KR101994797B1 - Pattern formation method, composition for protective film formation, and method for producing electronic device - Google Patents

Abstract

(a) applying an actinic ray-sensitive or radiation-sensitive resin composition onto a substrate to form an actinic ray-sensitive or radiation-sensitive film; (b) forming a protective film-forming composition on the actinic ray-sensitive or radiation-sensitive film; (C) exposing the actinic ray-sensitive or radiation-sensitive film coated with the passivation film, and (d) exposing the actinic ray-sensitive or radiation-sensitive film exposed to an organic solvent. The pattern formation method containing the process of image development with the developing solution to contain. The said protective film contains resin (X) which has a proton accepting functional group.

Description

Pattern forming method, protective film forming composition and electronic device manufacturing method {PATTERN FORMATION METHOD, COMPOSITION FOR PROTECTIVE FILM FORMATION, AND METHOD FOR PRODUCING ELECTRONIC DEVICE}

INDUSTRIAL APPLICABILITY The present invention is suitably used in a pattern forming method and a pattern forming method, which are used in the production of semiconductor substrates such as ICs, the production of circuit boards such as liquid crystals and thermal heads, and further lithography processes of other photofabrication methods. The composition for protective film formation, and the manufacturing method of an electronic device. TECHNICAL FIELD This invention relates especially to the pattern formation method suitable for exposing with a immersion projection exposure apparatus, the composition for protective film formation used in this pattern formation method, and the manufacturing method of an electronic device.

After the resist for KrF excimer laser (248 nm), an image forming method called chemical amplification has been used as an image forming method of the resist in order to compensate for the decrease in sensitivity due to light absorption. Taking an example of a positive chemical amplification image forming method, an acid generator in an exposed portion is decomposed by exposure to generate an acid, and the generated acid is used as a reaction catalyst in a post exposure bake (PEB). It is an image forming method of changing an insoluble group into an alkali soluble group and removing an exposed part by alkali development.

On the other hand, in addition to the positive type, recently, a negative image forming method using a developer containing an organic solvent (hereinafter also referred to as an "organic solvent developer") (hereinafter also referred to as a "NTI process" (NTI process) (NTI)) (See Patent Documents 1 and 2, for example). For example, in Patent Literature 2, in pattern formation by alkali development using a conventional negative resist composition, line width variation (Line Width Roughness: LWR) and focus margin (presumably swelling during development) are presumed to be the main factors. Depth of Focus (DOF) and other negative compounds, in view of the need for further improvement of the performance, in the negative pattern formation method using a developer containing an organic solvent, a specific compound containing at least one of a fluorine atom and a silicon atom The chemically amplified resist composition to which was added was used.

In addition, for miniaturization of semiconductor devices, shortening of the exposure light source and high aperture number (high NA) of the projection lens have progressed, and an exposure machine using ArF excimer laser having a wavelength of 193 nm as a light source has been developed. In addition, as a technique for further increasing the resolution, a so-called immersion method has been proposed in which a high refractive index liquid (hereinafter also referred to as "immersion liquid") is conventionally filled between the projection lens and the sample.

When the chemically amplified resist is applied to the liquid immersion exposure, the resist layer comes into contact with the immersion liquid during exposure, thereby deteriorating the resist layer and releasing components that adversely affect the immersion liquid from the resist layer. It is becoming. In patent document 3, the example by which the resist performance changes by immersing the resist for ArF exposure in water before and behind exposure is described, and points out that it is a problem in liquid immersion exposure.

As a solution to avoid such a problem, a method is known in which a protective film (hereinafter also referred to as a "top coat") is provided between a resist and a lens so that the resist and water do not directly contact (for example, Patent Document 4). ~ 6).

When an acid is excessively generated in the resist surface layer due to decomposition of the acid generator by exposure, the NTI process causes an excessive deprotection reaction of the acid-decomposable group in the surface layer and leaves the exposed portion as a pattern after development. ) It is easy to become a shape. When the pattern has a T-top shape, for example, performances such as depth of focus (DOF), exposure latitude (EL), and the like deteriorate. For this reason, for example, in patent documents 7 and 8, the technique of adding a low molecular weight basic difference to the top coat layer which coats a resist film in order to neutralize the excess acid which generate | occur | produced on the resist surface is disclosed.

Japanese Unexamined Patent Publication No. 2008-292975 Japanese Unexamined Patent Publication No. 2011-141494 International Publication No. 04-068242 International Publication No. 04-074937 International Publication No. 05-019937 Japanese Laid-Open Patent Publication 2005-109146 Japanese Unexamined Patent Publication No. 2013-61647 Japanese Unexamined Patent Publication No. 2013-61648

As a result of the intensive study by the present inventors, when basic difference is added to a top coat layer, the excess acid moves from a resist surface layer to a top coat layer, and a low molecular basic difference moves from a top coat layer to a resist layer. . For this reason, it turned out that the film | membrane reduction of a pattern arises and Line Edge Roughness (LER) deteriorates. In the NTI process of leaving the exposed portion as a pattern after development, this is a serious problem.

The present invention provides a NTI process, that is, a negative image forming process using an organic solvent developer, in which a pattern having excellent focus margin (DOF) and exposure margin (EL) and excellent line width variation (LWR) is suppressed. It is a subject to provide the pattern formation method which can be formed, and the composition for protective film formation used suitably in this pattern formation method. This invention also makes it a subject to provide the manufacturing method of the electronic device containing this pattern formation method.

This invention is as follows in one aspect.

[One]

(a) applying an actinic ray-sensitive or radiation-sensitive resin composition onto a substrate to form an actinic ray-sensitive or radiation-sensitive film,

(b) applying a composition for forming a protective film on the actinic ray-sensitive or radiation-sensitive film to form a protective film,

(c) exposing the actinic ray-sensitive or radiation-sensitive film coated with the protective film, and

(d) A pattern forming method comprising the step of developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer containing an organic solvent,

The pattern formation method in which the said protective film contains resin (X) which has a proton accepting functional group.

[2]

The pattern formation method as described in [1] whose said proton accepting functional group is a functional group containing the nitrogen atom which comprises aliphatic amine, aromatic amine, or heterocyclic amine.

[3]

The pattern formation method as described in [1] whose said proton accepting functional group is an ether bond, a thioether bond, a carbonyl bond, or a thiocarbonyl bond.

[4]

[1] to [3, in which the resin (X) includes a repeating unit having the proton accepting functional group, and the content rate of the repeating unit is 0.1 to 10 mol% with respect to all the repeating units in the resin (X). The pattern formation method in any one of]].

[5]

The pattern formation method in any one of [1]-[4] whose resin (X) is resin which does not contain a fluorine atom substantially.

[6]

[1] to 1, further comprising a step of heating the substrate coated with the actinic ray-sensitive or radiation-sensitive film and the protective film to 100 ° C. or higher after the step (b) of forming a protective film and before the step (c) of exposing. The pattern formation method in any one of [5].

[7]

As a protective film formation composition used for formation of the protective film which coats an actinic-ray-sensitive or radiation-sensitive film, it contains resin (X) which has a proton acceptor functional group, and this proton acceptor functional group is an aliphatic amine, aromatic The composition for protective film formation which is a functional group containing the nitrogen atom which comprises an amine or a heterocyclic amine.

[8]

As a protective film formation composition used for formation of the protective film which coat | covers an actinic-ray-sensitive or a radiation-sensitive film, it contains resin (X) which has a proton acceptor functional group, and this proton acceptor functional group contains an ether bond and a cy A composition for forming a protective film which is an ether bond, a carbonyl bond or a thiocarbonyl bond.

[9]

The manufacturing method of an electronic device containing the pattern formation method in any one of [1]-[6].

[10]

The electronic device manufactured by the manufacturing method of the electronic device of [9].

INDUSTRIAL APPLICATION According to this invention, it is suitable in the pattern formation method which can form the pattern which was excellent in the focus margin (DOF) and exposure margin (EL), and the line width deviation (LWR) was suppressed, and this pattern formation method suitably. It became possible to provide the composition for protective film formation which can be used. Moreover, according to this invention, it became possible to provide the manufacturing method of the electronic device containing this pattern formation method.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

In the description of group (atom group) in this specification, the description which is not describing substitution and unsubstitution includes what has a substituent with the thing which does not have a substituent. For example, an "alkyl group" includes not only the alkyl group (unsubstituted alkyl group) which does not have a substituent but the alkyl group (substituted alkyl group) which has a substituent.

The term "active light" or "radiation" in the present specification means, for example, a bright spectrum of mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet light (EUV light), X-ray, electron beam (EB) and the like. In addition, in this invention, light means actinic light or a radiation.

In addition, unless otherwise indicated, "exposure" in this specification is a particle beam, such as an electron beam, an ion beam, as well as exposure by the ultraviolet rays, extreme ultraviolet rays (EUV light), X-rays, etc. which are represented by a mercury lamp and an excimer laser. Drawing is also included in the exposure.

EMBODIMENT OF THE INVENTION Hereinafter, the pattern formation method of this invention, the composition for protective film formation used suitably for this pattern formation method, and actinic-ray-sensitive or radiation-sensitive resin composition are demonstrated in detail.

<Composition for forming a protective film>

The pattern formation method of this invention includes the protective film formation process of forming a protective film so that an actinic-ray-sensitive or a radiation-sensitive film may be coat | covered in the NTI process which forms a negative image using the organic solvent developing solution. The composition for protective film formation used for formation of this protective film contains resin (X) demonstrated below. Moreover, it is preferable that this composition for protective film formation contains a solvent in order to form a film uniformly on an actinic-ray-sensitive or radiation-sensitive film. Moreover, this composition for protective film formation may contain surfactant further.

[Resin (X)]

Resin (X) contains a proton accepting functional group. Although it demonstrates in detail below, a proton accepting functional group is a functional group which has group or lone electron pair which can interact electrostatically with proton.

As described above, by neutralizing the acid generated excessively in the resist surface layer by exposure with the low molecular basic difference added to the top coat layer, the pattern shape is suppressed from becoming a T-top, and the deterioration of DOF and EL performance is suppressed. The technique to make is known (refer patent document 7, 8).

However, as a result of intensive studies by the present inventors, the low molecular basic difference is neutralized by referring to the acid which has moved from the resist surface layer to the top coat layer, while the low molecular basic difference is shifted from the top coat layer to the resist layer, As a result of neutralizing the acidity in the miner, a problem has been found in that the pattern is reduced and the LER deteriorates.

As a result of further studies by the present inventors, instead of the low molecular weight basic or secondary basic tea in the composition for forming a protective film, the pattern shape is T-top shaped by supporting a proton acceptor functional group in the resin in the composition for forming a protective film. It has been found that pattern formation with reduced LER can be made possible by suppressing the film reduction while suppressing this, improving DOF and EL performance.

The reason why the LER is reduced by suppressing the occurrence of film reduction while improving the DOF and EL performance by supporting the proton acceptor functional group on the resin is not necessarily clear. That is, as described above, a proton acceptor functional group is a functional group having a group or an lone electron pair capable of electrostatically interacting with protons, and neutralizes the acid, or does not cause neutralization, and does not cause neutralization to interact with the acid. Trapping can suppress the movement of the acid. For this reason, a proton accepting functional group neutralizes or traps the excess acid which moved to the top coat layer from the resist surface layer in a top coat layer. On the other hand, since there is no movement of the proton acceptor functional group from the top coat layer to the resist layer, the acid generated in the exposed portion of the resist layer is acid as it is, and it is possible to maintain a function related to pattern formation. As a result, it is guessed that it becomes possible to suppress that a pattern becomes a T-top shape, to improve DOF and EL performance, and to suppress film reduction and to reduce LER.

The proton accepting functional group contained in resin (X) is demonstrated in more detail.

As described above, the proton acceptor functional group is a functional group having a group or an lone electron pair capable of electrostatically interacting with the protons, and for example, a contribution of a functional group having a macrocyclic structure such as a cyclic polyether or a π conjugate. And a functional group having a nitrogen atom having few lone electron pairs, an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, and the like.

The nitrogen atom which has a lone pair having few contribution of (pi) conjugate | conjugation can mention the nitrogen atom which has a partial structure shown to the following general formula, for example.

[Formula 1]

In one embodiment, the proton acceptor functional group includes a functional group containing a nitrogen atom constituting a primary amine, a secondary amine, or a tertiary amine (for example, aliphatic amines, aromatic amines, and heterocyclic amines). Is preferably. Moreover, it is preferable that a proton acceptor functional group is an ether bond, a thioether bond, a carbonyl bond, or a thiocarbonyl bond in another form.

Primary, secondary or tertiary aliphatic amines, aromatic amines, or heterocyclic amines containing such proton accepting functional groups, ether bonds, thioether bonds, carbonyl bonds, or thiocarbonyls Preferable carbon number of the structure containing proton accepting functional groups, such as a bond, is 4-30. As group containing such a structure, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, etc. are mentioned.

The said alkyl group may have a substituent, Preferably it is a C1-C30 linear and branched alkyl group, and may have an oxygen atom, a sulfur atom, and a nitrogen atom in an alkyl chain. Specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group, etc. And branched alkyl groups such as linear alkyl group, isopropyl group, isobutyl group, t-butyl group, neopentyl group and 2-ethylhexyl group.

The cycloalkyl group may have a substituent, preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom or a nitrogen atom in the ring. Specifically, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, etc. are mentioned.

The said aryl group may have a substituent, Preferably it is a C6-C14 aryl group, For example, a phenyl group, a naphthyl group, etc. are mentioned.

The said aralkyl group may have a substituent, Preferably it is a C7-20 aralkyl group, For example, a benzyl group, a phenethyl group, a naphthyl methyl group, a naphthyl ethyl group is mentioned.

The alkenyl group may have a substituent and the group which has a double bond in arbitrary positions of the said alkyl group is mentioned.

As a substituent which each said group may have, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably C3-C10), an aryl group (preferably 6 to 14 carbon atoms, alkoxy group (preferably 1 to 10 carbon atoms), acyl group (preferably 2 to 20 carbon atoms), acyloxy group (preferably 2 to 10 carbon atoms), alkoxycarbonyl group (preferably C2-C20, an amino acyl group (preferably C2-C20), etc. are mentioned. About the cyclic structure in an aryl group, a cycloalkyl group, an alkyl group (preferably C1-C20) is mentioned as a substituent. About an aminoacyl group, an alkyl group (preferably C1-C20) is mentioned further as a substituent.

The proton acceptor functional group may be substituted by a group (hereinafter, also referred to as an "acid decomposable group") that is decomposed and released by the action of an acid. As the acid-decomposable group, for example, an amide group, an ester group (preferably tertiary alkyloxycarbonyl group), an acetal group (preferably 1-alkyloxy-alkyloxy group), carbamoyl group, carbonate group Etc. can be mentioned.

Moreover, a proton acceptor functional group may be introduce | transduced in the form contained in the side chain of a repeating unit in resin (X), and may be introduce | transduced in the form contained in the terminal structure couple | bonded with the main chain of resin (X).

When resin (X) contains the repeating unit which has a proton accepting functional group, it is preferable that the content rate of the repeating unit is 0.1-10 mol% with respect to all the repeating units in resin (X), and 0.5- It is more preferable that it is 5 mol%.

In one embodiment of the present invention, the proton accepting functional group preferably contains a nitrogen atom.

However, when the composition of this invention is especially for ArF exposure, it is preferable that the said proton acceptor functional group containing the said nitrogen atom does not have aromaticity, and is a nitrogen-containing aromatic ring in view of transparency to ArF light. It is more preferable not to have.

As a proton accepting functional group containing a nitrogen atom, the basic group represented by either of the following general formula (A)-(E) is mentioned, for example.

[Formula 2]

In General Formula (A), R ²⁰¹ and R ²⁰² each independently represent a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), or an aryl group (preferably Represents C6-C20).

In general formula (E), R <^203> , R <^204> , R <^205> and R <^206> represent an alkyl group (preferably C1-C20) or a cycloalkyl group (preferably C3-C20) each.

* Represents a bond which is bonded to another atom constituting the repeating unit (I).

In the structure represented by the general formula (A), R ²⁰¹ and R ²⁰² are, are bonded to form a ring.

In the structure represented by General Formula (B)-(D), two or more of the bond from a carbon atom and the bond from a nitrogen atom may combine with each other, and may form a ring.

In the structure represented by General Formula (E), even if two or more of R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , a bond loss from a carbon atom, and a bond loss from a nitrogen atom combine with each other to form a ring do. In this general formula (A), the alkyl group of R ²⁰¹ and R ²⁰² is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, or an n-butyl group. , n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetra Decyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, i-propyl group, i-butyl group, sec- Butyl group, t-butyl group, t-dodecyl group, etc. are mentioned.

The cycloalkyl group of R ²⁰¹ and R ²⁰² is preferably a cycloalkyl group having 3 to 20 carbon atoms, and examples thereof include a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

Among the alkyl groups and cycloalkyl groups of R ²⁰¹ and R ²⁰² , a C1-C10 linear alkyl group and a C4-C8 cycloalkyl group are preferable.

The aryl group of R ²⁰¹ and R ²⁰² is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include a phenyl group, toluyl group, benzyl group, methylbenzyl group, xylyl group, mesityl group, naphthyl group and anthryl group. have.

The alkyl group, cycloalkyl group, and aryl group of R ²⁰¹ and R ²⁰² may further have a substituent, and as such substituent, a halogen atom, a hydroxyl group, an amino group, a carboxyl group, a cyano group, a nitro group, an alkyl group, a cyclo group Alkyl group, aryl group, alkoxy group, aryloxy group, acyl group, arylcarbonyl group, alkoxyalkyl group, aryloxyalkyl group, alkylcarbonyloxy group, arylcarbonyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxycarbonyloxy group, Aryloxycarbonyloxy group, a lactone group, etc. are mentioned.

In general formula (E), the specific example of the alkyl group and cycloalkyl group of R <^203> , R <^204> , R <^205> and R <^206> is the same as the specific example of the alkyl group and cycloalkyl group of R <^201> and R <^202> , respectively.

The alkyl group and the cycloalkyl group of R ²⁰³ , R ²⁰⁴ , R ^205, and R ²⁰⁶ may further have a substituent, and specific examples of such substituents include the above specific examples of the substituent which R ²⁰¹ and R ²⁰² may further have. same.

In the group represented by the general formulas (A) to (E), the bond from the carbon atom and / or the nitrogen atom is bonded to another atom constituting the repeating unit (I).

In addition, as described above, in groups represented by the general formula (A), R ²⁰¹ and R ²⁰² are bonded to each other and form a ring, in groups represented by the general formula (B) ~ (D), from a carbon atom Two or more of the bond and the bond from the nitrogen atom may be bonded to each other to form a ring, and in the structure represented by General Formula (E), R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , and carbon atom Two or more of the bonds from and the bonds from the nitrogen atom may be bonded to each other to form a ring.

As said ring, an aromatic or non-aromatic nitrogen-containing heterocyclic ring is mentioned. As such a nitrogen-containing heterocycle, a 3-10 membered ring is mentioned, It is preferable that it is a 4-8 membered ring, It is more preferable that it is a 5 or 6 membered ring. Such a ring may further have a substituent and is the same as the specific example mentioned above as a substituent which R ²⁰¹ and R ²⁰² may have further as the specific example.

As a proton acceptor functional group containing a nitrogen atom, the functional group containing the nitrogen atom which comprises primary, secondary or tertiary aliphatic amines, aromatic amines, or heterocyclic amines is mentioned, for example. .

Examples of the aliphatic amines include ethylamine, n-propylamine, sec-butylamine, tert-butylamine, hexylamine, cyclohexylamine, octylamine, dodecylamine, ethylenediamine, tetraethylenepentamine, dimethylamine, Diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dihexylamine, dicyclohexylamine, dioctyl Amine, didodecylamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepentamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri- n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, tridecylamine, tridodecylamine, N, N , N ', N'-tetrame Methylenediamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyltetraethylenepentamine, dimethylethylamine, methylethylpropylamine, benzylamine, Phenethylamine, benzyldimethylamine, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2-aminoethanol, 3-amino -1-propanol, 4-amino-1-butanol, and the like are exemplified.

Examples of the aromatic amines and the heterocyclic amines include aniline derivatives, diphenyl (p-tolyl) amines, methyldiphenylamines, triphenylamines, phenylenediamines, naphthylamines, diaminonaphthalenes, pyrrole derivatives, and oxazole derivatives. , Thiazole derivatives, imidazole derivatives, pyrazole derivatives, furazane derivatives, pyrroline derivatives, pyrrolidine derivatives, imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (preferably 2- (2-hydroxy Ethyl) pyridine), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives (preferably 1- (2-hydroxyethyl) piperazine, 1 -[2- (2-hydroxyethoxy) ethyl] piperazine), morpholine derivatives (preferably 4- (2-hydroxyethyl) morpholine), indole derivatives, isoindole derivatives, 1H-indazole derivatives , Indoline derivatives, quinones Lean derivatives, isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like are exemplified.

The proton acceptor functional group containing a nitrogen atom may be substituted with the group (acid-decomposable group) decomposed | disassembled and detached by the action of an acid. For example, the form in which the proton acceptor functional group represented by either of said general formula (A)-(E) is substituted by the acid-decomposable group is also preferable, More preferably, the structure represented by the following general formula (Ap) is mentioned. Can be.

[Formula 3]

In general formula (Ap),

Ra, Rb ₁ , Rb ₂ and Rb ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Two of Rb ₁ to Rb ₃ may be bonded to each other to form a ring. However, all of Rb ₁ to Rb ₃ do not become hydrogen atoms at the same time.

