and when combined with R ₆₂ to form a ring, represents a (n + 2) -valent aromatic hydrocarbon group.
Y ₂ represents a group desorbed by the action of a hydrogen atom or an acid independently when n ≧ 2. However, at least one of Y ₂ represents a group that is eliminated by the action of an acid. The groups desorbed by the action of the _acid as Y2 are preferably of the formulas (Y1) to (Y4).
n represents an integer of 1 to 4.

Each of the above groups may have a substituent, and 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 a substituent. Examples thereof include an alkoxycarbonyl group (2 to 6 carbon atoms), and those having 8 or less carbon atoms are preferable.

The resin (X) may contain the repeating unit Y1 alone or in combination of two or more.

When the resin (X) contains the repeating unit Y1 (the total if 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 preferable, 10 to 60% by mass is more preferable, and 10 to 50% by mass is further preferable.

≪Repeating unit with 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 a repeating unit represented by the following general formula (I).

In formula (I),
R ₄₁ , R ₄₂ and R ₄₃ independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. However, R ₄₂ may be bonded to Ar ₄ to form a ring, in which case R ₄₂ 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 a (n + 1) -valent aromatic group, and when combined with R ₄₂ to form a ring, represents a (n + 2) -valent aromatic group.
n represents an integer of 1 to 5.
For the purpose of increasing the polarity of the repeating unit represented by the general formula (I), it is also preferable that n is an integer of ₂ or more, or X4 is -COO- or -CONR _64- .

The alkyl group represented by R ₄₁ , R ₄₂ , and R ₄₃ in the general formula (I) may have a substituent, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and an n-butyl group. , Se-butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group and other alkyl groups having 20 or less carbon atoms are preferable, alkyl groups having 8 or less carbon atoms are more preferable, and alkyl groups having 3 or less carbon atoms are more preferable. 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, an iodine atom, and the like, and a fluorine atom is preferable.
The alkyl group contained in the alkoxycarbonyl group represented by R ₄₁ , R ₄₂ , and R ₄₃ in the general formula (I) is preferably the same as the alkyl group in R ₄₁ , R ₄₂ , and R ₄₃ .

Preferred substituents in each of the above groups include, for example, an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group and an acyl group. Examples thereof include a group, an acyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group and the like, and the substituent preferably has 8 or less carbon atoms.

Ar ₄ represents an (n + 1) -valent aromatic group. The divalent aromatic hydrocarbon group when n is 1 may have a substituent, and for example, an arylene having 6 to 18 carbon atoms such as a phenylene group, a tolylen group, a naphthylene group, and an anthrasenylene group. A group or an aromatic hydrocarbon group containing a heterocycle such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzoimidazole, triazole, thiadiazol, and thiazole is preferred.

As a specific example of the (n + 1) -valent aromatic group when n is an integer of 2 or more, (n-1) arbitrary hydrogen atoms are removed from the above-mentioned specific example of the divalent aromatic group. A suitable group can be mentioned.
The (n + 1) -valent aromatic group may further have a substituent.
Preferred substituents in the above (n + 1) -valent aromatic group include, for example, a halogen atom (preferably a fluorine atom or an iodine atom) and an alkyl halide group (preferably a perfluoroalkyl group).

The alkyl group of R ₆₄ in -CONR _64- (where R ₆₄ represents a hydrogen atom or an alkyl group) represented by X ₄ may have a substituent, a methyl group, an ethyl group, or a propyl group. , Isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group and other alkyl groups having 20 or less carbon atoms are preferable, and alkyl groups having 8 or less carbon atoms are more preferable. ..
As _X4 , a single bond, -COO-, or -CONH- is preferable, a single bond or -COO- is more preferable, and a single bond is further preferable.

The _divalent linking group as L4 is preferably an alkylene group, and the alkylene group may have a substituent, a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and the like. And an alkylene group having 1 to 8 carbon atoms such as an octylene group is preferable.
As _L4 , a single bond is particularly preferable.

As Ar ₄ , an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent is preferable, a benzene ring group, a naphthalene ring group, or a biphenylene ring group is more preferable, and a benzene ring group is further preferable. ..
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, it is preferable that Ar ₄ represents a benzene ring group and X ₄ and L ₄ represent a single bond.

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

The resin (X) may have one type of repeating unit Y2 alone, or may contain two or more types in combination.
When the resin (X) contains the repeating unit Y2 (the total if there are a plurality of repeating units Y2), the content of the repeating unit Y2 is 5 to 60 mass with respect to all the repeating units in the resin (X). % Is preferable, 10 to 50% by mass is more preferable, and 10 to 30% by mass is further preferable.

<< 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, a (alkylsulfonyl) (alkylcarbonyl) methylene group, a (alkylsulfonyl) (alkylcarbonyl) imide group, and a bis (alkylcarbonyl). Examples thereof include a methylene group, a bis (alkylcarbonyl) imide group, a bis (alkylsulfonyl) methylene group, a bis (alkylsulfonyl) imide group, a tris (alkylcarbonyl) methylene group, a tris (alkylsulfonyl) methylene group and the like. Further, it is preferable that the hydrogen atom contained in these acid groups is replaced with a fluorine atom.

Specific examples of the repeating unit Y3 will be given 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.

The resin (X) may have one type of repeating unit Y3 alone, or may contain two or more types in combination.
When the resin (X) contains the repeating unit Y3 (the total if 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). % Is preferable, 15 to 50% by mass is more preferable, and 15 to 40% by mass is further preferable.

<< Repeating unit with polar group >>
Further, the 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.
The repeating unit Y4 is 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-mentioned repeating unit. A repeating unit having a 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 may have a lactone structure or a 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 in which another ring structure is condensed in a form forming a bicyclo structure or a spiro structure, or a 5- to 7-membered ring in the form of forming a bicyclo structure or a spiro structure. A sultone structure in which another ring structure is fused is more preferable.
The resin (X) has 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). It is more preferred to include repeating units with the represented sultone structure. Further, the lactone structure or the sultone structure may be directly bonded to the main chain. Preferred structures include general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-8), general formula (LC1-16), or general formula (LC1). Examples thereof include a lactone structure represented by -21) and a sultone structure represented by the general formula (SL1-1).

The lactone-structured portion or the sultone-structured 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. , Halogen atom, hydroxyl group, cyano group, acid-degradable group and the like, and an alkyl group having 1 to 4 carbon atoms, a cyano group, or an acid-degradable group is preferable. n ₂ represents an integer from 0 to 4. When n ₂ is 2 or more, the plurality of substituents (Rb ₂ ) may be the same or different. Further, a plurality of existing substituents (Rb ₂ ) may be bonded to each other 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 above 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—, represents an integer of 0 to 5, is preferably 0 or 1, and more preferably 0. When n is 0, -R ₀ -Z- does not exist and a single bond is formed.
_R0 represents an alkylene group, a cycloalkylene group, or a combination thereof. When there are a plurality of R _0s , each R ₀ independently represents an 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's, 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 _R0 may have a substituent.
As Z, an ether bond or an ester bond is preferable, and an ester bond is more preferable.

