WO2013172239A1 - 酸拡散制御剤、感放射線性樹脂組成物、レジストパターン形成方法、化合物及び化合物の製造方法 - Google Patents
酸拡散制御剤、感放射線性樹脂組成物、レジストパターン形成方法、化合物及び化合物の製造方法 Download PDFInfo
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- WO2013172239A1 WO2013172239A1 PCT/JP2013/062981 JP2013062981W WO2013172239A1 WO 2013172239 A1 WO2013172239 A1 WO 2013172239A1 JP 2013062981 W JP2013062981 W JP 2013062981W WO 2013172239 A1 WO2013172239 A1 WO 2013172239A1
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- 0 *C(*)(C(*)(N(*)*)S)C(O*)=O Chemical compound *C(*)(C(*)(N(*)*)S)C(O*)=O 0.000 description 10
- WLOQLWBIJZDHET-UHFFFAOYSA-N c(cc1)ccc1[S+](c1ccccc1)c1ccccc1 Chemical compound c(cc1)ccc1[S+](c1ccccc1)c1ccccc1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
- C07C2603/74—Adamantanes
Definitions
- the present invention relates to an acid diffusion controller, a radiation sensitive resin composition, a resist pattern forming method, a compound, and a method for producing the compound.
- the chemically amplified radiation-sensitive resin composition generates an acid from an acid generator at an exposed portion by irradiation with exposure light such as ArF excimer laser light or KrF excimer laser light, and the reaction is carried out by reaction using this acid as a catalyst.
- exposure light such as ArF excimer laser light or KrF excimer laser light
- the dissolution rate of the part and the unexposed part in the developer is changed to form a resist pattern on the substrate.
- Such a radiation-sensitive resin composition is required to improve various performances such as resolution as processing technology becomes finer.
- an acid diffusion control agent is contained in the radiation sensitive resin composition for the purpose of appropriately controlling the diffusion of the acid generated from the acid generator.
- an acid diffusion controller a nitrogen atom-containing compound having a polar group and a ring structure is known, and it is said that resolution and depth of focus can be improved (Japanese Patent Laid-Open No. 2002-363148 and JP, 2002-226470, A).
- the line width of the resist pattern is varied. It is also required to have excellent line width roughness (LWR) performance.
- LWR line width roughness
- the formed resist pattern tends to have a top loss or the like, and it is also required to improve the rectangularity of the cross-sectional shape of the resist pattern.
- the above conventional radiation-sensitive resin composition cannot satisfy these requirements.
- the present invention has been made based on the circumstances as described above, and its purpose is to provide an acid diffusion controller excellent in the LWR performance, resolution, rectangularity of the cross-sectional shape and depth of focus of the radiation-sensitive resin composition. It is to provide.
- An acid diffusion controller comprising at least one selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2).
- R 1 is a hydrocarbon group having a monovalent alicyclic structure having 3 to 30 carbon atoms, and —O—, —CO—, —COO—, —SO 2 O—, —B—
- a group containing at least one selected from the group consisting of NR a SO 2 — and —NR a CO—, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or part or all of the hydrogen atoms of these groups Is a group substituted with at least one selected from the group consisting of a hydroxy group and a halogen atom.
- R a is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
- R 2 and R 3 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and at least one of R 2 and R 3 is a monovalent hydrocarbon having 1 to 10 carbon atoms. It is a hydrocarbon group.
- R 4 and R 5 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- R 6 and R 7 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a ring with a nitrogen atom to which R 6 and R 7 are bonded to each other.
- a ring structure having 3 to 10 members is formed.
- R 8 is a group which forms an (n + 2) -valent monocyclic heterocyclic group having 5 to 8 ring members together with the carbon atom to which the ester group and R 10 are bonded.
- n is an integer of 1 to 6.
- R 9 is a monovalent hydrocarbon group having 1 to 20 carbon atoms when n is an integer of 1 to 6, and when n is 2 or more, two or more of a plurality of R 9 are bonded to each other Ring structures having 3 to 10 ring members, or —O—, —CO—, —COO—, —SO 2 O—, —NR b SO 2 and —NR between carbon and carbon of these groups or ring structures b
- a group containing at least one selected from the group consisting of CO—, or a part or all of hydrogen atoms of these groups or ring structures are substituted with at least one selected from the group consisting of a hydroxy group and a halogen atom.