Rc represents a single bond or a divalent linking group.

x represents 0 or 1, y represents 1 or 2, respectively, and x + y = 2.

When x = 1, Ra and Rc may combine with each other to form a nitrogen-containing heterocycle.

Specific examples of the alkyl group, the cycloalkyl group, and the aryl group as Ra, Rb ₁ , Rb _2, and Rb ₃ include the above-mentioned embodiments of the alkyl group, the cycloalkyl group, and the aryl group of R ²⁰¹ and R ^{202 in} the group represented by the general formula (A). Same as the example.

Specific examples of the aralkyl group as Ra, Rb ₁ , Rb ₂ and Rb ₃ are preferably aralkyl groups having 6 to 12 carbon atoms, for example, benzyl, phenethyl, naphthylmethyl, naphthylethyl and naphthylbutyl groups. Can be mentioned.

Ra, Rb ₁ , Rb ₂ and Rb ₃ are preferably linear or branched alkyl groups, cycloalkyl groups, and aryl groups. More preferably, they are a linear or branched alkyl group and a cycloalkyl group.

As Rc, Preferably it is a C2-C12 (more preferably C2-C6, More preferably, it is C2-C4) bivalent coupling group, For example, an alkylene group, a phenylene group, an ether group, an ester group, And amide groups, and groups formed by combining two or more thereof.

Ra, Rb ₁ , Rb ₂ , Rb _3, and Rc may each further have a substituent, and specific examples of such substituents include, for example, halogen atoms (fluorine atoms, etc.), hydroxyl groups, nitro groups, and the like. Anano groups, carboxy groups, carbonyl groups, cycloalkyl groups (preferably having 3 to 10 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), alkoxy groups (preferably having 1 to 10 carbon atoms), acyl groups (preferably Is 2 to 20 carbon atoms, acyloxy group (preferably 2 to 10 carbon atoms), alkoxycarbonyl group (preferably 2 to 20 carbon atoms), amino acyl group (preferably 2 to 10 carbon atoms), amino group, pyrroli Dino group, a piperidino group, a morpholino group, the group which has a silicon atom, etc. are mentioned. About the cyclic structure in an aryl group, a cycloalkyl group, an alkyl group (preferably C1-C10) is mentioned further as a substituent. About an aminoacyl group, an alkyl group (preferably C1-C10) is mentioned further as a substituent.

When both of Rb ₁ , Rb ₂ and Rb ₃ are both hydrogen atoms, the other one is preferably an aryl group, and examples of the aryl group include a phenyl group and a naphthyl group.

Moreover, as a nitrogen-containing heterocycle which Ra and Rc couple | bond with each other and form, an aromatic or non-aromatic nitrogen-containing heterocycle (preferably C3-C20) is mentioned. Examples of such nitrogen-containing heterocycles include pyrrolidine, piperidine, morpholine, 1,4,5,6-tetrahydropyrimidine, 1,2,3,4-tetrahydroquinoline, 1,2 , 3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzotriazole, 1H-1,2,3-triazole, 1,4,7-triaza Cyclononane, tetrazole, 7-azaindole, indazole, benzimidazole, imidazo [1,2-a] pyridine, (1S, 4S)-(+)-2,5-diazabicyclo [2.2. 1] heptane, 1,5,7-triazabicyclo [4.4.0] des-5-ene, indole, indolin, 1,2,3,4-tetrahydroquinoxaline, perhydroquinoline, 1, And a ring corresponding to a heterocyclic compound such as 5,9-triaza cyclododecane.

Examples of the ring formed by bonding of two of Rb ₁ to Rb ₃ include a monocyclic cycloalkane ring such as a cyclopentane ring and a cyclohexane ring, a norbornene ring, a tetracyclodecane ring, a tetracyclododecane ring, and ace. However, polycyclic cycloalkane rings, such as a tin ring, are preferable. Particularly preferred is a monocyclic cycloalkane ring having 5 to 6 carbon atoms.

The nitrogen-containing heterocycle formed by bonding of Ra and Rc to each other and the ring formed by bonding of two of Rb ₁ to Rb _{3 may} each have one or more substituents or one or more substituents. specific examples _{include, Ra, Rb 1, Rb 2} , Rb 3 , and is the same as the specific examples of the substituent which may further have a Rc.

The group represented by general formula (Ap) can be conveniently synthesized with respect to a group having a general amine structure by the method described in Protective Groups in Organic Synthesis, 4th edition and the like. The most common method is a method obtained by reacting a bicarbonate ester or haloformic acid ester with respect to a group having an amine structure. In the formula, X represents a halogen atom. Ra, Rb _1, Rb _2, Rb _3, Rc is an Ra, Rb _1, Rb _2, Rb _3, Rc and agreement in the formula (Ap), respectively.

[Formula 4]

The proton acceptor functional group containing a nitrogen atom may be introduced in the form contained in the side chain of the repeating unit (I) in the resin (X), or in the form contained in the terminal structure bonded to the main chain of the resin (X). It may be introduced.

Repeating unit (I) which has a proton acceptor functional group containing a nitrogen atom in a side chain is at least 1 sort (s) of the polymerizable component in the synthesis | combination of resin (X), and has a proton acceptor functional group containing a nitrogen atom. It can obtain by using the monomer (1) provided.

The terminal structure which has a nitrogen atom containing a proton acceptor functional group couple | bonded with the main chain of resin (X) is a chain transfer agent in the synthesis | combination of resin (X), and has a proton acceptor functional group containing a nitrogen atom. By using the compound (2) with which it is equipped, or by using the compound (3) provided with the proton accepting functional group containing a nitrogen atom as a polymerization initiator in the synthesis | combination of resin (X).

As a repeating unit corresponding to the monomer (1) provided with the proton accepting functional group containing a nitrogen atom, the repeating unit represented with the following general formula (P1)-(P3) is mentioned, for example.

[Formula 5]

In general formula (P1)-(P3),

X ₁ represents a hydrogen atom or an alkyl group.

X ₂ represents a single bond or a divalent linking group.

R <_1> represents the structure containing the proton accepting functional group containing a nitrogen atom.

R ₂ represents a hydrogen atom or an alkyl group.

R ₁ and R ₂ may be connected to each other to form a ring.

In general formula (P1)-(P3), a C1-C10 alkyl group is preferable and the alkyl group of X <_1> , R <_2> may be substituted by the fluorine atom, a chlorine atom, a hydroxyl group, etc.

Examples of the divalent linking group for X ₂ include an alkylene group, an arylene group, an oxy group, a carbonyl group alone, and a combination of two or more thereof.

The structure containing the proton accepting functional group containing the nitrogen atom of R <_1> is mentioned above as a structure containing the proton accepting functional group containing a nitrogen atom.

If the repeating unit corresponding to the monomer (1) which has a proton accepting functional group containing a nitrogen atom is shown more concretely, the repeating unit represented by the following general formula (P4)-(P10) is mentioned, for example.

[Formula 6]

[Formula 7]

In general formula (P4)-(P10),

X ₁ is a X ₁ and agreed in the general formula (P1).

R ₃ to R ₉ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or an aralkyl group. R ₃ and R ₄ may be connected to each other to form a ring. R <_5> , R <_6> , R <_7> and R <_8> may mutually connect, respectively and may form the ring (preferably aromatic ring).

Z represents an alkylene group or -NH-.

The alkyl group of R ₃ to R ₉ is preferably an alkyl group having 1 to 10 carbon atoms, the cycloalkyl group is preferably a cycloalkyl group having 1 to 20 carbon atoms, an alkenyl group is preferably an alkenyl group having 1 to 10 carbon atoms, and aryl The group is preferably an aryl group having 6 to 20 carbon atoms, and an aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and these groups are substituted with a fluorine atom, a chlorine atom, a hydroxyl group, a carbonyl group, a cyano group, a sulfone group, or the like. You may be.

Hereinafter, although the specific example of the repeating unit corresponding to the monomer (1) provided with the proton accepting functional group containing a nitrogen atom is given, this invention is not limited to this.

[Formula 8]

[Formula 9]

As a monomer (1) which has a proton acceptor functional group containing a nitrogen atom, As a repeating unit corresponding to the monomer (1 ') in which the proton acceptor functional group containing a nitrogen atom is substituted by the acid-decomposable group, for example, The repeating unit represented by the following general formula (P'1)-(P'3) is mentioned.

[Formula 10]

In general formula (P'1)-(P'3),

X ₁ represents a hydrogen atom or an alkyl group.

X ₂ represents a single bond or a divalent linking group.

R ₂ represents a hydrogen atom or an alkyl group.

R <_3> represents the structure containing the proton acceptor functional group containing a nitrogen atom substituted by the acid-decomposable group.

delete

In general formula (P'1)-(P'3), a C1-C10 alkyl group is preferable and the alkyl group of X <_1> , R <_2> may be substituted by the fluorine atom, a chlorine atom, a hydroxyl group, etc. Examples of the divalent linking group for X ₂ include an alkylene group, an arylene group, an oxy group, a carbonyl group alone, and a combination of two or more thereof.

R ₃ having the structure represented by, the acid-decomposable groups by substitution, as the proton acceptor functional group containing a nitrogen atom, may be mentioned one described in the above.

Hereinafter, although the specific example of the repeating unit corresponding to the monomer (1 ') which has the proton accepting functional group containing a nitrogen atom substituted by the acid-decomposable group is given, this invention is not limited to this.

In the following specific examples, Rx represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[Formula 11]

Moreover, as mentioned above, it is also preferable that a proton accepting functional group is an ether bond, a thioether bond, a carbonyl bond, or a thiocarbonyl bond.

In one embodiment of the present invention, the resin (X) preferably contains a repeating unit containing an ether bond. It is preferable that the repeating unit containing an ether bond contains 2 or more ether bonds, for example, it is more preferable that 3 or more ether bonds are included, and it is more preferable that 4 or more ether bonds are included. .

In one embodiment of the present invention, the resin (X) preferably contains a repeating unit containing an oxyalkylene structure represented by the following General Formula (1).

[Formula 12]

In the formula,

R ₁₁ represents an alkylene group which may have a substituent.

n represents the integer of 2 or more.

* Represents a bonding hand.

Although carbon number of the alkylene group represented by R <_11> in General formula (1) in particular is not restrict | limited, It is preferable that it is 1-15, It is more preferable that it is 1-5, It is more preferable that it is 2 or 3, It is two Particularly preferred. When this alkylene group has a substituent, a substituent is not specifically limited, It is preferable that it is an alkyl group (preferably C1-C10).

It is preferable that it is an integer of 2-20, and, as for n, it is more preferable that it is 10 or less especially for reasons, such as DOF becoming larger.

In order for DOF to become larger, the average value of n is preferably 20 or less, more preferably 2 to 10, still more preferably 2 to 8, and particularly preferably 4 to 6. Here, the "average value of n" means the value of n determined so that the weight average molecular weight of resin (X) is measured by GPC, and the weight average molecular weight obtained and general formula match. If n is not an integer, the value is rounded off.

Two or more R <_11> may be same or different.

Moreover, it is preferable that the repeating unit which has a partial structure represented by the said General formula (1) is a repeating unit which has a partial structure represented by following General formula (1-1) for the reason that DOF becomes larger.

[Formula 13]

In the formula,

R ₁₁ represents an alkylene group which may have a substituent.

R ₁₂ represents a hydrogen atom or an alkyl group.

m represents an integer of 1 or more.

* Represents a bonding hand.

Specific examples of the alkyl group represented by R ₁₁ for example, and a suitable embodiment is the same as R ₁₁ in the above-mentioned general formula (1).

Although carbon number of the alkyl group represented by R <_12> is not specifically limited, It is preferable that it is 1-15.

It is preferable that m is an integer of 1-20, and it is more preferable that it is 10 or less especially because a DOF becomes larger especially.

The average value of m is preferably 20 or less, more preferably 1 to 10, still more preferably 1 to 8, and particularly preferably 4 to 6, because the DOF becomes larger. Here, "average value of m" is synonymous with "average value of n" mentioned above.

When m is two or more, two or more R <_11> may be same or different.

The structure containing the ether bond, the thioether bond, the carbonyl bond, or the thiocarbonyl bond which is a proton acceptor functional group as a partial structure is introduce | transduced in the form contained in the side chain of a repeating unit in resin (X). It may be introduced in the form contained in the terminal structure bonded to the main chain of the resin (X).

When these groups are contained in a repeating unit, as a preferable repeating unit, the repeating unit represented by the following general formula (P11), (P12), (P13) is mentioned, for example.

[Formula 14]

In general formula (P11)-(P13),

X ₁ represents a hydrogen atom or an alkyl group.

X ₂ represents a single bond or a divalent linking group.

R ₁₁ represents an organic group containing an ether bond, a thioether bond, a carbonyl bond, or a thiocarbonyl bond.

R ₂ represents a hydrogen atom or an alkyl group.

delete

The definition, the specific example, and the suitable aspect of X <_1> , X <_2> , R <_2> are the same as each in General Formula (P1)-(P3) mentioned above.

The organic group represented by R ₁₁ is preferably an organic group having 4 to 30 carbon atoms including an ether bond, a thioether bond, a carbonyl bond, or a thiocarbonyl bond.

When the organic group represented by R ₁₁ has an ether bond, R ₁₁ is preferably a partial structure represented by General Formula (1), and more preferably a partial structure represented by General Formula (1-1).

Below, the specific example of the repeating unit which has a proton accepting functional group is shown.

[Formula 15]

Moreover, as mentioned above, the proton accepting functional group may be introduce | transduced in the form contained in the terminal structure couple | bonded with the main chain of resin (X).

The terminal structure which has a proton acceptor functional group couple | bonded with the main chain of resin (X) is used as a chain transfer agent in the synthesis | combination of resin (X), by using the compound provided with a proton acceptor functional group, or resin ( It can obtain by using the compound provided with a proton accepting functional group as a polymerization initiator in the synthesis | combination of X).

Resin (X) in which the proton accepting functional group containing a nitrogen atom was introduce | transduced into the terminal structure couple | bonded with the main chain of resin can be obtained according to the method of Paragraph 0077-0108 of Unexamined-Japanese-Patent No. 2013-218223.

It is preferable that resin (X) which can be used suitably for the composition for protective film formation is transparent in the exposure light source to be used in order for light to pass through the protective film and reach the actinic ray-sensitive or radiation-sensitive film during exposure. When using for ArF immersion exposure, it is preferable that resin (X) does not have an aromatic group from the point of transparency to ArF light.

In one embodiment of the present invention, the resin (X) is preferably a resin that does not substantially contain a fluorine atom. Specifically, the content of fluorine atoms in the resin (X) is preferably 20% by mass or less, more preferably 10% by mass or less, ideally substantially 0% by mass, based on the weight average molecular weight of the resin (X). Means%.

Further, in another aspect of the present invention, the resin (X) is preferably a resin having a partial structure in the side chain CH ₃ parts.

Here, to the resin (X) CH ₃ having a partial structure of side chain portions (hereinafter also referred to as simply "the side chain CH ₃ partial structure") are, including CH ₃ partial structure having the ethyl group, a propyl group or the like.

On the other hand, a methyl group (e. G., Of the repeating structural unit having a methacrylic acid α- methyl group) that is directly bonded to the main chain of the resin (X) is assumed which is not included in CH ₃ a partial structure of the present invention.

More specifically, when resin (X) contains the repeating unit derived from the monomer which has a polymeric site which has a carbon-carbon double bond, such as a repeating unit represented by the following general formula (M), for example, When R ₁₁ to R ₁₄ are CH ₃ "self", the CH ₃ is not included in the CH ₃ partial structure of the side chain portion in the present invention.

On the other hand, CH ₃ partial structure exists via any atom from the CC main chain, it is assumed for the CH ₃ a partial structure of the present invention. For example, when R ₁₁ is an ethyl group (CH ₂ CH ₃ ), it is assumed to have "one" CH ₃ partial structure in the present invention.

[Formula 16]

In said general formula (M),

R ₁₁ to R ₁₄ each independently represent a side chain moiety.

As R <_11> -R <_14> of a side chain part, a hydrogen atom, monovalent organic group, etc. are mentioned.

Examples of the monovalent organic group for R ₁₁ to R ₁₄ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, and arylamino Carbonyl group etc. are mentioned, These groups may further have a substituent.

A resin (X) has the following general formula (II) repeating unit, and the following general formula (III) represented by a repeating unit is preferably a resin, and this has a repeating unit having a CH ₃ a partial structure in a side chain part It is more preferable to have at least 1 sort (s) of repeating unit (x) among the repeating units shown. In particular, in the case of using KrF, EUV, and electron beam (EB) as the exposure light source, the resin (X) may suitably include a repeating unit represented by General Formula (III).

Hereinafter, the repeating unit represented by general formula (II) is demonstrated in detail.

[Formula 17]

In General Formula (II), X _b1 represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom, and R ₂ represents an organic group that is stable with respect to an acid having one or more CH ₃ partial structures. Here, the organic group stable with respect to an acid is more specifically, decomposed | disassembled by the action of an acid and generating alkali-soluble group demonstrated in the acid-decomposable resin contained in the actinic-ray-sensitive or radiation-sensitive resin composition mentioned later. It is preferable that it is an organic group which does not have group. "

The alkyl group of X _b1 preferably has 1 to 4 carbon atoms, and may include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a trifluoromethyl group, and the like, but is preferably a methyl group.

X _b1 is preferably a hydrogen atom or a methyl group.

Examples of R ₂ include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, and an aralkyl group having one or more CH ₃ partial structures. Said cycloalkyl group, alkenyl group, cycloalkenyl group, aryl group, and aralkyl group may further have an alkyl group as a substituent.

R ₂ is preferably an alkyl group or an alkyl substituted cycloalkyl group having one or more CH ₃ partial structures.

Groups in the acid having at least one partial structure as R ₂ CH ₃ stable organic, it is more preferable to have preferred, and 2 or more than 8 having two or less than 10 CH ₃ a partial structure.

As the alkyl group having at least 1 CH ₃ a partial structure of the R _2, a branched alkyl group having 3 to 20 carbon atoms are preferred. Specific examples of the preferred alkyl group include isopropyl group, isobutyl group, 3-pentyl group, 2-methyl-3-butyl group, 3-hexyl group, 2-methyl-3-pentyl group, and 3-methyl-4- Hexyl group, 3,5-dimethyl-4-pentyl group, isooctyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-di Methyl-3-heptyl group, 2,3,5,7-tetramethyl-4-heptyl group, and the like. More preferably, isobutyl group, t-butyl group, 2-methyl-3-butyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group, 3,5-dimethyl-4- Pentyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3,5,7-tetra Methyl-4-heptyl group.

The cycloalkyl group having one or more CH ₃ partial structures in R ₂ may be monocyclic or polycyclic. Specifically, group which has a C5 or more monocyclo, bicyclo, tricyclo, tetracyclo structure, etc. are mentioned. 6-30 are preferable and, as for the carbon number, 7-25 are especially preferable. As a preferable cycloalkyl group, an adamantyl group, a noadamantyl group, a decalin residue, a tricyclodecaneyl group, a tetracyclo dodecaneyl group, a norbornyl group, a cedrol group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclo Decanyl group and cyclododecaneyl group are mentioned. More preferably, an adamantyl group, a norbornyl group, a cyclohexyl group, a cyclopentyl group, a tetracyclo dodecaneyl group, and a tricyclodecaneyl group are mentioned. More preferably, they are a norbornyl group, a cyclopentyl group, and a cyclohexyl group.

According to R _2, as the alkenyl group having at least one CH ₃ a partial structure, an alkenyl group of a straight-chain or branched having 1 to 20 carbon atoms are preferred, and more preferably an alkenyl group of branches.

Examples of the aryl group having, at least one CH ₃ a partial structure of the R _2, can be mentioned preferably an aryl group having from 6 to 20 carbon atoms, and examples thereof include a phenyl group, an naphthyl, preferably a phenyl group.

In R _2, As the aralkyl group having at least one CH ₃ partial structure, preferably an aralkyl group having a carbon number of 7-12, and for example, a benzyl group, a phenethyl group, a naphthylmethyl group and the like.

Specific examples of the hydrocarbon group having two or more CH ₃ partial structures in R ₂ include isopropyl group, isobutyl group, t-butyl group, 3-pentyl group and 2-methyl-3-butyl group. , 3-hexyl group, 2,3-dimethyl-2-butyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, isoocta Methyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, 2,6-dimethylheptyl, 1,5-dimethyl-3-heptyl, 2,3,5,7-tetramethyl A 4-heptyl group, a 3, 5- dimethyl cyclohexyl group, 4-isopropyl cyclohexyl group, 4-t- butylcyclohexyl group, an isobornyl group, etc. are mentioned. More preferably, isobutyl group, t-butyl group, 2-methyl-3-butyl group, 2,3-dimethyl-2-butyl group, 2-methyl-3-pentyl group, 3-methyl-4- Hexyl group, 3,5-dimethyl-4-pentyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3- Heptyl group, 2,3,5,7-tetramethyl-4-heptyl group, 3,5-dimethylcyclohexyl group, 3,5-ditert-butylcyclohexyl group, 4-isopropylcyclohexyl group, 4 -t-butylcyclohexyl group and isobornyl group.

Preferable specific examples of the repeating unit represented by General Formula (II) are shown below. However, the present invention is not limited thereto.

[Formula 18]

It is preferable that the repeating unit represented by General formula (II) is a repeating unit which is stable to an acid (non-acid-decomposable), and specifically, it is preferable that it is a repeating unit which does not have the group which decomposes by the action of an acid and produces a polar group. Do.

Hereinafter, the repeating unit represented by General formula (III) is demonstrated in detail.