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

In the general formula (A-1), _RA 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.
_RA ² represents a substituent. When n is 2 or more, _RA ² independently represents a substituent.
A represents a single bond or a divalent linking group.
Z represents an atomic group forming a monocyclic structure or a polycyclic structure together with the group represented by —O—C (= O) —O— in the formula.

Hereinafter, specific examples of the monomer corresponding to the repeating unit represented by the general formula (III) and the specific example of the monomer corresponding to the repeating unit represented by the general formula (A-1) will be given. 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 RA 1 in the general formula ( _A - ¹ ) are methyl groups, but R ₇ and _RA ¹ are hydrogen atoms and halogen atoms. , Or can be optionally replaced with a monovalent organic group.

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

It is also preferable that the resin (X) contains, as the repeating unit Y4-1, the repeating unit described in paragraphs <0370> to <0414> of US Patent Application Publication No. 2016/0070167A1.

The resin (X) may have one type of repeating unit Y4-1 alone, or may contain two or more types in combination.
When the resin (X) contains the repeating unit Y4-1, the content of the repeating unit Y4-1 is preferably 5 to 40% by mass, preferably 5 to 30% by mass, based on all the repeating units in the resin (X). More preferably, 5 to 25% by mass is further preferable.

A repeating unit having a polar group other than the repeating unit Y4-1 (repeating unit Y4-2).
The resin (X) preferably contains the repeating unit Y4-2.
The polar group includes a hydroxyl group, a cyano group, an amide group, a carboxylic acid group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, and a (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. Can be mentioned.
Examples of the repeating unit Y4-2 include a repeating unit having an alicyclic hydrocarbon structure (specifically, a cyclohexyl group, an adamantyl group, a norbornane group, etc.) substituted with a polar group such as a hydroxyl group and a cyano group. Be done.

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

In addition, as a specific example of the repeating unit Y4-2, the repeating unit disclosed in paragraphs <0415> to <0433> of US Patent Application Publication No. 2016/0070167A1 can be mentioned.

The resin (X) may have the repeating unit Y4-2 alone or may contain two or more of them in combination.
When the resin (X) contains the repeating unit Y4-2, the content of the repeating unit Y4-2 is preferably 5 to 40% by mass, preferably 5 to 30% by mass, based on all the repeating units in the resin (X). More preferably, 5 to 25% by mass is further preferable.

The resin (X) may have other repeating units other than the above-mentioned repeating units Y1 to Y4.

The 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 2,000 to 30,000, more preferably 3,500 to 15,000, and more preferably 5,000 to 12 in that the formed pattern is more excellent in suppressing collapse. 000 is more preferred. 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 further preferably 1.1 to 2.0. preferable.

The resin (X) may be used alone or in combination of two or more.
In the composition of the present invention, the content of the resin (X) (in the case where a plurality of types are present, the total thereof) is generally 20.0% by mass or more with respect to the total solid content of the composition. 30.0% by mass or more is preferable, 40.0% by mass or more is more preferable, and 50.0% by mass or more is further preferable. The upper limit is not particularly limited, but 99.9% by mass or less is preferable, 99.5% by mass or less is more preferable, and 99.0% by mass or less is further preferable.

[Compounds that generate acid by irradiation with active light or radiation]
The composition of the present invention contains a compound that generates an acid by irradiation with active light or radiation (hereinafter, also referred to as "photoacid generator").
The photoacid generator may be in the form of a small molecule compound or may be incorporated in a part of the polymer. Further, the form of the small molecule compound and the form incorporated in a part of the polymer may be used in combination.
When the photoacid generator is in the form of a small molecule compound, its molecular weight is preferably 3000 or less, more preferably 2000 or less, still more preferably 1000 or less.
When the photoacid generator is in the form incorporated in a part of the polymer, it may be incorporated in a part of the resin (X) or may be incorporated in a resin different from the resin (X).
Among them, the photoacid generator is preferably in the form of a small molecule compound.
The photoacid generator is not particularly limited as long as it is known, but a compound that generates an organic acid by irradiation with active light or radiation (preferably electron beam or extreme ultraviolet) is preferable.
As the organic acid, for example, at least one of sulfonic acid, bis (alkylsulfonyl) imide, and tris (alkylsulfonyl) methide is preferable.
As the photoacid generator, a compound represented by the following general formula (ZI), the following general formula (ZII), or the following general formula (ZIII) is preferable.

In the above general formula (ZI)
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.
The number of carbon atoms of the organic group represented by R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.
Further, 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 bonding two of R ₂₀₁ to R ₂₀₃ include an alkylene group (for example, a butylene group and a pentylene group).
Z ^- represents a non-nucleophilic anion (anion with a significantly lower ability to cause a nucleophilic reaction).

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

Examples of the non-nucleophilic anion include a sulfonic acid anion (aliphatic sulfonic acid anion, aromatic sulfonic acid anion, and camphor sulfonic acid anion, etc.) and a carboxylic acid anion (aliphatic carboxylic acid anion, aromatic carboxylic acid anion, etc.). And aralkyl carboxylic acid anion, etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.

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

The aryl group in the aromatic sulfonic acid anion and the aromatic carboxylic acid 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, but specifically, a halogen atom such as a nitro group and a fluorine atom, a carboxy group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably 1 to 15 carbon atoms) and an alkyl group (preferably having 1 to 15 carbon atoms). Preferred are 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 7 carbon atoms). Preferred are 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 thereof include a sulfonyl group (preferably 1 to 15 carbon atoms), an aryloxysulfonyl group (preferably 6 to 20 carbon atoms) and the like.

As the aralkyl group in the aralkyl carboxylic acid anion, an aralkyl group having 7 to 14 carbon atoms is preferable, 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 a saccharin anion.

As the alkyl group in the bis (alkylsulfonyl) imide anion and the tris (alkylsulfonyl) methide anion, an alkyl group having 1 to 5 carbon atoms is preferable. 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, and fluorine. Alkyl groups substituted with an atom or a fluorine atom are preferred.
Further, 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.

Other non-nucleophilic anions include, for example, phosphorus fluorinated (eg, PF _6- ⁾ , boron fluorinated (eg, BF _4- ⁾ , and antimony fluorinated (eg, SbF _6- ⁾ .

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

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

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

During the ceremony
Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ¹ and R ² independently represent a hydrogen atom, a fluorine atom, or an alkyl group, and when a plurality of them are present, R ¹ and R ² may be the same or different from each other.
L represents a divalent linking group, and when a plurality of L are present, 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 number of carbon atoms 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, as the alkyl group substituted with the fluorine atom of Xf, a perfluoroalkyl group is preferable.
As Xf, a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms is preferable. Specific examples of Xf include 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, fluorine atom or CF ₃ is preferred. In particular, it is preferable that both Xf are fluorine atoms.