- R b is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- R 10 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- R 11 and R 12 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- R 13 and R 14 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a ring with a nitrogen atom to which R 13 and R 14 are bonded to each other.
- a ring structure having 3 to 10 members is formed.
- the radiation sensitive resin composition of the present invention is A polymer having an acid dissociable group, It contains an acid generator and the acid diffusion controller.
- the resist pattern forming method of the present invention comprises: A step of forming a resist film using the radiation-sensitive resin composition; A step of exposing the resist film; and a step of developing the exposed resist film.
- R 1 is a hydrocarbon group having a monovalent alicyclic structure having 3 to 30 carbon atoms, and —O—, —CO—, —COO—, —SO 2 O—, —B—
- a group containing at least one selected from the group consisting of NR a SO 2 — and —NR a CO—, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or part or all of the hydrogen atoms of these groups Is a group substituted with at least one selected from the group consisting of a hydroxy group and a halogen atom.
- R a is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
- R 2 and R 3 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and at least one of R 2 and R 3 is a monovalent hydrocarbon having 1 to 10 carbon atoms. It is a hydrocarbon group.
- R 4 and R 5 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- R 6 and R 7 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a ring with a nitrogen atom to which R 6 and R 7 are bonded to each other. A ring structure having 3 to 10 members is formed. )
- R 8 is a group which forms an (n + 2) -valent monocyclic heterocyclic group having 5 to 8 ring members together with the carbon atom to which the ester group and R 10 are bonded.
- n is an integer of 1 to 6.
- R 9 is a monovalent hydrocarbon group having 1 to 20 carbon atoms when n is an integer of 1 to 6, and when n is 2 or more, two or more of a plurality of R 9 are bonded to each other Ring structures having 3 to 10 ring members, or —O—, —CO—, —COO—, —SO 2 O—, —NR b SO 2 and —NR between carbon and carbon of these groups or ring structures b
- a group containing at least one selected from the group consisting of CO—, or a part or all of hydrogen atoms of these groups or ring structures are substituted with at least one selected from the group consisting of a hydroxy group and a halogen atom. It is a group.
- R b is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- R 10 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- R 11 and R 12 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- R 13 and R 14 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a ring with a nitrogen atom to which R 13 and R 14 are bonded to each other.
- a ring structure having 3 to 10 members is formed.
- the method for producing the compound of the present invention comprises: A method for producing a compound represented by the following formula (1), which comprises a step of reacting a compound represented by the following formula (ia) with an amine compound represented by the following formula (ib).
- R 1 is a hydrocarbon group having a monovalent alicyclic structure having 3 to 30 carbon atoms, and —O—, —CO—, —COO—, —SO 2 O—, —B—
- a group containing at least one selected from the group consisting of NR a SO 2 — and —NR a CO—, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or part or all of the hydrogen atoms of these groups Is a group substituted with at least one selected from the group consisting of a hydroxy group and a halogen atom.
- R a is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
- R 2 and R 3 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and at least one of R 2 and R 3 is a monovalent hydrocarbon having 1 to 10 carbon atoms. It is a hydrocarbon group.
- R 4 and R 5 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- R 6 and R 7 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a ring with a nitrogen atom to which R 6 and R 7 are bonded to each other.
- a ring structure having 3 to 10 members is formed.
- the method for producing another compound of the present invention includes: A method for producing a compound represented by the following formula (2), which comprises a step of reacting a compound represented by the following formula (ii-a) with an amine compound represented by the following formula (ii-b).
- R 8 is a group which forms an (n + 2) -valent monocyclic heterocyclic group having 5 to 8 ring members together with the carbon atom to which the ester group and R 10 are bonded.
- n is an integer of 1 to 6.
- R 9 is a monovalent hydrocarbon group having 1 to 20 carbon atoms when n is an integer of 1 to 6, and when n is 2 or more, two or more of a plurality of R 9 are bonded to each other Ring structures having 3 to 10 ring members, or —O—, —CO—, —COO—, —SO 2 O—, —NR b SO 2 and —NR between carbon and carbon of these groups or ring structures b
- a group containing at least one selected from the group consisting of CO—, or a part or all of hydrogen atoms of these groups or ring structures are substituted with at least one selected from the group consisting of a hydroxy group and a halogen atom. It is a group.