[Formula 19]

In General Formula (III), X _b2 represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom, R ₃ represents an organic group stable to an acid having one or more CH ₃ partial structures, and n is 1 Represents an integer of 5.

The alkyl group of X _b2 preferably has 1 to 4 carbon atoms, and includes a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a trifluoromethyl group, and the like, but is preferably a hydrogen atom.

It is preferable that X _b2 is a hydrogen atom.

Since R <_3> is an organic group which is stable with respect to an acid, it is preferable that it is an organic group which does not have the "group which decomposes by the action of an acid and produces | generates an alkali-soluble group" demonstrated in the acid-decomposable resin mentioned later more specifically. .

Examples of R ₃ include an alkyl group having one or more CH ₃ partial structures.

Groups in the acid having at least one CH ₃ partial structure as R ₃ stable organic, CH ₃ and the partial structure is more preferable to have preferred, and one or more than 8 having 10 or less at least one, at least one 4 It is more preferable to have up to.

As the alkyl group having at least one CH ₃ a partial structure of the R _3, a branched alkyl group having 3 to 20 carbon atoms are preferred. Specific examples of the preferred alkyl group include isopropyl group, isobutyl group, 3-pentyl group, 2-methyl-3-butyl group, 3-hexyl group, 2-methyl-3-pentyl group, and 3-methyl-4- Hexyl group, 3,5-dimethyl-4-pentyl group, isooctyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-di Methyl-3-heptyl group, 2,3,5,7-tetramethyl-4-heptyl group, and the like. More preferably, isobutyl group, t-butyl group, 2-methyl-3-butyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group, 3,5-dimethyl-4- Pentyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3,5,7-tetra Methyl-4-heptyl group.

Specific examples of the alkyl group having two or more CH ₃ partial structures in R ₃ include isopropyl group, isobutyl group, t-butyl group, 3-pentyl group, 2,3-dimethylbutyl group, 2 -Methyl-3-butyl group, 3-hexyl group, 2-methyl-3-pentyl group, 3-methyl-4-hexyl group, 3,5-dimethyl-4-pentyl group, isooctyl group, 2,4 , 4-trimethylpentyl group, 2-ethylhexyl group, 2,6-dimethylheptyl group, 1,5-dimethyl-3-heptyl group, 2,3,5,7-tetramethyl-4-heptyl group Etc. can be mentioned. More preferably, it is more preferable that it is C5-C20, and isopropyl group, t-butyl group, 2-methyl-3- butyl group, 2-methyl-3- pentyl group, 3-methyl-4-hexyl group , 3,5-dimethyl-4-pentyl group, 2,4,4-trimethylpentyl group, 2-ethylhexyl group, 1,5-dimethyl-3-heptyl group, 2,3,5,7- Tetramethyl-4-heptyl group, and 2,6-dimethylheptyl group.

n represents an integer of 1 to 5, more preferably an integer of 1 to 3, and more preferably 1 or 2.

Preferable specific examples of the repeating unit represented by General Formula (III) are shown below. However, the present invention is not limited thereto.

[Formula 20]

It is preferable that the repeating unit represented by General formula (III) is an acid stable (non-acid-decomposable) repeating unit, and specifically, it is preferable that it is a repeating unit which does not have the group which decomposes by action of an acid and produces a polar group. Do.

Resin (X) is, the case comprising a CH ₃ a partial structure in a side chain part, and repeat that appears as a repeating unit, and the general formula (III) appearing in particular, does not have a fluorine atom and a silicon atom, the general formula (II) It is preferable that it is 90 mol% or more with respect to all the repeating units of resin (X), and, as for content of at least 1 sort (s) of repeating unit (x) in a unit, it is more preferable that it is 95 mol% or more. Content of a repeating unit (x) is 100 mol% or less normally with respect to all the repeating units of resin (X).

Resin (X) is a repeating unit represented by General Formula (II) and at least 1 type of repeating unit (x) among the repeating units represented by General Formula (III), with respect to all the repeating units of Resin (X). By containing in mol% or more, the surface free energy of resin (X) increases. As a result, the resin (X) becomes difficult to ubiquitous on the surface of the actinic ray-sensitive or radiation-sensitive composition film, and reliably improves the static / dynamic contact angle of the actinic ray-sensitive or radiation-sensitive film with respect to water, resulting in immersion liquid followability. Can be improved.

Moreover, in another form of this invention, it is preferable that resin (X) is resin containing the repeating unit derived from the monomer containing at least 1 fluorine atom and / or at least 1 silicon atom, and it is at least 1 It is more preferable that it is a water-insoluble resin containing the repeating unit derived from the monomer containing a fluorine atom and / or at least 1 silicon atom. By containing the repeating unit derived from the monomer containing at least 1 fluorine atom and / or at least 1 silicon atom, favorable solubility with respect to the organic solvent developing solution is obtained, and the effect of this invention is fully acquired.

The fluorine atom or silicon atom in resin (X) may have in the principal chain of resin, and may substitute by the side chain.

It is preferable that resin (X) is resin which has the alkyl group which has a fluorine atom, the cycloalkyl group which has a fluorine atom, or the aryl group which has a fluorine atom as a partial structure which has a fluorine atom.

The alkyl group (preferably C1-C10, more preferably C1-C4) which has a fluorine atom is a linear or branched alkyl group in which at least one hydrogen atom was substituted by the fluorine atom, and may have another substituent further.

The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have another substituent.

As an aryl group which has a fluorine atom, the thing by which at least 1 hydrogen atom of the aryl groups, such as a phenyl group and a naphthyl group, was substituted by the fluorine atom is mentioned, You may have another substituent further.

Although the specific example of the alkyl group which has a fluorine atom, the cycloalkyl group which has a fluorine atom, or the aryl group which has a fluorine atom is shown below, this invention is not limited to this.

[Formula 21]

In general formula (F2)-(F3),

R ₅₇ to R ₆₄ each independently represent a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R ₅₇ to R ₆₁ and R ₆₂ to R ₆₄ represents an alkyl group (preferably having 1 to 4 carbon atoms) in which a fluorine atom or at least one hydrogen atom is substituted with a fluorine atom. It is preferable that all of R ₅₇ to R ₆₁ are fluorine atoms. R ₆₂ and R ₆₃ are preferably an alkyl group (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and more preferably a perfluoroalkyl group having 1 to 4 carbon atoms. R ₆₂ and R ₆₃ may be connected to each other to form a ring.

As a specific example of group represented by general formula (F2), a p-fluorophenyl group, a pentafluorophenyl group, a 3, 5- di (trifluoromethyl) phenyl group, etc. are mentioned, for example.

As a specific example of group represented by general formula (F3), a trifluoroethyl group, pentafluoropropyl group, pentafluoroethyl group, heptafluoro butyl group, hexafluoro isopropyl group, heptafluoro isopropyl group, hexafluoro Low (2-methyl) isopropyl group, nonafluorobutyl group, octafluoro isobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoro isopentyl group, perfluorooctyl group And a perfluoro (trimethyl) hexyl group, a 2,2,3,3-tetrafluorocyclobutyl group, a perfluorocyclohexyl group, and the like. Hexafluoro isopropyl group, heptafluoro isopropyl group, hexafluoro (2-methyl) isopropyl group, octafluoro isobutyl group, nonafluoro-t-butyl group, and perfluoro isopentyl group are preferable. , Hexafluoroisopropyl group, and heptafluoroisopropyl group are more preferable.

It is preferable that resin (X) is resin which has an alkylsilyl structure (preferably trialkylsilyl group) or cyclic siloxane structure as a partial structure which has a silicon atom.

Specific examples of the alkylsilyl structure or the cyclic siloxane structure include groups represented by general formulas (CS-1) to (CS-3) shown below.

[Formula 22]

In general formula (CS-1)-(CS-3),

R ₁₂ to R ₂₆ each independently represent a linear or branched alkyl group (preferably having 1 to 20 carbon atoms) or a cycloalkyl group (preferably having 3 to 20 carbon atoms).

L ₃ to L ₅ represent a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, a phenyl group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a urethane group, or a combination of two or more groups selected from the group consisting of urea groups. .

n represents the integer of 1-5.

As resin (X), resin which has at least 1 sort (s) chosen from the group of the repeating unit represented by the following general formula (C-I)-(C-V) is mentioned.

[Formula 23]

In general formula (C-I)-(C-V),

R <_1> -R <_3> respectively independently represents a hydrogen atom, a fluorine atom, a C1-C4 linear or branched alkyl group, or a C1-C4 linear or branched fluorinated alkyl group.

W ₁ to W ₂ represent an organic group having at least one of a fluorine atom and a silicon atom.

R <_4> -R <_7> respectively independently represents a hydrogen atom, a fluorine atom, a C1-C4 linear or branched alkyl group, or a C1-C4 linear or branched fluorinated alkyl group. However, R ~ ₄ R _7, at least one of which is a fluorine atom. R ₄ and R ₅ or R ₆ and R ₇ may form a ring.

R <_8> represents a hydrogen atom or a C1-C4 linear or branched alkyl group.

R <_9> represents a C1-C4 linear or branched alkyl group or a C1-C4 linear or branched fluorinated alkyl group.

L ₁ to L ₂ represent a single bond or a divalent linking group and are the same as L ₃ to L ₅ .

Q represents a monocyclic or polycyclic cyclic aliphatic group. That is, the atom group containing two carbon atoms (C-C) couple | bonded and forming an alicyclic structure is shown.

R ₃₀ and R ₃₁ each independently represent hydrogen or a fluorine atom.

R ₃₂ and R ₃₃ each independently represent an alkyl group, a cycloalkyl group, a fluorinated alkyl group or a fluorinated cycloalkyl group.

However, the repeating unit represented by General Formula (CV) has at least one fluorine atom in at least one of R ₃₀ , R ₃₁ , R ₃₂ and R ₃₃ .

It is preferable that resin (X) has a repeating unit represented with general formula (C-I), and it is more preferable to have a repeating unit represented with the following general formula (C-Ia)-(C-Id).

[Formula 24]

In general formula (C-Ia)-(C-Id),

R <_10> and R <_11> represents a hydrogen atom, a fluorine atom, a C1-C4 linear or branched alkyl group, or a C1-C4 linear or branched fluorinated alkyl group.

W ₃ to W ₆ represent an organic group having at least one of a fluorine atom and a silicon atom.

When W ₃ to W ₆ is an organic group having a fluorine atom, it is a fluorinated, straight chain, branched alkyl group or cycloalkyl group having 1 to 20 carbon atoms, or a fluorinated linear, branched, or cyclic alkyl ether group having 1 to 20 carbon atoms. It is preferable.

Examples of the fluorinated alkyl group for W ₃ to W ₆ include trifluoroethyl group, pentafluoropropyl group, hexafluoroisopropyl group, hexafluoro (2-methyl) isopropyl group, heptafluorobutyl group and heptafluoroisopropyl group. Propyl group, octafluoroisobutyl group, nonafluorohexyl group, nonafluoro-t-butyl group, perfluoroisopentyl group, perfluorooctyl group, perfluoro (trimethyl) hexyl group, etc. are mentioned. Can be.

Yi W ₃ W ~ _6, it is preferable that when the organic group having a silicon atom, alkyl silyl structure, or a cyclic siloxane structure. Specifically, the group etc. represented by the said general formula (CS-1)-(CS-3) are mentioned.

Hereinafter, the specific example of the repeating unit represented by general formula (CI) is shown. X represents a hydrogen atom, -CH ₃ , -F or -CF ₃ .

[Formula 25]

[Formula 26]

[Formula 27]

[Formula 28]

[Formula 29]

[Formula 30]

Resin (X) may have a repeating unit represented by the following general formula (Ia) in order to adjust the solubility to the organic solvent developing solution.

[Formula 31]

In general formula (Ia),

Rf represents an alkyl group in which a fluorine atom or at least one hydrogen atom is substituted with a fluorine atom.

R ₁ represents an alkyl group.

R ₂ represents a hydrogen atom or an alkyl group.

In general formula (Ia), it is preferable that it is C1-C3, and, as for the alkyl group which the at least 1 hydrogen atom of Rf substituted by the fluorine atom, a trifluoromethyl group is more preferable.

The alkyl group of R ₁ is preferably a linear or branched alkyl group having 3 to 10 carbon atoms, and more preferably a branched alkyl group having 3 to 10 carbon atoms.

R ₂ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and more preferably a linear or branched alkyl group having 3 to 10 carbon atoms.

Hereinafter, although the specific example of the repeating unit represented by general formula (Ia) is given, this invention is not limited to this.

[Formula 32]

Resin (X) may further have a repeating unit represented by the following general formula (III).

[Formula 33]

In general formula (III),

R ₄ represents a group having an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, a trialkylsilyl group or a cyclic siloxane structure.

L ₆ represents a single bond or a divalent linking group.

In General Formula (III), the alkyl group of R ₄ is preferably a linear or branched alkyl group having 3 to 20 carbon atoms.

The cycloalkyl group is preferably a cycloalkyl group having 3 to 20 carbon atoms.

The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms.

The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 20 carbon atoms.

The trialkylsilyl group is preferably a trialkylsilyl group having 3 to 20 carbon atoms.

The group having a cyclic siloxane structure is preferably a group having a cyclic siloxane structure.

The divalent linking group of L ₆ is preferably an alkylene group (preferably having 1 to 5 carbon atoms) and an oxy group.

Resin (X) may have the same group as an acid-decomposable group in lactone group, an ester group, an acid anhydride, and acid-decomposable resin mentioned later. Resin (X) may further have a repeating unit represented by the following general formula (VIII).

[Formula 34]

As resin (X), it is preferable to contain the repeating unit (d) derived from the monomer which has alkali-soluble group. Thereby, solubility in immersion water and solubility in a coating solvent can be controlled. As an alkali-soluble group, a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonyl imide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbon Nil) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, The group which has a tris (alkylsulfonyl) methylene group, etc. are mentioned.

As a monomer which has an alkali-soluble group, the monomer whose acid dissociation constant pKa is 4 or more is preferable, More preferably, it is a monomer whose pKa is 4-13, Most preferably, it is a monomer whose pKa is 8-13. By containing a monomer having a pKa of 4 or more, swelling at the time of negative and positive development is suppressed, and not only good developability with respect to the organic solvent developer but also good developability can be obtained even when a weakly basic alkaline developer is used. .

The acid dissociation constant pKa is described in Chemical Handbook (II) (Rev. 4, 1993, Japanese Chemical Society, Maruzen Co., Ltd.), and the value of pKa of the monomer containing an alkali-soluble group is, for example, infinite dilution. It can measure at 25 degreeC using a solvent.

Monomer pKa of 4 or more is not particularly limited, for example, include a phenolic hydroxyl group, sulfonamide group, -COCH ₂ CO-, acid group, such as an alcohol group, a carboxylic acid group in the monomer having a fluoro (alkali-soluble group), etc. Can be. In particular, the monomer containing a fluoro alcohol group is preferable. The fluoroalcohol group is a fluoroalkyl group substituted with at least one hydroxyl group, preferably having 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. Specific examples of the fluoroalcohol group include, for example, -CF ₂ OH, -CH ₂ CF ₂ OH, -CH ₂ CF ₂ CF ₂ OH, -C (CF ₃ ) ₂ OH, and -CF ₂ CF (CF ₃ ) OH , -CH ₂ C (CF ₃ ) ₂ OH, and the like. Particularly preferred as the fluoroalcohol group is a hexafluoroisopropanol group.

Preferably the total amount of the repeating unit derived from the monomer which has alkali-soluble group in resin (X) is 0-90 mol% with respect to all the repeating units which comprise resin (X), More preferably, it is 0-80 mol% More preferably, it is 0-70 mol%.

The monomer which has alkali-soluble group may contain only one acidic radical, and may contain two or more. It is preferable that the repeating unit derived from this monomer has two or more acidic groups per repeating unit, It is more preferable to have 2-5 acidic groups, It is especially preferable to have 2-3 acidic groups.

Although the preferable specific example of the repeating unit derived from the monomer which has alkali-soluble group is shown below, it is not limited to these.

[Formula 35]

[Formula 36]

[Formula 37]

[Formula 38]

[Formula 39]

[Formula 40]

[Formula 41]

[Formula 42]

[Formula 43]

[Formula 44]

It is preferable that resin (X) is any resin chosen from following (X-1)-(X-8).

(X-1) Resin which has a repeating unit (a) which has a fluoroalkyl group (preferably C1-C4), More preferably, resin which has only a repeating unit (a).

(X-2) Resin which has a repeating unit (b) which has a trialkylsilyl group or a cyclic siloxane structure, More preferably, resin which has only a repeating unit (b).

(X-3) A repeating unit (a) having a fluoroalkyl group (preferably having 1 to 4 carbon atoms), a branched alkyl group (preferably having 4 to 20 carbon atoms), and a cycloalkyl group (preferably having 4 to 20 carbon atoms) A resin having a repeating unit (c) having a branched alkenyl group (preferably having 4 to 20 carbon atoms), a cycloalkenyl group (preferably having 4 to 20 carbon atoms) or an aryl group (preferably having 4 to 20 carbon atoms), More preferably, copolymerized resin of a repeating unit (a) and a repeating unit (c).

(X-4) A repeating unit (b) having a trialkylsilyl group or a cyclic siloxane structure, a branched alkyl group (preferably C4-20), a cycloalkyl group (preferably C4-20), branched Resin having a repeating unit (c) having an alkenyl group (preferably having 4 to 20 carbon atoms), a cycloalkenyl group (preferably having 4 to 20 carbon atoms) or an aryl group (preferably having 4 to 20 carbon atoms), more preferably Is a copolymer of the repeating unit (b) and the repeating unit (c).

(X-5) Resin which has a repeating unit (a) which has a fluoroalkyl group (preferably C1-C4), and a repeating unit (b) which has a trialkylsilyl group or a cyclic siloxane structure, More preferably, Copolymer resin of a repeating unit (a) and a repeating unit (b).

(X-6) A repeating unit (a) having a fluoroalkyl group (preferably having 1 to 4 carbon atoms), a repeating unit (b) having a trialkylsilyl group or a cyclic siloxane structure, and a branched alkyl group (preferably Is 4 to 20 carbon atoms, cycloalkyl group (preferably 4 to 20 carbon atoms), branched alkenyl group (preferably 4 to 20 carbon atoms), cycloalkenyl group (preferably 4 to 20 carbon atoms) or aryl group (preferably Preferably the resin which has a repeating unit (c) which has C4-C20, More preferably, the copolymer resin of a repeating unit (a), a repeating unit (b), and a repeating unit (c).

As repeating unit (c) which has a branched alkyl group, a cycloalkyl group, a branched alkenyl group, a cycloalkenyl group, or an aryl group in resin (X-3), (X-4), (X-6), Considering aqueous, interactivity, etc., a suitable functional group can be introduced.

(X-7) Repeating unit which has alkali-soluble group (d) in the repeating unit which comprises said (X-1)-(X-6), respectively (preferably the repeating unit which has alkali-soluble group whose pKa is 4 or more). Resin having more).

(X-8) Resin which has only a repeating unit which has alkali-soluble group (d) which has a fluoro alcohol group.

Resin (X-3), (X-4), (X-6), and (X-7) WHEREIN: The repeating unit (a) and / or trialkylsilyl group which has a fluoroalkyl group, or cyclic siloxane structure It is preferable that it is 10-99 mol%, and, as for the repeating unit (b) which has a thing, it is more preferable that it is 20-80 mol%.

Moreover, by having alkali-soluble group (d) in resin (X-7), not only the peelability at the time of using the organic solvent developing solution but other peeling liquid, for example, alkaline aqueous solution was used as peeling liquid. Easiness of peeling in the case improves.

It is preferable that resin (X) is solid at normal temperature (25 degreeC). Moreover, it is preferable that glass transition temperature (Tg) is 50-200 degreeC, and 80-160 degreeC is more preferable.

Solid at 25 degreeC means that melting | fusing point is 25 degreeC or more.

The glass transition temperature (Tg) can be measured by differential scanning calorimetry, for example, the cost change when the temperature of the sample is raised to 5 ° C./min after the temperature is raised and cooled once. It can be measured by interpreting one value.

It is preferable that resin (X) is insoluble with respect to an immersion liquid (preferably water), and is soluble with respect to the organic solvent developing solution (preferably developing solution containing an ester type solvent). When the pattern formation method of this invention further includes the process of developing using alkaline developing solution, it is preferable that resin (X) is soluble also about an alkaline developing solution from a viewpoint that it can develop and peel using an alkaline developing solution. .

When resin (X) has a silicon atom, it is preferable that it is 2-50 mass% with respect to the molecular weight of resin (X), and, as for content of a silicon atom, it is more preferable that it is 2-30 mass%. Moreover, it is preferable that it is 10-100 mass% in resin (X), and, as for the repeating unit containing a silicon atom, it is more preferable that it is 20-100 mass%.

By making content of a silicon atom and content of the repeating unit containing a silicon atom into the following range, the insoluble with respect to immersion liquid (preferably water), the peelability of a protective film at the time of using the organic solvent developing solution, and also actinic ray Both incompatibility with sex or radiation-sensitive films can be improved.

By making content of a fluorine atom and content of the repeating unit containing a fluorine atom into the said range, the insoluble to immersion liquid (preferably water), the peelability of a protective film at the time of using the organic solvent developing solution, and also actinic ray Both incompatibility with sex or radiation-sensitive films can be improved.

When resin (X) has a fluorine atom, it is preferable that it is 5-80 mass% with respect to the molecular weight of resin (X), and, as for content of a fluorine atom, it is more preferable that it is 10-80 mass%. Moreover, it is preferable that it is 10-100 mass% in resin (X), and, as for the repeating unit containing a fluorine atom, it is more preferable that it is 30-100 mass%.