The alkyl groups 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 alkyl groups having substituents on 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 and CH ₂ CH ₂ C ₄ F ₉ and the like can be mentioned, with CF ₃ being preferred.
As R ¹ and R ² , a fluorine atom or CF ₃ is preferable.

x is preferably 1 to 10, more preferably 1 to 5.
y is preferably 0 to 4, more preferably 0.
z is preferably 0 to 5, more preferably 0 to 3.
The divalent linking group of L is not particularly limited, and -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO _2- , alkylene group, cycloalkylene group, Examples thereof include an alkaneylene group and a linking group in which a plurality of these are linked, and a linking group having a total carbon number of 12 or less is preferable. 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). (Including those that do not), etc.
The alicyclic group may be monocyclic or polycyclic, and a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group and a cyclooctyl group is preferable, and in addition, a norbornyl group, a tricyclodecanyl group and a tetracyclo Polycyclic cycloalkyl groups such as a decanyl group, a tetracyclododecanyl group, and an adamantyl group are preferred. Among them, alicyclic groups 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, are used in the post-exposure heating step. It is preferable from the viewpoint of improving MEEF (Mask Error Enhancement Factor) because it can suppress the diffusivity in the membrane.
Examples of the aromatic ring group include a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring and the like.
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, a pyridine ring and the like. Of these, those derived from a furan ring, a thiophene ring, or a pyridine ring are preferable.

Further, examples of the cyclic organic group include a lactone structure, and specific examples thereof include lactone structures represented by the above-mentioned general formulas (LC1-1) to (LC1-17).

The cyclic organic group may have a substituent. The substituent may be an alkyl group (which may be linear, branched, or cyclic, preferably 1 to 12 carbon atoms) or a cycloalkyl group (single ring or polycyclic). It may be present, and if it is a polycycle, it may be a spiro ring. The carbon number is preferably 3 to 20.), An aryl group (preferably 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, and the like. 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 the general formula (ZII) and the general formula (ZIII),
R ₂₀₄ to R ₂₀₇ independently represent 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 above general formula (ZI). be.
The substituents 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-mentioned 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 the general formula (ZI), and the preferred embodiment is also the same.

In addition, as a photoacid generator, the volume of 130 Å ³ or more is achieved by irradiation with electron beam or extreme ultraviolet rays in terms of suppressing the diffusion of the acid generated by exposure to the non-exposed portion and improving the resolution. Compounds that generate acids of the size of (more preferably sulfonic acid) are preferred. As the photoacid generator, a compound that generates an acid having a volume of 190 Å ³ or more (more preferably sulfonic acid) is more preferable, and an acid having a volume of 270 Å ³ or more (more preferably sulfonic acid) is more preferable. A compound that generates an acid (more preferably, a sulfonic acid) having a volume of 400 Å ³ or more is particularly preferable. However, from the viewpoint of sensitivity or solubility in the coating solvent, the volume is preferably 2000 Å ³ or less, and more preferably 1500 Å ³ or less. The value of the volume is obtained by 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 force field calculation using the MM (Molecular Mechanics) 3 method with this structure as the initial structure is performed for each acid. The "accessible volume" of each acid can be calculated by determining the most stable conformation and then performing molecular orbital calculations for these most stable conformations using the PM3 method.

Hereinafter, specific examples of the acid generated by the photoacid generator (acid in which a proton is bonded to the anion portion) and its volume are shown, but the present invention is not limited thereto. The volume shown in the following example is a calculated value (unit: Å ³ ). Also, 1 Å is 1 × 10 ^-10 m.

Examples of the photoacid generator include paragraphs <0368> to <0377> of Japanese Patent Application Laid-Open No. 2014-41328 and paragraphs <0240> to <0262> of Japanese Patent Application Laid-Open No. 2013-228681 (corresponding US Patent Application Publication No. 2015). / 004533 <0339>) can be incorporated and these contents are incorporated herein. In addition, the following compounds can be mentioned as preferable specific examples, but the present invention is not limited thereto.

The photoacid generator may be used alone or in combination of two or more.
In the composition of the present invention, the content of the photoacid generator (if a plurality of types are present, the total thereof) is preferably 0.1 to 50.0% by mass with respect to the total solid content of the composition. 0 to 40.0% by mass is more preferable, and 5.0 to 35.0% by mass is further preferable.

[Acid diffusion control agent]
The composition of the present invention may contain an acid diffusion control agent as long as the effects of the present invention are not impaired.
The acid diffusion control agent acts as a quencher that traps the acid generated from the acid generator or the like at the time of exposure and suppresses the reaction of the acid-decomposable resin in the unexposed portion due to the excess generated acid. Examples of the acid diffusion control agent include a basic compound (DA), a basic compound (DB) whose basicity is reduced or disappears by irradiation with active light or radiation, and onium which is a relatively weak acid with respect to an acid generator. A salt (DC), a low molecular weight compound (DD) having a nitrogen atom and having a group desorbed by the action of an acid, or an onium salt compound (DE) having a nitrogen atom in the cation part is used as an acid diffusion control agent. can.
In the composition of the present invention, a known acid diffusion control agent can be appropriately used. For example, paragraphs <0627> to <0664> of US Patent Application Publication No. 2016/0070167A1, paragraphs <0995> to <0187> of US Patent Application Publication No. 2015/0004544A1, US Patent Application Publication No. 2016/0237190A1. The known compounds disclosed in paragraphs <0403> to [0423] of the specification and paragraphs <0259> to <0328> of US Patent Application Publication No. 2016/02744558A1 can be suitably used as the acid diffusion control agent. ..

As the basic compound (DA), a compound having a structure represented by the following formulas (A) to (E) is preferable.

In the general formula (A), ^R200 , ^R201 and ^R202 are independently hydrogen atoms, alkyl groups (preferably 1 to 20 carbon atoms), cycloalkyl groups (preferably 3 to 20 carbon atoms), respectively. Alternatively, it represents an aryl group (preferably 6 to 20 carbon atoms). R ²⁰¹ and R ²⁰² may be coupled to each other to form a ring.
In the general formula (E), R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ each independently represent an alkyl group having 1 to 20 carbon atoms.

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

As the basic compound (DA), guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholin, aminoalkylmorpholin, piperidine and the like are preferable, and imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, etc. A trialkylamine structure, a compound having 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, and the like are more preferable.

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole and the like.
Compounds having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] nona-5-ene, and 1,8-diazabicyclo [5,4]. , 0] Undeca-7-en and the like.
Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfoniumhydroxydo, and sulfonium hydroxide having a 2-oxoalkyl group (specifically, triphenylsulfonium hydroxide and tris (t-butyl). Phenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, etc.) can be mentioned.
Examples of the compound having an onium carboxylate structure include those in which the anion portion of the compound having an onium hydroxide structure is carboxylated, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkyl carboxylate. ..
Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine.
Examples of the 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, tris (methoxyethoxyethyl) amine and the like.
Examples of the aniline derivative having a hydroxyl group and / or an ether bond include N, N-bis (hydroxyethyl) aniline and the like.