- R b is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- R 10 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- R 11 and R 12 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- R 13 and R 14 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a ring with a nitrogen atom to which R 13 and R 14 are bonded to each other.
- a ring structure having 3 to 10 members is formed.
- chain hydrocarbon group refers to a hydrocarbon group that does not include a cyclic structure and is composed only of a chain structure.
- hydrocarbon group having an alicyclic structure refers to a hydrocarbon group containing an alicyclic structure as a ring structure. However, it is not necessary to be composed only of the alicyclic structure, and an aromatic ring structure or a chain structure may be included in a part thereof.
- Aromaatic hydrocarbon group refers to a hydrocarbon group containing only an aromatic ring structure as a ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and a part thereof may include a chain structure.
- the radiation-sensitive resin composition containing the acid diffusion-controlling agent, and the resist pattern forming method using the radiation-sensitive resin composition the LWR is small and the cross-sectional shape is exhibited while exhibiting a wide depth of focus. It is possible to form a resist pattern with excellent rectangularity and high resolution.
- the compound of the present invention can be suitably used as the acid diffusion controller. According to the method for producing a compound of the present invention, the compound can be easily produced. Therefore, they can be suitably used for pattern formation in semiconductor device manufacturing, which is expected to become increasingly finer in the future.
- the acid diffusion controller (hereinafter also referred to as “acid diffusion controller (I)”) is a compound represented by the above formula (1) (hereinafter also referred to as “compound (1)”) and the following formula (2). At least one selected from the group consisting of compounds represented by the following (hereinafter also referred to as “compound (2)”) (hereinafter also referred to as “compound (I)”). Since the acid diffusion controller (I) is composed of the compound (I), the radiation-sensitive resin composition containing the compound is excellent in LWR performance, resolution, rectangularity of the cross-sectional shape, and depth of focus.
- the reason why the above effect is achieved when the acid diffusion controller (I) is composed of the compound (I) is not necessarily clear, but can be inferred as follows, for example.
- Compound (I) has an ester group with a nitrogen atom capable of interacting with an acid, has a ring structure in the vicinity of this ester group or a ring structure containing an ester group, and further has a hydrocarbon in the vicinity of this ester group. It has a specific structure having a specific group which is a group or a derivative group thereof. In this way, compound (I) is considered to exhibit a synergistic effect when a polar ester group, a bulky ring structure, and a specific group exhibiting a steric effect are present in the vicinity of each other.
- the affinity between the compound (I) and the polymer constituting the resist film is increased, the sublimation property is reduced, and the heat resistance is excellent. Thereby, the diffusion and uneven distribution of the compound (I) in the resist film are moderately suppressed.
- the radiation-sensitive resin composition containing compound (I) is excellent in LWR performance, resolution, rectangularity of the cross-sectional shape, and depth of focus.
- the compound (I) since the compound (I) has the above specific structure, it can be easily synthesized from an acrylate ester compound or ⁇ -methylene lactone compound and an amine compound, so that the raw materials are easily available and the production cost is high. This is also advantageous.
- the compound (1) and the compound (2) will be described in this order.
- R 1 is a hydrocarbon group having a monovalent alicyclic structure having 3 to 30 carbon atoms, and —O—, —CO—, —COO—, —SO 2 O—, —B—
- a group containing at least one selected from the group consisting of NR a SO 2 — and —NR a CO—, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or part or all of the hydrogen atoms of these groups Is a group substituted with at least one selected from the group consisting of a hydroxy group and a halogen atom.
- R a is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
- R 2 and R 3 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and at least one of R 2 and R 3 is a monovalent hydrocarbon having 1 to 10 carbon atoms. It is a hydrocarbon group.
- R 4 and R 5 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- R 6 and R 7 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a ring with a nitrogen atom to which R 6 and R 7 are bonded to each other.
- a ring structure having 3 to 10 members is formed.
- Examples of the hydrocarbon group having a monovalent alicyclic structure having 3 to 30 carbon atoms represented by R 1 include a hydrocarbon group having a non-acid-dissociable alicyclic structure, and an acid-dissociable alicyclic structure. Examples thereof include a hydrocarbon group having a cyclic structure.
