TWI833701B - Photosensitive radiation or radiation-sensitive resin composition, resist film, pattern forming method, manufacturing method of electronic component - Google Patents

Abstract

The present invention provides a photosensitive radiation-sensitive or radiation-sensitive resin composition capable of obtaining a resist film with excellent EL performance and a pattern with excellent LWR performance, and a resist using a photosensitive radiation-sensitive or radiation-sensitive resin composition. Film, pattern forming method, and electronic component manufacturing method. A photosensitive radiation-sensitive or radiation-sensitive resin composition includes a resin having at least one repeating unit selected from the group consisting of a repeating unit represented by general formula (1) and a repeating unit represented by general formula (2), and Photoacid generator.

Description

Photosensitive radiation or radiation-sensitive resin composition, resist film, pattern forming method, manufacturing method of electronic component

The present invention relates to a photosensitive radiation or radiation-sensitive resin composition, a resist film, a pattern forming method, and a manufacturing method of electronic components.

Previously, in the manufacturing process of semiconductor components such as IC (Integrated Circuit) and LSI (Large Scale Integrated Circuit), photosensitive radiation or radiation-sensitive resin compositions were used. Micromachining by photolithography. For example, Patent Document 1 discloses a radiation-sensitive resin composition containing an acid-dissociable group-containing polymer having a predetermined repeating unit. [Prior art documents] [Patent documents]

[Patent Document 1] Japanese Patent Application Publication No. 2007-052182

The inventors of the present invention conducted research on the photosensitive radiation-sensitive or radiation-sensitive resin composition specifically described in the Example column of Patent Document 1 and found that the composition of the photosensitive radiation-sensitive or radiation-sensitive resin There is room for improvement due to the formation of the resist film, the exposure latitude (EL: Exposure Latitude) of the resist film, and the fluctuation of the pattern line width (LWR: Line Width Roughness).

An object of the present invention is to provide a photosensitive radiation or radiation-sensitive resin composition capable of obtaining a resist film with excellent EL performance and a pattern with excellent LWR performance. Furthermore, an object of the present invention is to provide a resist film, a pattern forming method, and an electronic component manufacturing method using the above-mentioned photosensitive radiation or radiation-sensitive resin composition.

The present inventors conducted intensive research in order to achieve the above-mentioned subject, and as a result found that the above-mentioned subject can be solved by using a resin containing a repeating unit having a specific structure, and completed the present invention. That is, it was discovered that the above-mentioned problems can be solved by the following configuration.

[1] A photosensitive radiation-sensitive or radiation-sensitive resin composition containing a repeating unit selected from the group consisting of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2). At least one repeating unit resin, and a photoacid generator. [2] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to [1], wherein the content of the resin is 10% by mass relative to the total solid content of the photosensitive radiation-sensitive or radiation-sensitive resin composition. above. [3] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein in the general formula (2) described below, at least one of R ₃ and R ₄ is an organic group. [4] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein in the general formula (1) described below, at least one of R ₁ and R ₂ It is a group represented by the general formula (R) to be described later. In the general formula (2) to be described later, at least one of R ₃ and R ₄ is a group represented by the general formula (R) to be described later. [5] The photosensitive radiation or radiation-sensitive resin composition according to [4], wherein in the general formula (1) described below, R ₅ represents an alkali-decomposable group. [6] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein in the general formula (1) described below, L ₁ may have a substituent, having An alkylene group of an ether group or an alkylene group having two groups represented by the general formula (A) to be described later. In the general formula (2) to be described later, L ₂ is an alkylene group having an ether group which may have a substituent. Or an alkylene group having two groups represented by the general formula (A) described below. [7] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to [4] or [6], wherein in the general formula (1) to be described later, R ₁ and R ₂ are represented by the general formula (R) to be described later. is a group, and L ₁ is a group having two groups represented by the general formula (A) described below. [8] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the resin has a repeating unit represented by the general formula (3) described below. [9] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the resin further has a repeating unit selected from the group consisting of a lactone group-containing unit and an acid-free unit. At least one repeating unit in a group consisting of repeating units of either a decomposable group or a polar group. [10] A resist film formed using the photosensitive radiation or radiation-sensitive resin composition described in any one of [1] to [9]. [11] A pattern forming method, which includes: a resist film forming step of forming a resist film using the photosensitive radiation-sensitive or radiation-sensitive resin composition described in any one of [1] to [9]; The exposure step is to expose the above resist film; and the development step is to use a developer to develop the exposed resist film. [12] A method of manufacturing an electronic component, which includes the pattern forming method according to [11]. [Effects of the invention]

According to the present invention, it is possible to provide a photosensitive radiation or radiation-sensitive resin composition capable of obtaining a resist film with excellent EL performance and a pattern with excellent LWR performance. Furthermore, according to the present invention, it is possible to provide a resist film, a pattern forming method, and an electronic component manufacturing method using the above-mentioned photosensitive radiation 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 representative embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, for labels of groups (atomic groups), labels that do not indicate substituted or unsubstituted include groups without a substituent, and groups with a substituent are also included. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, "organic group" refers to a group having at least one carbon atom. In this specification, “actinic rays” or “radiation rays” refer to, for example, the bright line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays and electron beams (EB). : Electron Beam) etc. In this specification, "light" refers to actinic rays or radiation. In this manual, "exposure", unless otherwise specified, includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet, extreme ultraviolet, X-ray and EUV light represented by excimer laser, but also includes exposure using Drawing by particle beams such as electron beams and ion beams. In this specification, "～" is used in the sense that the numerical values described before and after it are included as the lower limit value and the upper limit value.

In this specification, "(meth)acrylate" means acrylate and methacrylate. In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn) and dispersion (also called molecular weight distribution) (Mw/Mn) of the resin are defined based on GPC (Gel Permeation Chromatography) Chromatography)) GPC measurement of device (HLC-8120GPC manufactured by TOSOH CORPORATION) (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION, column temperature: 40°C , flow rate: 1.0mL/min, detector: differential refractive index detector (Refractive Index Detector)) polystyrene conversion value. The bonding direction of the bivalent group (eg -COO-) marked in this specification is not limited unless otherwise specified. For example, in the case where M is -COO- in a compound represented by the general formula "L-M-N", let the position of the bond on the L side be *1 and the position of the bond on the N side be *1 *2, then M can be *1-O-CO-*2 or *1-CO-O-*2. In this specification, an organic group refers to a group having carbon atoms. Examples include hydrocarbon groups and hydrocarbon groups having heteroatoms.

[Photosensitive radiation-sensitive or radiation-sensitive resin composition] The photosensitive radiation-sensitive or radiation-sensitive resin composition of the present invention (hereinafter, also simply referred to as "composition" or "composition of the present invention") will be described. The composition of the present invention is a so-called resist composition, and may be a positive resist composition or a negative resist composition. Moreover, 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.

A characteristic point of the composition of the present invention is that it contains a resin having a repeating unit represented by the general formula (1) or (2) described below. By using the composition of the present invention containing the above resin, it is possible to form a resist film with excellent EL performance and a pattern with excellent LWR performance (hereinafter, this property of the composition of the present invention is also simply referred to as the "effect of the present invention" ). Although the details of this mechanism are not clear, it is speculated as follows. The repeating unit represented by the general formula (1) or (2) described below, which the resin contained in the composition of the present invention has, reduces the mobility of the main chain by introducing a ring structure into the main chain of the resin, and improves the mobility of the main chain. Glass transfer point (Tg). In addition, by having a certain number or more of polar groups containing heteroatoms on the main chain and side chains, the interaction between the groups becomes larger, and the effect of improving Tg becomes greater. This reduces the solubility of the resin and makes it easy to appropriately suppress the diffusion of acid generated from the photoacid generator by exposure. As a result, it is presumed that a resist film composed of the composition of the present invention can exhibit excellent development contrast and be able to realize the effect of the present invention.

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

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

[Chemical formula 1]

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

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

At least one of R ₁ and R ₂ is a group represented by the above general formula (A), and any one of R ₃ and R ₄ may be a group represented by the above general formula (A), or both of them may be. All are groups represented by the above general formula (A). When only one of R ₁ and R ₂ is the group represented by the general formula (A), the other represents a hydrogen atom or an organic group other than the group represented by the general formula (A). In addition, both R ₁ and R ₂ are groups represented by the above general formula (A), and when the group represented by L ₁ described below has one hetero atom, two hetero atoms are represented by the above general formula (A). ) in the group represented by at least one of the two R's represents a hydrocarbon group having a heteroatom.

Examples of the heteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom. Among them, an oxygen atom, a nitrogen atom or a sulfur atom is preferred, and an oxygen atom is more preferred.

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

In the general formula (2), R ₃ and R ₄ each independently represent a hydrogen atom or an organic group. It is preferred that at least one of R ₃ and R ₄ is an organic group. Either one of R ₃ and R ₄ may be an organic group, or both may be an organic group.

As the organic group represented by R ₃ and R ₄ , a hydrocarbon group having a heteroatom is preferred. Examples of heteroatoms include oxygen atoms, nitrogen atoms, sulfur atoms, selenium atoms, tellurium atoms, phosphorus atoms, silicon atoms and boron atoms. Among them, an oxygen atom, a nitrogen atom or a sulfur atom is preferred, and an oxygen atom is more preferred. Furthermore, it is preferable that the oxygen atom and the carbon atom jointly form an ester group, and it is preferable that the above-mentioned ester group is directly bonded to the main chain of the repeating unit represented by the general formula (2). Furthermore, it is preferable that a hydrogen atom or another organic group is bonded to the main chain via the ester group. As another organic group bonded to the main chain via an ester group, a hydrocarbon group that may have a heteroatom is preferred. That is, the organic group represented by R ₃ and R ₄ is preferably a group represented by the general formula (A). In addition, both R ₃ and R ₄ are groups represented by the above general formula (A), and when the group represented by L ₂ described below has one hetero atom, two hetero atoms are represented by the above general formula (A). It is preferred that at least one of the two R's in the group represented by A) represents a hydrocarbon group having a heteroatom.

In the general formula (A), examples of the hydrocarbon group represented by R that may have a hetero atom include an alkyl group that may have a hetero atom, an alkenyl group that may have a hetero atom, and an alkynyl group that may have a hetero atom. In addition, the above-mentioned alkyl group, alkenyl group and alkynyl group may be either linear or branched. The carbon number system is preferably 1 to 20. The above-mentioned alkyl group, alkenyl group and alkynyl group may or may not have a cyclic structure. Among them, from the viewpoint of suppressing a decrease in the Tg of the resin and further improving the effects of the present invention, it is preferable that R has an alicyclic group, and that the alicyclic group constitutes a part of the acid-leaving group.

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

*-C (=O)-OR ₅ (R) *Indicates the bonding position.

In the general formula (R), R ₅ represents a hydrogen atom, an alkali-decomposable group or an acid-detaching group. More specifically, R ₅ represents a hydrogen atom, a hydrocarbon group that may have a hetero atom and a group that represents alkali decomposability, or a hydrocarbon group that may have a hetero atom and represents an acid-detachable group. Among them, R ₅ is preferably an alkali-decomposable group or an acid-releasable group from the viewpoint of more excellent LWR performance of the pattern. In addition, from the viewpoint of more excellent sensitivity of the resist film, R ₅ is preferably a hydrogen atom or an alkali-decomposable group. That is, R ₅ is more preferably an alkali-decomposable group.