Further, as the basic compound (DA), a super organic base can also be used.
Examples of the superorganic base include guanidine bases such as tetramethylguanidine and polyguanidine (including guanidine and its variants and polyguanides as guanidine derivatives), diazabicyclononene (DBN), and diazabicycloundecene (diazabicycloundecene). DBU), guanidine-based and guanidine-based polynitrogen polycomplex cyclic compounds typified by triazabicyclodecene (TBD), N-methyl-triazabicyclodecene (MTBD), etc., and their polymer-bearing strong bases, Schweissinger. ) Bases, as well as Proazaphosphatlan (Verkade) bases.

Further, as the basic compound (DA), an amine compound and an ammonium salt compound 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 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 may be, for example, a cycloalkyl group (preferably having 3 to 3 carbon atoms) in addition to the above-mentioned alkyl group. 20), an aryl group (preferably 6 to 12 carbon atoms) and the like can be mentioned.
Further, the amine compound preferably contains an oxyalkylene group. The number of oxyalkylene groups is preferably 1 or more in the molecule, more preferably 3 to 9, and even 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 an 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.
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 may be, for example, a cycloalkyl group in addition to the above-mentioned alkyl group. Preferred examples thereof include 3 to 20 carbon atoms) and an aryl group (preferably 6 to 12 carbon atoms).
Further, the ammonium salt compound preferably contains an oxyalkylene group. The number of oxyalkylene groups is preferably 1 or more in the molecule, more preferably 3 to 9, and even 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 oxy Ethylene groups are more preferred.

Examples of the anion of the ammonium salt compound include a halogen atom, a sulfonate, a borate, and a phosphate, and among them, a halogen atom or a sulfonate is preferable.
As the halogen atom, a chlorine atom, a bromine atom, or an iodine atom is preferable.
The sulfonate is preferably an organic sulfonate having 1 to 20 carbon atoms, 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, an aromatic ring group and the like. 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. 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, the naphthalene ring group, and the anthracene ring group may have is an alkyl group having 1 to 6 carbon atoms (either linear or branched chain) or a branched group. 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 and the like.
The alkyl group and the cycloalkyl group may further have another substituent, for example, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, an acyl group, and an acyloxy. The group etc. can be mentioned.

Further, 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 have a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the above-mentioned amine compound or the above-mentioned ammonium salt compound.
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. The group etc. can be mentioned. The substitution position of the substituent may be any of 2 to 6 positions. The number of substituents may be any of 1 to 5.

The amine compound having a phenoxy group and the ammonium salt compound having a phenoxy group preferably contain at least one oxyalkylene group between the phenoxy group and the nitrogen atom. The number of oxyalkylene groups is preferably 1 or more in the molecule, more preferably 3 to 9, and even 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 oxyethylene. Groups are more preferred.

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

A compound (DB) whose basicity is reduced or disappears by irradiation with active light or radiation (hereinafter, also referred to as “compound (DB)”) has a proton-accepting functional group and is of active light or radiation. It is a compound that decomposes by irradiation and whose proton acceptor property is reduced, disappears, or changes from proton acceptor property to acidity.

A proton-accepting 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-conjugated group. 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 shown in the following general formula.

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

The compound (DB) is decomposed by irradiation with active light or radiation to generate a compound whose proton acceptor property is reduced or eliminated, or whose 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 acidity is a change in the proton acceptor property due to the addition of a proton to the proton acceptor property functional group. In particular, it means that when a proton adduct is formed from a compound (DB) having a proton acceptor functional group and a proton, the equilibrium constant in its chemical equilibrium decreases.
The proton acceptor property can be confirmed by measuring the pH.

Specific examples of the compound (DB) are described in, for example, paragraphs <0421> to <0428> of JP-A-2014-413328 and paragraphs <0108>-<0116> of JP-A-2014-134686. Those may be incorporated and these contents are incorporated herein.

In the composition of the present invention, an onium salt (DC), which is a weak acid relative to the acid generator, can be used as the acid diffusion control agent.
When an acid generator and an onium salt that generates an acid that is relatively weak to the acid generated from the acid generator are mixed and used, the acid generator is generated by active light or irradiation with radiation. When the acid collides with an onium salt having an unreacted weak acid anion, salt exchange releases the weak acid to produce an onium salt with a strong acid anion. In this process, the strong acid is replaced with a weak acid having a lower catalytic ability, so that the acid is apparently inactivated and the acid diffusion can be controlled.

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

In the formula, R ⁵¹ is a hydrocarbon group which may have a substituent, and Z ^2c is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (however, 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. It is a hydrocarbon group containing, and M ⁺ is independently an ammonium cation, a sulfonium cation or an iodonium cation.

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

The onium salt (DC), which is a relatively weak acid with respect to the acid generator, is a compound having 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, it may also be referred to as “compound (DCA)”).
The compound (DCA) is preferably a compound represented by any of the following general formulas (C-1) to (C-3).

In the general formulas (C-1) to (C-3),
R ₁ , R ₂ , and R ₃ each independently represent a substituent having one or more carbon atoms.
L ₁ represents a divalent linking group or single bond that links the cation site and the anion site.
_-X- represents an anion site selected from -COO- ^, -SO _3- ^, -SO ^{2- ,} and -N ^--- R ₄ . _R4 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 of them.
R ₁ , R ₂ , R ₃ , R ₄ , and L ₁ may be coupled to each other to form a ring structure. Further, in the general formula (C-3), two of R ₁ to R ₃ are combined to represent one divalent substituent, which may be bonded to an N atom by a double bond.

Substituents having 1 or more carbon atoms in R ₁ to R ₃ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group and a cycloalkylamino. Examples thereof include a carbonyl group and an arylaminocarbonyl group. Of these, an alkyl group, a cycloalkyl group, or an aryl group is preferable.

L ₁ as a divalent linking group is a linear or branched alkylene group, a cycloalkylene group, an arylene group, a carbonyl group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, and two kinds thereof. A group obtained by combining the above can be mentioned. 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 of these.

A small molecule compound (DD) having a nitrogen atom and having a group desorbed by the action of an acid (hereinafter, also referred to as “compound (DD)”) has a group desorbed by the action of an acid on the nitrogen atom. It is preferably an amine derivative having.
As the group desorbed by the action of the acid, an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group or a hemiaminol ether group is preferable, and a carbamate group or a hemiaminol ether group is more preferable. ..
The molecular weight of the compound (DD) is preferably 100 to 1000, more preferably 100 to 700, and even 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 the general formula (d-1)
Rb is independently 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), and an aralkyl group (preferably 3 to 30 carbon atoms). It preferably 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 independently hydroxyl groups, cyano groups, amino groups, pyrrolidino groups, piperidino groups, morpholino groups, oxo groups and other functional groups, alkoxy groups, or halogens. It may be substituted with an atom. The same applies to the alkoxyalkyl group indicated by Rb.

As Rb, a linear or branched alkyl group, a cycloalkyl group, or an aryl group is preferable, and a linear or branched alkyl group or a cycloalkyl group is more preferable.
Examples of the ring formed by connecting the two Rbs to each other include an alicyclic hydrocarbon, an aromatic hydrocarbon, a heterocyclic hydrocarbon, and a derivative thereof.
Specific examples of the structure of the group represented by the general formula (d-1) include, but are not limited to, the structure disclosed in paragraph <0466> of the US Patent Publication No. US2012 / 0135348A1.