The weight average molecular weight of standard polystyrene conversion of resin (X) becomes like this. Preferably it is 1,000-100,000, More preferably, it is 1,000-50,000, More preferably, it is 2,000-15,000, Especially preferably, it is 3,000-15,000.

Although it is natural that resin (X) has few impurities, such as a metal, it is preferable that the amount of residual monomers is 0-10 mass% from a viewpoint of the elution reduction from a protective film to an immersion liquid, More preferably, it is 0-5 mass % And 0-1 mass% are more preferable. Moreover, 1-5 are preferable, as for molecular weight distribution (Mw / Mn, dispersion degree), More preferably, it is 1-3, More preferably, it is the range of 1-1.5.

Various commercial items can also be used for resin (X), and it can synthesize | combine according to a conventional method (for example, radical polymerization). For example, as a general synthetic method, the batch polymerization method which melt | dissolves a monomer species and an initiator in a solvent, and superposes | polymerizes by heating, and the dropping polymerization method which adds the solution of a monomer species and an initiator dropwise for 1 to 10 hours, and adds to a heating solvent Etc. are mentioned, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and ester solvents such as ethyl acetate and dimethyl formamide. And amide solvents such as dimethylacetamide, and solvents for dissolving the composition of the present invention such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone which will be described later. .

It is preferable that a polymerization reaction is performed in inert gas atmosphere, such as nitrogen and argon. As a polymerization initiator, superposition | polymerization is started using a commercially available radical initiator (azo initiator, peroxide, etc.). As a radical initiator, an azo initiator is preferable and the azo initiator which has an ester group, a cyano group, and a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate) and the like. A chain transfer agent can also be used as needed. The concentration of the reactant is usually 5 to 50% by mass, preferably 20 to 50% by mass, more preferably 30 to 50% by mass. Reaction temperature is 10 degreeC-150 degreeC normally, Preferably it is 30 degreeC-120 degreeC, More preferably, it is 60-100 degreeC.

After the reaction is completed, the mixture is left to cool to room temperature and purified. Purification is performed by dropping a resin solution into a poor solvent, or a method for purification in a solution state such as a liquid solution extraction method for removing residual monomer and oligomer components by combining water washing and an appropriate solvent, ultrafiltration for extracting and removing only those having a specific molecular weight or less. By coagulating the resin in the poor solvent, conventional methods such as a reprecipitation method for removing residual monomer and the like and a purification method in a solid state such as washing the filtered resin slurry with a poor solvent can be applied. For example, the resin is precipitated as a solid by contacting a solvent (poor solvent) in which the resin is poorly soluble or insoluble in a volume amount of 10 times or less, preferably 10 to 5 times the volume of the reaction solution.

The solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent of this polymer, and depending on the type of polymer, for example, hydrocarbons (pentane, hexane, heptane) Aliphatic hydrocarbons such as octane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene), halogenated hydrocarbons (methylene chloride, chloroform, tetrachloride) Halogenated aliphatic hydrocarbons such as carbon, halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene, etc., nitro compounds (such as nitromethane and nitroethane), nitrile (acetonitrile, benzo) Nitrile, etc.), ether (diethyl ether, diisopropyl ether, chain ether such as dimethoxy ether; cyclic ether such as tetrahydrofuran and dioxane), ketone (acetone, methyl Ketones, diisobutyl ketones, etc.), esters (ethyl acetate, butyl acetate, etc.), carbonates (dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, etc.), alcohols (methanol, ethanol, propanol, isopropyl alcohol, butyl) Tanol etc.), carboxylic acid (acetic acid etc.), water, mixed solvent containing these solvent, etc. can be selected suitably, and can be used. Among these, as a precipitation or reprecipitation solvent, a solvent containing at least alcohol (especially methanol) or water is preferable. In such a solvent containing at least hydrocarbons, the ratio of alcohol (especially methanol, etc.) and other solvents (e.g., esters such as ethyl acetate, ethers such as tetrahydrofuran, etc.) is, for example, the former. / Latter (volume ratio; 25 ° C.) = 10/90 to 99/1, preferably the former / the latter (volume ratio; 25 ° C.) = 30/70 to 98/2, more preferably the former / the latter (volume ratio; 25 ° C.) ) = 50/50 to 97/3.

Although the usage-amount of precipitation or reprecipitation solvent can be suitably selected in consideration of efficiency, a yield, etc., it is generally 100-10000 mass parts with respect to 100 mass parts of polymer solutions, Preferably it is 200-2000 mass parts, More preferably It is 300-1000 mass parts.

The opening diameter of the nozzle at the time of supplying the polymer solution in the precipitation or reprecipitation solvent (poor solvent) is preferably 4 mmφ or less (for example, 0.2 to 4 mmφ). The feed rate (dropping rate) of the polymer solution in the poor solvent is a linear speed, for example, about 0.1 to 10 m / sec, preferably about 0.3 to 5 m / sec.

Precipitation or reprecipitation operation is preferably performed under stirring. Stirring blades used for stirring, for example, disk turbines, fan turbines (including puddle), curved wing turbines, arrow-shaped turbines, piddlers, bull margin, angled vane fan turbines fan turbines, propellers, cascades, anchors (or horseshoes), gates, double ribbons, screws, and the like. It is preferable to perform stirring further 10 minutes or more, especially 20 minutes or more even after completion | finish of supply of a polymer solution. When there is little stirring time, the case where the monomer content in a polymer particle cannot fully be reduced arises. In addition, a polymer mixer and a poor solvent may be mixed and stirred using a line mixer instead of the stirring blade.

The temperature at the time of precipitation or reprecipitation can be appropriately selected in consideration of efficiency and operability, but is usually about 0 to 50 ° C, preferably around room temperature (for example, about 20 to 35 ° C). Precipitation or reprecipitation operation can be performed by well-known methods, such as a batch type and a continuous type, using common mixing vessels, such as a stirring tank.

The particulate polymer precipitated or reprecipitated is usually subjected to solid liquid separation such as filtration and centrifugation, and dried to be used for use. Filtration is performed under pressure using the filter medium of solvent resistance. Drying is performed at a temperature of about 30 to 100 ° C, preferably about 30 to 50 ° C, under normal pressure or under reduced pressure (preferably under reduced pressure).

Furthermore, once a resin is precipitated and separated, it may be dissolved in a solvent again and may be made to contact with a solvent insoluble or insoluble.

That is, after completion of the radical polymerization reaction, a polymer is contacted with a solvent that is poorly soluble or insoluble to precipitate the resin (step a), the resin is separated from the solution (step b), and dissolved in the solvent again to prepare a resin solution A. (Step c) Then, the resin solid is made by contacting this resin solution A with a solvent in which the resin is poorly soluble or insoluble in a volume amount (preferably 5 times or less) of the resin solution A. May be precipitated (step d) and the precipitated resin is separated (step e).

The solvent used at the time of preparation of resin solution A can use the same solvent as the solvent which melt | dissolves a monomer at the time of a polymerization reaction, and may be the same as or different from the solvent used at the time of a polymerization reaction.

[solvent]

It is preferable that the composition for protective film formation used for the pattern formation method of this invention dissolves resin in a solvent, and uses it in order to form the protective film formation composition on actinic-ray-sensitive or radiation-sensitive film uniformly.

In order to form a favorable pattern without dissolving the actinic ray-sensitive or radiation-sensitive film, the protective film-forming composition of the present invention preferably contains a solvent which does not dissolve the actinic ray-sensitive or radiation-sensitive film, and is negative. It is more preferable to use the solvent of a component different from a developing solution. Moreover, it is preferable that the solubility with respect to an immersion liquid is low from a viewpoint of the elution prevention with respect to an immersion liquid, and it is more preferable that the solubility with respect to water is low. In this specification, "low solubility in immersion liquid" means that it is insoluble in immersion liquid. Likewise, "low solubility in water" indicates water insoluble. Moreover, as for the boiling point of a solvent, 90 degreeC-200 degreeC is preferable from a viewpoint of volatility and applicability | paintability.

The low solubility in the immersion liquid is, for example, the solubility in water, after coating and drying the composition for forming a protective film on a silicon wafer to form a film. The film thickness after immersing in pure water at 23 ° C. for 10 minutes and drying. The reduction rate of is said to be within 3% of the initial film thickness (typically 50 nm).

In this invention, from a viewpoint of apply | coating a protective film uniformly, a solvent is used so that solid content concentration may be 0.01-20 mass%, More preferably, it is 0.1-15 mass%, Most preferably, it is 1-10 mass%.

As a solvent which can be used, there is no restriction | limiting in particular, unless it melt | dissolves resin (X) mentioned later and does not melt an actinic-ray-sensitive or a radiation-sensitive film, It is preferable to use alcohol solvent, a fluorine-type solvent, and a hydrocarbon-type solvent, It is more preferable to use a non-fluorine alcohol solvent. As a result, the cost-effectiveness of the actinic ray-sensitive or radiation-sensitive film is further improved, and when the composition for forming a protective film is applied onto the actinic-ray-sensitive or radiation-sensitive film, the actinic ray-sensitive or radiation-sensitive film is not dissolved. The protective film can be formed more uniformly.

As an alcohol solvent, a monohydric alcohol is preferable from a viewpoint of applicability | paintability, More preferably, it is a C4-C8 monohydric alcohol. As a C4-8 monohydric alcohol, linear, branched, or cyclic alcohols can be used, but linear or branched alcohols are preferable. As such an alcoholic solvent, for example, 1-butanol, 2-butanol, 3-methyl-1-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1- Hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, 4- Methyl-1-pentanol, 4-methyl-2-pentanol, etc. can be used, Especially, 1-butanol, 1-hexanol, 1-pentanol, 3-methyl-1- butanol , 4-methyl-2-pentanol.

As the fluorine-based solvent, for example, 2,2,3,3,4,4-hexafluoro-1-butanol, 2,2,3,3,4,4,5,5-octafluoro-1- Pentanol, 2,2,3,3,4,4,5,5,6,6-decafluoro-1-hexanol, 2,2,3,3,4,4-hexafluoro-1, 5-pentanediol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol, 2,2,3,3,4,4,5, 5,6,6,7,7-dodecafluoro-1,8-octanediol, 2-fluoroanisole, 2,3-difluoroanisole, perfluorohexane, perfluoro Heptane, perfluoro-2-pentanone, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, perfluorotributylamine, perfluorotetrapentylamine, and the like. Among them, fluorinated alcohols or fluorinated hydrocarbon solvents can be suitably used.

As a ketone solvent, 4-methyl- 2-pentanone, 2, 4- dimethyl- 2-pentanone, 3-penten- 2-one, 2-nonanone, 3-heptanone, 3-methyl, for example Cyclopentanone and the like can be used.

As a hydrocarbon solvent, Aromatic hydrocarbon solvents, such as toluene, xylene, and anisole, n-heptane, n-nonane, n-octane, n-decane, 2-methylheptane, 3-methyl And aliphatic hydrocarbon solvents such as heptane, 3,3-dimethylhexane, and 2,3,4-trimethylpentane.

You may use these solvents individually by 1 type or in mixture of multiple.

When mixing the solvent of that excepting the above, the mixing ratio is 0-30 mass% normally with respect to the total solvent amount of the composition for protective film formation, Preferably it is 0-20 mass%, More preferably, it is 0-10 mass%. . By mixing the solvent of that excepting the above, the solubility to actinic-ray-sensitive or a radiation-sensitive film, the solubility of resin in the composition for protective film formation, actinic-ray-rays, or the elution characteristic from a radiation-sensitive film can be adjusted suitably.

[Surfactants]

It is preferable that the composition for protective film formation of this invention contains surfactant further. There is no restriction | limiting in particular as surfactant, If an composition for protective film formation can be formed uniformly, and if it can melt | dissolve in the solvent of the composition for protective film formation, all anionic surfactant, cationic surfactant, and nonionic surfactant can be used. have.

The addition amount of surfactant becomes like this. Preferably it is 0.001-20 mass%, More preferably, it is 0.01-10 mass%.

Surfactant may be used individually by 1 type, and may use 2 or more types together.

As said surfactant, an alkyl cationic surfactant, an amide type quaternary cationic surfactant, ester type quaternary cationic surfactant, an amine oxide type surfactant, a betaine type surfactant, an alkoxylate type surfactant, Fatty acid ester-based surfactants, amide-based surfactants, alcohol-based surfactants, and ethylenediamine-based surfactants, fluorine-based and / or silicon-based surfactants (fluorine-based surfactants, silicon-based surfactants, interfaces having both fluorine atoms and silicon atoms) Active agent) can be suitably used.

As a specific example of surfactant, Polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol Polyoxyethylene alkylallyl ethers such as ethers and polyoxyethylene nonylphenol ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, Sorbitan fatty acid esters such as sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, Surfactants, such as polyoxyethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate, and the following It may be used a commercially available surface active agent as is.

As a commercially available surfactant which can be used, F-top EF301, EF303 (made by Shin-Akita Kasei Co., Ltd.), fluoride FC430, 431, 4430 (made by Sumitomo 3M Corporation), Megapak F171, F173, F176 , F189, F113, F110, F177, F120, R08 (made by Dainippon Ink & Chemicals Co., Ltd.), Supron S-382, SC101, 102, 103, 104, 105, 106 (made by Asahi Glass Co., Ltd.) , Troisol S-366 (made by Troy Chemical Co., Ltd.), GF-300, GF-150 (made by Toa Kosei Kagaku Co., Ltd.), Supron S-393 (made by Seimi Chemical Co., Ltd.), F top Ef121, ef122a, ef122b, rf122c, ef125m, ef135m, ef351, ef352, ef801, ef802, ef601 And fluorine-based surfactants or silicone-based surfactants such as, 230G, 204D, 208D, 212D, 218D, and 222D (manufactured by Neos). Moreover, polysiloxane polymer KP-341 (made by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone type surfactant.

<Preparation method of the composition for protective film formation>

It is preferable that the composition for protective film formation of this invention melt | dissolves each component mentioned above in a solvent, and filters. As a filter, it is preferable that pore size is 0.1 micrometer or less, More preferably, it is 0.05 micrometer or less, More preferably, it is made of polytetrafluoroethylene, polyethylene, or nylon which is 0.03 micrometer or less. In addition, you may connect and use multiple types of filters in series or in parallel. Moreover, you may filter the composition for protective film formation multiple times, and the circulation filtration process may be sufficient as the process of filtering multiple times. In addition, before and after filter filtration, you may perform a degassing process etc. with respect to the composition for protective film formation. It is preferable that the composition for protective film formation does not contain impurities, such as a metal. As content rate of the metal component contained in these materials, 10 ppm or less is preferable, 5 ppm or less is more preferable, 1 ppm or less is more preferable, It is especially preferable that it is not contained substantially (it is below the detection limit of a measuring apparatus). .

<Pattern forming method>

As described above, the pattern forming method of the present invention,

Applying an actinic ray-sensitive or radiation-sensitive resin composition onto a substrate to form an actinic ray-sensitive or radiation-sensitive film,

Forming a protective film (top coat) by applying a protective film-forming composition onto the actinic ray-sensitive or radiation-sensitive film;

Exposing the actinic ray-sensitive or radiation-sensitive film coated with the protective film;

And developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer containing an organic solvent.

In one embodiment, the pattern forming method of the present invention may include a heating step or may include a heating step a plurality of times.

Moreover, in one form, the pattern formation method of this invention may include the exposure process in multiple times.

Moreover, in one aspect, the pattern formation method of this invention may include the image development process multiple times, for example, may further include the image development process using the developing solution containing aqueous alkali solution.

Moreover, the pattern formation method of this invention may include the rinse process in one form.

Moreover, in one aspect, the pattern formation method of this invention may peel a protective film simultaneously with organic solvent image development, by melt | dissolving a protective film in the organic solvent image development process in an organic solvent image development process, or separately from an organic solvent image development process, You may include the process of removing a protective film using a predetermined peeling agent.

Hereinafter, each process contained in the pattern formation method of this invention is demonstrated in detail.

<Step of forming actinic ray-sensitive or radiation-sensitive film>

The coating of the actinic ray-sensitive or radiation-sensitive resin composition onto the substrate may be performed by any method as long as the actinic ray-sensitive or radiation-sensitive resin composition can be applied onto the substrate. A spray method, a roller coat method, an immersion method, etc. can be used, Preferably, a resist composition is apply | coated by the spin coat method.

Not necessarily a substrate in forming a film in the present invention is particularly limited, such as silicon, SiN, SiO ₂ or TiN, etc. of the inorganic substrate, a semiconductor manufacturing process, a liquid crystal, a thermal head, such as such as, IC is applied based inorganic substrate such as SOG The board | substrate generally used in the manufacturing process of a circuit board and also the lithography process of other fabrication can be used.

Before forming the actinic ray-sensitive or radiation-sensitive film, an antireflection film may be coated on the substrate in advance.

As the antireflection film, both an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, amorphous silicon, and an organic film type made of a light absorber and a polymer material can be used. Moreover, as an organic antireflection film, such as DUV-30 series made by Brewer Science Corporation, DUV-40 series, AR-2, AR-3, AR-5 made by Shipley, ARC series, such as ARC29A made by Nissan Chemical Industries, Ltd. A commercially available organic antireflection film can also be used.

In addition, the actinic-ray-sensitive or radiation-sensitive resin composition which can be used is demonstrated in detail in the following description.

<Step of Forming Protective Film>

The pattern formation method of this invention is actinic-ray-sensitive or radiation-sensitive after the formation process of an actinic-ray-sensitive or radiation-sensitive film, and before performing the process of exposing an actinic-ray-sensitive or radiation-sensitive film with an organic solvent developing solution. The process of apply | coating the above-mentioned composition for protective film formation on film-forming and forming a protective film (top coat) is included. Functions necessary for the top coat include coating suitability for actinic ray-sensitive or radiation-sensitive upper film, transparency for radiation, in particular 193 nm, and poorly soluble immersion liquid (preferably water). It is preferable that the composition for protective film formation can be apply | coated uniformly to the actinic-ray-sensitive or radiation-sensitive film surface further, without mixing with an actinic-ray-sensitive or radiation-sensitive film.

The method of application | coating of the composition for protective film formation is not restrict | limited, For example, the spin coat method etc. can be applied.

Although the film thickness of a protective film is not specifically limited, From a viewpoint of transparency with respect to an exposure light source, it is usually formed in thickness of 1 nm-300 nm, Preferably it is 10 nm-300 nm, More preferably, 20 nm-200 nm, More preferably, 30 nm-100 nm. do.

After forming a protective film, a board | substrate is heated as needed.

The refractive index of the protective film is preferably close to the refractive index of the actinic ray-sensitive or radiation-sensitive film from the viewpoint of resolution.

It is preferable that it is insoluble in an immersion liquid, and, as for a protective film, it is more preferable that it is insoluble in water.

From the viewpoint of immersion liquid followability, the receding contact angle of the protective film is preferably a receding contact angle (23 ° C.) of the immersion liquid with respect to the protective film of 50 degrees to 100 degrees, and more preferably 60 degrees to 80 degrees. Even more preferably, the receding contact angle (23 ° C.) of water to the protective film is 50 degrees to 100 degrees, and most preferably, the receding contact angle (23 ° C.) of water to the protective film is 60 degrees to 80 degrees.

In the case where the exposure step in the pattern forming method of the present invention is a liquid immersion exposure step, the exposure head scans the wafer image at high speed to follow the movement of forming the exposure pattern, and the liquid immersion liquid needs to move on the wafer. The contact angle of the immersion liquid to the actinic ray-sensitive or radiation-sensitive film in the phosphorus state becomes important, and in order to obtain better resist performance, it is preferable to have a receding contact angle in the above-mentioned specific range.

<Step of Peeling Protective Film>

As above-mentioned, when peeling a protective film, you may use the organic solvent developing solution, and you may use a peeling agent separately. When peeling is performed separately from a developing process, the time of peeling is preferable after exposure, and, after including the PEB process mentioned later, PEB after PEB is more preferable. As the release agent, a solvent having a small penetration into the actinic ray-sensitive or radiation-sensitive film is preferable. In that a peeling process can be performed simultaneously with the image processing process of an actinic-ray-sensitive or a radiation-sensitive film, it is preferable that it can peel by an organic solvent developing solution. The organic solvent developer used for the peeling is not particularly limited as long as it can dissolve and remove the low exposure portion of the actinic ray-sensitive or radiation-sensitive film, and is not particularly limited. Ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents It can be selected from a developer containing a polar solvent such as a polar solvent and a hydrocarbon solvent, and it is preferable to use a developer containing a ketone solvent, an ester solvent, an alcohol solvent, an ether solvent, and a developer containing an ester solvent. It is more preferable to use, and it is most preferable to use the developing solution containing butyl acetate. From a viewpoint of peeling with an organic solvent developing solution, 1 nm / sec-300 nm / sec of the dissolution rate with respect to an organic solvent developing solution are preferable, and 10 nm / sec-100 nm / sec are more preferable.

Here, the dissolution rate with respect to the organic solvent developer of a protective film is a film thickness reduction rate when it exposes to a developing solution after forming a protective film, and in this invention, it is a speed | rate when immersed in a 23 degreeC butyl acetate solution.

By setting the dissolution rate of the protective film in the organic solvent developer to 1 nm / sec or more, preferably 10 nm / sec or more, there is an effect of reducing the occurrence of development defects after development. Moreover, by setting it as 300 nm / sec or less, Preferably it is 100 nm / sec, there exists an effect that the line edge roughness of the pattern after image development becomes favorable by the influence which the exposure nonuniformity at the time of exposure probably reduced.