In addition, in this specification, an alkali-decomposable group means a group which decomposes by the action of an alkaline solution and increases the solubility in an alkaline solution. For example, a group having a lactone group (for example, a hydrocarbon group having a lactone group), a group having a sultone group (for example, a hydrocarbon group having a sultone group), a group having a carbonate group ( For example, a hydrocarbon group having a carbonate group (preferably a cyclic carbonate group), a group having an acid anhydride group (for example, a hydrocarbon group having an acid anhydride group), a group having a lactone group, a group having a sultone group A group or a group having a carbonate group (preferably a cyclic carbonate group) is preferred.

When R ₅ is an alkali-decomposable group, the group represented by the general formula (R) is preferably the group represented by the following general formula (R´).

*-C(=O)-O-Ab-V(R´) * indicates bonding position.

Ab-V in the general formula (R´) is equivalent to R ₅ in the general formula (R). Ab represents a single bond, an alkylene group, a monocyclic or polycyclic alicyclic group, an ether group, an ester group, a carbonyl group, or a bivalent linking group formed by a combination thereof. Among them, Ab is preferably a single bond or an alkylene group (preferably having 1 to 2 carbon atoms).

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

As the lactone group, a 5- to 7-membered ring lactone group is preferred. Among them, a group with other rings condensed in a 5- to 7-membered ring lactone group to form a bicyclic or spirocyclic ring is more preferred. Specifically, a group obtained by removing one hydrogen atom from the lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-21), wherein: Removal of structures represented by formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-8), general formula (LC1-16) or general formula (LC1-21) A group derived from 1 hydrogen atom is preferred. As the sultone group, a 5- to 7-membered ring sultone group is preferred. Among them, a group in which a 5- to 7-membered ring sultone group has other rings condensed to form a bicyclic or spirocyclic ring is more preferred. Specifically, a group obtained by removing one hydrogen atom from the sultone structure represented by any one of the following general formulas (SL1-1) to (SL1-3), wherein: The structure represented by formula (SL1-1) is preferably a group obtained by removing one hydrogen atom.

[Chemical formula 2]

_{The above-mentioned lactone and sultone groups may or may not have a substituent (Rb 2 )} . As the substituent (Rb ₂ ), an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, or a carboxyl group, A halogen atom, a hydroxyl group, or a cyano group is preferred, and an alkyl group or a cyano group having 1 to 4 carbon atoms is more preferred. n ₂ represents an integer from 0 to 4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different. In addition, a plurality of substituents (Rb ₂ ) may be bonded to each other to form a ring. Moreover, the lactone group and the sultone group may have the acid-decomposable group mentioned later as a substituent ( _Rb2 ).

As the cyclic carbonate group, a group in which one hydrogen atom is removed from the structure represented by the following general formula is preferred.

[Chemical formula 3]

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

From the viewpoint that -C(=O)-O- and R ₅ explicitly stated in the formula together form an acid-decomposable group and the effect of the present invention is more excellent, a group represented by the general formula (R) is preferred. In addition, in this specification, an acid-decomposable group means a group which decomposes by the action of an acid and increases polarity. The acid-decomposable group preferably has a structure in which a polar group is protected by a group (acid-decomposable group) that is decomposed and detached by the action of an acid. That is, from the viewpoint that the effect of the present invention is more excellent, it is also preferable that R ₅ is the above-mentioned acid-detaching group. In this case, the group represented by the general formula (R) forms an acid-decomposable group. Among them, when the group represented by the general formula (R) forms an acid-decomposable group, the sensitivity of the formed resist film tends to decrease, so it should be noted. When the group represented by the general formula (R) forms an acid-decomposable group, it is preferred that the group represented by the general formula (R) is a group represented by the following general formula (R´´).

*-C (=O)-OR _c (R´´) * indicates the bonding position.

In the general formula (R´´), R _c is equivalent to R ₅ of the general formula (R). Moreover, the above-mentioned -R _c represents -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ) or -C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ).

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 bonded to each other to form a ring. R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

The alkyl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include methyl, ethyl, propyl, n-butyl, second butyl, Hexyl and octyl, etc. The cycloalkyl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ may be a monocyclic ring or a polycyclic ring. As the monocyclic cycloalkyl group, a cycloalkyl group having 3 to 8 carbon atoms is preferred, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl. As the polycyclic cycloalkyl group, a cycloalkyl group having 6 to 20 carbon atoms is preferred, and examples thereof include adamantyl, norbornyl, isobornyl, camphenyl, dicyclopentyl, and α-pinenyl ( pinel group), tricyclodecyl group, tetracyclododecyl group and androstanyl group (androstanyl group), etc. In addition, at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom. The aryl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include phenyl, naphthyl and anthracenyl. 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 benzyl, phenethyl and naphthylmethyl. 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 vinyl, allyl, butenyl, and cyclohexenyl. As the ring formed by bonding R ₃₆ and R ₃₇ to each other, a cycloalkyl group (monocyclic or polycyclic) is preferred. The cycloalkyl group is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl or adamantyl. .

Specific examples of the group represented by the general formula (R´´) are shown. In addition, in the following examples, * indicates the bonding position with the main chain.

[Chemical formula 4]

(L ₁ and L ₂ ) L ₁ and L ₂ in the general formula (1) are bivalent linking groups having one or more hetero atoms, and L ₁ represents an alkylene group which may have a substituent. A part of the carbon atoms in the above-mentioned alkylene group may be substituted with a group having a heteroatom. Substituents may have heteroatoms. Among them, the group represented by L ₁ has one or more heteroatoms. In addition, as mentioned above, both R ₁ and R ₂ in the general formula (1) are groups represented by the above general formula (A), and when the hetero atom of the group represented by L ₁ is 1 In this case, at least one of the two R's in the two groups represented by the above general formula (A) represents a hydrocarbon group having a heteroatom. In other words, both R ₁ and R ₂ in the general formula (1) are groups represented by the above general formula (A), and both R in the two groups represented by the above general formula (A) are When it represents a hydrocarbon group having no hetero atoms, the group represented by L ₁ has two or more hetero atoms. L ₁ and L ₂ may be a linking group in which an alkylene group and an alkylene group are connected via a heteroatom. L ₂ in the general formula (2) represents an alkylene group which may have a substituent. A part of the carbon atoms in the above-mentioned alkylene group may be substituted with a group having a heteroatom. Substituents may have heteroatoms. Among them, the group represented by L ₂ has one or more heteroatoms. The alkylene groups represented by L ₁ and L ₂ are bonded to two carbon atoms specified in the formula at their respective terminal ends to form a cyclic group. In addition, the group having a hetero atom may be the hetero atom itself.

L ₁ and L ₂ are preferably divalent linking groups containing carbon atoms, nitrogen atoms, oxygen atoms, sulfur atoms or halogen atoms, wherein the heteroatoms contained in L ₁ and L ₂ are oxygen atoms, nitrogen atoms Atom, sulfur atom or fluorine atom is preferred. There is no restriction on the manner in which the groups represented by L ₁ and L ₂ have heteroatoms. Part of the carbon atoms in the chain of the alkylene group may be substituted by a group having heteroatoms. The substitution of the alkylene group The radicals may have heteroatoms. Examples of the group having a heteroatom include an ether group (-O-), a thioether group (-S-), a carbonyl group (-C(=O)-), and an ester group (-C(=O)O- ), amide group (-NHC (=O)-) and sulfonyl group (-S (=O) ₂ -), etc. From the viewpoint of more excellent LWR performance of the pattern, when a group having a hetero atom is present in the alkylene chain, it is preferable that the group having a hetero atom is an ether group. When the substituent has a heteroatom, it is preferable that the heteroatom and the carbon atom together form an ester group, and more preferably a group represented by the above general formula (A). The carbon number of the alkylene group is preferably from 2 to 10, more preferably from 2 to 6, and further preferably 2. In addition, the number of carbon atoms mentioned above does not include the number of heteroatoms that the alkylene group has in the chain and the number of carbon atoms that the substituent that the alkylene group has has. In addition, the number of atoms constituting these rings does not include the number of atoms of the substituent.

Examples of the state in which the alkylene group has a substituent include a case where part of the hydrogen atoms in the alkylene group is substituted by a substituent. The type of substituent is not particularly limited. As mentioned above, the substituent may have a heteroatom. Examples of the substituent include a halogen atom (-F, -Cl, -I, etc.), an alkyl group, -S(=O) ₂ -alkyl group, an alkoxy group, an aryl group, a hydroxyl group, a cyano group, or a group composed of The group represented by the above-mentioned general formula (A), etc. Among these, a group represented by general formula (A) is preferable as a substituent from the viewpoint of more excellent LWR performance of the pattern. When the alkylene group has a group represented by the general formula (A), it is more preferred that the alkylene group has 2 or more (preferably 2 to 4) groups represented by the general formula (A), and 2 One is further better. In addition, a plurality of groups represented by the general formula (A) may be the same or different. In addition, from the viewpoint of more excellent effects of the present invention, when the alkylene group has two groups represented by the general formula (A), R ₁ and R ₂ (or R ₃ and R ₄ ) are represented by the general formula (A). The group represented by R) is better. In other words, in the general formula (1), R ₁ and R ₂ are groups represented by the general formula (R), and L ₁ is preferably a group having two groups represented by the general formula (A). . Furthermore, in the general formula (2), R ₃ and R ₄ are groups represented by the general formula (R), and L ₂ is preferably a group having two groups represented by the general formula (A). . In addition, when the alkylene group has a group represented by the general formula (A), it is preferred that R in the general formula (A) is a hydrocarbon group which may have a heteroatom. Preferable aspects of the hydrocarbon group which may have a heteroatom are as described above, and may form an alkali-decomposable group or an acid-detaching group as represented by R ₅ in the general formula (R).

The alkylene group represented by L ₁ and L ₂ which may have a substituent is preferably represented by the general formula (L) shown below.

*-(CH ₂ ) _n -Z-(CH ₂ ) _n -* (L) * indicates the bonding position.

In the general formula (L), n each independently represents an integer of 0 or more, 0 to 4 are preferred, 0 to 1 is more preferred, and 1 is further preferred. In addition, at least one of the two n's represents an integer of 1 or more.

Z represents a group having heteroatoms. Examples of Z include ether group (-O-), thioether group (-S-), carbonyl group (-C(=O)-), ester group (-C(=O)O-), and amide group group (-NHC(=O)-), sulfonyl group (-S(=O) ₂ -), -C(Y ₁ )(Y ₂ )- and -N(Y ₃ )-. Y ₁ , Y ₂ and Y ₃ each independently represent a hydrogen atom or a substituent. At least one of Y ₁ and Y ₂ represents a substituent having a heteroatom. The substituents represented by Y ₁ , Y ₂ and Y ₃ are each independently a halogen atom (-F, -Cl, -I, etc.), an alkyl group, -S (=O) ₂ -alkyl group or a general formula A group represented by (A) is preferred, and a group represented by -S(=O) ₂ -alkyl or general formula (A) is more preferred. In addition, the alkyl group that Y ₁ , Y ₂ and Y ₃ may have (including the case where Y ₁ , Y ₂ and Y ₃ are alkyl groups themselves) preferably has 1 to 2 carbon atoms, and may also have a substituent (more preferably Preferably it is a halogen atom, more preferably -F). Z is an ether group or -C (Y ₁ ) (Y ₂ ) - of the group where Y ₁ and Y 2 are represented by the general formula (A), preferably, it is -C (Y ₁ ) ( _{Y 2 )} - and Y The group represented by the general formula (A) between ₁ and Y ₂ is more preferred. In addition, when Z is -C(Y ₁ )(Y ₂ )-, and Y ₁ and Y ₂ are groups represented by the general formula (A), there are multiple groups represented by the general formula (A) and they may be the same. It can also be different. In addition, R in the general formula (A) represented by Y ₁ , Y ₂ and Y ₃ is preferably a hydrocarbon group which may have a heteroatom. Preferable aspects of the hydrocarbon group which may have a heteroatom are as described above, and may form an alkali-decomposable group or an acid-detaching group as represented by R ₅ in the general formula (R).