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

In the general formula (6)
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and 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, the two Ras may be the same or different, and the two Ras may be interconnected to form a heterocycle with the nitrogen atom in the equation. This heterocycle may contain a heteroatom other than the nitrogen atom in the equation.
Rb has the same meaning as Rb in the above general formula (d-1), and the same applies to preferred examples.
In the general formula (6), the alkyl group as Ra, the cycloalkyl group, the aryl group, and the aralkyl group are each independently substituted with the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Rb. As a good group, it may be substituted with a group similar to the group described above.

Specific examples of the above-mentioned Ra alkyl group, cycloalkyl group, aryl group, and aralkyl group (these groups may be substituted with the above group) include groups similar to the above-mentioned specific examples for Rb. Be done.
Specific examples of a particularly preferred compound (DD) in the present invention include, but are not limited to, the compound disclosed in paragraph <0475> of U.S. Patent Application Publication No. 2012/01335348A1.

The onium salt compound (DE) having a nitrogen atom in the cation portion (hereinafter, also referred to as “compound (DE)”) is preferably a compound having a basic moiety containing a nitrogen atom in the cation portion. The basic moiety is preferably an amino group, more preferably an aliphatic amino group. It is even more preferred that all of the atoms adjacent to the nitrogen atom in the basic moiety are hydrogen or carbon atoms. Further, from the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) is not directly linked to the nitrogen atom.
Preferred specific examples of the compound (DE) include, but are not limited to, the compound disclosed in paragraph <0203> of US Patent Application Publication 2015/0309408A1.

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

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

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

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

[Surfactant]
The composition of the present invention may contain a surfactant. By containing a surfactant, it is possible to form a resist pattern having excellent adhesion and fewer development defects with good sensitivity and resolution when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less is used. It will be possible.
As the surfactant, a fluorine-based and / or a silicon-based surfactant is preferable.
Examples of the fluorine-based and / or silicon-based surfactant include the surfactant described in paragraph <0276> of Japanese Patent Application Publication No. 2008/0248425. In addition, Ftop EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Florard FC430, 431, and 4430 (manufactured by Sumitomo 3M Co., Ltd.); Megafuck F171, F173, F176, F189, F113, F110, F177, F120 and R08 (manufactured by DIC Co., Ltd.); Surflon S-382, SC101, 102, 103, 104, 105, and 106 (manufactured by Asahi Glass Co., Ltd.); Troysol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300, GF-150 (manufactured by Toa Synthetic Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.); , EF802, and EF601 (manufactured by Gemco Co., Ltd.); PF636, PF656, PF6320, and PF6520 (manufactured by OMNOVA); KH-20 (manufactured by Asahi Kasei Co., Ltd.); FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D, and 222D (manufactured by Neos Co., Ltd.) may be used. The polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

In addition to the known surfactants as shown above, 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). May be synthesized 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, a surfactant other than the fluorine-based and / or silicon-based surfactant 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% by mass, more preferably 0.0005 to 1.0% by 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 sensitive light-sensitive or radiation-sensitive film can be controlled. This makes it possible to improve development characteristics, suppress outgas, improve immersion liquid followability in immersion exposure, reduce immersion defects, and the like.
Hydrophobic resins are preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, they do not necessarily have to have hydrophilic groups in the molecule and are a uniform mixture of polar / non-polar substances. It does not have to contribute to doing so.

The hydrophobic resin is at least one selected from the group consisting of "fluorine atom", "silicon atom", and " _CH3 partial structure contained in the side chain portion of the resin" from the viewpoint of uneven distribution on the surface layer of the film. It is preferably a resin having a repeating unit having seeds.
When the hydrophobic resin contains a fluorine atom and / or a silicon atom, the fluorine atom and / or the silicon atom in the hydrophobic resin may be contained in the main chain of the resin and may be contained in the side chain. You may.

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

The hydrophobic resin preferably has at least one group selected from the following groups (x) to (z).
(X) Acid group (y) A group that decomposes by the action of an alkaline developer and increases its solubility in an alkaline developer (hereinafter, also referred to as a polarity conversion group).
(Z) A group that decomposes 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, a (alkylsulfonyl) (alkylcarbonyl) methylene group, and (alkylsulfonyl) (alkyl). A carbonyl) imide group, a bis (alkylcarbonyl) 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) group. ) Methylene group and the like can be mentioned.
As the acid group, a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfoneimide group, or a bis (alkylcarbonyl) methylene group is preferable.

Examples of the group (y) that decomposes due to the action of the alkaline developing solution and increases the solubility in the alkaline developing solution include a lactone group, a carboxylic acid ester group (-COO-), and an acid anhydride group (-C (O) OC). (O)-), acidimide 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.
Examples of the repeating unit containing these groups include repeating units in which these groups are directly bonded to the main chain of the resin, and examples thereof include repeating units made of acrylic acid ester and methacrylic acid ester. In this repeating unit, these groups may be bonded to the main chain of the resin via a linking group. Alternatively, the repeating unit may be introduced into the terminal of the resin by using a polymerization initiator or a chain transfer agent having these groups at the time of polymerization.
Examples of the repeating unit having a lactone group include the same repeating units having a lactone structure described above in the section of resin (X).

The content of the repeating unit having a group (y) that decomposes 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 even more preferable.

Examples of the repeating unit having a group (z) that decomposes by the action of an acid in the hydrophobic resin include the same as the repeating unit having an acid-degradable group mentioned in the resin (X). The repeating unit having a group (z) decomposed 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 the group (z) decomposed by the action of the acid is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, and 20 to 20 to all the repeating units in the hydrophobic resin. 60 mol% is more preferred.
The hydrophobic resin may further have a repeating unit different from the repeating unit described above.

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

On the other hand, particularly when the hydrophobic resin contains a _CH3 partial structure in the side chain portion, a form in which the hydrophobic resin does not substantially contain fluorine atoms and silicon atoms is also preferable. Further, it is preferable that the hydrophobic resin is substantially composed of only repeating units composed of only atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms and sulfur atoms.

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

The total content of the residual monomer and / or the oligomer component 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, and more preferably in the range of 1 to 3.

As the hydrophobic resin, a known resin can be appropriately selected and used alone or as a mixture thereof. For example, publicly known disclosed in paragraphs <0451> to <0704> of U.S. Patent Application Publication No. 2015/016883A1 and paragraphs <0340> to <0356> of U.S. Patent Application Publication No. 2016/0274458A1. Can be suitably used as the hydrophobic resin (E). Further, the repeating unit disclosed in paragraphs <0177> to <0258> of US Patent Application Publication No. 2016/0237190A1 is also preferable as the repeating unit constituting the hydrophobic resin (E).

A preferred example of the monomer corresponding to the repeating unit constituting the hydrophobic resin is shown below.

The hydrophobic resin may be used alone or in combination of two or more.
It is preferable to mix and use two or more kinds 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 (the total of a plurality of types, if present) is preferably 0.01 to 10.0% by mass, preferably 0.05 to 8.% of the total solid content in the composition. 0% by mass is more preferable.