You may remove a protective film using other well-known developing solution, for example, aqueous alkali solution. Specifically as aqueous alkali solution which can be used, the aqueous solution of tetramethylammonium hydroxide is mentioned.

Exposure process

Exposure to the actinic ray-sensitive or radiation-sensitive film can be carried out by a generally known method. Preferably, actinic ray or a radiation is irradiated to actinic ray-sensitive or radiation-sensitive film | membrane through a predetermined mask. Although exposure amount can be set suitably, it is 1-100mJ / cm <^2> normally.

Although there is no restriction | limiting in particular in the wavelength of the light source used for the exposure apparatus in this invention, It is preferable to use the light of wavelength 250 nm or less, As examples, KrF excimer laser beam (248 nm), ArF excimer laser beam (193 nm), and the like. F ₂ excimer laser light (157nm), EUV light (13.5nm), there may be mentioned an electron beam or the like. Among these, it is more preferable to use ArF excimer laser beam (193 nm).

In the case of performing the exposure process, a process of washing the surface of the film with an aqueous chemical liquid after (1) forming a film on the substrate, before the exposing step, and / or (2) after the exposing step and before heating the film is performed. You may carry out.

In the case of performing immersion exposure, the liquid is preferably as small as possible with a temperature coefficient of refractive index such that the immersion liquid is transparent to the exposure wavelength and minimizes the distortion of the optical image projected onto the film. Particularly, the exposure light source is an ArF excimer. In the case of laser light (wavelength: 193 nm), in addition to the above-mentioned viewpoint, it is preferable to use water from the viewpoints of the availability and the ease of handling.

When using water, you may add the additive (liquid) which reduces surface tension of water, and increases surface active force in a small ratio. It is preferable that this additive does not dissolve the actinic ray-sensitive or radiation-sensitive film on the wafer and can ignore the influence on the optical coat of the lower surface of the lens element. As water to be used, distilled water is preferable. Further, pure water filtered through an ion exchange filter or the like may be used. Thereby, distortion of the optical image projected on a resist by mixing of an impurity can be suppressed.

Moreover, since the refractive index can be improved further, the medium of refractive index 1.5 or more can also be used. The medium may be an aqueous solution or an organic solvent.

The pattern formation method of this invention may have an exposure process in multiple times. In that case, although the same light source may be used for the multiple times of exposure, and another light source may be used, ArF excimer laser beam (wavelength: 193 nm) is preferable for the 1st exposure.

<Organic Solvent Development Process>

The pattern formation method of this invention includes the process of image development using the organic solvent developing solution.

As an organic solvent which can be used when developing an organic solvent, polar solvents, such as a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, an ether solvent, and a hydrocarbon solvent, can be used. For example, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, Methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, acetone yl acetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methylnaphthyl ketone, isophorone, propylene carbonate, etc. Ketone solvent, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl Ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, foam Butyl, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ester solvents such as 2-hydroxy-iso-butyric acid methyl, butyl view carbonate can be used.

As the alcohol solvent, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n Alcohols such as octyl alcohol and n-decanol; glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, and propylene glycol Glycol ether solvents such as monomethyl ether, ethylene glycol, propylene glycol, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol Can be mentioned.

Examples of the ether solvent include dioxane, tetrahydrofuran and the like in addition to the glycol ether solvent.

As the amide solvent, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imide Dazolidinone etc. can be used.

Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents such as aromatic hydrocarbon solvents such as toluene and xylene, pentane, hexane, octane, and decane.

Two or more said solvents may be mixed, and you may use it, mixing with a solvent and water of that excepting the above.

As a developing method, a method of developing by raising a developer solution on a surface of a substrate by surface tension and stopping for a predetermined time (puddle method), a method of spraying a developer solution on a surface of a substrate (spray method), and a constant on a substrate rotating at a constant speed There is a method of continuously discharging the developer while scanning the developer discharge nozzle at a speed (dynamic dispensing method).

The vapor pressure of the negative developer is preferably 5 kPa or less, more preferably 3 kPa or less, and most preferably 2 kPa or less at 20 ° C. By setting the vapor pressure of the negative developer at 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, thereby improving the temperature uniformity in the wafer surface and consequently improving the dimensional uniformity in the wafer surface.

As a specific example which has a vapor pressure of 5 kPa or less at 20 degreeC, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl ketone, cyclohexane Ketone solvents such as ionic, methylcyclohexanone, phenylacetone, methyl isobutyl ketone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol Colonobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, formic acid butyl, formic acid Ester solvents such as propyl, ethyl lactate, butyl lactate, propyl lactate, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n Heptyl alcohol alcohol solvents such as n-octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, and propylene Glycol ethers such as glycol monomethyl ether, ethylene glycol, propylene glycol, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol Solvents, ether solvents such as tetrahydrofuran, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, amide solvents of N, N-dimethylformamide, aromatics such as toluene and xylene And aliphatic hydrocarbon solvents such as hydrocarbon solvents, octane and decane.

As a specific example which has a vapor pressure of 2 kPa or less in 20 degreeC which is the most preferable range, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 4-heptanone, 2-hexanone, diisobutyl Ketone solvents such as ketones, cyclohexanone, methylcyclohexanone, and phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and diethylene glycol Monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate , Ester solvents such as lactic acid propyl, alcohols such as n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol Solvent, ethylene glycol Glycol solvents such as diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol, propylene glycol, diethylene Glycol ether solvents such as glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethylbutanol, N-methyl-2-pyrrolidone, N, N-dimethylacetamide And aromatic hydrocarbon solvents such as amide solvents of N, N-dimethylformamide and aromatic hydrocarbon solvents such as xylene, and aliphatic hydrocarbon solvents such as octane and decane.

A suitable amount of surfactant can be added to the developing solution which can be used when performing negative development.

Although it does not specifically limit as surfactant, For example, ionic and nonionic fluorine type and / or silicone type surfactant etc. can be used. As these fluorine type and / or silicone type surfactant, For example, Unexamined-Japanese-Patent No. 62-36663, Unexamined-Japanese-Patent No. 61-226746, Unexamined-Japanese-Patent No. 61-226745, and Japan Unexamined-Japanese-Patent No. 62- 170950, Japanese Patent Laid-Open No. 63-34540, Japanese Patent Laid-Open No. 7-230165, Japanese Patent Laid-Open No. 8-62834, Japanese Patent Laid-Open No. 9-54432, Japanese Patent Laid-Open No. 9- Surfactants described in 5988, U.S. Patent No. 557520, 5360692, 5529881, 5296330, 5436098, 5576143, 5294511, 5824451, and preferably non- It is an ionic surfactant. Although it does not specifically limit as nonionic surfactant, It is more preferable to use a fluorochemical surfactant or silicone type surfactant.

The usage-amount of surfactant is 0.001-5 mass% normally with respect to the total amount of a developing solution, Preferably it is 0.005-2 mass%, More preferably, it is 0.01-0.5 mass%.

The organic solvent developing solution may contain the basic compound. Specific examples and preferred examples of the basic compound which may be contained in the organic solvent developer used in the present invention are the same as those described below as the basic compound which may be included in the actinic ray-sensitive or radiation-sensitive resin composition.

As a developing method, for example, a method of immersing a substrate in a bath filled with a developer for a certain time (dip method), a method of developing a developer by raising the developer solution on the surface of the substrate by surface tension to stop for a certain time (puddle method), and a developer on the substrate surface. The spraying method (spray method) and the method (dynamic dispensing method) etc. which continue to discharge a developing solution while scanning a developing nozzle discharge nozzle at a fixed speed on the board | substrate which rotates at a fixed speed are applicable.

Rinse process

Moreover, you may perform the rinse process which stops image development, substituting to other solvent, after the process of organic solvent image development.

As a rinse liquid used for the rinse process after organic-solvent image development, if a resist pattern is not melt | dissolved, there will be no restriction | limiting in particular, The solution containing the general 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 a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent. More preferably, after the negative development, a step of washing using a rinse liquid containing at least one organic solvent selected from a ketone solvent, an ester solvent, an alcohol solvent, and an amide solvent is performed. Even more preferably, after the negative development, a step of washing with a rinse liquid containing an alcohol solvent or an ester solvent is performed. Especially preferably, after negative development, the process of washing | cleaning using the rinse liquid containing monohydric alcohol is performed. Here, as a monohydric alcohol used by the rinsing process after negative image development, a linear, branched, cyclic monohydric alcohol is mentioned, Specifically, 1-butanol, 2-butanol, 3-methyl -1-Butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol , 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used, and preferably 1-hexanol, 2-hexanol, 1-pentanol, 3-methyl-1- Butanol.

Two or more said each components may be mixed, and you may use it, mixing with the organic solvent of that excepting the above.

10 mass% or less is preferable, as for the water content in a rinse liquid, More preferably, it is 5 mass% or less, Especially preferably, it is 3 mass% or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

As for the vapor pressure of the rinse liquid used after organic solvent image development, 0.05 kPa or more and 5 kPa or less are preferable at 20 degreeC, 0.1 kPa or more and 5 kPa or less are more preferable, 0.12 kPa or more and 3 kPa or less are the most preferable. By setting the vapor pressure of the rinse liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity in the wafer surface is improved, and further, the swelling caused by the penetration of the rinse liquid is suppressed, and the dimensional uniformity in the wafer surface is improved.

An appropriate amount of surfactant can also be added and used for a rinse liquid.

In the rinsing step, the wafer on which the organic solvent development has been performed is washed using a rinse liquid containing the above organic solvent. Although the method of a washing process is not specifically limited, For example, the method of continuing to discharge a rinse liquid on the board | substrate which rotates by a fixed speed (rotary coating method), and the method of immersing a board | substrate for a predetermined time in the tank filled with the rinse liquid (dip method) ), A method of spraying a rinse liquid onto the surface of the substrate (spray method) and the like can be applied. Among them, the cleaning treatment is performed by a rotary coating method, and after washing, the substrate is rotated at a rotational speed of 2000 rpm to 4000 rpm to obtain a rinse liquid. It is desirable to remove from the substrate.

<Alkali development process>

The pattern formation method of this invention may further include the process of image development using alkaline developing solution.

Examples of the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and aqueous ammonia, first amines such as ethylamine and n-propylamine, diethylamine and di-n-butylamine Third amines such as second amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, fourth such as tetramethylammonium hydroxide and tetraethylammonium hydroxide Alkaline aqueous solutions, such as cyclic amines, such as a quaternary ammonium salt, a pyrrole, and piperidine, can be used. Among these, it is preferable to use the aqueous solution of tetraethylammonium hydroxide.

Moreover, alcohol and surfactant can also be added and used for the said alkaline developing solution.

The alkali concentration of alkali developing solution is 0.01-20 mass% normally.

The pH of alkaline developing solution is 10.0-15.0 normally.

The time for developing using alkaline developing solution is 10 to 300 second normally.

The alkali concentration (and pH) and developing time of an alkaline developing solution can be suitably adjusted according to the pattern to form.

As a rinse liquid of the rinse process performed after an alkali image development process, pure water can be used, and surfactant can also be added and used an appropriate amount.

In addition, after the development treatment or the rinse treatment, a treatment for removing the developer or rinse liquid attached to the pattern by a supercritical fluid can be performed.

In addition, after the rinse treatment or the treatment with the supercritical fluid, heat treatment may be performed to remove moisture remaining in the pattern.

[Heating process]

The pattern formation method of this invention may further include the heating process, and may include the heating process in multiple times.

The pattern formation method of this invention WHEREIN: In one aspect, after the formation of an actinic-ray-sensitive or radiation-sensitive film, and / or after formation of a protective film, it is preheated ("PB" (Prebake; PB) or "free"). Baking ").

That is, the pattern formation method of this invention may include the prebaking process between the process of forming an actinic-ray-sensitive or radiation-sensitive film, and the process of forming a protective film, and the process of forming a protective film, and exposure It may be included between processes, and may include the prebaking process in both. By prebaking, an insoluble residual solvent can be removed and a uniform film | membrane can be formed. Below, the process of forming an actinic-ray-sensitive or radiation-sensitive film and the prebaking process performed between the process of forming a protective film are called "PB process before protective film formation", and the process of forming a protective film and the exposure process of The prebaking process performed in between is called "PB process after protective film formation", etc.

50 degreeC-160 degreeC is preferable, for example, and, as for the heating temperature in the PB process before protective film formation, 60 degreeC-140 degreeC is more preferable.

80 degreeC-160 degreeC is preferable, for example, as for the heating temperature in the PB process after protective film formation, 100 degreeC-150 degreeC is more preferable, 110 degreeC-145 degreeC is more preferable, 120 degreeC-140 degreeC is Particularly preferred. By making the prebaking temperature after protective film formation high, it becomes easy to collect a low molecular component in the resist film side of a top coat, and the effect of improving DOF becomes higher.

Moreover, it is preferable that the pattern formation method of this invention includes a post exposure baking (PEB) process after an exposure process and before a image development process in another form. The reaction of the exposed portion is promoted by the PEB, and the sensitivity and the pattern profile are improved.

As for the heating temperature in a PEB process, 40 degreeC-160 degreeC is preferable, for example.

The heating time is not particularly limited in any of the PB process and the PEB process, for example, 30 to 300 seconds is preferable, 30 to 180 seconds is more preferable, and 30 to 90 seconds is more preferable.

Heating can be performed by the means with which the normal exposure and developing apparatus were equipped, and you may perform using a hotplate etc.

<Active ray sensitive or radiation sensitive resin composition>

Next, the actinic ray sensitive or radiation sensitive resin composition used suitably in the pattern formation method of this invention is demonstrated.

delete

(A) Resin whose polarity is increased by the action of acid

Resin whose polarity is increased by the action of acid used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is decomposed by the action of acid on both the main chain and the side chain of the resin, or both the main chain and the side chain. To form an alkali-soluble group (hereinafter also referred to as "acid-decomposable group") (referred to as "acid-decomposable resin", "acid-decomposable resin (A)" or "resin (A)"), and monocyclic Or a resin having a polycyclic alicyclic hydrocarbon structure, which has an increased polarity by the action of an acid, an increase in solubility in an alkaline developer, and a decrease in solubility in an organic solvent (hereinafter referred to as an "alicyclic hydrocarbon-based acid-decomposable resin"). Is also referred to as). Although the reason is not clear, the positive developer (preferably, alkaline developer) and the negative developer (preferably, organic solvent) may be caused by a large change in the polarity of the resin before and after irradiation of actinic light or radiation. It is thought that it is due to the improvement of the dissolution contrast at the time of developing using. Furthermore, a resin having a monocyclic or polycyclic alicyclic hydrocarbon structure has high hydrophobicity and develops a region in which light irradiation intensity of the actinic ray-sensitive or radiation-sensitive film is weak by a negative developer (preferably an organic solvent). It is thought that developability in the case of improvement is made.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention containing a resin whose polarity increases by the action of an acid can be suitably used when irradiating an ArF excimer laser beam.

As an alkali-soluble group contained in alicyclic hydrocarbon type acid-decomposable resin, a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonyl imide group, (alkylsulfonyl) (alkylcarbonyl) methylene Group, (alkylsulfonyl) (alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group And groups having a tris (alkylcarbonyl) methylene group and a tris (alkylsulfonyl) methylene group.

Preferred alkali-soluble groups include carboxylic acid groups, fluorinated alcohol groups (preferably hexafluoroisopropanol), and sulfonic acid groups.

A group preferable as an acid-decomposable group is group which substituted the hydrogen atom of these alkali-soluble groups with the group which detach | desorbs with an acid.

As a group which detach | desorbs with an acid, it is, for example, -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), -C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ) etc. are mentioned.

In the formula, each of R ₃₆ to R ₃₉ independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

R ₀₁ to 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 acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group, or the like. More preferably, it is a tertiary alkyl ester group.

As alicyclic hydrocarbon type acid-decomposable resin of this invention, it is represented by the repeating unit which has a partial structure containing alicyclic hydrocarbon represented by the following general formula (pI)-general formula (pV), and the following general formula (II-AB) It is preferable that it is resin containing at least 1 sort (s) chosen from the group of a repeating unit.

[Formula 45]

In general formula (pI)-(pV),

R ₁₁ represents a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group or sec-butyl group, and Z represents an atomic group necessary for forming a cycloalkyl group together with a carbon atom.

R <_12> -R <_16> respectively independently represents a C1-C4 linear or branched alkyl group or a cycloalkyl group. Provided that at least one of R ₁₂ to R ₁₄ or any one of R ₁₅ and R ₁₆ represents a cycloalkyl group.

R <_17> -R <_21> respectively independently represents a hydrogen atom, a C1-C4 linear or branched alkyl group or a cycloalkyl group. Provided that at least one of R ₁₇ to R ₂₁ represents a cycloalkyl group. In addition, any one of R <_19> , R <_21> represents a C1-C4 linear or branched alkyl group or a cycloalkyl group.

R <_22> -R <_25> respectively independently represents a hydrogen atom, a C1-C4 linear or branched alkyl group or a cycloalkyl group. Provided that at least one of R ₂₂ to R ₂₅ represents a cycloalkyl group. In addition, R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

[Formula 46]

In general formula (II-AB),

R ₁₁ ′ and R ₁₂ ′ each independently represent a hydrogen atom, a cyano group, a halogen atom, or an alkyl group.

Z 'contains the combined 2 carbon atoms (C-C), and represents the atomic group for forming an alicyclic structure.

Moreover, it is more preferable that said general formula (II-AB) is the following general formula (II-AB1) or general formula (II-AB2).

[Formula 47]

In formulas (II-AB1) and (II-AB2),

R ₁₃ 'to R ₁₆ ' each independently represent a hydrogen atom, a halogen atom, a cyano group, -COOH, -COOR ₅ , a group decomposed by the action of an acid, -C (= O) -X-A '-R ₁₇ ' represents an alkyl group or a cycloalkyl group. At least two of R ₁₃ 'to R ₁₆ ' may be bonded to each other to form a ring.

Here, R <_5> represents the group which has an alkyl group, a cycloalkyl group, or a lactone structure.

X is an oxygen atom, a sulfur atom, -NH-, -NHSO ₂ - or denotes a -NHSO ₂ NH-.

A 'represents a single bond or a bivalent coupling group.

R ₁₇ ′ represents a group having a —COOH, —COOR ₅ , —CN, a hydroxyl group, an alkoxy group, —CO—NH—R ₆ , —CO—NH—SO ₂ —R _6, or a lactone structure.

R ₆ is an alkyl or cycloalkyl group.

n represents 0 or 1.

In general formula (pI)-(pV), as an alkyl group in R <_12> -R <_25> , the linear or branched alkyl group which has 1-4 carbon atoms is represented.

Monocyclic or polycyclic may be sufficient as the cycloalkyl group in R <_11> -R <_25> , or the cycloalkyl group which Z and a carbon atom form. Specifically, group which has a C5 or more monocyclo, bicyclo, tricyclo, tetracyclo structure, etc. are mentioned. 6-30 are preferable and, as for the carbon number, 7-25 are especially preferable. These cycloalkyl groups may have a substituent.

As a preferable cycloalkyl group, an adamantyl group, a noadamantyl group, a decalin residue, a tricyclodecaneyl group, a tetracyclo dodecaneyl group, a norbornyl group, a cedrol group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclo Decanyl group and cyclododecaneyl group are mentioned. More preferably, an adamantyl group, a norbornyl group, a cyclohexyl group, a cyclopentyl group, a tetracyclo dodecaneyl group, and a tricyclodecaneyl group are mentioned.

As further substituents of these alkyl groups and cycloalkyl groups, an alkyl group (C1-C4), a halogen atom, a hydroxyl group, an alkoxy group (C1-C4), a carboxyl group, an alkoxycarbonyl group (C2-C6) is mentioned. As a substituent which the said alkyl group, the alkoxy group, the alkoxycarbonyl group, etc. may further have, a hydroxyl group, a halogen atom, an alkoxy group is mentioned.

The structure represented by general formula (pI)-(pV) in the said resin can be used for protection of alkali-soluble group. Examples of the alkali-soluble group include various groups known in the art.

Specifically, the structure in which the hydrogen atom of a carboxylic acid group, a sulfonic acid group, a phenol group, and a thiol group was substituted by the structure represented by general formula (pI)-(pV) is mentioned, Preferably the hydrogen of a carboxylic acid group and a sulfonic acid group is mentioned. It is a structure where the atom substituted by the structure represented by general formula (pI)-(pV).

As a repeating unit which has the alkali-soluble group protected by the structure represented by general formula (pI)-(pV), the repeating unit represented by the following general formula (pA) is preferable.

[Formula 48]

Here, R represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. Some R may be same or different, respectively.

A is a single bond, an alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a combination of two or more groups selected from the group consisting of urea groups Indicates. Preferably it is a single bond.

Rp ₁ represents any one of the formulas (pI) to (pV).

The repeating unit represented by general formula (pA) is particularly preferably a repeating unit with 2-alkyl-2-adamantyl (meth) acrylate and dialkyl (1-adamantyl) methyl (meth) acrylate. to be.

Hereinafter, although the specific example of the repeating unit represented by general formula (pA) is shown, this invention is not limited to this.

[Formula 49]

[Formula 50]

As the halogen atom in the general formula _{(II-AB), R 11} ', R 12', there may be mentioned a chlorine atom, a bromine atom, a fluorine atom, iodine atom and the like.

Examples of the alkyl group in R ₁₁ ′ and R ₁₂ ′ include a linear or branched alkyl group having 1 to 10 carbon atoms.