Resin (A) may have one type of repeating unit represented by general formula (1) or (2) alone, or may have two or more types in combination. The content of the repeating unit represented by the general formula (1) or (2) is not particularly limited, but from the viewpoint of more excellent effects of the present invention, 5 to 70 moles based on all the repeating units in the resin (A) % is preferred, 5 to 60 mol% is more preferred, and 10 to 50 mol% is further preferred. In addition, when the resin (A) contains both the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2), the above content is the total amount of these.

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

(Repeating unit having an acid-decomposable group represented by the general formula (3)) The resin (A) preferably further has the following repeating unit having an acid-decomposable group represented by the general formula (3).

[Chemical formula 5]

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

In the general formula (3), L ₃ represents a divalent linking group which may have a substituent. L ₃ is preferably an alkylene group, an aryl group, a carbonyl group, an ester group, or a divalent linking group composed of a combination thereof, such as a carbonyl group, -alkylene-carbonyl-, -arylene-carbonyl- , -ester group-alkylene group-carbonyl group is more preferred, and carbonyl group is even more preferred. In addition, the above-mentioned alkylene group and aryl group may have a substituent, and a halogen atom is preferred as the substituent.

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

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

In addition, the following groups can also be cited as examples of -L ₃ -OX.

[Chemical formula 6]

Resin (A) may have one type of repeating unit represented by general formula (3) alone, or may have two or more types in combination.

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

(Having a repeating unit of a lactone group, a sultone group or a carbonate group) The resin (A) has a group containing at least one selected from the group consisting of a lactone group, a sultone group and a carbonate group. Repeating units are preferred. Among them, unless otherwise specified, the repeating unit having a lactone group described here refers to the repeating unit represented by the above general formula (1) or (2) and is other than the repeating unit having a lactone group (especially It is a repeating unit other than a repeating unit having a group represented by the general formula (R´)).

The above-mentioned lactone group and sultone group are the same as the lactone group and sultone group that can form V described in the general formula (R´), and the preferred ranges are also the same.

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

[Chemical Formula 7]

In the above general formula (III), A represents an ester group (-COO-) or a amide group (-CONH-). n represents an integer from 0 to 5, 0 or 1 is preferred, and 0 is more preferred. R ₀ represents an alkylene group or a cycloalkylene group which may have a substituent, or a combination thereof. When there are multiple R _0's , R _0's may be the same or different. Z represents a single bond, ether group, ester group, amide group, urethane group or urea group. When there are multiple Zs, Zs may be the same or different. As Z, an ether group or an ester group is preferred, and an ester group is more preferred. R ₈ represents a lactone group or a sultone group. R ₇ represents a hydrogen atom, a halogen atom or an organic group (preferably a methyl group).

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

[Chemical formula 8]

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

The resin (A) has the repeating unit described in paragraphs <0370> to <0414> of the specification of U.S. Patent Application Publication No. 2016/0070167A1 as having one selected from the group consisting of a lactone group, a sultone group, and a carbonate group. Repeating units of at least one group are also preferred.

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

Specific examples of the monomer corresponding to the repeating unit represented by the general formula (III) and specific examples of the monomer corresponding to the repeating unit represented by the general formula (A-1) are listed below, but the present invention is not limited to these. Wait for specific examples. The following specific examples correspond to the case where R ₇ in the general formula (III) and R _A ¹ in the general formula (A-1) are methyl groups, but R ₇ and R _A ¹ can optionally be composed of a hydrogen atom or a halogen atom. Or organic substitution.

[Chemical formula 9]

In addition to the above-mentioned monomers, the monomers shown below can also be suitably used as raw materials for the resin (A).

[Chemical formula 10]

The content of repeating units having at least one group selected from the group consisting of lactone group, sultone group and carbonate group is 5 to 70 mol% relative to all repeating units in the resin (A). Preferably, 10-65 mol% is more preferable, and 20-60 mol% is still more preferable. In addition, when there are a plurality of repeating units having at least one group selected from the group consisting of a lactone group, a sultone group, and a carbonate group, the above-mentioned content is the sum of the respective units.

(Repeating unit having a polar group) In addition to the repeating unit represented by the general formula (1) or (2), the resin (A) may have a repeating unit containing a polar group. Examples of the polar group include a hydroxyl group, a cyano group, a carboxyl group, a fluorinated alcohol group, and the like. As the repeating unit having a polar group, a repeating unit having an alicyclic group substituted with a polar group is preferred. Among them, the resin (A) is preferably a repeating unit having a polar group, and preferably a repeating unit having no acid-decomposable group. Among the alicyclic groups substituted with a polar group, an adamantyl group or a norbornyl group is preferred as the alicyclic group.

Specific examples of the monomer corresponding to the repeating unit having a polar group are listed below, but the present invention is not limited to these specific examples.

[Chemical formula 11]

In addition, specific examples of the repeating unit having a polar group include the repeating units disclosed in paragraphs <0415> to <0433> of US Patent Application Publication No. 2016/0070167A1. Resin (A) may have one type of repeating unit containing a polar group alone, or may have two or more types in combination. The content of the repeating unit having a polar group relative to the total repeating units in the resin (A) is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, and further preferably 10 to 25 mol%. .

(Repeating unit that does not have either an acid-decomposable group or a polar group) It is also preferred that the resin (A) has a repeating unit that does not have any of an acid-decomposable group and a polar group. It is preferred that the repeating unit having neither an acid-decomposable group nor a polar group has an alicyclic group. Examples of the repeating unit having neither an acid-decomposable group nor a polar group include the repeating units described in paragraphs <0236> to <0237> of US Patent Application Publication No. 2016/0026083A1. Preferred examples of monomers corresponding to repeating units having neither an acid-decomposable group nor a polar group are shown below.

[Chemical formula 12]

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

In addition to the above-mentioned repeating units, resin (A) can also be used to adjust dry etching resistance, standard developer adaptability, substrate adhesion, resist profile, or generally required characteristics of resists, namely resolution and heat resistance. , or sensitivity, etc. have various repeating units. Examples of such repeating units include, but are not limited to, repeating units corresponding to predetermined monomers.

Examples of the predetermined monomer include those having 1 selected from the group consisting of acrylates, methacrylates, acrylamide, methacrylamide, allyl compounds, vinyl ethers, and vinyl esters. Compounds with addition polymerizable unsaturated bonds, etc. In addition, addition polymerizable unsaturated compounds that can be copolymerized with monomers corresponding to the above-mentioned various repeating structural units can also be used. In the resin (A), the content molar ratio of each repeating structural unit can be appropriately set in order to adjust various properties.

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

In the resin (A), it is preferable that the acrylate repeating unit is 50 mol% or less based on the total repeating units of the resin (A).

When the composition of the present invention is used for KrF exposure, EB exposure or EUV exposure, it is preferred that the resin (A) contains a repeating unit having an aromatic hydrocarbon group. It is more preferable that the resin (A) contains a repeating unit having a phenolic hydroxyl group. Examples of the repeating unit having a phenolic hydroxyl group include a hydroxystyrene repeating unit or a hydroxystyrene (meth)acrylate repeating unit. When the composition of the present invention is used for KrF exposure, EB exposure or EUV exposure, the resin (A) has a structure in which the hydrogen atoms of the phenolic hydroxyl group are decomposed and detached by the action of an acid (acid detachable group). For better. The content of the repeating unit having the aromatic hydrocarbon group contained in the resin (A) is preferably 30 to 100 mol%, more preferably 40 to 100 mol%, and 50 mol% relative to all the repeating units in the resin (A). ~100 mol% is further preferred.

The weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, further preferably 3,000 to 15,000, and particularly preferably 3,000 to 11,000. 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.

Resin (A) may be used individually by 1 type, or may use 2 or more types together. The content of the resin (A) in the total solid content of the composition of the present invention is not particularly limited, but it is preferably 10% by mass or more, more preferably 20% by mass or more, preferably 40 to 99.5% by mass, and 60 to 99% by mass. It is more preferable that it is mass %, and it is further more preferable that it is 80-97 mass %.

<Photoacid generator (C)> The composition of the present invention contains a photoacid generator (hereinafter, also referred to as “photoacid generator (C)”). A photoacid generator is a compound that generates acid by irradiation with actinic rays or radioactive rays. As the photoacid generator, a compound that generates an organic acid upon irradiation with actinic rays or radioactive rays is preferred. Examples include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imine sulfonate compounds, oxime sulfonate compounds, diazodisulfonate compounds, disulfonate compounds, and o-nitrobenzyl sulfonate. salt compound.

As the photoacid generator, known compounds that generate acid upon irradiation with actinic rays or radioactive rays can be appropriately selected and used alone or as a mixture thereof. For example, paragraphs <0125>～<0319> of the specification of US Patent Application Publication No. 2016/0070167A1, paragraphs <0086>～<0094> of the specification of US Patent Application Publication No. 2015/0004544A1, and paragraphs <0094> of the specification of US Patent Application Publication No. 2016 can be preferably used. The known compounds disclosed in paragraphs <0323> to <0402> of Specification No. 0237190A1 serve as the photoacid generator (C).

As the photoacid generator (C), for example, a compound represented by the following general formula (ZI), general formula (ZII) or general formula (ZIII) is preferred.

[Chemical formula 13]

In the above general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group. The carbon number of the organic group of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is usually 1 to 30, and preferably 1 to 20. Moreover, 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, a amide bond or a carbonyl group. Examples of the group formed by two bonds between R ₂₀₁ to R ₂₀₃ include an alkylene group (for example, butylene group, pentylene group) and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ - . Z ^- represents anion.

Preferred embodiments of the cation in the general formula (ZI) include those corresponding to the compounds (ZI-1), compounds (ZI-2), compounds (ZI-3) and compounds (ZI-4) described below. group. In addition, the photoacid generator (C) may be a compound having a plurality of structures represented by the general formula (ZI). For example, it may be a compound having a structure in which at least one of R ₂₀₁ to R ₂₀₃ of the compound represented by the general formula (ZI) and R ₂₀₁ to R of another compound represented by the general formula (ZI) are used. A structure in which at least one of ₂₀₃ is bonded via a single bond or a linking group.

First, compound (ZI-1) will be described. Compound (ZI-1) is an arylsulfonium compound in which at least one of R ₂₀₁ to R ₂₀₃ of the general formula (ZI) is an aryl group, that is, a compound having arylsulfonium as a cation. In the aryl sulfonium compound, all of R ₂₀₁ to R ₂₀₃ may be an aryl group, or part of R ₂₀₁ to R ₂₀₃ may be an aryl group and the remainder may be an alkyl group or a cycloalkyl group. Examples of the aryl sulfonium compounds include triarylsulfonium compounds, diarylalkyl sulfonium compounds, aryldialkyl sulfonium compounds, diarylcycloalkyl sulfonium compounds, and arylbicycloalkyl sulfonium compounds.