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

The component (M1) and the component (M2) are shown below.
Component (M1): Propylene glycol monoalkyl ether carboxylate Component (M2): Solvent selected from the following components (M2-1) or solvent selected from the following components (M2-2) Component (M2-1) :. Propropylene glycol monoalkyl ether, lactic acid ester, acetic acid ester, butyl butyrate, alkoxypropionic acid ester, chain ketone, cyclic ketone, lactone, or alkylene carbonate component (M2-2): Flamming point (hereinafter, also referred to as fp) is 37. Solvent above ℃

When the above solvent and the above-mentioned resin (X) are used in combination, the coatability of the composition is improved and a pattern with a small number of development defects can be obtained. The reason is not always clear, but since the solvent has a good balance of solubility, boiling point and viscosity of the resin (X) described above, uneven film thickness of the resist film and generation of precipitates in spin coating may occur. It is thought that this is due to the fact that it can be suppressed.

As the component (M1), 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 is preferable, and propylene glycol monomethyl ether acetate is preferable. (PGMEA) is more preferred.

The following components (M2-1) are preferable.
As the 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 acetic acid ester, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl acetate, ethyl acetate, butyl acetate, propyl acetate, or 3-methoxybutyl acetate are preferable.
As the alkoxypropionic acid ester, methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferable.
Chain ketones include 1-octanone, 2-octanone, 1-nonanonone, 2-nonanonone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, phenylacetone, methylethylketone, and methylisobutyl. Ketones, acetylacetones, acetonylacetones, ionones, diacetonyl alcohols, acetylcarbinols, acetophenones, methylnaphthylketones, or methylamylketones 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.

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

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

The mixing ratio (mass ratio: M1 / M2) of the component (M1) and the component (M2) is preferably 100/0 to 15/85, 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 even more preferable.

Further, the solvent may further contain other solvents in addition to the above-mentioned 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 an ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12 and even more preferably 7 to 10) and having a heteroatom number of 2 or less. .. The ester solvent having 7 or more carbon atoms and 2 or less heteroatoms does not include the solvent corresponding to the above-mentioned component (M2).

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

[Other additives]
The composition of the present invention is a dissolution-inhibiting compound (a compound that decomposes by the action of an acid to reduce its 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 developing solution (for example, a phenol compound having a molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxy group) may be further contained.

[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 1.0 to 10.0 in terms of better coatability. The mass% is more preferable, and 1.0 to 5.0% by mass is particularly preferable. The solid content concentration is the 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 (active light-sensitive or radiation-sensitive film) made of the composition of the present invention is generally 200 nm or less, preferably 100 nm or less, from the viewpoint of improving the resolving power. For example, in order to resolve a 1: 1 line-and-space pattern having a line width of 20 nm or less, the film thickness of the resist film formed is preferably 90 nm or less. When the film thickness is 90 nm or less, pattern collapse is less likely to occur when the development process described later is applied, and more excellent resolution performance can be obtained.
In the case of EUV exposure or exposure with an electron beam, the 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 coatability or the film forming property.

In the composition of the present invention, the above-mentioned components are dissolved in a predetermined organic solvent, preferably the above-mentioned mixed solvent, filtered through a filter, and then applied onto a predetermined support (substrate) for use. The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, still more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as disclosed in Japanese Patent Application Publication No. 2002-62667 (Japanese Patent Laid-Open No. 2002-62667), 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. Also, the composition may be filtered multiple times. Further, the composition may be degassed before and after the filter filtration.

[Use]
The composition of the present invention relates to a sensitive light-sensitive or radiation-sensitive resin composition whose properties change in response to irradiation with active light or radiation. More specifically, the composition of the present invention comprises a semiconductor manufacturing process such as an IC (Integrated Circuit), a circuit board manufacturing such as a liquid crystal or a thermal head, a molding structure for imprinting, another photofabrication step, or a photofabrication step. The present invention relates to a sensitive light-sensitive or radiation-sensitive resin composition used for producing a flat plate printing plate or an acid-curable composition. The pattern formed in the present invention can be used in an etching step, an ion implantation step, a bump electrode forming step, a rewiring forming step, a MEMS (Micro Electro Mechanical Systems), and the like.

[Pattern formation method]
The present invention also relates to a pattern forming method using the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition. Hereinafter, the pattern forming method of the present invention will be described. 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 is
(I) A step of forming a resist film (sensitive light-sensitive or radiation-sensitive film) on a support by the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition (resist film forming step).
(Ii) A step (exposure step) of exposing the resist film (irradiating with active light rays or radiation), and
(Iii) A step of developing the exposed resist film using a developing solution (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) above, and may further include the following steps.
In the pattern forming method of the present invention, the exposure method in the (ii) exposure step may be immersion exposure.
The pattern forming method of the present invention preferably includes (iv) preheating (PB: PreBake) step before the (ii) exposure step.
The pattern forming method of the present invention preferably includes (v) a post-exposure Bake (PEB) step after (ii) an exposure step and before (iii) a developing 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-mentioned (i) film forming step, (ii) exposure step, and (iii) developing step can be performed by a generally known method.
Further, if necessary, a resist underlayer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon), and an 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, US Patent Application Publication No. 2007/0178407, US Patent Application Publication No. 2008/805466, US Patent Application Publication No. 2007/0275326, US Patent Application Publication No. 2016/0299432, The composition for forming a protective film disclosed in US Patent Application Publication No. 2013/02444438 and International Patent Application Publication No. 2016/157988A can be preferably used. The composition for forming a protective film preferably contains the above-mentioned acid diffusion control agent.
The film thickness of the protective film is preferably 10 to 200 nm, more preferably 20 to 100 nm, and even more preferably 40 to 80 nm.

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

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

The wavelength of the light source used in the exposure process is not limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, polar ultraviolet light (EUV), X-ray, and electron beam. Among them, the light source wavelength is preferably 250 nm or less, more preferably 220 nm or less, and further preferably 1 to 200 nm. Specifically, it is a KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser ₍ 157 nm), X-ray, EUV (13 nm), electron beam or the like, and is a KrF excimer laser, ArF excimer laser, etc. EUV or electron beam is preferable, EUV or electron beam is more preferable, and EUV is further preferable.

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

As the alkaline component contained in the alkaline developer, a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used. In addition to this, an alkaline aqueous solution containing an alkaline component such as an inorganic alkali, a primary to tertiary amine, an alcohol amine, and a cyclic amine can also be used.
Further, the alkaline developer may contain an appropriate amount of alcohols and / or a surfactant. The alkaline concentration of the alkaline developer is usually 0.1 to 20% by mass. The pH of the alkaline developer is usually 10 to 15.
The time for developing with an alkaline developer is usually 10 to 300 seconds.
The alkali concentration, pH, and development time of the alkaline 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 a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, an ether solvent, and a hydrocarbon solvent. Is preferable.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanonone, 2-nonanonone, acetone, 2-heptanone (methylamylketone), 4-heptanone, 1-hexanone, 2-hexanone, and diisobutylketone. Cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate and the like can be mentioned.