- the “hydrocarbon group having an acid dissociable alicyclic structure” is a hydrocarbon group having an alicyclic structure that replaces a hydrogen atom such as a carboxy group or a hydroxy group, and is a group that dissociates by the action of an acid. Say.
- hydrocarbon group having a non-acid dissociable alicyclic structure examples include: Cyclopropyl group, cyclobutyl group, cyclopentyl group, 1-i-propylcyclopentan-1-yl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, 2-methyladamantan-2-yl group, 2-i A monocyclic cycloalkyl group such as a propyladamantan-2-yl group; A polycyclic cycloalkyl group such as a norbornyl group, an adamantyl group, a tricyclodecyl group, a tetracyclododecyl group; A monocyclic cycloalkenyl group such as a cyclopentenyl group and a cyclohexenyl group; Examples thereof include polycyclic cycloalkenyl groups such as norbornenyl group,
- a monocyclic cycloalkyl group and a polycyclic cycloalkyl group are preferable, a polycyclic cycloalkyl group is more preferable, a group having an adamantane ring, and a group having a tricyclodecane ring are more preferable, and 1-adamantyl And the group 8-tricyclodecyl is particularly preferred.
- hydrocarbon group having an acid dissociable alicyclic structure examples include a group in which the carbon atom at the binding site is tertiary, and the like.
- Alkyl group-substituted monocyclic cycloalkyl groups such as 1-methyl-1-cyclopentyl group, 1-ethyl-1-cyclopentyl group, 1-i-propyl-1-cyclopentyl group, 1-methyl-1-cyclohexyl group;
- Alkyl group-substituted polycyclic cycloalkyl groups such as 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, 2-i-isopropyl-2-adamantyl group, 2-methyl-2-norbornyl group and the like;
- Examples thereof include cycloalkyl group-substituted alkyl groups such as 2-cyclopentyl-2-propyl group, 2-cyclohexyl-2-propyl group, 2-norbornyl-2
- an alkyl group-substituted monocyclic cycloalkyl group and an alkyl group-substituted polycyclic cycloalkyl group are preferable, and a 1-alkyl-1-monocyclic cycloalkyl group and a 2-alkyl-2-polycyclic cycloalkyl group are more preferable, 1-alkyl-1-cyclopentyl group, 2-alkyl-2-adamantyl group are more preferable, 1-i-propyl-1-cyclopentyl group, 2-ethyl-2-adamantyl group, 2-i-propyl. A -2-adamantyl group is particularly preferred.
- R 1 is a hydrocarbon group having an acid-dissociable alicyclic structure
- the compound (1) is dissociated by the action of an acid generated from the acid generator to generate a carboxy group in the exposed portion.
- the diffusion of the compound (1) in the resist film is more appropriately controlled.
- R 1 is dissociated by the action of an acid, the affinity for the developer is changed, so that the dissolution contrast of the radiation-sensitive resin composition containing the acid diffusion controller is improved.
- the solubility with respect to an alkaline developer is improved, and the dissolution inhibiting effect is improved with respect to an organic solvent developer.
- Examples of the group containing —O— between carbon-carbon of the hydrocarbon group having an alicyclic structure include groups having an oxacycloalkane structure such as an oxacyclopentyl group and an oxacyclohexyl group; A group having a cyclic acetal ring (including a cyclic ketal ring) such as a 1,3-dioxa-2,2-dimethylcyclopentan-5-ylmethyl group and a 1,3-dioxacyclopentan-5-ylmethyl group; 7- (1,3-Dioxa-2,2-dimethylcyclopentan-4-yl) -3,3-dimethyl-2,4,8-trioxabicyclo [3,3,0] octane-6-yl group 7- (1,3-Dioxa-spiro [adamantane-2,2 ′] cyclopentan-4-yl) -spiro [adamantane-3,
- a group having a cyclic acetal ring, an oxacycloalkane structure and a group having a cyclic acetal ring are preferable, and a 1,3-dioxa-2,2-dimethylcyclopentan-5-ylmethyl group, 7- (1, 3-dioxa-2,2-dimethylcyclopentan-4-yl) -3,3-dimethyl-2,4,8-trioxabicyclo [3,3,0] octane-6-yl group, 7- (1 , 3-Dioxa-spiro [adamantane-2,2 ′] cyclopentan-4-yl) -spiro [adamantane-3,3 ′]-2,4,8-trioxabicyclo [3,3,0] octane
- a 6-yl group is more preferred.