The atomic group for forming the alicyclic structure of Z 'is an atomic group for forming a repeating unit of an alicyclic hydrocarbon which may have a substituent in the resin, and among them, a bridge bridge forming a repeating unit of an alicyclic type alicyclic hydrocarbon. Atom groups for forming an alicyclic structure are preferable.

As a skeleton of the alicyclic hydrocarbon formed, the thing similar to the alicyclic hydrocarbon group of R <_12> -R <_25> in general formula (pI)-(pV) is mentioned.

The skeleton of the alicyclic hydrocarbon may have a substituent. As such a substituent, R <_13>'-R<_16>' in the said general formula (II-AB1) or (II-AB2) is mentioned.

In the alicyclic hydrocarbon-based acid-decomposable resin according to the present invention, the group decomposed by the action of an acid includes a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by the above general formulas (pI) to (pV). , The repeating unit represented by General Formula (II-AB), and the repeating unit of the following copolymerization component can be contained in at least one repeating unit. The group decomposed by the action of an acid is preferably contained in a repeating unit having a partial structure containing an alicyclic hydrocarbon represented by General Formulas (pI) to (pV).

Various substituents of R ₁₃ 'to R ₁₆ ' in General Formula (II-AB1) or General Formula (II-AB2) are atomic groups for forming an alicyclic structure in General Formula (II-AB). It may also be a substituent of the atomic group Z to form a bridged alicyclic structure.

Although the following specific examples are mentioned as a repeating unit represented by the said general formula (II-AB1) or general formula (II-AB2), This invention is not limited to these specific examples.

[Formula 51]

It is preferable that the alicyclic hydrocarbon type acid-decomposable resin of this invention has a lactone group. Although any contribution can be used as long as it contains a lactone structure, Preferably it is a group containing a 5-7 member cyclic lactone structure, It is a form which forms a bicyclo structure and a spiro structure in a 5-7 member cyclic lactone structure. It is preferable that the other ring structure is condensed. It is more preferable to have a repeating unit having a group having a lactone structure represented by any one of the following General Formulas (LC1-1) to (LC1-16). Moreover, the group which has a lactone structure may couple | bond directly with the main chain. As a preferable lactone structure, it is group represented by general formula (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), and shows a specific lactone structure By using it, the line edge roughness and a development defect become favorable.

[Formula 52]

The lactone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂₎ As the alkyl group having 1 to 8 carbon atoms, having a carbon number of 4-7 of the cycloalkyl group, having from 1 to 8 carbon atoms in the alkoxy group, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, among Anano group, an acid-decomposable group, etc. are mentioned. n ₂ represents an integer of 0-4. n Rb ₂ to ₂ when 2 or more, a plurality is present, be the same or be different, and may be also bonded to form a plurality presence ring is bonded between the _two Rb.

Of R ₁₃ '~ R _16' in general formula (LC1-1) ~ Examples of any one repeating unit having a group having a lactone structure represented the general formula (II-AB1) or (II-AB2) of (LC1-16) At least one having a group represented by formulas (LC1-1) to (LC1-16) (for example, R ₅ of -COOR ₅ represents a group represented by formulas (LC1-1) to (LC1-16)) Or a repeating unit represented by the following General Formula (AI).

[Formula 53]

In general formula (AI),

R _b0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.

As a preferable substituent is an alkyl group of R _b0 which may have, there may be mentioned a halogen atom a hydroxyl group, a.

As a halogen atom of R <_b0> , a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

R _b0 is preferably a hydrogen atom or a methyl group.

A _b represents a divalent linking group having a single bond, an alkylene group, a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, or a divalent group having a combination thereof. Preferably, it is a coupling group represented by a single bond, -Ab ₁ -CO _2- . Ab ₁ is a linear, branched alkylene group, monocyclic or polycyclic cycloalkylene group, and preferably methylene group, ethylene group, cyclohexylene group, adamantylene group, norbornylene group.

V represents a group represented by any one of General Formulas (LC1-1) to (LC1-16).

The repeating unit having a lactone structure usually has an optical isomer, but any optical isomer may be used. Moreover, 1 type of optical isomers may be used independently, and several optical isomers may be mixed and used. When mainly using one type of optical isomer, it is preferable that the optical purity (ee) is 90 or more, More preferably, it is 95 or more.

Although the specific example of the repeating unit which has group which has a lactone structure is given to the following, this invention is not limited to these.

[Formula 54]

[Formula 55]

[Formula 56]

It is preferable that the alicyclic hydrocarbon type acid-decomposable resin of this invention has a repeating unit containing the organic group which has a polar group, especially the repeating unit which has an alicyclic hydrocarbon structure substituted by the polar group. As a result, substrate adhesion and developer affinity are improved. As an alicyclic hydrocarbon structure of the alicyclic hydrocarbon structure substituted by the polar group, an adamantyl group, a diamanthyl group, and a norbornene group are preferable. As a polar group, a hydroxyl group and a cyano group are preferable.

As an alicyclic hydrocarbon structure substituted by the polar group, the partial structure represented by the following general formula (VIIa)-(VIId) is preferable.

[Formula 57]

In general formula (VIIa)-(VIIc),

R _2c to R _4c each independently represent a hydrogen atom, a hydroxyl group, or a cyano group. Provided that at least one of R _2c to R _4c represents a hydroxyl group or a cyano group. Preferably R _2c ~ R _4c One or two of them are hydroxyl groups and the rest are hydrogen atoms.

In general formula (VIIa), More preferably, two of R <_2c> -R <_4c> are hydroxyl groups, and the other is a hydrogen atom.

As the repeating unit having a group represented by the general formula (VIIa) ~ (VIId), the general formula (II-AB1) or (II-AB2) of the R ₁₃ '~ R _16' is at least one of the following general formula (VIIa) ~ will appear as shown by having a (VIId) (for example, a represents an R ₅ in -COOR ₅ represented by the general formula (VIIa) ~ (VIId)) , or the following formula (AIIa) ~ (AIId) Repeating units; and the like.

[Formula 58]

In general formula (AIIa)-(AIId),

R _1c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

R _2c ~ R _4c is a ~ R _2c and R _4c agree in the general formula (VIIa) ~ (VIIc).

Although the specific example of the repeating unit which has a structure represented by general formula (AIIa)-(AIId) is given to the following, this invention is not limited to these.

[Formula 59]

The alicyclic hydrocarbon-based acid decomposable resin of the present invention may have a repeating unit represented by the following General Formula (VIII).

[Formula 60]

In the general formula (VIII),

Z ₂ represents -O- or -N (R ₄₁ )-. R ₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group or -OSO ₂ -R ₄₂ . R ₄₂ represents an alkyl group, a cycloalkyl group, or a camphor residue. The alkyl group of R ₄₁ and R ₄₂ may be substituted with a halogen atom (preferably a fluorine atom) or the like.

Although the following specific examples are mentioned as a repeating unit represented by said general formula (VIII), This invention is not limited to these.

[Formula 61]

It is preferable to have a repeating unit which has an alkali-soluble group, and, as for the alicyclic hydrocarbon type acid-decomposable resin of this invention, it is more preferable to have a repeating unit which has a carboxyl group. By containing this, the resolution in contact hole use increases. As a repeating unit which has a carboxyl group, the repeating unit which the carboxyl group couple | bonds with the principal chain of resin directly, such as the repeating unit by acrylic acid or methacrylic acid, or the repeating unit which the carboxyl group couple | bonds with the main chain of resin through a coupling group, and also alkali Any of the repeating units introduced at the terminal of the polymer chain using a polymerization initiator or a chain transfer agent having a soluble group at the time of polymerization is preferable, and the linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure. Especially preferably, it is a repeating unit by acrylic acid and methacrylic acid.

The alicyclic hydrocarbon-based acid-decomposable resin of the present invention may further have a repeating unit having 1 to 3 groups represented by General Formula (F1). This improves line edge roughness performance.

[Formula 62]

In general formula (F1),

R ₅₀ to R ₅₅ each independently represent a hydrogen atom, a fluorine atom or an alkyl group. However, at least one of R ₅₀ to R ₅₅ represents an alkyl group in which a fluorine atom or at least one hydrogen atom is substituted with a fluorine atom.

Rx represents a hydrogen atom or an organic group (preferably an acid-decomposable protecting group, alkyl group, cycloalkyl group, acyl group, alkoxycarbonyl group).

The alkyl group of R ₅₀ to R ₅₅ may be substituted with a halogen atom such as a fluorine atom, a cyano group, or the like, and preferably an alkyl group having 1 to 3 carbon atoms, for example, a methyl group or a trifluoromethyl group. .

It is preferable that all of R ₅₀ to R ₅₅ are fluorine atoms.

As the organic group represented by Rx, an alkyl group, a cycloalkyl group, an acyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkoxycarbonylmethyl group, an alkoxymethyl group and 1-alkoxyethyl group which may have an acid-decomposable protecting group and a substituent are preferable.

As a repeating unit which has group represented by general formula (F1), It is a repeating unit preferably represented by the following general formula (F2).

[Formula 63]

In general formula (F2),

Rx represents a hydrogen atom, a halogen atom, or a C1-C4 alkyl group. As a preferable substituent which the alkyl group of Rx may have, a hydroxyl group and a halogen atom are mentioned.

Fa represents a single bond, a straight chain or a branched alkylene group (preferably a single bond).

Fb represents a monocyclic or polycyclic cyclic hydrocarbon group.

Fc represents a single bond, a straight chain or a branched alkylene group (preferably a single bond, a methylene group).

F ₁ represents a group represented by General Formula (F1).

P ₁ represents 1-3.

As a cyclic hydrocarbon group in Fb, a cyclopentylene group, a cyclohexylene group, and a norbornylene group is preferable.

Although the specific example of the repeating unit which has group represented by general formula (F1) is shown below, this invention is not limited to this.

[Formula 64]

The alicyclic hydrocarbon-based acid decomposable resin of the present invention may further contain a repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposability. Thereby, the elution of the low molecular component from the actinic ray-sensitive or radiation-sensitive film to the immersion liquid at the time of immersion exposure can be reduced. As such a repeating unit, 1-adamantyl (meth) acrylate, tricyclodecaneyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. are mentioned, for example.

The alicyclic hydrocarbon-based acid-decomposable resin of the present invention can be used for various purposes such as dry etching resistance, standard developer aptitude, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc., which are general necessary characteristics of resist, in addition to the above repeating units. It may contain a repeating unit.

Although a repeating unit corresponded to the following monomer is mentioned as such a repeating unit, It is not limited to these.

As a result, the performance required for the alicyclic hydrocarbon-based acid-decomposable resin, in particular, (1) solubility in a coating solvent, (2) film forming property (glass transition temperature), (3) solubility in positive developer and negative developer, Fine adjustment of (4) film | membrane reducing property (selection of hydrophilicity, alkali-soluble group), (5) adhesiveness with respect to the board | substrate of an unexposed part, (6) dry etching resistance, etc. becomes possible.

As such a monomer, for example, having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like. Compounds and the like.

In addition, as long as it is an addition polymerizable unsaturated compound copolymerizable with the monomer corresponding to the said various repeating unit, you may copolymerize.

In the alicyclic hydrocarbon-based acid-decomposable resin, the molar ratio of each repeating unit is used to adjust the dry etching resistance of the resist, the standard developer aptitude, the substrate adhesion, the resist profile, and the resolution, heat resistance, sensitivity, etc., which are general necessary performances of the resist. Is set appropriately.

As a preferable aspect of the alicyclic hydrocarbon type acid-decomposable resin of this invention, the following are mentioned.

(1) It contains the repeating unit which has a partial structure containing the alicyclic hydrocarbon represented by said general formula (pI)-(pV) (side chain type).

Preferably, it contains the (meth) acrylate repeating unit which has a structure of (pI)-(pV).

(2) The repeating unit represented by general formula (II-AB) is contained (backbone type).

However, in (2), the following are further mentioned, for example.

(3) Having a repeating unit represented by general formula (II-AB), a maleic anhydride derivative, and a (meth) acrylate structure (hybrid type).

As for content of the repeating unit which has an acid-decomposable group, in alicyclic hydrocarbon type acid-decomposable resin, 10-60 mol% is preferable in all the repeating units, More preferably, it is 20-50 mol%, More preferably, it is 25-40 mol %to be.

In an acid-decomposable resin, 10-60 mol% is preferable in all the repeating units, and, as for content of the repeating unit which has an acid-decomposable group, 20-50 mol%, More preferably, it is 25-40 mol%.

As for content of the repeating unit which has a partial structure containing alicyclic hydrocarbon represented by general formula (pI)-(pV), in alicyclic hydrocarbon type acid-decomposable resin, 20-70 mol% is preferable in all the repeating units, More preferably, it is 20-50 mol%, More preferably, it is 25-40 mol%.

As for content of the repeating unit represented by general formula (II-AB), in alicyclic hydrocarbon type acid-decomposable resin, 10-60 mol% is preferable in all the repeating units, More preferably, it is 15-55 mol%, More preferably Is 20-50 mol%.

As for content of the repeating unit which has a lactone ring in acid-decomposable resin, 10-70 mol% is preferable in all the repeating units, More preferably, it is 20-60 mol%, More preferably, it is 25-40 mol%.

As for content of the repeating unit which has an organic group which has a polar group in acid-decomposable resin, 1-40 mol% is preferable in all the repeating units, More preferably, it is 5-30 mol%, More preferably, it is 5-20 mol%. .

Moreover, although content in resin of the repeating unit based on the monomer of the said additional copolymerization component can also be set suitably according to the performance of a desired resist, Generally, alicyclic hydrocarbon represented by said general formula (pI)-(pV) is used. 99 mol% or less is preferable with respect to the total total number of moles of the repeating unit which has a partial structure containing, and the repeating unit represented with the said general formula (II-AB), More preferably, it is 90 mol% or less, More preferably, 80 Mol% or less.

When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is for ArF exposure, the resin preferably has no aromatic group in terms of transparency to ArF light.

As alicyclic hydrocarbon type acid-decomposable resin used for this invention, Preferably, the whole repeating unit is comprised from the (meth) acrylate type repeating unit. In this case, although all the repeating units may be any of a mixture of methacrylate-based repeating units, the entire repeating unit is an acrylate-based repeating unit, and the entire repeating unit is a mixture of methacrylate-based repeating units / acrylate-based repeating units, It is preferable that an acrylate type repeating unit is 50 mol% or less of all the repeating units.

The alicyclic hydrocarbon-based acid-decomposable resin includes at least an (meth) acrylate-based repeating unit having an organic group substituted with at least one of a (meth) acrylate-based repeating unit having a lactone ring, a hydroxyl group and a cyano group, and an acid-decomposable It is preferable that it is a copolymer which has three types of repeating units of the (meth) acrylate type repeating unit which has group.

Preferably 20-50 mol% of repeating units which have a partial structure containing alicyclic hydrocarbon represented by general formula (pI)-(pV), 20-50 mol% of repeating units which have a lactone structure, alicyclic substituted by a polar group It is a ternary copolymer polymer containing 5-30 mol% of repeating units which have a hydrocarbon structure, or the quaternary copolymer polymer containing 0-20 mol% of other repeating units further.

As especially preferable resin, 20-50 mol% of repeating units which have an acid-decomposable group represented by the following general formula (ARA-1)-(ARA-7), and lactone represented by the following general formula (ARL-1)-(ARL-7) Ternary copolymer containing 20-50 mol% of repeating units which have a group, and 5-30 mol% of repeating units which have an alicyclic hydrocarbon structure substituted by the polar group represented by the following general formula (ARH-1)-(ARH-3) Or a 4-membered copolymer polymer further comprising 5 to 20 mol% of repeating units having a carboxyl group or a structure represented by General Formula (F1) or an alicyclic hydrocarbon structure and not exhibiting acid decomposability.

(In the formulas, Rxy ₁ is a hydrogen atom or a methyl group, Rxa ₁ and Rxb ₁ each independently, represent a methyl group or an ethyl group, Rxc ₁ represents a hydrogen atom or a methyl group.)

[Formula 65]

(In formula, Rxy ₁ represents a hydrogen atom or a methyl group, Rxd ₁ represents a hydrogen atom or a methyl group, Rxe ₁ represents a trifluoromethyl group, a hydroxyl group, and a cyano group.)

[Formula 66]

(In the formulas, Rxy ₁ represents a hydrogen atom or a methyl group.)

[Formula 67]

Alicyclic hydrocarbon type acid-decomposable resin used for this invention can be synthesize | combined according to a conventional method (for example, radical polymerization). For example, as a general synthetic method, the batch polymerization method which melt | dissolves a monomer species and an initiator in a solvent, and superposes | polymerizes by heating, and the dropping polymerization method which adds the solution of a monomer species and an initiator dropwise for 1 to 10 hours, and adds to a heating solvent Etc. are mentioned, and the dropping polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and ester solvents such as ethyl acetate and dimethyl formamide. And amide solvents such as dimethylacetamide, and solvents for dissolving the composition of the present invention such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone which will be described later. . More preferably, polymerization is carried out using the same solvent as the solvent used in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. As a result, generation of particles during storage can be suppressed.

It is preferable that a polymerization reaction is performed in inert gas atmosphere, such as nitrogen and argon. As a polymerization initiator, superposition | polymerization is started using a commercially available radical initiator (azo initiator, peroxide, etc.). As a radical initiator, an azo initiator is preferable and the azo initiator which has an ester group, a cyano group, and a carboxyl group is preferable. Preferred initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate) and the like. According to the purpose, an initiator is added or added in portions, and after completion of the reaction, it is added to a solvent to recover a desired polymer by a method such as powder or solid recovery. The concentration of the reactants is 5 to 50% by mass, preferably 10 to 30% by mass. Reaction temperature is 10 degreeC-150 degreeC normally, Preferably it is 30 degreeC-120 degreeC, More preferably, it is 60-100 degreeC.

The purification can use the same method as resin (C) mentioned later, The solution state, such as the liquid-liquid extraction method which removes a residual monomer and an oligomer component by washing with water and combining an appropriate solvent, and the ultrafiltration which extracts and removes only the thing below a specific molecular weight. In a solid state, such as a refining method for refining, a reprecipitation method for removing residual monomers, etc. by solidifying the resin in the poor solvent by dropping the resin solution into the poor solvent, or washing the filtered resin slurry with the poor solvent. Conventional methods, such as a purification method, can be applied.

The weight average molecular weight of resin which concerns on this invention is polystyrene conversion value by GPC method, Preferably it is 1,000-200,000, More preferably, it is 1,000-20,000, Most preferably, it is 1,000-15,000. By setting a weight average molecular weight to 1,000-200,000, deterioration of heat resistance and dry etching resistance can be prevented, and developability deteriorates, a viscosity becomes high, and it can prevent that film forming property deteriorates.

Dispersion degree (molecular weight distribution) is 1-5 normally, Preferably it is 1-3, More preferably, it is 1.2-3.0, Especially preferably, the thing of the range of 1.2-2.0 is used. The smaller the dispersion degree, the better the resolution and the resist shape, the smoother the sidewall of the resist pattern, and the better the roughness.

In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the blending amount of the acid-decomposable resin in the whole composition is preferably 50 to 99.9 mass% in the total solids, more preferably 60 to 99.9 mass%.

In addition, in this invention, acid-decomposable resin may be used by 1 type, and may be used together in plurality.

The alicyclic hydrocarbon-based acid-decomposable resin of the present invention, more preferably, in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, does not contain a fluorine atom and a silicon atom from the viewpoint of compatibility with the composition for forming a protective film. It is preferable.

(B) a compound which generates an acid by irradiation of actinic light or radiation

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a compound (also referred to as "photoacid generator" or "compound (B)") which generates an acid by irradiation of actinic light or radiation.

As such a photo-acid generator, the well-known photo-acid generator which generate | occur | produces the acid by irradiation of the actinic light or radiation used for the photoinitiator of photocationic polymerization, the photoinitiator of photoradical polymerization, the photochromic agent of pigment | dye, photochromic agent, or microresist etc. Compounds and mixtures thereof may be appropriately selected and used.

For example, a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt, an imide sulfonate, an oxime sulfonate, a diazo disulfone, a disulfone, o-nitrobenzyl sulfonate is mentioned.

Moreover, the compound which introduce | transduced the group or compound which generate | occur | produces an acid by irradiation of these actinic rays or radiation, for example, US Patent No. 3,849,137, German Patent No. 3914407, Japanese Unexamined Patent JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038, JP-A-63-163452, JP-A The compound described in Unexamined-Japanese-Patent No. 62-153853, Unexamined-Japanese-Patent No. 63-146029, etc. can be used.

Furthermore, the compound which generate | occur | produces an acid by the light as described in US Pat.

As a preferable compound among the compounds which decompose | disassemble by irradiation of actinic light or a radiation and generate | occur | produces an acid, the compound represented by the following general formula (ZI), (ZII), (ZIII) is mentioned.

[Formula 68]

In said general formula (ZI), R <_201> , R <_202> and R <_203> represent an organic group each independently.

X ^- is, represents a non-nucleophilic anion, preferably a sulfonic acid anion, carboxylic acid anion, bis (alkylsulfonyl) amide anion, tris (alkylsulfonyl) methide _{^{anion, BF 4 -, PF 6 -}} , SbF 6 - These etc. are mentioned, More preferably, it is an organic anion containing a carbon atom.

As a preferable organic anion, the organic anion shown by a following formula is mentioned.

[Formula 69]

In the formula,

Rc ₁ represents an organic group.