As the aryl group contained in the arylsulfonium compound, a phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred. The aryl group may be an aryl group containing a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, a benzothiophene residue, and the like. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl group or cycloalkyl group that the arylsulfonium compound has as necessary is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms. Preferred examples include methyl, ethyl, propyl, n-butyl, secondary butyl, tertiary butyl, cyclopropyl, cyclobutyl and cyclohexyl.

The aryl group, alkyl group and cycloalkyl group of R ₂₀₁ to R ₂₀₃ may each independently have an alkyl group (for example, carbon number 1 to 15), a cycloalkyl group (for example, carbon number 3 to 15), or an aryl group (for example, carbon number 6). ~14), alkoxy group (for example, carbon number 1-15), halogen atom, hydroxyl group or phenylthio group as a substituent.

Next, compound (ZI-2) will be described. Compound (ZI-2) is a compound in which R ₂₀₁ to R ₂₀₃ in the formula (ZI) each independently represent an organic group that does not have an aromatic ring. Here, the aromatic ring also includes aromatic rings having heteroatoms. The organic group that does not have an aromatic ring as R ₂₀₁ to R ₂₀₃ usually has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. R ₂₀₁ to R ₂₀₃ are each independently an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group or an alkyl group. Oxycarbonylmethyl is more preferred, and linear or branched 2-oxoalkyl is still more preferred.

As the alkyl group and cycloalkyl group of R ₂₀₁ to R ₂₀₃ , a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, methyl, ethyl, propyl, butyl, etc.) group and pentyl group, etc.) and cycloalkyl groups with 3 to 10 carbon atoms (for example, cyclopentyl, cyclohexyl and norbornyl) are preferred. R ₂₀₁ to R ₂₀₃ may be further substituted by a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group or a nitro group.

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

[Chemical formula 14]

In the general formula (ZI-3), R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, Cycloalkylcarbonyloxy group, halogen atom, hydroxyl group, nitro group, alkylthio group or arylthio group. R _6c and R _7c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group. R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.

Any two or more of R _1c to R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y may each be bonded to form a ring structure, and the ring structure may contain respectively Independently oxygen atom, sulfur atom, ketone group, ester bond or amide bond. Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, and a polycyclic condensed ring formed by combining two or more of these rings. As for the ring structure, it is usually a ring with 3 to 10 members, preferably a ring with 4 to 8 members, and even more preferably a ring with 5 or 6 members.

Examples of the group formed by bonding two or more of R _1c to R _5c , R _6c and R _7c , and R _x and R _y include butylene group, pentylene group, and the like. The group formed by bonding R _5c and R _6c and R _5c and R _x is preferably a single bond or an alkylene group. Examples of the alkylene group include methylene group, ethylene group, and the like. Zc ^- represents anion.

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

[Chemical formula 15]

In the general formula (ZI-4), l represents an integer from 0 to 2. r represents an integer from 0 to 8. R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group or a group having a cycloalkyl group. These groups may have substituents. R ₁₄ represents a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group or a group having a cycloalkyl group. These groups may have substituents. When there are plural R _14s , they may be the same or different. R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have substituents. Two R _15's may be bonded to each other to form a ring. When two R _15s are bonded to each other to form a ring, heteroatoms such as oxygen atoms or nitrogen atoms may be included in the ring skeleton. In one aspect, it is preferable that two R ₁₅ are alkylene groups and are bonded to each other to form a ring structure. Z ^- represents anion.

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

Next, general formulas (ZII) and (ZIII) will be described. In general formulas (ZII) and (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group. As the aryl group of R ₂₀₄ to R ₂₀₇ , a phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred. The aryl group of R ₂₀₄ to R ₂₀₇ may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, and the like. As the alkyl group and cycloalkyl group of R ₂₀₄ to R ₂₀₇ , a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, methyl, ethyl, propyl, butyl, etc.) group or pentyl) or a cycloalkyl group with 3 to 10 carbon atoms (such as cyclopentyl, cyclohexyl or norbornyl) is preferred.

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

As Z ^- in the general formula (ZI), Z - in the general formula (ZII), Zc ^- in the general formula (ZI-3), and ^{Z - in} the general formula (ZI-4), the following general formula (3) The anion represented is preferred.

[Chemical formula 16]

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

Xf represents a fluorine atom or an alkyl group substituted by at least one fluorine atom. The alkyl group preferably has a carbon number of 1 to 10, more preferably 1 to 4. Furthermore, as the alkyl group substituted by at least one fluorine atom, a perfluoroalkyl group is preferred. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF ₃ . In particular, the Xf-based fluorine atom of both is further preferred.

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

L represents a divalent linking group. When there are multiple L's, L's may be the same or different. Examples of the divalent linking group include -COO-(-C(=O)-O-), -CONH-, -CO-, -O-, -S-, -SO-, and -SO ₂ -. , alkylene group (preferably carbon number 1 to 6), cycloalkylene group (preferably carbon number 3 to 15), alkenylene group (preferably carbon number 2 to 6) and the plural of these A bivalent linking group obtained by combining the two. Among them, -COO-, -CONH-, -CO-, -O-, -SO ₂ -, -COO-alkylene-, -OCO-alkylene-, -CONH-alkylene- or -NHCO- Alkylene- is preferred, and -COO-, -OCO-, -CONH-, -SO ₂ -, -COO-alkylene- or -OCO-alkylene- is more preferred.

W represents an organic group with a cyclic structure. Among these, cyclic organic groups are preferred. Examples of the cyclic organic group include an alicyclic group, an aryl group and a heterocyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl group, and adamantyl group. Among them, alicyclic groups having a fluffy structure with 7 or more carbon atoms, such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl, are preferred.

The aryl group may be monocyclic or polycyclic. Examples of the aryl group include phenyl, naphthyl, phenanthrenyl and anthracenyl. The heterocyclic group may be monocyclic or polycyclic. Polycyclic rings are more capable of inhibiting acid diffusion. In addition, the heterocyclic group may or may not have aromatic properties. Examples of the aromatic heterocyclic ring include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the nonaromatic heterocyclic ring include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. Examples of the lactone ring and the sultone ring include the lactone group and the sultone group exemplified in the aforementioned resin. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring or a decahydroisoquinoline ring is preferred.

The above-mentioned cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, preferably having 1 to 12 carbon atoms), a cycloalkyl group (which may be monocyclic or polycyclic (for example, it may also include any one of spiro ring), preferably with 3 to 20 carbon atoms), aryl group (preferably with 6 to 14 carbon atoms), hydroxyl group, alkoxy group, ester group, amide group, urethane group , urea group, thioether group, sulfonamide group and sulfonate group. In addition, the carbon atoms constituting the cyclic organic group (carbon atoms contributing to ring formation) may be carbon atoms forming the carbonyl group.

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

In one aspect, as Z ^- in the general formula (ZI), Z - in the general formula (ZII), Zc ^- in the general formula (ZI-3), and ^{Z - in} the general formula (ZI-4), Anions represented by the following general formula (4) are also preferred.

[Chemical formula 17]

In the general formula (4), X ^B1 and X ^B2 each independently represent a hydrogen atom or an organic group without a fluorine atom. X ^B1 and X ^B2 are preferably hydrogen atoms. X ^B3 and X ^B4 each independently represent a hydrogen atom or an organic group. It is preferable that at least one of X ^B3 and ^{X B4} is a fluorine atom or an organic group having a fluorine atom, and it is more preferable that both X ^B3 and It is further preferred that both X ^B3 and X ^B4 are alkyl groups substituted by fluorine atoms. L, q and W have the same meaning as in general formula (3).

Z ^- in the general formula (ZI), Z - in the general formula (ZII), Zc ^- in the general formula (ZI-3) ^and Z ^- in the general formula (ZI-4) can be benzenesulfonic acid anion, Benzenesulfonate anions substituted by branched alkyl or cycloalkyl groups are preferred.

As Z ^- in the general formula (ZI), Z - in the general formula (ZII), Zc ^- in the general formula (ZI-3), and ^{Z - in} the general formula (ZI-4), the following general formula An aromatic sulfonic acid anion represented by (SA1) is also preferred.

[Chemical formula 18]

In Formula (SA1), Ar represents an aryl group, and may have a substituent other than a sulfonic acid anion and a (D-B) group. Examples of substituents that may be included include fluorine atoms, hydroxyl groups, and the like.

n represents an integer above 0. As n, 1 to 4 are preferred, 2 to 3 are more preferred, and 3 is even more preferred.

D represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, a carbonyl group, a triylene group, a sulfonate group, a sulfonate ester group, an ester group, and a group consisting of a combination of two or more of these.

B represents a hydrocarbon group.

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

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

[Chemical formula 19]

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

[Chemical formula 20]

The above-mentioned cations and anions can be used in any combination as a photoacid generator.

The photoacid generator may be in the form of a low molecular compound or may be incorporated into a part of the polymer. Furthermore, a form of a low molecular compound and a form of being incorporated into a part of the polymer may be used together. The photoacid generator is preferably in the form of a low molecular compound. When the photoacid generator is in the form of a low molecular compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and further preferably 1,000 or less. When the photoacid generator is incorporated into a part of the polymer, it may be incorporated into a part of the aforementioned resin (A), or may be incorporated into a resin different from the resin (A). One type of photoacid generator may be used alone, or two or more types may be used in combination. In the composition, the content of the photoacid generator (the total amount when there are multiple species) is based on the total solid content of the composition. It is preferably 0.1 to 35 mass %, more preferably 0.5 to 25 mass %, and 3 to 20 The mass % is further more preferable, and 3 to 7 mass % is particularly preferable. When the photoacid generator contains a compound represented by the above general formula (ZI-3) or (ZI-4), the content of the photoacid generator contained in the composition (the total amount when there are multiple types) is Based on the total solid content of the composition, 5 to 35 mass % is preferred, and 7 to 30 mass % is more preferred.

<Resin (B)> When the composition of the present invention contains a cross-linking agent (G) described below, the composition of the present invention contains an alkali-soluble resin (B) having a phenolic hydroxyl group (hereinafter, also referred to as "resin (B)" ) is better. The resin (B) preferably contains a repeating unit having a phenolic hydroxyl group. At this time, typically, a negative pattern can be preferably formed. The cross-linking agent (G) may be supported on the resin (B). Resin (B) may have the aforementioned acid-decomposable group.

As the repeating unit having a phenolic hydroxyl group that the resin (B) has, a repeating unit represented by the following general formula (II) is preferred.

[Chemical formula 21]

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

<Acid diffusion control agent (D)> The composition of the present invention preferably contains an acid diffusion control agent (D). The acid diffusion control agent (D) functions as a quencher that captures acid generated from a photoacid generator or the like during exposure and suppresses the reaction of the acid-decomposable resin in the unexposed portion due to excessive generation of acid. For example, it is possible to use a basic compound (DA), a basic compound (DB) whose alkalinity is reduced or eliminated by irradiation with actinic rays or radiation, an onium salt (DC) that becomes a relatively weak acid relative to the acid generator, and A low-molecular compound (DD) containing a nitrogen atom and having a group that can be separated 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. In the composition of the present invention, known acid diffusion control agents can be suitably used. For example, paragraphs <0627> to <0664> of US Patent Application Publication No. 2016/0070167A1, paragraphs <0095> to <0187> of US Patent Application Publication No. 2015/0004544A1, and US Patent Application Publication No. 2016 can be preferably used. Known compounds disclosed in paragraphs <0403> to <0423> of the specification No. 0237190A1 and paragraphs <0259> to <0328> of the specification of US Patent Application Publication No. 2016/0274458A1 serve as the acid diffusion control agent (D).