- R 1 is a group having a cyclic acetal ring
- the compound (1) When R 1 is a group having a cyclic acetal ring, the compound (1) generates two hydroxy groups by the action of an acid generated from the acid generator in the exposed area. As a result, the diffusion of the compound (1) in the resist film is more appropriately controlled. Further, the dissociation by the action of the acid generated from the acid generator changes the affinity for the developer, so that the dissolution contrast is improved. Specifically, in the exposed portion, the solubility with respect to an alkaline developer is improved, and the dissolution inhibiting effect is improved with respect to an organic solvent developer.
- Examples of the group containing —CO— between carbon and carbon of the hydrocarbon group having the alicyclic structure include, for example, Cyclic ketone groups such as oxocyclopentyl group, oxocyclohexyl group, oxonorbornyl group, oxoadamantyl group, dioxocyclopentyl group, dioxocyclohexyl group, dioxonorbornyl group, dioxoadamantyl group; Examples thereof include a chain group having a cyclic ketone group such as a norbornylcarbonylmethyl group and an adamantylcarbonylmethyl group. Among these, a chain group having a cyclic ketone group is preferable, and a norbornylcarbonylmethyl group is more preferable.
- Examples of the group containing —COO— between carbon and carbon of the hydrocarbon group having an alicyclic structure include, for example, Lactones such as butyrolactone-yl group, valerolactone-yl group, caprolactone-yl group, norbornane lactone-yl group, 5-oxo-4-oxatricyclo [4.3.1.1 3,8 ] undecan-yl group A group having a structure;
- Examples include ester group-containing chain groups having a lactone structure such as a lactone-yloxycarbonylalkyl group such as a norbornanelactone-yloxycarbonylmethyl group and a butyrolactone-yloxycarbonylmethyl group. Of these, norbornanelactone-yl group and norbornanelactone-yloxycarbonylmethyl group are preferable.
- Examples of the group containing —SO 2 O— between carbon-carbon of the hydrocarbon group having the alicyclic structure have a sultone structure such as a butyrosulton-yl group, a valerosulton-yl group, and a norbornane sultone-yl group. Groups and the like. Of these, norbornane sultone-yl groups are preferred.
- Examples of the group containing —NR a SO 2 — between the carbon and carbon of the hydrocarbon group having an alicyclic structure include sultam structures such as butyrosultam-yl, valerosultam-yl, norbornanesultam-yl, etc. A group having Of these, norbornane sultam-yl groups are preferred.
- Examples of the group containing —NR a CO— between the carbon and carbon of the hydrocarbon group having the alicyclic structure include butyrolactam-yl group, valerolactam-yl group, caprolactam-yl group, norbornane lactam-yl group, etc. And a group having a lactam structure. Of these, caprolactam-yl group and norbornane lactam-yl group are preferable.
- hydrocarbon group having 1 to 10 carbon atoms represented by Ra above examples include, for example, a chain hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and 6 to 6 carbon atoms. 10 aromatic hydrocarbon groups and the like.
- Examples of the chain hydrocarbon group having 1 to 10 carbon atoms include, for example, Alkyl groups such as methyl, ethyl, propyl and butyl groups; An alkenyl group such as an ethenyl group, a propenyl group, a butenyl group; Examples thereof include alkynyl groups such as ethynyl group, propynyl group, and butynyl group.
- Examples of the alicyclic hydrocarbon group having 3 to 10 carbon atoms include: Cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group, tricyclodecyl group; And cycloalkenyl groups such as cyclobutenyl group, cyclopentenyl group, cyclohexenyl group and norbornenyl group.
- aromatic hydrocarbon group having 6 to 10 carbon atoms examples include, for example, Aryl groups such as phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group; Examples include aralkyl groups such as benzyl group, phenethyl group, and phenylpropyl group.
- R a is preferably a hydrogen atom or a chain hydrocarbon group, more preferably a hydrogen atom or an alkyl group, still more preferably a hydrogen atom, a methyl group or an ethyl group, and particularly preferably a hydrogen atom.