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

As the alcohol-based solvent, the amide-based solvent, the ether-based solvent, and the hydrocarbon-based 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 developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, further preferably less than 10% by mass, and particularly preferably substantially free of water.
The content of the organic solvent in the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, further preferably 90 to 100% by mass, and 95 to 100% by mass with respect to the total amount of the developer. % Is particularly preferable.

The organic developer may contain an appropriate amount of a known surfactant, if necessary.

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

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

Examples of the developing method include a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dip method), a method of raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time (paddle method), and a substrate. A method of spraying the developer on the surface (spray method) or a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic discharge method) can be mentioned. Be done.

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

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

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

The rinsing solution used in the rinsing step after the developing step using the developing solution containing an organic solvent is not particularly limited as long as it does not dissolve the pattern, and a general solution containing an organic solvent can be used. As the rinsing solution, a rinsing solution containing at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent shall be used. Is preferable.
Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent include the same as those described for the developing solution containing the organic solvent.
As the rinsing liquid used in the rinsing step in this case, a rinsing 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 methylisobutylcarbinol can be mentioned. Examples of the monohydric alcohol having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, methyl isobutylcarbinol and the like. ..

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 solution is preferably 10% by mass or less, more preferably 5% by mass or less, and even 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 developed with an organic developer is washed with a rinsing solution containing an organic solvent. The cleaning treatment method is not particularly limited, but for example, a method of continuously discharging the rinse liquid onto a substrate rotating at a constant speed (rotational coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. Examples thereof include a method (dip method) and a method of spraying a rinse liquid on the substrate surface (spray method). Above all, it is preferable to perform a cleaning treatment by a rotary coating method, and after cleaning, rotate the substrate at a rotation 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 step, 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 sensitive light-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 developing solution, a rinsing solution, an antireflection film forming composition, or The composition for forming a top coat, etc.) preferably does not contain impurities such as metal components, isomers, and residual monomers. The content of these impurities contained in the above-mentioned various materials is preferably 1 ppm or less, more preferably 100 ppt or less, further preferably 10 ppt or less, and substantially not contained (below the detection limit of the measuring device). Is particularly preferable.

Examples of the method for removing impurities such as metals from the above-mentioned various materials include filtration using a filter. The filter pore diameter is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel for use. When using a plurality of types of filters, filters having different pore diameters and / or materials may be used in combination. Further, various materials may be filtered a plurality of times, and the step of filtering the various materials a plurality of times may be a circulation filtration step. The filter preferably has a reduced amount of 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 by an adsorbent, or filter filtration and an adsorbent may be used in combination. As the adsorbent, a known adsorbent can be used, and 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).
Further, 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 such as lining the inside of the apparatus with Teflon (registered trademark) to perform distillation under conditions in which contamination is suppressed as much as possible can be mentioned. The preferred conditions for filter filtration performed on the raw materials constituting the various materials are the same as the above-mentioned conditions.

The above-mentioned various materials are described in US 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 with impurities. It is preferable to store it in a 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. Examples of the method for improving the surface roughness of the pattern include a method of treating the pattern with plasma of a gas containing hydrogen disclosed in US Patent Application Publication No. 2015/010497. In addition, Japanese Patent Application Publication No. 2004-235468 (Japanese Patent Laid-Open No. 2004-235468), US Patent Application Publication No. 2010/0020297, Proc. of SPIE Vol. A known method as described in 832883280N-1 “EUV Resist Curing Technology for LWR Resistion and Etch Sensitivity Enhancement” may be applied.
Further, the pattern formed by the above method is a spacer process disclosed in, for example, Japanese Patent Application Publication No. 1991-270227 (Japanese Patent Laid-Open No. 3-270227) and US Patent Application Publication No. 2013/209941. Can be used as a core material (Core).

[Manufacturing method of electronic device]
The present invention also relates to a method for manufacturing an electronic device, including the above-mentioned pattern forming method. 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, a home appliance, an OA (Office Automation) related device, a media related device, an optical device, a communication device, etc.). Will be done.

Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the examples shown below.

[Actinic cheilitis or radiation-sensitive resin composition]
Below, first, various components contained in the sensitive light-sensitive or radiation-sensitive resin composition (hereinafter referred to as “resist composition”) of the formulation shown in Table 2 are shown.

[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 resins A-1 and A-2 for comparative examples 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 the general formula (B-1).

An example of resin synthesis shown in Table 1 is shown below.
(Synthesis Example 1: Synthesis of Resin P-1)
The monomers corresponding to each repeating unit (M-1 / M-11 / M-12) of the resin P-1 were added in order from the left to 50.0 g, 15.0 g, 35.0 g, and the polymerization initiator V-601 (the polymerization initiator V-601). Wako Pure Chemical Industries, Ltd. (12.72 g) and cyclohexanone (358 g) were dissolved. The solution thus obtained was used as a monomer solution.
Cyclohexanone (198 g) was placed in the reaction vessel, and the monomer solution was added dropwise over 4 hours in the reaction vessel adjusted so that the temperature in the system was 85 ° C. under a nitrogen gas atmosphere. The obtained reaction solution was stirred in a reaction vessel for 2 hours at 85 ° C., and then allowed to cool to room temperature.
The reaction solution after allowing to cool was added dropwise to 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 the 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 comparative examples resins A-1 and A-2)
The same operation as in Synthesis Example 1 was carried out to synthesize the resins P-2 to P-59 described later, and the resins A-1 and A-2 for Comparative Examples. In the resins P-2 to P-59 and the comparative examples resins A-1 and A-2, the composition (mass ratio), weight average molecular weight (Mw), and dispersity (Mw / Mn) of each repeating unit. Was obtained by the same method as the above-mentioned resin P-1.

<Photoacid 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 shown individually. That is, the photoacid generator shown in Table 2 is composed of a combination of a cation portion and an anion portion. 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 control agent shown in Table 2 is shown below.

<Additional polymer (hydrophobic resin)>
The structure of the added polymer (hydrophobic resin) shown in Table 2 is shown below.
The numerical values in the following formulas represent the mass ratio (mass%) of each repeating unit.

<Surfactant>
The surfactants shown in Table 2 are shown below.
W-1: Megafuck F176 (manufactured by DIC Corporation; fluorine-based)
W-2: Megafuck R08 (manufactured by 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. Then, the obtained mixed solution 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 content (% by mass) of each component described in the columns of "resin", "photoacid generator", "acid diffusion control agent", "added polymer", and "surfactant" below is all. Represents the ratio of each component to the solid content. The description in the column of "solvent" represents the mass ratio of the content of each solvent.

[Pattern formation and evaluation]
A pattern was formed using the above resist composition. In forming the pattern, the developer and rinse solutions and the underlayer film shown below 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 membrane>
UL-1: AL412 (manufactured by Brewer Science)
UL-2: SHB-A940 (manufactured by Shin-Etsu Chemical Co., Ltd.)