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

[Chemical formula 22]

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

The alkyl groups in the general formulas (A) and (E) may have a substituent or may be unsubstituted. Regarding the above-mentioned 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 preferred. It is more preferred that the alkyl groups in general formulas (A) and (E) are unsubstituted.

As a basic compound (DA), guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazoline, aminomorpholine, aminoalkylmorpholine or piperidine are preferred, and those having imidazole structure, dinitrogen Compounds with heterobicyclic structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure or pyridine structure, alkylamine derivatives with hydroxyl and/or ether bonds, or compounds with hydroxyl and/or ether bonds Bonded aniline derivatives, etc. are more preferred.

A basic compound (DB) whose alkalinity is reduced or eliminated by irradiation with actinic rays or radioactive rays (hereinafter also referred to as "compound (DB)") has a proton-accepting functional group and is Compounds that are decomposed by irradiation with rays or radioactive rays and have reduced or disappeared proton-accepting properties or changed from proton-accepting properties to acidic properties.

Proton acceptor functional groups refer to groups that can electrostatically interact with protons or functional groups with electrons. For example, they refer to functional groups with macrocyclic structures such as cyclic polyethers or functional groups that do not contribute to π conjugation. A functional group that shares an electron pair with the nitrogen atom. A nitrogen atom having an unshared electron pair that does not contribute to π conjugation means, for example, a nitrogen atom having a partial structure represented by the following formula.

[Chemical formula 23]

Preferred partial structures of the proton-accepting functional group include, for example, crown ether structures, azacrown ether structures, primary to tertiary amine structures, pyridine structures, imidazole structures, and pyridine structures.

Compound (DB) is a compound that is decomposed by irradiation with actinic rays or radioactive rays, thereby reducing or disappearing its proton acceptor properties or changing its proton acceptor properties to acidic properties. Among them, the reduction or disappearance of proton acceptor properties or the change from proton acceptor properties to acidic refers to the change in proton acceptor properties caused by the addition of protons to the proton acceptor functional group. Specifically, it refers to the change in proton acceptor properties caused by the addition of protons to the proton acceptor functional group. When a compound (DB) with a proton-accepting functional group forms a proton adduct with a proton, the equilibrium constant in its chemical equilibrium decreases. Proton acceptor properties can be confirmed by performing pH measurements.

The acid dissociation constant pKa of the compound produced by the decomposition of compound (DB) by irradiation of actinic rays or radioactive rays is preferably pKa＜-1, preferably -13＜pKa＜-1, and -13＜pKa <-3 is further preferred.

The acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, and is defined, for example, by Chemistry Handbook (II) (revised 4th edition, 1993, edited by the Chemical Society of Japan, Maruzen Company, Limited). The lower the value of the acid dissociation constant pKa, the greater the acid strength. Specifically, the acid dissociation constant pKa in the aqueous solution was actually measured by measuring the acid dissociation constant at 25°C by infinitely diluting the aqueous solution. Alternatively, the following software package 1 can also be used to calculate the Hammett substituent constant and the value of the database of known literature values. All pKa values described in this manual represent values obtained through calculation using this software package.

Software Suite 1: Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).

In the composition of the present invention, an onium salt (DC), which is a relatively weak acid relative to the photoacid generator, can be used as the acid diffusion control agent. When a photoacid generator is mixed with an onium salt that generates an acid that is relatively weak relative to the acid generated by the photoacid generator, if the acid generated by the photoacid generator is irradiated with actinic rays or radioactive rays, Collision with an onium salt having unreacted weak acid anions will release the weak acid through salt exchange and generate an onium salt having strong acid anions. In this process, the strong acid is exchanged into a weak acid with lower catalytic energy, so the acid is deactivated in appearance and the acid diffusion can be controlled.

As an onium salt that is a relatively weak acid relative to the photoacid generator, compounds represented by the following general formulas (d1-1) to (d1-3) are preferred.

[Chemical formula 24]

In the formula, R ⁵¹ is a hydrocarbon group that may have a substituent, Z ^2c is a hydrocarbon group with 1 to 30 carbon atoms that may have a substituent (where the fluorine atom on the carbon adjacent to S is unsubstituted), and R ⁵² It is an organic group, Y ³ is a linear, branched or cyclic alkylene group or aryl group, Rf is a hydrocarbon group with a fluorine atom, and M ⁺ is independently an ammonium cation, a sulfonium cation or a iodine cation.

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

The onium salt (DC), which is a relatively weak acid compared to the photoacid generator, may also be a compound having a cationic site and an anionic site in the same molecule, and the cationic site and the anionic site are connected by a covalent bond (hereinafter, also referred to as " Compound (DCA)".). The compound (DCA) is preferably a compound represented by any one of the following general formulas (C-1) to (C-3).

[Chemical formula 25]

In the general formulas (C-1) to (C-3), R ₁ , R ₂ and R ₃ each independently represent a substituent having 1 or more carbon atoms. L ₁ represents a divalent linking group or a single bond that connects the cationic site and the anionic site. -X ^- represents an anionic site selected from -COO ^- , -SO ₃ ^- , -SO ₂ ^- and N ^- -R ₄ . R ₄ represents a carbonyl group (-C(=O)-), a sulfonyl group (-S(=O) ₂ -) and a sulfinyl group (-S(=O)) at the linking site with the adjacent N atom. -) at least one substituent. R ₁ , R ₂ , R ₃ , R ₄ and L ₁ may be bonded to each other to form a ring structure. Moreover, in the general formula (C-3), two of R ₁ to R ₃ together represent one divalent substituent, and can be bonded to an N atom through a double bond.

Examples of the substituent having 1 or more carbon atoms in R ₁ to R ₃ include an alkyl group, a cycloalkyl group, an aryl group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkyl group. Alkylaminocarbonyl and arylaminecarbonyl, etc. Preferred are alkyl, cycloalkyl or aryl.

Examples of the divalent linking group L ₁ include a linear or branched alkylene group, a cycloalkyl group, an aryl group, a carbonyl group, an ether bond, an ester bond, an amide bond, and a urethane group. bond, urea bond and a group obtained by combining two or more of these, and an alkylene group, an aryl group, an ether bond, an ester bond or a group obtained by combining two or more of these are preferred.

A low molecular compound (DD) having a nitrogen atom and a group that can be separated by the action of an acid (hereinafter also referred to as "compound (DD)"). The nitrogen atom has a group that can be separated by the action of an acid. Amine derivatives of the group are preferred. As the group that is released by the action of acid, an acetal group, a carbonate group, a urethane group, a tertiary ester group, a tertiary hydroxyl group or a semiamine acetal ether group is preferred, and a urethane group is preferred. Or semiamine acetal ether group is more preferred. The molecular weight of the compound (DD) is preferably 100 to 1,000, more preferably 100 to 700, and further preferably 100 to 500. Compound (DD) may have a urethane group having a protective group on a nitrogen atom. The protective group constituting the urethane group is represented by the following general formula (d-1).

[Chemical formula 26]

In the general formula (d-1), R _b each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), or an aryl group (preferably It is a C3-30 group, an aralkyl group (preferably C1-10), or an alkoxyalkyl group (preferably C1-10). R _b may be bonded to each other to form a ring. The alkyl group, cycloalkyl group, aryl group and aralkyl group represented by R _b can be independently replaced by functional groups such as hydroxyl, cyano group, amino group, pyrrolidinyl, piperidinyl, morpholinyl, oxo group, etc. Alkoxy or halogen atom substitution. The same applies to the alkoxyalkyl group represented by R _b .

As R _b , a linear or branched alkyl group, a cycloalkyl group or an aryl group is preferred, and a linear or branched alkyl group or a cycloalkyl group is more preferred. Examples of the ring formed by two R _b's bonded to each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group and their derivatives. As a specific structure of the group represented by general formula (d-1), the structure disclosed in paragraph <0466> of US Patent Publication No. US2012/0135348A1 can be cited, but is not limited thereto.

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

[Chemical formula 27]

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

Specific examples of the alkyl group, cycloalkyl group, aryl group and aralkyl group (these groups may be substituted by the above-mentioned groups) of R a include the same groups _as the specific examples described above for R _b . Specific examples of particularly preferred compounds (DD) in the present invention include the compounds disclosed in paragraph <0475> of US Patent Application Publication No. 2012/0135348A1, but are not limited thereto.

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

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

[Chemical formula 28]

[Chemical formula 29]

In the composition of the present invention, one type of acid diffusion control agent (D) may be used alone, or two or more types may be used in combination. The content of the acid diffusion control agent (D) in the composition (the total amount when there are plural species) is preferably 0.1 to 10 mass % based on the total solid content of the composition, and more preferably 0.1 to 5 mass %.

<Hydrophobic resin (E)> The composition of the present invention may contain a hydrophobic resin (E). In addition, the hydrophobic resin (E) is preferably a resin different from the resin (A) and the resin (B). The composition of the present invention contains a hydrophobic resin (E), whereby the static and/or dynamic contact angle on the surface of the resist film can be controlled. This can improve development characteristics, suppress outgassing, improve immersion liquid followability during liquid immersion exposure, and reduce liquid immersion defects. It is preferable that the hydrophobic resin (E) is designed to exist locally on the surface of the resist film. However, unlike the surfactant, it does not necessarily have a hydrophilic group in the molecule, and it may not contribute to uniform mixing of polar substances and non-resistants. Polar substances.

From the viewpoint of being localized on the surface of the film, the hydrophobic resin (E) contains a group selected from the group consisting of "fluorine atoms", "silicon atoms" and "CH ₃ partial structure contained in the side chain part of the resin" Resins containing at least one repeating unit are preferred. When the hydrophobic resin (E) contains fluorine atoms and/or silicon atoms, the fluorine atoms and/or silicon atoms in the hydrophobic resin (E) may be included in the main chain of the resin or may be included in the side chain.

When the hydrophobic resin (E) has a fluorine atom, the partial structure having the fluorine atom is preferably 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 (E) preferably has at least one group selected from the group consisting of the following (x) to (z). (x) Acid group (y) Alkali-decomposable group (z) Group decomposed by the action of 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 sulfonyl imide group, (alkyl sulfonyl group) (alkyl carbonyl group) ) methylene, (alkylcarbonyl)(alkylcarbonyl)imide, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imide, bis(alkylcarbonyl) ) methylene, bis(alkylsulfonyl)imide, tris(alkylcarbonyl)methylene and tris(alkylsulfonyl)methylene, etc. As the acid group, a fluorinated alcohol group (preferably hexafluoroisopropyl alcohol), a sulfonyl imide group or a bis(alkylcarbonyl)methylene group is preferred.