Examples of the organic group in Rc ₁ include those having 1 to 30 carbon atoms, preferably an alkyl group which may be substituted, an aryl group, or a plurality thereof, a single bond, -O-, -CO _2- , -S And groups connected with a linker such as-, -SO _3- , or -SO ₂ N (Rd ₁ )-. Rd ₁ represents a hydrogen atom or an alkyl group.

Rc ₃ , Rc ₄ and Rc ₅ each independently represent an organic group. Rc _3, Rc _4, preferably used as the organic group of Rc ₅ may include the same preferred organic groups in Rc _1, and most preferably a perfluoroalkyl group having from 1 to 4 carbon atoms.

Rc ₃ and Rc ₄ may be bonded to each other to form a ring. Examples of the group formed by bonding of Rc ₃ and Rc ₄ include an alkylene group and an arylene group. Preferably it is a C2-C4 perfluoroalkylene group.

As the organic group of Rc ₁ , Rc ₃ to Rc ₅ , particularly preferably, the first position is a phenyl group substituted with an alkyl group substituted with a fluorine atom or a fluoroalkyl group, a fluorine atom or a fluoroalkyl group. By having a fluorine atom or a fluoroalkyl group, the acidity of the acid produced | generated by light irradiation becomes high and a sensitivity improves. Further, by forming a ring by combining Rc ₃ and Rc ₄ the higher the acidity of the acid generated by light irradiation, the sensitivity is improved.

_{Carbon number} of the organic group as R <_201> , R <_202> and R <_203> is 1-30 normally, Preferably it is 1-20.

In addition, two of R ₂₀₁ to R _{203 may be} bonded to each other to form a ring structure, and the ring may include an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbonyl group. Examples of the group formed by bonding of two of R ₂₀₁ to R ₂₀₃ include an alkylene group (for example, butylene group and pentylene group).

As a specific example of the organic group as R <_201> , R <_202> and R <_203> , the corresponding group in the compound (ZI-1), (ZI-2), and (ZI-3) mentioned later is mentioned.

Moreover, the compound which has two or more structures represented by general formula (ZI) may be sufficient. For example, even if at least one of R ₂₀₁ to R ₂₀₃ of the compound represented by General Formula (ZI) is a compound having a structure bonded with at least one of R ₂₀₁ to R ₂₀₃ of another compound represented by General Formula (ZI), do.

As more preferable (ZI) component, the compound (ZI-1), (ZI-2), and (ZI-3) demonstrated below are mentioned.

The 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.

Aryl sulfonium compounds, R ₂₀₁ ~ R ₂₀₃ are all aryl contribution, R ₂₀₁ ~ R ₂₀₃ is part of an aryl group, and the remaining credit is alkyl, cycloalkyl.

As an aryl sulfonium compound, a triaryl sulfonium compound, a diaryl alkyl sulfonium compound, an aryl dialkyl sulfonium compound, a diaryl cycloalkyl sulfonium compound, an aryl dicycloalkyl sulfonium compound is mentioned, for example.

As an aryl group of an arylsulfonium compound, heteroaryl groups, such as an aryl group, such as a phenyl group and a naphthyl group, an indole residue, and a pyrrole residue, are preferable, More preferably, they are a phenyl group and an indole residue. When an arylsulfonium compound has two or more aryl groups, two or more aryl groups may be same or different.

The alkyl group which an arylsulfonium compound has as needed has a C1-C15 linear or branched alkyl group, For example, a methyl group, an ethyl group, a propyl group, n-butyl group, sec-butyl group, t-view Til group etc. are mentioned.

The cycloalkyl group which an arylsulfonium compound has as needed has a C3-C15 cycloalkyl group, and a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, etc. are mentioned, for example.

The aryl group, alkyl group and cycloalkyl group of R ₂₀₁ to R ₂₀₃ are an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, having 6 to 14 carbon atoms), You may have an alkoxy group (for example, C1-C15), a halogen atom, a hydroxyl group, and a phenylthio group as a substituent. As a preferable substituent, it is a C1-C12 linear or branched alkyl group, a C3-C12 cycloalkyl group, a C1-C12 linear, branched or cyclic alkoxy group, Especially preferably, it is a C1-C4 alkyl group and carbon number It is an alkoxy group of 1-4. The substituent may be substituted with any one of three R ₂₀₁ to R ₂₀₃ , or may be substituted with all three. In the case where R ₂₀₁ to R ₂₀₃ are an aryl group, the substituent is preferably substituted at the p-position of the aryl group.

Next, a compound (ZI-2) is demonstrated. The compound (ZI-2) is a compound in the case where R ₂₀₁ to R ₂₀₃ in Formula (ZI) each independently represent an organic group containing no aromatic ring. Here, an aromatic ring also includes the aromatic ring containing a hetero atom.

The organic group which does not contain an aromatic ring as R ₂₀₁ to R ₂₀₃ is generally 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

R ₂₀₁ to R ₂₀₃ are each independently, preferably an alkyl group, a cycloalkyl group, an allyl group, and a vinyl group, more preferably a straight chain, branched, cyclic 2-oxoalkyl group, alkoxycarbonylmethyl group, and particularly preferably straight chain And a branched 2-oxoalkyl group.

The alkyl group as R ₂₀₁ to R ₂₀₃ may be either linear or branched, and preferably a linear or branched alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group) Can be mentioned. The alkyl group as R ₂₀₁ to R ₂₀₃ is preferably a linear or branched 2-oxoalkyl group or an alkoxycarbonylmethyl group.

The cycloalkyl group as R ₂₀₁ to R ₂₀₃ is preferably a cycloalkyl group (cyclopentyl group, cyclohexyl group, norbornyl group) having 3 to 10 carbon atoms. It is preferable that the cycloalkyl group as R ₂₀₁ -R ₂₀₃ is a cyclic 2-oxoalkyl group.

The linear, branched, cyclic 2-oxoalkyl group as R ₂₀₁ to R ₂₀₃ is preferably a group having> C═O at the second position of the alkyl group and the cycloalkyl group.

As an alkoxy group in the alkoxycarbonylmethyl group as R <_201> -R <_203> , Preferably, the C1-C5 alkoxy group (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group) is mentioned.

R ₂₀₁ to R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, 1 to 5 carbon atoms), a hydroxyl group, a cyano group, and a nitro group.

A compound (ZI-3) is a compound represented by the following general formula (ZI-3), and is a compound which has a phenacylsulfonium salt structure.

[Formula 70]

In general formula (ZI-3),

R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a halogen atom.

R _6c and R _7c each independently represent a hydrogen atom, an alkyl group, or a cycloalkyl group.

Rx and Ry each independently represent an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group.

At least two of R _1c to R _7c , and R _x and R _y may be bonded to each other to form a ring structure, and the ring structure may include an oxygen atom, a sulfur atom, an ester bond, and an amide bond. . _Examples of the group formed by bonding two or more of R _1c to R _7c and R _x and R _y to form a butylene group, a pentylene group, and the like.

X <^-> represents a non-nucleophilic anion and the same thing as the non-nucleophilic anion of X <^-> in general formula (ZI) is mentioned.

The alkyl group as R _1c to R _7c may be either linear or branched, for example, a straight or branched alkyl group having 1 to 20 carbon atoms, preferably a straight or branched alkyl group having 1 to 12 carbon atoms (eg, For example, a methyl group, an ethyl group, a linear or branched propyl group, a linear or branched butyl group, a linear or branched pentyl group) is mentioned.

The cycloalkyl group as R _1c to R _7c is preferably a cycloalkyl group having 3 to 8 carbon atoms (for example, a cyclopentyl group and a cyclohexyl group).

The alkoxy group as R _1c to R _5c may be any of linear, branched or cyclic, for example, an alkoxy group having 1 to 10 carbon atoms, preferably a linear and branched alkoxy group having 1 to 5 carbon atoms (for example, methoxide). Time period, an ethoxy group, a linear or branched propoxy group, a linear or branched butoxy group, a linear or branched pentoxy group, and a C3-C8 cyclic alkoxy group (for example, a cyclopentyloxy group, a cyclohexyloxy group) are mentioned. Can be.

Preferably, any one of R _1c to R _5c is a linear or branched alkyl group, a cycloalkyl group or a linear, branched or cyclic alkoxy group, and more preferably the sum of the carbon numbers of R _1c to R _5c is 2 to 15. Thereby, solvent solubility improves and particle generation is suppressed at the time of storage.

_Examples of the alkyl group as R _x and R _y include the same alkyl groups as R _1c to R _7c . The alkyl group as R _x and R _y is preferably a linear or branched 2-oxoalkyl group or an alkoxycarbonylmethyl group.

_Examples of the cycloalkyl group as R _x and R _y include the same cycloalkyl groups as R _1c to R _7c . It is preferable that the cycloalkyl group as R _x and R _y is a cyclic 2-oxoalkyl group.

Examples of the linear, branched, cyclic 2-oxoalkyl group include a group having> C═O at the 2nd position of the alkyl group and the cycloalkyl group as R _1c to R _7c .

Examples of the alkoxy group in the alkoxycarbonylmethyl group include the same alkoxy groups as R _1c to R _5c .

R _x and R _y are preferably alkyl groups of 4 or more carbon atoms, more preferably 6 or more, still more preferably 8 or more alkyl groups.

In general formula (ZII), (ZIII),

R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group, or a cycloalkyl group.

R ₂₀₄ ~ R ₂₀₇ of the aryl group include a phenyl group, a naphthyl group are preferred, and more preferably a phenyl group.

The alkyl group as R ₂₀₄ to R ₂₀₇ may be either linear or branched, and preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group) Can be mentioned.

The cycloalkyl group as R ₂₀₄ to R ₂₀₇ is preferably a cycloalkyl group (cyclopentyl group, cyclohexyl group, norbornyl group) having 3 to 10 carbon atoms.

R ₂₀₄ to R ₂₀₇ may have a substituent. R substituent is ₂₀₄ ~ R ₂₀₇ is may contain, for example, alkyl groups (e.g. having from 1 to 15 carbon atoms), cycloalkyl groups (e.g. having from 3 to 15 carbon atoms), an aryl group (for example, a carbon number of 6 to 15 g.), An alkoxy group (for example, C1-C15), a halogen atom, a hydroxyl group, a phenylthio group, etc. are mentioned.

X <^-> represents a non-nucleophilic anion and the same thing as the non-nucleophilic anion of X <^-> in general formula (ZI) is mentioned.

As a preferable compound among the compound which generate | occur | produces an acid by irradiation of actinic light or a radiation, the compound represented by the following general formula (ZIV), (ZV), (ZVI) is mentioned.

[Formula 71]

In general formulas (ZIV) to (ZVI),

Ar ₃ and Ar ₄ each independently represent an aryl group.

R ₂₂₆ represents an alkyl group or an aryl group.

R ₂₂₇ and R ₂₂₈ each independently represent an alkyl group, an aryl group, or an electron withdrawing group. R ₂₂₇ is preferably an aryl group.

R ₂₂₈ is preferably an electron withdrawing group, and more preferably a cyano group and a fluoroalkyl group.

A represents an alkylene group, an alkenylene group or an arylene group.

As a compound which generate | occur | produces an acid by irradiation of actinic light or a radiation, the compound represented by general formula (ZI)-(ZIII) is preferable.

It is preferable that a compound (B) is a compound which produces the aliphatic sulfonic acid which has a fluorine atom, or the benzene sulfonic acid which has a fluorine atom by irradiation of actinic light or a radiation.

It is preferable that a compound (B) has a triphenylsulfonium structure.

It is preferable that a compound (B) is a triphenylsulfonium salt compound which has the alkyl group or cycloalkyl group which is not fluorine-substituted in a cation part.

Among the compounds which generate an acid by irradiation with actinic light or radiation, examples of particularly preferable ones are given below.

[Formula 72]

[Formula 73]

[Formula 74]

[Formula 75]

[Formula 76]

[Formula 77]

Photo-acid generators can be used individually by 1 type or in combination of 2 or more types. When using in combination of 2 or more type, it is preferable to combine the compound which produces 2 types of organic acids in which all the atomic numbers except a hydrogen atom differ 2 or more.

As for content of a photo-acid generator, 0.1-20 mass% is preferable based on the total solid of an actinic-ray-sensitive or radiation-sensitive resin composition, More preferably, it is 0.5-10 mass%, More preferably, 1- 7 mass%. By setting the content of the photoacid generator in this range, the improvement of the exposure margin when the resist pattern is formed and the crosslinking reactivity with the crosslinking layer forming material are improved.

(C) solvent

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may contain a solvent. As a solvent which can be used when melt | dissolving each said component and preparing an actinic-ray-sensitive or radiation-sensitive resin composition, For example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactic acid And organic solvents such as alkyl esters, alkyl alkoxypropionates, cyclic lactones having 4 to 10 carbon atoms, monoketone compounds which may contain rings having 4 to 10 carbon atoms, alkylene carbonates, alkyl alkoxyacetic acids, and alkyl pyruvate.

Examples of the alkylene glycol monoalkyl ether carboxylates include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol mono Butyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate are preferred. It can be heard.

As alkylene glycol monoalkyl ether, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene Glycol monomethyl ether and ethylene glycol monoethyl ether are mentioned preferably.

Examples of the lactic acid alkyl esters include methyl lactate, ethyl lactate, propyl lactic acid and butyl lactate.

As alkyl alkoxy propionate, 3-ethoxy propionate ethyl, 3-methoxy methyl propionate, 3-ethoxy propionate methyl, and 3-methoxy ethylpropionate are mentioned preferably, for example.

Examples of the cyclic lactone having 4 to 10 carbon atoms include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, (gamma) -valerolactone, (gamma) -caprolactone, (gamma) -octanoic lactone, and (alpha) -hydroxy- (gamma) -butyrolactone are mentioned preferably.

As a monoketone compound which may contain a C4-C10 ring, for example, 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentane On, 4-methyl-2-pentanone, 2-methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4, 4-tetramethyl-3-pentanone, 2-hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3- Heptanone, 5-methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2 -Decanone, 3-decanone, 4-decanone, 5-hexen-2-one, 3-penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2, 2-dimethylcyclopentanone, 2,4,4-trimethylcyclopentanone, cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-di Methylcyclohexanone, 2,6-dimethylcyclohexanone, 2,2,6-tra Methyl cyclohexanone, cyclo-heptanone, 2-methyl-bicyclo-heptanone, 3-methyl-bicyclo-heptanone can be preferably mentioned.

As alkylene carbonate, a propylene carbonate, vinylene carbonate, ethylene carbonate, butylene carbonate is mentioned preferably, for example.

As an alkoxy acetic acid alkyl, for example, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl, Acetic acid-1-methoxy-2-propyl is mentioned preferably.

Examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate and propyl pyruvate.

As a solvent which can be used preferably, the solvent of boiling point 130 degreeC or more is mentioned under normal temperature and normal pressure. Specifically, cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethyl 3-ethoxypropionate, ethyl pyruvate , Acetic acid-2-ethoxyethyl, acetic acid-2- (2-ethoxyethoxy) ethyl, and propylene carbonate. Butyl butyrate, isoamyl acetate, and methyl 2-hydroxyisobutyrate may be used as the solvent.

In this invention, the said solvent may be used independently and may use two or more types together.

In this invention, you may use the mixed solvent which mixed the solvent containing a hydroxyl group in the structure, and the solvent which does not contain a hydroxyl group as an organic solvent.

Examples of the solvent containing a hydroxyl group include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, and propylene glycol. Colonoethyl ether, ethyl lactate, etc. are mentioned, Among these, propylene glycol monomethyl ether and ethyl lactate are especially preferable.

As a solvent which does not contain a hydroxyl group, For example, propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, (gamma)-butyrolactone, cyclohexanone, butyl acetate, N-methyl-pi Ralidone, N, N- dimethylacetamide, dimethyl sulfoxide, etc. are mentioned, Among these, a propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, (gamma) -beauty Lolactone, cyclohexanone and butyl acetate are particularly preferred, with propylene glycol monomethyl ether acetate, ethyl ethoxypropionate and 2-heptanone being most preferred.

The mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99-99/1, Preferably it is 10/90-90/10, More preferably, it is 20/80-60/40. . The mixed solvent which contains 50 mass% or more of solvents which does not contain a hydroxyl group is especially preferable at the point of coating uniformity.

It is preferable that a solvent is two or more types of mixed solvents containing propylene glycol monomethyl ether acetate.

(D) basic compound

It is preferable that the actinic-ray-sensitive or radiation-sensitive resin composition of this invention contains the (D) basic compound in order to reduce the performance change with time from exposure to heating.

As a basic compound, The compound which has a structure preferably represented by following formula (A)-(E) is mentioned.

[Formula 78]

In general formula (A)-(E),

R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and are a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), or an aryl group (having 6 to 20 carbon atoms) In this case, R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring.

As an alkyl group which has a substituent with respect to the said alkyl group, a C1-C20 aminoalkyl group, a C1-C20 hydroxyalkyl group, or a C1-C20 cyanoalkyl group is preferable.

R <^203> , R <^204> , R <^205> and R <^206> may be same or different, and represent a C1-C20 alkyl group.

As for the alkyl group in these general formula (A)-(E), it is more preferable that it is unsubstituted.

Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and more preferred compounds include imidazole structure and diazabicyclo Structures, onium hydroxide structures, onium carboxylate structures, trialkylamine structures, compounds having aniline structures or pyridine structures, alkylamine derivatives having hydroxyl groups and / or ether bonds, aniline derivatives having hydroxyl groups and / or ether bonds, and the like. Can be mentioned.

Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and the like. Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, 1,8-diamond Java ecyclo [5, 4, 0] undes-7-en. Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, and sulfonium hydroxide having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide and tris (t -Butylphenyl) sulfonium hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, 2-oxopropylthiophenium hydroxide, etc. are mentioned. As a compound which has an onium carboxylate structure, the anion part of the compound which has an onium hydroxide structure became a carboxylate, For example, an acetate, adamantane-1-carboxylate, a perfluoroalkyl carboxylate, etc. are mentioned. . Tri (n-butyl) amine, tri (n-octyl) amine, etc. are mentioned as a compound which has a trialkylamine structure. Examples of the compound having an aniline structure include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline, and the like. Examples of the alkylamine derivative having a hydroxyl group and / or an ether bond include ethanolamine, diethanolamine, triethanolamine, tris (methoxyethoxyethyl) amine, and the like. As an aniline derivative which has a hydroxyl group and / or an ether bond, N, N-bis (hydroxyethyl) aniline etc. are mentioned.

These basic compounds are used individually or in combination of 2 or more types.

The usage-amount of a basic compound is 0.001-10 mass% normally, Preferably it is 0.01-5 mass% based on solid content of actinic-ray-sensitive or radiation-sensitive resin composition.

It is preferable that the use ratio in the composition of an acid generator and a basic compound is an acid generator / basic compound (molar ratio) = 2.5-300. That is, the molar ratio is preferably 2.5 or more in terms of sensitivity and resolution, and 300 or less is preferable in view of suppressing the decrease in resolution due to the thickening of the resist pattern with time until the post-exposure heat treatment. The acid generator / basic compound (molar ratio) is more preferably 5.0 to 200, and still more preferably 7.0 to 150.

(E) hydrophobic resin

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may further contain a hydrophobic resin. As the hydrophobic resin can be preferably used one having a fluorine atom, a silicon atom, and one of the CH ₃ a partial structure containing in the side chain portion of the resin 1 or more. Specifically, the same resin as resin (X) contained in the above-mentioned composition for protective film formation can be used.

(F) surfactant

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably further contains a surfactant (F), and is preferably a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant, silicon-based surfactant, fluorine atom and silicon atom). It is more preferable to contain any one or 2 types or more of surfactant which has both.

When the actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains the above-mentioned (F) surfactant, when using an exposure light source of 250 nm or less, especially 220 nm or less, the adhesiveness and the development defect are small with good sensitivity and resolution. It is possible to give a resist pattern.

As a fluorine type and / or silicone type surfactant, For example, Unexamined-Japanese-Patent No. 62-36663, Unexamined-Japanese-Patent No. 61-226746, Unexamined-Japanese-Patent No. 61-226745, and Japan Unexamined-Japanese-Patent No. 62-170950 Japanese Patent Laid-Open No. 63-34540, Japanese Patent Laid-Open No. Hei 7-230165, Japanese Patent Laid-Open No. Hei 8-62834, Japanese Patent Laid-Open No. Hei 9-54432, Japanese Patent Laid-Open No. 9-5988 Surfactants described in Japanese Patent Application Laid-Open No. 2002-277862, US Patent Publication No. 557520, 5360692, 5529881, 5296330, 5436098, 5576143, 5294511, 5824451 And the following commercially available surfactants can also be used as it is.

As a commercially available surfactant which can be used, F-top EF301, EF303 (made by Shin-Akita Kasei Co., Ltd.), fluoride FC430, 431, 4430 (made by Sumitomo 3M Corporation), Megapak F171, F173, F176 , F189, F113, F110, F177, F120, R08 (made by Dainippon Ink & Chemicals Co., Ltd.), Supron S-382, SC101, 102, 103, 104, 105, 106 (made by Asahi Glass Co., Ltd.) , Troisol S-366 (made by Troy Chemical Co., Ltd.), GF-300, GF-150 (made by Toa Kosei Kagaku Co., Ltd.), Supron S-393 (made by Seimi Chemical Co., Ltd.), F top Ef121, ef122a, ef122b, rf122c, ef125m, ef135m, ef351, ef352, ef801, ef802, ef601 And fluorine-based surfactants or silicone-based surfactants such as, 230G, 204D, 208D, 212D, 218D, and 222D (manufactured by Neos). Moreover, polysiloxane polymer KP-341 (made by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicone type surfactant.