- Examples of the aromatic hydrocarbon group having 6 to 30 carbon atoms represented by R 1 include, for example, Aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl, methylanthryl; Examples thereof include aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group and naphthylmethyl group.
- Examples of the group in which the hydrogen atom of these groups is substituted with a hydroxy group include: Hydroxy-substituted monocyclic cycloalkyl groups such as a hydroxycyclopentyl group, a hydroxycyclohexyl group, a dihydroxycyclopentyl group, a dihydroxycyclohexyl group; Hydroxy-substituted polycyclic cycloalkyl groups such as hydroxynorbornyl group, hydroxyadamantyl group, dihydroxynorbornyl group, dihydroxyadamantyl group; Examples include hydroxy-substituted aryl groups such as hydroxyphenyl group, hydroxytolyl group, hydroxynaphthyl group, and hydroxyanthryl group. Of these, a hydroxy-substituted polycyclic cycloalkyl group is preferable, a hydroxyadamantyl group is more preferable, and a 3-hydroxy-1-adamantyl group is more preferable
- Halogen atom-substituted monocyclic cycloalkyl groups such as a halocyclopentyl group, a halocyclohexyl group, a dihalocyclopentyl group, and a dihalocyclohexyl group
- Halogen atom-substituted polycyclic cycloalkyl groups such as a halonorbornyl group, a haloadamantyl group, a dihalonorbornyl group, and a dihaloadamantyl group
- halogen atom-substituted aryl groups such as a halophenyl group, a halotolyl group, a halonaphthyl group, and a haloanthryl group.
- a halogen atom-substituted monocyclic cycloalkyl group is
- R 1 includes a non-acid-dissociable monocyclic or polycyclic cycloalkyl group, an acid-dissociable cycloalkyl group, a cycloalkyl group substituted with a hydroxy group, and —O— between the carbon-carbon of the cycloalkyl group.
- an unsubstituted monocyclic cycloalkyl group an unsubstituted polycyclic cycloalkyl group, a 1-alkyl-1-monocyclic cycloalkyl group, and a hydroxy-substituted polycyclic cycloalkyl group, a cyclohexyl group, and 1-adamantyl.
- a 3-hydroxy-1-adamantyl group and a 1-alkyl-1-cyclopentyl group are particularly preferred.
- Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R 2 and R 3 include the same groups as those exemplified as the monovalent hydrocarbon group represented by Ra above. It is done. Among these, a chain hydrocarbon group is preferable, an alkyl group is more preferable, a methyl group and an ethyl group are further preferable, and a methyl group is particularly preferable.
- the combination of R 2 and R 3 is preferably a combination of a hydrogen atom and a monovalent hydrocarbon group from the viewpoint of ease of synthesis of the compound (1).
- Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R 4 and R 5 include the same groups as those exemplified as the monovalent hydrocarbon group represented by Ra above. It is done. Among these, a chain hydrocarbon group is preferable, an alkyl group is more preferable, a methyl group and an ethyl group are further preferable, and a methyl group is particularly preferable.
- R 4 and R 5 are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom.
- Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R 6 and R 7 include the same groups as those exemplified as the monovalent hydrocarbon group represented by Ra above. It is done. Among these, a chain hydrocarbon group is preferable, an alkyl group is more preferable, a methyl group, an ethyl group, an n-propyl group, and an i-propyl group are further preferable, and an ethyl group is particularly preferable.
- Examples of the ring structure having 3 to 10 ring members formed together with the nitrogen atom to which R 6 and R 7 are bonded to each other include: Monocyclic azacycloalkane structures such as azacyclopropane structure, azacyclobutane structure, azacyclopentane structure (pyrrolidine structure), azacyclohexane structure (piperidine structure), azacycloheptane structure, azacyclooctane structure, azacyclodecane structure; A polycyclic azacycloalkane structure such as an azabicyclo [2.2.1] heptane structure, an azabicyclo [2.2.2] octane structure, an azatricyclo [3.3.1.1 3,7 ] decane structure; And azaoxacycloalkane structures such as an azaoxacyclopropane structure and an azaoxacyclohexane structure (including a morpholine structure).