Examples of the alkali-decomposable group (y) that the hydrophobic resin may have include a lactone group, a carboxylate group (-COO-), an acid anhydride group (-C(O)OC(O)-), and an acid ester group. Amine group (-NHCONH-), carboxylic thioester group (-COS-), carbonate group (-OC(O)O-), sulfate group (-OSO ₂ O-) and sulfonate group (-SO ₂ O-), etc., lactone group or carboxylate group (-COO-) is preferred. 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. Examples thereof include repeating units composed of acrylate and methacrylate. In the repeating unit, these groups can also be bonded to the main chain of the resin via a linking group. Alternatively, the repeating unit may be introduced to the end of the resin using a polymerization initiator or a chain transfer agent having such groups during polymerization. Examples of the repeating unit having a lactone group include the same repeating unit as the repeating unit having a lactone structure described above in the resin (A) section.

The content of the repeating unit having an alkali-decomposable group (y) is preferably 1 to 100 mol%, more preferably 3 to 98 mol%, and 5 to 95 mol% relative to all the repeating units in the hydrophobic resin (E). Mol% is further preferred.

Examples of the repeating unit having a group (z) decomposable by the action of an acid in the hydrophobic resin (E) include the same repeating units as the repeating units having an acid-decomposable group exemplified in the resin (A). 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 acid is preferably 1 to 80 mol%, and 10 to 80 mol% relative to all the repeating units in the hydrophobic resin (E). It is more preferable, and 20-60 mol% is still more preferable. The hydrophobic resin (E) may further have another repeating unit different from the above-mentioned repeating unit.

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

On the other hand, especially when the hydrophobic resin (E) has a CH ₃ partial structure in the side chain portion, a form in which the hydrophobic resin (E) does not substantially contain fluorine atoms and silicon atoms is also preferred. Moreover, it is preferable that the hydrophobic resin (E) consists essentially of only repeating units consisting only of atoms selected from the group consisting of carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms, and sulfur atoms.

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

The total content of residual monomer and/or oligomer components contained in the hydrophobic resin (E) is preferably 0.01 to 5 mass %, more preferably 0.01 to 3 mass %. In addition, the dispersion degree (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 (E), known resins can be appropriately selected and used alone or as a mixture thereof. For example, the known knowledge disclosed in paragraphs <0451> to <0704> of US Patent Application Publication No. 2015/0168830A1 and paragraphs <0340> to <0356> of US Patent Application Publication No. 2016/0274458A1 can be preferably used. The resin is used as hydrophobic resin (E). In addition, the repeating units disclosed in paragraphs <0177> to <0258> of US Patent Application Publication No. 2016/0237190A1 are also preferred as repeating units constituting the hydrophobic resin (E).

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

[Chemical formula 30]

[Chemical Formula 31]

One type of hydrophobic resin (E) may be used alone, or two or more types may be used in combination. From the viewpoint of balancing the immersion liquid followability and development characteristics in liquid immersion exposure, it is preferable to use a mixture of two or more hydrophobic resins (E) with different surface energies. The content of the hydrophobic resin (E) in the composition is preferably 0.01 to 10% by mass, and more preferably 0.05 to 8% by mass relative to the total solid content in the composition of the present invention.

<Solvent (F)> The composition of the present invention may contain a solvent. In the composition of the present invention, a known resist solvent can be appropriately used. For example, paragraphs <0665> to <0670> of US Patent Application Publication No. 2016/0070167A1, paragraphs <0210> to <0235> of US Patent Application Publication No. 2015/0004544A1, and US Patent Application Publication No. 2016 can be preferably used. Well-known solvents disclosed in paragraphs <0424> to <0426> of the specification No. 0237190A1 and paragraphs <0357> to <0366> of the specification of US Patent Application Publication No. 2016/0274458A1. Examples of solvents that can be used when preparing the composition include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, and alkyl alkoxy propionate. , cyclic lactone (preferably carbon number 4 to 10), monoketone compound which may have a ring (preferably carbon number 4 to 10), alkyl carbonate, alkyl alkoxyacetate and alkyl pyruvate organic solvents such as esters.

As the organic solvent, a mixed solvent obtained by mixing a solvent having a hydroxyl group in the structure and a solvent not having a hydroxyl group can be used. As the solvent having a hydroxyl group and the solvent not having a hydroxyl group, the above-mentioned exemplified compounds can be appropriately selected. As a solvent having a hydroxyl group, alkylene glycol monoalkyl ether or alkyl lactate are preferred, and propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether (PGEE), 2-hydroxyisobutyric acid methyl ester or Ethyl lactate is more preferred. Furthermore, examples of solvents that do not have a hydroxyl group include alkylene glycol monoalkyl ether acetate, alkyl alkoxy propionate, a monoketone compound that may have a ring, a cyclic lactone, or an alkyl acetate, etc. Preferably, propylene glycol monomethyl ether acetate (PGMEA), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate are more preferred, propylene glycol Monomethyl ether acetate, γ-butyrolactone, ethoxyethyl propionate, cyclohexanone, cyclopentanone or 2-heptanone are further preferred. As a solvent that does not have a hydroxyl group, propylene carbonate is also preferred. The mixing ratio (mass ratio) of the solvent having a hydroxyl group and the solvent not having a hydroxyl group (mass ratio) is usually 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 60/40. A mixed solvent containing 50% by mass or more of a solvent that does not have a hydroxyl group is preferable in terms of coating uniformity. The solvent preferably contains propylene glycol monomethyl ether acetate, and it can be a single solvent of propylene glycol monomethyl ether acetate, or a mixed solvent of two or more types containing propylene glycol monomethyl ether acetate.

<Crosslinking agent (G)> The composition of the present invention may contain a compound that crosslinks the resin by the action of an acid (hereinafter, also referred to as a crosslinking agent (G)). As the cross-linking agent (G), known compounds can be used appropriately. For example, the known knowledge disclosed in paragraphs <0379> to <0431> of US Patent Application Publication No. 2016/0147154A1 and paragraphs <0064> to <0141> of US Patent Application Publication No. 2016/0282720A1 can be preferably used. The compound acts as a cross-linking agent (G). The cross-linking agent (G) is a compound having a cross-linking group capable of cross-linking a resin. Examples of the cross-linking group include hydroxymethyl, alkoxymethyl, acyloxymethyl, and alkoxy methyl ether. group, ethylene oxide ring group and oxetane ring group, etc. The crosslinking group is preferably a hydroxymethyl group, an alkoxymethyl group, an oxirane ring group or an oxetane ring group. The cross-linking agent (G) is preferably a compound (including resin) having two or more cross-linking groups. It is more preferable that the cross-linking agent (G) has a hydroxymethyl group or an alkoxymethyl group, a phenol derivative, a urea compound (a compound having a urea structure) or a melamine compound (a compound having a melamine structure). One type of cross-linking agent may be used alone, or two or more types of cross-linking agents may be used in combination. The content of the cross-linking agent (G) is preferably 1 to 50 mass %, more preferably 3 to 40 mass %, and further preferably 5 to 30 mass % with respect to the total solid content of the resist composition.

<Surfactant (H)> The composition of the present invention may contain a surfactant. When it contains a surfactant, a fluorine-based and/or silicone-based surfactant (specifically, a fluorine-based surfactant, a silicone-based surfactant Surfactants or surfactants containing both fluorine atoms and silicon atoms) are preferred.

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

One type of these surfactants may be used alone, or two or more types may be used in combination. When the composition of the present invention contains a surfactant, the content of the surfactant relative to the total solid content of the composition is preferably 0.0001 to 2 mass %, and more preferably 0.0005 to 1 mass %. On the other hand, by setting the content of the surfactant to 10 ppm or more relative to the total solid content of the composition, the surface localization of the hydrophobic resin (E) is improved. Thereby, the surface of the resist film can be made more hydrophobic, and the water followability during liquid immersion exposure can be improved.

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

<Preparation method> The total solid content concentration of the composition of the present invention is preferably 1.0 to 10% by mass, more preferably 2.0 to 5.7% by mass, and further preferably 2.0 to 5.3% by mass. Solid component concentration refers to the mass percentage of the mass of other components except the solvent relative to the total mass of the composition.

In addition, from the viewpoint of improving resolution, the film thickness of the resist film composed of the composition of the present invention is preferably 20 nm or less, and more preferably 15 nm or less. The lower limit of the film thickness of the resist film is preferably 20 nm or more, and more preferably 40 nm or more. This film thickness can be achieved by setting the solid content concentration in the composition to an appropriate range and having a moderate viscosity to adjust the coating properties or film-forming properties.

Regarding the composition of the present invention, the above-mentioned components are dissolved in a predetermined organic solvent, preferably the above-mentioned mixed solvent, filtered with a filter, and then applied to a predetermined support (substrate) before 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, and further preferably 0.03 μm or less. As this filter, a filter made of polytetrafluoroethylene, polyethylene or nylon is preferred. In filter filtration, for example, as disclosed in Japanese Patent Application Laid-Open No. 2002-062667, cyclic filtration may be performed, or a plurality of filters may be connected in series or in parallel to perform filtration. Alternatively, the composition may be filtered multiple times. In addition, the composition can also be degassed before and after filtration with the filter.

<Application> The composition of the present invention relates to a photosensitive radiation-sensitive or radiation-sensitive resin composition that reacts with irradiation of actinic rays or radiation to change its properties. More specifically, the composition of the present invention relates to a method used in the manufacturing steps of semiconductors such as ICs, the manufacturing of circuit boards such as liquid crystals and thermal heads (thermal heads), the manufacturing of mold structures for imprinting, and other photosensitive etching processing steps. or lithographic printing plates. Patterns using the composition of the present invention can be used in etching steps, ion implantation steps, bump electrode formation steps, rewiring formation steps, MEMS (Micro Electro Mechanical Systems: Micro Electro Mechanical Systems), and the like.

[Pattern Forming Method] The present invention also relates to a pattern forming method using the above-mentioned photosensitive radiation or radiation sensitive resin composition. Hereinafter, the pattern forming method of the present invention will be described. In addition, together with the description of the pattern forming method, the resist film (photosensitive radiation or radiation sensitive film) of the present invention will also be described.

The pattern forming method of the present invention has the following steps: (i) A step of forming a resist film on a support using the above-mentioned photosensitive radiation or radiation-sensitive resin composition (film forming step (resist film forming step) ); (ii) the step of exposing the above-mentioned resist film (irradiating actinic rays or radiation) (exposure step), and (iii) the step of developing the above-mentioned exposed resist film using a developer ( development step).

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 also include the following steps. In the pattern forming method of the present invention, the exposure method in (ii) the exposure step may be immersion exposure. In the pattern forming method of the present invention, it is preferable to include (iv) a pre-bake (PB: PreBake) step before (ii) the exposure step. In the pattern forming method of the present invention, it is preferable to include (v) a post-exposure bake (PEB: Post Exposure Bake) step after the (ii) exposure step and before the (iii) development step. The pattern forming method of the present invention may include a plurality of (ii) exposure steps. The pattern forming method of the present invention may include a plurality of (iv) pre-baking steps. The pattern forming method of the present invention may include a plurality of (v) post-exposure baking steps.