As the surfactant, in addition to the known ones described above, fluorine derived from fluoro aliphatic compounds produced by the telomerization method (also called telomer method) or the oligomerization method (also called oligomer method) As the surfactant, a surfactant using a polymer having an aliphatic group can be used. A fluoro aliphatic compound can be synthesize | combined by the method of Unexamined-Japanese-Patent No. 2002-90991.

As the polymer having a fluoro aliphatic group, a copolymer of a monomer having a fluoro aliphatic group with (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable, and is distributed irregularly. It may be present and may be block copolymerized. Moreover, as a poly (oxyalkylene) group, a poly (oxyethylene) group, a poly (oxypropylene) group, a poly (oxybutylene) group, etc. are mentioned, Poly (oxyethylene, oxypropylene, and oxyethylene Or a unit having an alkylene having a different chain length in the same chain length, such as a block linker) or poly (block linker of oxyethylene and oxypropylene). In addition, the copolymer of the monomer which has a fluoro aliphatic group, and (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but the monomer which has another 2 or more types of fluoro aliphatic groups, or another 2 Three or more types of copolymers which simultaneously copolymerize two or more kinds of (poly (oxyalkylene)) acrylates (or methacrylates) may be used.

For example, as a commercially available surfactant, Megapak F178, F-470, F-473, F-475, F-476, F-472 (made by Dainippon Ink Chemical Co., Ltd.) is mentioned. Further, copolymers of acrylate (or methacrylate) having a C ₆ F ₁₃ group and (poly (oxyalkylene)) acrylate (or methacrylate), acrylate (or methacrylate having a C ₃ F ₇ group) And copolymers of (poly (oxyethylene)) acrylate (or methacrylate) and (poly (oxypropylene)) acrylate (or methacrylate).

Moreover, in this invention, surfactant other than fluorine type and / or silicone type surfactant can also be used. Specifically, polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, and polyoxyethylene octyl phenol ether Polyoxyethylene alkylallyl ethers such as polyoxyethylene nonyl phenol ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan Sorbitan fatty acid esters such as monooleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxy Polyoxyethylene sorbitan fatty acid esters, such as ethylene sorbitan trioleate and polyoxyethylene sorbitan tristearate Nonionic surfactants, such as these, etc. are mentioned.

These surfactants may be used alone or in combination of several.

(F) The usage-amount of surfactant is 0.01-10 mass%, More preferably, it is 0.1-5 mass% with respect to actinic-ray-sensitive or radiation-sensitive resin composition whole quantity (excluding a solvent).

(G) carboxylic acid onium salt

The actinic ray sensitive or radiation sensitive resin composition in this invention may contain the (G) onium salt of carboxylic acid. Examples of the carboxylic acid onium salt include carboxylic acid sulfonium salts, carboxylic acid iodonium salts, and carboxylic acid ammonium salts. In particular, as the onium salt of (G) carboxylic acid, an iodonium salt and a sulfonium salt are preferable. Moreover, it is preferable that the carboxylate residue of (G) carboxylic acid onium salt of this invention does not contain an aromatic group and a carbon-carbon double bond. As an especially preferable anion part, a C1-C30 linear, branched, monocyclic or polycyclic cyclic alkylcarboxylic acid anion is preferable. More preferably, anions of carboxylic acids in which some or all of these alkyl groups are fluorine substituted. You may contain the oxygen atom in the alkyl chain. As a result, transparency to light of 220 nm or less is secured, sensitivity and resolution are improved, and roughness dependency and exposure margin are improved.

Examples of the anion of the fluorine-substituted carboxylic acid include fluoroacetic acid, difluoroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, heptafluorobutyric acid, nonafluoropentanoic acid, perfluorododecanoic acid and perfluorotridecane. Acids, perfluorocyclohexanecarboxylic acids, anions of 2,2-bistrifluoromethylpropionic acid, and the like.

These (G) onium salts can be synthesized by reacting sulfonium hydroxide, iodonium hydroxide, ammonium hydroxide and carboxylic acid with silver oxide in a suitable solvent.

(G) Content in the composition of a carboxylic acid onium salt is 0.1-20 mass% with respect to the total solid of a composition generally, Preferably it is 0.5-10 mass%, More preferably, it is 1-7 mass%.

(H) other additives

In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, a compound which promotes solubility in dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors, and developing agents (for example, A phenol compound having a molecular weight of 1,000 or less, an alicyclic or aliphatic compound having a carboxyl group), and the like.

Such phenol compounds having a molecular weight of 1000 or less are described in, for example, the methods described in JP-A 4-122938, JP-A 2-28531, US Patent No. 4,916,210, European Patent No. 219294, and the like. For reference, those skilled in the art can easily synthesize.

Specific examples of the cycloaliphatic or aliphatic compound having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid and lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, and cyclohexane Although dicarboxylic acid etc. are mentioned, It is not limited to these.

The organic solvent developer, alkaline developer and / or rinse solution which can be used in the present invention preferably have few impurities such as various fine particles and metal elements. In order to obtain chemical liquids with few such impurities, these chemical liquids may be produced in a clean room, and filtered with various filters such as a Teflon (registered trademark) filter, a polyolefin filter, an ion exchange filter, and the like to reduce impurities. It is preferable to carry out. It is preferable that all metallic element concentrations of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn are 10 ppm or less, and, as for a metal element, it is more preferable that it is 5 ppm or less.

Moreover, about the storage container of a developing solution and a rinse liquid, it does not specifically limit, Although containers, such as polyethylene resin, a polypropylene resin, and polyethylene-polypropylene resin, which are used for an electronic material use can be used suitably, it is eluted from a container. In order to reduce impurities, it is also preferable to select a container having few components eluted from the inner wall of the container into the chemical liquid. As such a container, a container in which the inner wall of the container is a perfluoro resin (e.g., FluoroPure PFA composite drum made from Integris (contact surface; PFA resin lining), manufactured by JFE Co., Ltd.) ) Drum can (liquid inner surface; zinc phosphate coating)).

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention and various materials used in the pattern forming method of the present invention (for example, developer, rinse solution, composition for forming antireflection film, composition for forming top coat, etc.) It is preferable not to contain impurities, such as a metal. As content of the metal component contained in these materials, 10 ppm or less is preferable, 5 ppm or less is more preferable, 1 ppm or less is more preferable, It is especially preferable that it does not contain substantially (it is below the detection limit of a measuring apparatus). .

As a method of removing impurities, such as a metal, from the said various materials, the filtration using a filter is mentioned, for example. As a filter hole diameter, pore size 50 nm or less is preferable, 10 nm or less is more preferable, 5 nm or less is more preferable. As a material of a filter, the filter made from polytetrafluoroethylene, polyethylene, and nylon is preferable. In the filter filtration process, you may connect and use multiple types of filter in series or in parallel. When using multiple types of filters, you may use combining the filter from which a hole diameter and / or material differs. Moreover, you may filter various materials multiple times, and a circulating filtration process may be sufficient as the process of filtering multiple times.

Moreover, as a method of reducing impurities, such as a metal contained in the said various materials, the method of filter filtering with respect to the raw material which comprises various materials which selects the raw material with few metal content as a raw material which comprises various materials, etc. Can be mentioned. Preferable conditions in the filter filtration performed with respect to the raw material which comprises various materials are the same as the above-mentioned conditions.

In addition to filter filtration, impurities with an adsorbent may be removed or a combination of filter filtration and an adsorbent may be used. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used.

Although the pattern formed by the method of this invention is typically used as a mask in the etching process of semiconductor manufacture, it can be used also for the other uses. As another use thereof, guide pattern formation in DSA (Directed Self-Assembly) (see ACS Nano Vol. 4 No. 8, page 4815-4823, etc.), as a core material (core) of a so-called spacer process. Use (for example, see Japanese Unexamined Patent Publication No. Hei 3-270227, Japanese Unexamined Patent Application Publication No. 2013-164509, etc.).

This invention relates also to the manufacturing method of the electronic device containing the pattern formation method of above-mentioned this invention.

The electronic device obtained by the manufacturing method of the electronic device of this invention is suitably mounted in an electrical and electronic equipment (a home appliance, OA, a media related apparatus, an optical apparatus, a communication apparatus, etc.).

Example

Hereinafter, although an Example demonstrates this invention in detail, the content of this invention is not limited to this.

<Synthesis of Resin (X)>

Resin X1-X27 shown to the following description was synthesize | combined by the method based on Paragraph 0521 etc. of Unexamined-Japanese-Patent No. 2013-218223.

<Synthesis of Acid Degradable Resin>

Synthesis Example: Synthesis of Resin (1)

102.3 mass parts of cyclohexanone was heated at 80 degreeC under nitrogen stream. While stirring this liquid, 22.2 mass parts of monomers represented by the following structural formula M-1, 22.8 mass parts of monomers represented by the following structural formula M-2, 6.6 mass parts of monomers represented by the following structural formula M-3, 189.9 mass parts of cyclohexanone, 2 2.40 parts by mass of a 2'-azobisisobutyric acid dimethyl [V-601, manufactured by Wako Junyaku Kogyo Co., Ltd.] was added dropwise over 5 hours. After completion of dropping, the mixture was further stirred at 80 ° C for 2 hours. After cooling the reaction liquid, 41.1 mass parts of resin (1) was obtained by reprecipitating with a large amount of hexane / ethyl acetate (mass ratio 9: 1), and filtering and drying the obtained solid under vacuum.

[Formula 79]

The weight average molecular weight (Mw: polystyrene conversion) calculated | required from GPC (carrier: tetrahydrofuran (THF)) of obtained resin (1) was Mw = 9500, and dispersion degree Mw / Mn = 1.62. ^The composition ratio measured by ¹³ C-NMR was 40/50/10 in molar ratio.

Operation similar to the said synthesis example was performed, and resin (2)-(12) described below was synthesize | combined as acid-decomposable resin.

[Preparation of Resist Composition]

The components shown in Table 1 were dissolved in a solvent, the solution of 3.5 mass% of solid content concentration was prepared with respect to each, and this was filtered with the polyethylene filter which has a pore size of 0.03 micrometer, and the resist composition was prepared.

TABLE 1

The symbol in the table used the following.

<Acid degradable resin>

[Formula 80]

The composition ratio (molar ratio; corresponding in order from the left), the weight average molecular weight (Mw), and the dispersion degree (Mw / Mn) of each repeating unit are shown in Table 2 below. These were calculated | required by the method similar to resin (1) mentioned above.

TABLE 2

<Mine generator>

[Formula 81]

<Basic compound>

The following compounds were used as acid diffusion control agents.

[Formula 82]

<Hydrophobic resin>

As the hydrophobic resin, the following resins were used.

[Formula 83]

Table 3 shows the composition ratio (molar ratio; corresponding from left to right), weight average molecular weight (Mw), and dispersion degree (Mw / Mn) of each repeating unit. These were calculated | required by the method similar to resin (1) mentioned above.

TABLE 3

<Surfactant>

W-1: Megapak F176 (product made in DIC Corporation) (fluorine system)

W-2: Megapak R08 (made by DIC Corporation) (fluorine-based and silicon-based)

W-3: PF6320 (manufactured by Omni Nova Solutions, Inc.) (Fluorinometer)

<Solvent>

A1: propylene glycol monomethyl ether acetate (PGMEA)

A2: cyclohexanone

A3: γ-butyrolactone

B1: Propylene Glycol Monomethyl Ether (PGME)

[Preparation of Composition for Protective Film Formation]

The components shown in Table 4 were dissolved in 4-methyl-2-pentanol to prepare a solution having a solid content concentration of 2.7% by mass with respect to each of them, and similarly to the resist composition, this was filtered through a polyethylene filter having a pore size of 0.03 μm to protect the protective film. The composition for formation was prepared.

TABLE 4

The symbol in the table used the following.

<Resin (X)>

Each repeating unit contained in resin X1-X29 is as follows. In addition, the composition ratio (molar ratio), weight average molecular weight (Mw), and dispersion degree (Mw / Mn) of each repeating unit in resin X1-X29 were calculated | required by the method similar to resin (1) mentioned above.

[Repeat unit having proton acceptor functional group]

[Formula 84]

[Other repeating units]

[Formula 85]

<Low Molecular Basic Compound>

As a control compound, the following low molecular weight basic compound TQ-100 was used.

[Formula 86]

[Formation of Hole Pattern]

An organic antireflection film ARC29SR (manufactured by Brewer) was applied on the silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film with a film thickness of 86 nm, on which an actinic ray-sensitive or radiation-sensitive resin composition was applied. It apply | coated and baked (PB: Prebake) for 60 second at 100 degreeC, and formed the resist film of 90 nm in film thickness. Furthermore, the composition for protective film formation was apply | coated, and it baked at the temperature of Table 5 for 60 second, and formed the protective film which has a film thickness shown in the same table | surface.

The obtained wafer was squared using an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma 0.730, inner sigma 0.630, XY deflection) with a hole portion of 65 nm and a pitch between holes of 100 nm. Pattern exposure was performed through the halftone mask of an array. Ultrapure water was used as the immersion liquid. Then, it heated at 105 degreeC for 60 second (PEB: Post Exposure Bake). Subsequently, it was puddle-developed for 30 seconds with the organic-solvent developer shown in Table 5, and it was puddle-washed for 30 seconds with the rinse liquid shown in the same table | surface. However, about Example 28, the rinse process was not performed. Subsequently, the hole pattern with a hole diameter of 50 nm was obtained by rotating a wafer for 30 second at the rotation speed of 2000 rpm.

[Formation of Line and Space Pattern]

An organic antireflection film ARC29SR (manufactured by Breuer) was applied on the silicon wafer, and baked at 205 ° C. for 60 seconds to form an antireflection film having a film thickness of 86 nm, and thereon, an actinic ray-sensitive or radiation-sensitive resin composition was applied thereon, Baking (PB: Prebake) was performed at 100 degreeC for 60 second, and the resist film with a film thickness of 90 nm was formed. Furthermore, the composition for protective film formation was apply | coated, and it baked at the temperature of Table 5 for 60 second, and the protective film which has a film thickness shown in the same table | surface was formed.

The obtained wafer was subjected to an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, Dipole, outer sigma 0.800, inner sigma 0.564, Y deflection), and a halftone mask having a space portion of 55 nm and a pitch between holes 110 nm. Pattern exposure was performed through. Ultrapure water was used as the immersion liquid. Then, it heated at 105 degreeC for 60 second (PEB: Post Exposure Bake). Subsequently, it was puddle-developed for 30 seconds with the organic-solvent developer shown in Table 5, and it was puddle-washed for 30 seconds with the rinse liquid shown in the same table | surface. However, about Example 28, the rinse process was not performed. Subsequently, by rotating the wafer for 30 seconds at a rotational speed of 2000 rpm, a line pattern having a line width of 50 nm was obtained.

[evaluation]

Depth of Focus (DOF)

Under the exposure and development conditions of the above-mentioned "formation of a hole pattern", in the exposure amount which forms a hole pattern with a hole diameter of 50 nm, each obtained by performing exposure and image development by changing the conditions of an exposure focus at 20 nm intervals in a focus direction The hole diameter (CD) of the pattern was measured using a line width measuring scanning electron microscope SEM (Hitachi Seisakusho S-9380), and the maximum or maximum value of the curve obtained by plotting the respective CDs. We made corresponding focus the best focus. When the focus was changed around this best focus, the fluctuation range of the focus allowing the hole diameter to allow 50 nm ± 10%, that is, the focus margin (DOF) (nm) was calculated. The evaluation results are shown in Table 5.

<Line Edge Roughness (LER)>

In the exposure amount which forms a line pattern with a line width of 50 nm under the exposure and development conditions of "the formation of a line and space pattern", the measurement of the line edge roughness is performed by measuring a scanning electron microscope (SEM) The pattern was observed and 50 points of distances from the reference line where the edges in the longitudinal direction of the line pattern were to be at the edges in the range of 5 μm were measured by the length measurement SEM, and the standard deviation was determined to calculate 3σ (nm). Smaller values indicate better performance. The evaluation results are shown in Table 5.

<Exposure Latitude (EL)>

Under the exposure and development conditions of the above-mentioned "formation of hole pattern", when the exposure dose is changed to an exposure dose that reproduces a hole diameter (Critical Dimension: CD) having a hole diameter of 50 nm, the hole diameter is 50 nm ± 10%. The allowable exposure dose width was obtained, and this value was divided by the optimum exposure dose and expressed as a percentage. The larger the value, the smaller the change in performance due to the change in exposure amount, and the better the exposure margin. The evaluation results are shown in Table 5.

TABLE 5

From the results of Table 5, it can be seen that the pattern obtained by the pattern forming method of the present invention is excellent in the focus margin (DOF) and the exposure margin (EL), and the line width deviation (LWR) is also suppressed.

Claims (13)

(a) applying an actinic ray-sensitive or radiation-sensitive resin composition onto a substrate to form an actinic ray-sensitive or radiation-sensitive film,
(b) applying a composition for forming a protective film on the actinic ray-sensitive or radiation-sensitive film to form a protective film,
(c) exposing the actinic ray-sensitive or radiation-sensitive film coated with the protective film, and
(d) A pattern forming method comprising the step of developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer containing an organic solvent,
The said protective film contains resin (X) containing the repeating unit which has a proton accepting functional group,
When the said proton accepting functional group contains a nitrogen atom, the said proton accepting functional group is group represented by either of the following general formula (A)-(E), The pattern formation method.

[In General Formula (A), R ²⁰¹ and R ²⁰² each independently represent an alkyl group, a cycloalkyl group, or an aryl group. However, R ²⁰¹ and R ²⁰² are bonded to each other to form an aromatic or non-aromatic nitrogen-containing heterocycle.
In General Formulas (B) to (D), two or more of the bonds from the carbon atom and the bond from the nitrogen atom are bonded to each other to form at least one aromatic or non-aromatic nitrogen-containing heterocycle. .
In General Formula (E), R ²⁰³ , R ²⁰⁴ , R ^205, and R ²⁰⁶ each independently represent an alkyl group or a cycloalkyl group. Provided that two or more of R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , a bond from a carbon atom, and a bond from a nitrogen atom combine with each other to form at least one aromatic or non-aromatic nitrogen-containing heterocycle. Forming.
* Represents a bonding hand.] delete The method according to claim 1,
The proton acceptor functional group is an ether bond, a thioether bond, a carbonyl bond, or a thiocarbonyl bond. The method according to claim 1 or 3,
The pattern formation method whose content rate of the repeating unit which has the said proton accepting functional group is 0.1-10 mol% with respect to all the repeating units in resin (X). The method according to claim 1 or 3,
The pattern formation method in which resin (X) is resin which does not contain a fluorine atom substantially. The method according to claim 1 or 3,
And a step of heating the substrate coated with the actinic ray-sensitive or radiation-sensitive film and the protective film to 100 ° C or more after the step (b) of forming the protective film and before the step (c) of exposing. As a protective film formation composition used for formation of the protective film which coats an actinic-ray-sensitive or radiation-sensitive film,
It contains resin (X) containing the repeating unit which has a proton accepting functional group,
A composition for forming a protective film, wherein the proton acceptor functional group is a group represented by any one of the following general formulas (A) to (E).

[In General Formula (A), R ²⁰¹ and R ²⁰² each independently represent an alkyl group, a cycloalkyl group, or an aryl group. However, R ²⁰¹ and R ²⁰² are bonded to each other to form an aromatic or non-aromatic nitrogen-containing heterocycle.
In General Formulas (B) to (D), two or more of the bonds from the carbon atom and the bond from the nitrogen atom are bonded to each other to form at least one aromatic or non-aromatic nitrogen-containing heterocycle. .
In General Formula (E), R ²⁰³ , R ²⁰⁴ , R ^205, and R ²⁰⁶ each independently represent an alkyl group or a cycloalkyl group. Provided that two or more of R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , a bond from a carbon atom, and a bond from a nitrogen atom combine with each other to form at least one aromatic or non-aromatic nitrogen-containing heterocycle. Forming.
* Represents a bonding hand.] As a protective film formation composition used for formation of the protective film which coats an actinic-ray-sensitive or radiation-sensitive film,
A resin (X) comprising a repeating unit having a proton accepting functional group, wherein the proton accepting functional group is an ether bond, a thioether bond, a carbonyl bond, or a thiocarbonyl bond,
When the proton acceptor functional group is an ether bond, the composition for forming a protective film comprising two or more ether bonds. The manufacturing method of the electronic device containing the pattern formation method of Claim 1 or 3. The method according to claim 1,
The pattern formation method in which resin (X) further contains the repeating unit represented by the following general formula (II).

[In general formula (II), X <_b1> represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom,
R ₂ represents an unsubstituted branched alkyl group or an unsubstituted or alkyl substituted cycloalkyl group.] The method according to claim 7,
The composition for protective film formation in which resin (X) further contains the repeating unit represented by the following general formula (II).

[In general formula (II), X <_b1> represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom,
R ₂ represents an unsubstituted branched alkyl group or an unsubstituted or alkyl substituted cycloalkyl group.] The method according to claim 8,
When the said proton accepting functional group is an ether bond, the repeating unit which has the said proton accepting functional group has a partial structure represented by following General formula (1-1), The composition for protective film formation.

[In General Formula (1-1), R ₁₁ represents an alkylene group.
R ₁₂ represents an alkyl group.
m represents an integer of 1 or more.
* Represents a bonding hand] The method according to claim 8,
The composition for protective film formation in which resin (X) further contains the repeating unit represented by the following general formula (II).

[In general formula (II), X <_b1> represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom,
R ₂ represents an unsubstituted branched alkyl group or an unsubstituted or alkyl substituted cycloalkyl group.]