<Pattern formation>
The resist composition shown in Table 3 was applied onto a silicon wafer (12 inches) on which the underlayer film shown in Table 3 below was formed to form a coating film. The obtained coating film is heated under the bake conditions described in the "resist coating conditions" column in Table 3 to form a resist film having the film thickness shown in Table 3 to obtain a silicon wafer having the resist film. rice field.
Using an EUV exposure device (Micro Exposure Tool, NA0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36, manufactured by Exitech), pattern irradiation was performed on the silicon wafer having the obtained resist film. rice field. As the lectil, a mask having a line size of 20 nm and a line: space = 1: 1 was used.
Then, after baking (Post Exposure Bake; PEB) under the conditions shown in the "PEB / development conditions" column in Table 3 below, paddle with the developer shown in Table 3 for 30 seconds to develop, and then Table 3 It was paddled and rinsed with the rinse solution shown in. Then, the silicon wafer was rotated at a rotation speed of 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>
Using the resist film and pattern obtained by the above method, the evaluation shown below was performed. The results are summarized in Table 3.

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

(Inhibitory of collapse (inhibitory of pattern collapse))
The line width of the line-and-space pattern formed while changing the exposure amount was measured. At this time, the minimum line width in which the pattern is resolved without collapsing over 10 μm square is defined as the tilt line width. The smaller this value is, the wider the margin of pattern collapse is, and the better the pattern collapse suppression property is.

(LER performance)
In observing a line-and-space resist pattern resolved at the optimum exposure in sensitivity evaluation, observe from the top of the pattern with a long-measurement scanning electron microscope (SEM: Scanning Electron Microscope (CG-4100 manufactured by Hitachi High-Technologies)). At that time, 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 by 3σ. The smaller the value, the better the 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 by the resist composition of the example) had excellent sensitivity. Further, it was confirmed that the pattern formed by the resist composition of the example was excellent in anti-falling property and LER.
From the comparison between Example 1 and Examples 8 and 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 the was superior.
From the comparison between Examples 1 and 10 to 13, it was confirmed that when the weight average molecular weight of the resin (X) was 3,500 to 15,000, the pattern collapse inhibitory property was 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 ability to suppress the collapse of the formed pattern was more excellent.
From the comparison between Examples 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−. , -SO-, or -SO _2- , it was confirmed that the formed pattern is more excellent in the collapse suppressing property. Among them, it was confirmed that when the resin (X) contains a repeating unit represented by the general formula (B-4), the formed pattern is also superior to LER.
From the comparison of Examples 60 to 65, it was confirmed that the same effect can be obtained regardless of whether the development method is alkaline development or organic solvent development.

Claims (17)

Compounds that generate acid by irradiation with active light or radiation, and
Containing a resin whose polarity increases due to the action of acid,
The resin contains a repeating unit represented by the following 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.
A sensitive light-sensitive or radiation-sensitive resin composition in which the content of the halogen atom is 16% by mass or more with respect to the total mass of the resin.

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, which may have a substituent.
R ¹ and R ² may be coupled to each other to form a ring. R ¹ and R ² may independently bond with the atoms contained in the ring W ¹ to form a ring. When at least one of X and Y represents -NR ^3- , each R ³ independently combines with an atom contained in R ¹ , R ² , or ring W ¹ to form a ring. May be good. The actinic light-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 divalent concatenations independently 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 coupled to each other to form a ring. R ⁴ and R ⁵ may be coupled to each other to form a ring. If at least one of X and Y represents −NR ³⁻ , R ³ may independently combine with R ¹ , R ² , R ⁴ or R ⁵ to form a ring. The actinic light-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 independently represent -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 coupled to each other to form a ring. R ⁴ and R ⁵ may be coupled to each other to form a ring. The actinic 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- . The actinic 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 coupled to each other to form a ring. Compounds that generate acid by irradiation with active light or radiation, and
Containing a resin whose polarity increases due to the action of acid,
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. Sex resin composition.

In the above formula, X and Y are independently oxygen atom, sulfur atom, or -NR. ³ -Represents. R ¹ , R ² , And R ³ Independently represent a hydrogen atom or an organic group. However, R ¹ And R ² At least one of the above represents an organic group having at least one halogen atom selected from the group consisting of a fluorine atom and an iodine atom. The ring W ¹ Represents a ring containing two carbon atoms, X and Y, which may have a substituent.
R ¹ And R ² Independently, ring W ¹ The atoms contained therein may be bonded to each other to form a ring. At least one of X and Y is -NR ³ When representing-, R ³ Are independent of each other, R ¹ , R ² , Or ring W ¹ The atoms contained therein may be bonded to each other to form a ring. The actinic light-sensitive or radiation-sensitive resin composition according to claim 6, 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 are independently oxygen atom, sulfur atom, or -NR. ³ -Represents. L ¹ And L ² Are independently -CO- and -C (R). ⁴ ) (R ⁵ )-, -SO-, -SO ₂ -Represents a divalent linking group selected from the group consisting of and combinations thereof. R ¹ , R ² , R ³ , R ⁴ , And R ⁵ Independently represent a hydrogen atom or an organic group. However, R ¹ And R ² At least one of the above represents an organic group having at least one halogen atom selected from the group consisting of a fluorine atom and an iodine atom.
R ⁴ And R ⁵ May be combined with each other to form a ring. At least one of X and Y is -NR ³ When representing-, R ³ Are independent of each other, R ¹ , R ² , R ⁴ , Or R ⁵ May be combined with each other to form a ring. The actinic light-sensitive or radiation-sensitive resin composition according to claim 7, 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 are independently oxygen atom, sulfur atom, or -NR. ³ -Represents. L ³ And L ⁴ Are independently -CO- and -C (R). ⁴ ) (R ⁵ )-, -SO-, or -SO ₂ -Represents. R ¹ , R ² , R ³ , R ⁴ , And R ⁵ Independently represent a hydrogen atom or an organic group. However, R ¹ And R ² At least one of the above represents an organic group having at least one halogen atom selected from the group consisting of a fluorine atom and an iodine atom.
R ⁴ And R ⁵ May be combined with each other to form a ring. L ³ And L ⁴ At least one of is -CO-, -SO-, or -SO ₂ The actinic light-sensitive or radiation-sensitive resin composition according to claim 8. The actinic or radiation-sensitive resin according to claim 8 or 9, 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 Independently represent a hydrogen atom or an organic group. However, R ¹ And R ² At least one of the above represents an organic group having at least one halogen atom selected from the group consisting of a fluorine atom and an iodine atom. The actinic light-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 10 , wherein the resin has a weight average molecular weight of 2,000 to 30,000. The actinic light-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 11 , wherein the resin contains a fluorine atom. A resist film formed by the sensitive light-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 12 . A resist film forming step of forming a resist film using the sensitive light-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 12 .
The exposure process for exposing the resist film and
A pattern forming method comprising a developing step of developing the exposed resist film with a developing solution. The pattern forming method according to claim 14 , wherein the exposure step is a step of exposing the resist film with extreme ultraviolet light. The pattern forming method according to claim 14 , wherein the developer is a developer containing an organic solvent. A method for manufacturing an electronic device, which comprises the pattern forming method according to any one of claims 14 to 16 .