In the pattern forming method of the present invention, the above (i) film formation step, (ii) exposure step and (iii) development step can be performed by generally known methods. Furthermore, if necessary, a resist underlayer film (for example, SOG (Spin On Glass: spin-on glass), SOC (Spin On Carbon: spin-on carbon) and an anti-reflection film) can be formed between the resist film and the support. ). As a material constituting the resist underlayer film, known organic or inorganic materials can be appropriately used. A protective film (top coat layer) can be formed on the upper layer of the resist film. As the protective film, known materials can be used appropriately. For example, U.S. Patent Application Publication No. 2007/0178407, U.S. Patent Application Publication No. 2008/0085466, U.S. Patent Application Publication No. 2007/0275326, U.S. Patent Application Publication No. 2016/0299432, The composition for forming a protective film is disclosed in the specification of U.S. Patent Application Publication No. 2013/0244438 and the specification of International Patent Application Publication No. 2016/157988A. As the composition for forming a protective film, a composition for forming a protective film containing the above acid diffusion control agent is preferred. A protective film may be formed on the resist film containing the above-mentioned hydrophobic resin.

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

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

There is no limit to the wavelength of the light source used in the exposure step. Examples include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-rays and electron beams. The mid-to-far ultraviolet light is preferred, and its wavelength is preferably below 250 nm, more preferably below 220 nm, and further preferably between 1 and 200 nm. Specifically, KrF excimer laser (248nm), ArF excimer laser (193nm), F ₂ excimer laser (157nm), X-ray, EUV (13nm) or electron beam are preferred, and KrF accurate Molecular laser, ArF excimer laser, EUV or electron beam are better.

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

As an alkaline developer, quaternary ammonium salts represented by tetramethylammonium hydroxide are usually used. In addition, alkali aqueous solutions such as inorganic bases, primary to tertiary amines, alcoholamines, and cyclic amines can also be used. Furthermore, the above-mentioned alkaline developer may contain an appropriate amount of alcohols and/or surfactants. The alkali concentration of the alkaline developer is usually 0.1 to 20% by mass. The pH of an alkaline developer is usually 10 to 15. The development time using 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 preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents and hydrocarbon solvents.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methylamyl ketone), 4-heptanone, and 1-hexanone. Ketone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetoacetone, acetoneacetone, ionone , diacetone alcohol, acetyl methanol, acetophenone, methyl naphthyl ketone, isophorone and propylene carbonate, etc.

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isoamyl acetate, amyl acetate, and propylene glycol monomethyl ether. Acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxy Butyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate , butyl butyrate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate and butyl propionate, etc.

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

A plurality of types of the above-mentioned solvents may be mixed, and they may be mixed with solvents other than those mentioned above or water. The overall moisture content of the developer is preferably less than 50% by mass, more preferably less than 20% by mass, still more preferably less than 10% by mass, and it is particularly preferred that it contains substantially no 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, and further preferably 90 to 100% by mass, and 95 to 100% by mass relative to the total amount of the developer. % is particularly good.

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

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

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

Examples of developing methods include: a method in which the substrate is immersed in a tank filled with a developer for a certain period of time (immersion method); a method in which the developer is accumulated on the surface of the substrate by surface tension and allowed to stand for a certain period of time (immersion method). method); a method of spraying the developer onto the surface of the substrate (spray method); or a method of continuously spraying the developer while spraying the developer out of the nozzle at a certain speed for scanning on a substrate rotating at a certain speed (dynamic distribution method) )wait.

It is also possible to combine the step of developing using an alkali aqueous solution (alkaline development step) and the step of developing using a developer containing an organic solvent (organic solvent development step). Thereby, a pattern can be formed without melting only the area|region of intermediate exposure intensity, Therefore, a finer pattern can be formed.

(iii) After the development step, it is preferable to include a step of cleaning with a rinse solution (rinsing step).

For example, pure water can be used as the rinse liquid used in the rinse step after the development step using an alkaline developer. Pure water can contain appropriate amounts of surfactants. Furthermore, after the development step or the rinsing step, a process of removing the developer or rinsing liquid adhering to the pattern using a supercritical fluid may be added. In addition, heat treatment may be performed in order to remove moisture remaining in the pattern after the rinse treatment or the treatment using supercritical fluid.

The rinse liquid used in the rinse step after the development step using a developer containing an organic solvent is not particularly limited as long as it does not dissolve the pattern, and a solution containing a common organic solvent can be used. As the rinse liquid, it is preferable to use a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. Specific examples of hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents include the same examples as described for the developer containing an organic solvent. As a rinse liquid used in the rinse step at this time, a rinse liquid containing a monovalent alcohol is more preferred.

Examples of the monovalent alcohol used in the rinsing step include linear, branched, or cyclic monovalent alcohols. Specific examples include 1-butanol, 2-butanol, 3-methyl-1-butanol, tertiary butanol, 1-pentanol, 2-pentanol, 1-hexanol, and 4-methyl -2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and methyl isobutyl carbinol. Examples of monovalent alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and methylisobutanol. Butylmethanol, etc.

A plurality of types of each component may be mixed, and an organic solvent other than those mentioned above may be mixed and used. When a solution containing an organic solvent is used as the rinse liquid, the water content in the rinse liquid is preferably 10 mass% or less, more preferably 5 mass% or less, and further preferably 3 mass% or less. By setting the moisture content to 10% by mass or less, good development characteristics can be obtained.

When a solution containing an organic solvent is used as the rinse liquid, the rinse liquid may contain an appropriate amount of surfactant. In the rinsing step at this time, the substrate developed using the organic developer is cleaned using a rinsing solution containing an organic solvent. The method of cleaning treatment is not particularly limited. Examples include the following methods: a method of continuously spraying a rinse liquid on a substrate rotating at a certain speed (spin coating method); and immersing the substrate in a tank filled with rinse liquid for a certain period of time. method (immersion method); or method of spraying rinsing liquid onto the surface of the substrate (spray method), etc. Among them, it is preferable to perform the cleaning process by a spin coating method, and after cleaning, the substrate is rotated at a rotation speed of 2,000 to 4,000 rpm to remove the rinse liquid from the substrate. Furthermore, it is also preferable to include a heating step (Post Bake) after the rinsing step. This heating step removes the developer and rinse fluid remaining between and inside the patterns. In the heating step after the rinsing step, the heating temperature is usually 40 to 160°C, preferably 70 to 95°C, and the heating time is usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

The composition of the present invention and various materials used in the pattern forming method of the present invention (for example, a developer, a rinse liquid, an antireflection film forming composition or a top coat forming composition, etc.) do not contain metal components, foreign matter, etc. Impurities such as structures and residual monomers are preferred. The content of these impurities contained in the various materials mentioned above is preferably 1 ppm or less, more preferably 100 ppt or less, further preferably 10 ppt or less, and is particularly preferably substantially free (below the detection limit of the measuring device).

As a method of removing impurities such as metals from various materials, for example, filtration using a filter can be used. As the filter pore size, the pore size is preferably 10 nm or less, more preferably 5 nm or less, and further preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon is preferred. The filter can also be used after being cleaned with an organic solvent in advance. In the filter filtration step, multiple types of filters can be used by connecting them in series or in parallel. When using multiple types of filters, filters with different pore sizes and/or materials can also be used in combination. In addition, various materials can be filtered multiple times, and the step of filtering multiple times can also be a cyclic filtration step. As a filter, a filter that reduces eluted matter disclosed in Japanese Patent Application Publication No. 2016-201426 is preferred. In addition to filter filtration, adsorbent materials can also be used to remove impurities, and filter filtration and adsorbent materials can also be used in combination. As the adsorbent material, a known adsorbent material can be used. For example, an inorganic adsorbent material such as silica gel or zeolite or an organic adsorbent material such as activated carbon can be used. Examples of the metal adsorbent include the metal adsorbent disclosed in Japanese Patent Application Laid-Open No. 2016-206500. In addition, as a method of reducing impurities such as metals contained in the various materials mentioned above, the following methods can be cited: selecting raw materials with low metal content as the raw materials constituting the various materials, filtering the raw materials constituting the various materials, or filtering the raw materials constituting the various materials in the device. Methods such as distillation are carried out under conditions such as lining with TEFLON (registered trademark) to suppress contamination as much as possible. Preferable conditions for filter filtration of raw materials constituting various materials are the same as the above-mentioned conditions.

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

A method of improving the surface roughness of the pattern can be applied to the pattern formed by the pattern forming method of the present invention. As a method of improving the surface roughness of the pattern, for example, the method of treating the pattern with plasma containing hydrogen gas is disclosed in US Patent Application Publication No. 2015/0104957. In addition, it is also applicable to Japanese Patent Application Laid-Open No. 2004-235468, U.S. Patent Application Publication No. 2010/0020297, or Proc. Of SPIE Vol.8328 83280N-1 "EUV Resist Curing Technique for LWR Reduction and Etch Selectivity" Enhancement" is a well-known method described in "Enhancement". In addition, the pattern formed by the above method can be used as the core material (Core) of the spacer process disclosed in Japanese Patent Application Laid-Open No. 3-270227 and US Patent Application Publication No. 2013/0209941, for example. .

[Manufacturing method of electronic components] Furthermore, the present invention also relates to a manufacturing method of electronic components including the above-mentioned pattern forming method. Electronic components manufactured by the electronic component manufacturing method of the present invention are appropriately mounted on electrical and electronic equipment (for example, home appliances, OA (Office Automation)-related equipment, media-related equipment, optical equipment, communication equipment, etc.) ). [Example]

Hereinafter, the present invention will be described in further detail based on examples. The materials, usage amounts, ratios, processing contents, processing steps, 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 limitedly interpreted by the examples shown below. [Photosensitive radiation or radiation-sensitive resin composition]

The following describes the components used in the production of photosensitive radiation-sensitive or radiation-sensitive resin compositions tested in Examples and Comparative Examples.

<Resin (A)> (Synthesis example of resin (A-2)) Resin (A-2) was synthesized according to the scheme shown below.

[Chemical formula 32]

An aqueous solution composed of sodium hydroxide (14.1 g) and water (127 g) was cooled to 0° C., and compound A (manufactured by NIPPON SHOKUBAI CO., LTD.) (50 g) was added while stirring. After the aqueous solution was heated to room temperature (23°C), it was further stirred for 4 hours. Then, the aqueous solution was cooled to 0°C, and 1N HCl aqueous solution (500 mL) was added dropwise. The obtained aqueous solution was extracted twice with dichloromethane (300 mL), and the extracted organic phase was dried over sodium sulfate. The dried organic phase was filtered and further concentrated to obtain a crude product containing Compound B as the main component.

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

The results of monomer A obtained by ¹ H-NMR (Nuclear Magnetic Resonance) measurement are as follows. ¹ H-NMR, 400MHz, δ ((CDCl ₃ ) ppm: 2.30-2.40 (1H, m), 2.71-2.73 (1H, m), 4.01-4.10 (2H, m), 4.22 (2H, s), 4.33 (1H, q), 4.50 (1H, t), 5.21 (1H, d), 5.31 (1H, d), 5.50 (1H, t), 5.85-6.00 (1H, m), 6.02 (1H, s), 6.42 (1H, s).

Cyclohexanone (4.95 parts by mass) was heated to 85°C under nitrogen flow. Mix monomer A (2.26 parts by mass), monomer B (1.96 parts by mass) shown in the above scheme, cyclohexanone (9.19 parts by mass) and polymerization initiator AIBN (azobisisobutyronitrile) (0.046 parts by mass). ) was added dropwise to the liquid over 4 hours while stirring. After completion of the dropwise addition, the mixture was further stirred at 85° C. for 2 hours. After the reaction solution was allowed to cool, a large amount of methanol/water (mass ratio 9:1) was used for reprecipitation treatment. The precipitated solid was filtered out and further vacuum-dried, thereby obtaining resin (A-2) (2.62 parts by mass).

Other resins (A-1), (A-3) to (A-13) and (A-15) to (A-20) shown below were synthesized in the same manner. Furthermore, resin (A-14) was synthesized according to a common method. In addition, in the following tests, resins (A-1) to (A-13) and (A-18) to (A-20) were used in the examples, and resin (A-14) was used in the comparative examples. ~(A-17).

The repeating units of the resin (A) used in Examples and Comparative Examples are shown below. In addition, the numerical value written next to each repeating unit indicates the content (mol%) of each repeating unit in each resin.

[Chemical formula 33]

[Chemical formula 34]

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

[Table 1]

<Photo-acid generator> The structure of the photo-acid generator (C) used in Examples and Comparative Examples is shown below.

[Chemical formula 35]

<Acid diffusion control agent> The structure of the acid diffusion control agent (D) used in Examples and Comparative Examples is shown below.

[Chemical formula 36]

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

[Chemical formula 37]

In addition, the weight average molecular weight (Mw) of the hydrophobic resin (1b) is 7000, the dispersion degree (Mw/Mn) is 1.30, and the molar ratio of each repeating unit is 50/45/5 from the left. The weight average molecular weight (Mw) of the hydrophobic resin (2b) is 18,600, the dispersion (Mw/Mn) is 1.57, and the molar ratio of each repeating unit is 40/40/20 from the left.

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

<Surfactant> The surfactant (H) used in Examples and Comparative Examples is shown below. W-1: Poly Fox PF-6320 (manufactured by OMNOVA Solutions Inc.; fluorine-based surfactant)

[Preparation of photosensitive radiation or radiation-sensitive resin composition] A mixed liquid was prepared so that the solid content concentration of each component shown in Table 2 below would be 3.8 mass %. At this time, the solid components were blended so as to have the mass ratio shown in Table 2. In addition, the solid content mentioned here refers to all components except the solvent (F). The prepared mixed solution was filtered through a polyethylene filter with a pore size of 0.1 μm. The obtained liquid was evaluated as a photosensitive radiation-sensitive or radiation-sensitive resin composition in Examples and Comparative Examples.

[Evaluation] <Pattern formation> The organic antireflection film forming composition ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied to a silicon wafer and heated at 205°C for 60 seconds to form a film with a thickness of 95nm anti-reflective film. The photosensitive radiation or radiation-sensitive resin compositions of Examples and Comparative Examples were coated on the obtained anti-reflection film, and heated at 100°C for 60 seconds (PB: Prebake) to form a film. 85nm thick resist film. An ArF excimer laser immersion scanner (manufactured by ASML; The resist film on the obtained wafer was exposed using a 6% halftone mask. Use ultrapure water as the immersion fluid. Then, the exposed resist film is heated at 105°C for 60 seconds (PEB: Post Exposure Bake), and then a negative developer (organic developer, butyl acetate) is used by the liquid coating method. Development was performed for 30 seconds, and further rinsing was performed for 30 seconds using a rinse solution (methyl isobutyl carbinol (MIBC)) by the liquid coating method. Next, the silicon wafer was spin-dried at 4000 rpm for 30 seconds, thereby forming a 1:1 line and space pattern with a line width of 44 nm.

<Line Width Roughness (LWR, nm)> The obtained 44 nm 1:1 line and space pattern was observed from the top of the pattern using a length-measuring scanning electron microscope (S-8840, manufactured by Hitachi, Ltd.). At this time, the line width was measured at 50 points in a range of 2 μm from the edge of the line pattern in the longitudinal direction, and the standard deviation (3σ) was calculated for the measurement variation of the measured line widths. Indicates that the smaller the coefficient value, the better the LWR performance is. The results are shown in Table 2 below.

<Exposure latitude (EL, %)> Find the exposure amount that reproduces the 1:1 line and space mask pattern with a line width of 44 nm, and set it as the optimal exposure amount Eopt. Next, the exposure amount at which the line width became ±10% of the target value of 44 nm (that is, 39.6 nm and 48.4 nm) was determined. Using the obtained exposure value, the exposure latitude (EL) defined by the following formula is calculated. The larger the value of EL, the smaller the change in line width caused by changes in exposure, and the better the EL performance of the resist film. EL (%) = [[(Exposure amount when the line width becomes 48.4 nm) - (Exposure amount when the line width becomes 39.6 nm)]/Eopt]×100 The results are shown in Table 2 below.

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

Table 2 below shows the evaluation results of the photosensitive radiation or the blending of the radiation-sensitive resin composition, and the LWR and EL in each of the Examples and Comparative Examples. In Table 2, the value in parentheses in the column of each solid component indicates the ratio (mass part ratio) of the mixing amounts of the solid components. The value in parentheses in the solvent column indicates the ratio (mass ratio) of the blending amounts of each solvent. In addition, as mentioned above, the total added amount of the solvent is an amount such that the solid content concentration of each photosensitive radiation or radiation-sensitive resin composition becomes 3.8 mass %. In Table 2, the "General formula (R)" column indicates that the resin (A) contained in the photosensitive radiation-sensitive or radiation-sensitive resin composition has a repeating unit represented by the general formula (1) or (2) In this case, whether there is a group represented by the general formula (R) in the above-mentioned repeating unit. In Table 2, the "acid-detaching group" column indicates that when the repeating unit represented by the general formula (1) or (2) in the resin (A) has a group represented by the above-mentioned general formula (R) , whether there is an acid-leaving group in the group equivalent to R ₅ . In Table 2, the "ether group" column indicates that when the resin (A) contained in the photosensitive radiation-sensitive or radiation-sensitive resin composition has a repeating unit represented by the general formula (1) or (2) , whether there is an ether group in the alkylene group of the group represented by L ₁ or L ₂ in the above repeating unit. In Table 2, the column "General formula (A) × 2" indicates that the resin (A) contained in the photosensitive radiation-sensitive or radiation-sensitive resin composition has a repeat of the general formula (1) or (2). In the case of units, whether there are two groups represented by the general formula (A) in the alkylene group of the group represented by L ₁ or L ₂ in the above-mentioned repeating unit.

[Table 2]

It was confirmed from Table 2 that by using the photosensitive radiation or radiation-sensitive resin composition of the present invention, a resist film excellent in EL performance and a pattern excellent in LWR performance can be obtained. Furthermore, it was confirmed that the repeating unit represented by the general formula (1) or (2) of the resin (A) contained in the photosensitive radiation or radiation-sensitive resin composition of the present invention has the general formula (R) When the groups represented are used, more excellent effects of the present invention can be obtained (Comparison between Examples 2 and 6 to 17 and other Examples). It was confirmed that when the repeating unit represented by the general formula (1) or (2) is an alkylene group in which L ₁ or L ₂ has an ether group, the patterned LWR performance tends to be more excellent (Examples 2, 7 to 8 and the results from 11 to 14). Furthermore, it was confirmed that when the repeating unit represented by the general formula (1) or (2) is an alkylene group having two groups represented by the general formula (A) as _L1 or _L2 , a patterned LWR The performance also tends to be more excellent (results of Examples 15 to 17). When it is confirmed that the group R ₅ in the repeating unit represented by the general formula (1) or (2) corresponds to the group represented by the general formula (R) is a group other than an acid-leaving group, the resistance The sensitivity of the etching film is more excellent (comparison between Examples 14 and 17 and other Examples).

It was confirmed that even when the resist film formed in the above-mentioned Example is exposed to ArF and the exposed film is subjected to alkali development, a resist film excellent in EL performance and excellent LWR performance can be obtained. pattern. Similarly, it was confirmed that even when the resist film formed in the above-mentioned Example is subjected to KrF exposure, electron beam exposure, or EUV exposure, and the exposed film is subjected to alkali development or organic solvent development, it is also confirmed that Resist film with excellent EL performance and pattern with excellent LWR performance.

Claims (8)

A photosensitive radioactive or radiation-sensitive resin composition, which contains a repeating unit selected from the group represented by the general formula (1), a repeating unit represented by the general formula (2), and a repeating unit represented by the general formula (3). A resin of at least one repeating unit in a group of units, and a photoacid generator,

In the general formula (1), R ₁ and R ₂ are groups represented by the general formula (R), and L ₁ is a group having two groups represented by the general formula (A), *-C( =O)-OR ₅ (R) In the general formula (R), R ₅ represents a hydrogen atom, an alkali-decomposable group or an acid-detaching group, * represents a bonding position, *-C(=O)-OR (A) In the general formula (A), R represents a hydrocarbon group or a hydrogen atom that may have a heteroatom, and * represents a bonding position. In the general formula (2), at least one of R ₃ and R ₄ is represented by the general formula (R) group, L ₂ represents an alkylene group that may have a substituent, part of the carbon atoms in the alkylene group represented by L ₂ may be substituted by a group having hetero atoms, and the substituent may have hetero atoms, where , the group represented by L ₂ has one or more heteroatoms. In the general formula (3), R ₆ represents a hydrogen atom or an organic group having 1 to 20 carbon atoms, and L ₃ represents a divalent link that may have a substituent. Group, The unit or the repeating unit of the sultone group is a repeating unit represented by the general formula (III),

In the general formula (III), A represents an ester group (-COO-) or a amide group (-CONH-), n represents an integer from 0 to 5, and R ₀ represents an alkylene or cycloalkylene group with a substituent or In its combination, when there are multiple R _0's , R _0's can be the same or different respectively. Z represents a single bond, ether group, ester group, amide group, urethane group or urea group. When there are multiple Z's , Z can be the same or different, R ₈ represents a lactone group or a sultone group, R ₇ represents a hydrogen atom, a halogen atom or an organic group, and the repeating unit of the carbonate group is represented by the general formula (A-1) represents the repeating unit,

In the general formula (A-1), _RA ¹ represents a hydrogen atom, a halogen atom or an organic group, n represents an integer of 0 or more, and _RA ² represents a substituent. When n is 2 or more, _RA ² each independently represents a substitution. group, A represents a single bond or a divalent linking group, and Z represents an atomic group forming a monocyclic group or a polycyclic group together with the group represented by -OC(=O)-O- in the formula. The photosensitive radiation-sensitive or radiation-sensitive resin composition described in item 1 of the patent application, wherein the content of the resin is more than 10% by mass relative to the total solid content of the photosensitive radiation-sensitive or radiation-sensitive resin composition. . The photosensitive radiation or radiation-sensitive resin composition described in item 1 of the patent application, wherein R ₅ represents an alkali-decomposable group. The photosensitive radiation or radiation-sensitive resin composition described in any one of items 1 to 3 of the patent application, wherein L ₂ is an alkylene group that may have a substituent, an ether group, or a 2 An alkylene group of a group represented by the general formula (A). The photosensitive radiation or radiation-sensitive resin composition described in any one of items 1 to 3 of the patent application, wherein the resin also has repeating units selected from having a lactone group, and has neither acid The decomposable group also does not have at least one repeating unit in the group of repeating units of the polar group. A resist film formed using the photosensitive radiation or radiation-sensitive resin composition described in any one of items 1 to 5 of the patent application. A pattern forming method, which includes: a resist film forming step, using the photosensitive radiation or radiation-sensitive resin composition described in any one of items 1 to 5 of the patent application scope to form a resist film; The exposure step is to expose the resist film; and the development step is to use a developer to develop the exposed resist film. A method for manufacturing electronic components, which includes the pattern forming method described in Item 7 of the patent application.