- monocyclic azacycloalkane structure and azaoxacycloalkane structure are preferable, azacyclopentane structure, azacyclohexane structure and azaoxacyclohexane structure are more preferable, azacyclohexane structure and 1,4-azaoxacyclohexane structure (A morpholine structure) is more preferable.
- Examples of the compound (1) include compounds represented by the following formulas (i-1) to (i-20) (hereinafter also referred to as “compounds (i-1) to (i-20)”). It is done.
- the compounds (i-1) to (i-19) are preferable, the compounds (i-1) to (i-17) are more preferable, the compound (i-1), More preferred are compound (i-2), compound (i-4), compound (i-10) and compound (i-17).
- R 8 is a group which forms an (n + 2) -valent monocyclic heterocyclic group having 5 to 8 ring members together with the carbon atom to which the ester group and R 10 are bonded.
- n is an integer of 1 to 6.
- R 9 is a monovalent hydrocarbon group having 1 to 20 carbon atoms when n is an integer of 1 to 6, and when n is 2 or more, two or more of a plurality of R 9 are bonded to each other Ring structures having 3 to 10 ring members, or —O—, —CO—, —COO—, —SO 2 O—, —NR b SO 2 and —NR between carbon and carbon of these groups or ring structures b
- a group containing at least one selected from the group consisting of CO—, or a part or all of hydrogen atoms of these groups or ring structures are substituted with at least one selected from the group consisting of a hydroxy group and a halogen atom. It is a group.
- R b is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- R 10 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- R 11 and R 12 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- R 13 and R 14 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a ring with a nitrogen atom to which R 13 and R 14 are bonded to each other.
- a ring structure having 3 to 10 members is formed.
- Examples of the (n + 2) -valent monocyclic heterocyclic group having 5 to 8 ring members formed by R 8 together with the ester group and the carbon atom to which R 10 is bonded include: Butyrolactone, monocyclic lactone such as valerolactone, caprolactone; -, - -O between CH 2 -CH 2 of the lactone S -, - NR- (R is a hydrogen atom or a monovalent hydrocarbon group) , —CO—, —CS— or a group obtained by removing (n + 2) hydrogen atoms from a compound containing a combination thereof.
- a group obtained by removing (n + 2) hydrogen atoms from a monocyclic lactone is preferred, a group obtained by removing (n + 2) hydrogen atoms from butyrolactone, valerolactone or caprolactone is more preferred, and (n + 2) from butyrolactone.
- a group in which a single hydrogen atom is removed is more preferred.
- N is preferably 1 to 3, and more preferably 1 or 2.
- Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R 9 when n is an integer of 1 to 6 include, for example, a chain hydrocarbon group having 1 to 20 carbon atoms, 3 to Examples thereof include 20 alicyclic hydrocarbon groups and aromatic hydrocarbon groups having 6 to 20 carbon atoms.
- Examples of the chain hydrocarbon group having 1 to 20 carbon atoms include: Alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, octadecyl and icosyl; Alkenyl groups such as ethenyl group, propenyl group, butenyl group, hexenyl group, octenyl group, decenyl group, dodecenyl group, tetradecenyl group, octadecenyl group, icocenyl group; Examples thereof include alkynyl groups such as ethynyl group, propynyl group, butynyl group, hexynyl group, octynyl group, decynyl group, dodecynyl group and tetradecynyl
- Examples of the alicyclic hydrocarbon group include: Cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, norbornyl group, adamantyl group, tricyclodecyl group, tetracyclododecyl group; And cycloalkenyl groups such as a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a norbornenyl group, a tricyclodecenyl group, and a tetracyclododecenyl group.
- aromatic hydrocarbon group examples include: Aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl, methylanthryl; Examples thereof include aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group and anthrylmethyl group.
- Examples of the ring structure having 3 to 10 ring members formed by bonding two or more of a plurality of R 9 when n is 2 or more include: Cycloalkane structures such as cyclopropane structure, cyclobutane structure, cyclopentane structure, cyclohexane structure, norbornane structure, adamantane structure; Oxacycloalkane structures such as oxacyclobutane structure, oxacyclopentane structure, oxacyclohexane structure, oxanorbornane structure, oxaadamantane structure; Examples thereof include aromatic ring structures such as benzene ring structure and naphthalene ring structure.
- a substituent such as a hydroxy group, a halogen atom, or a hydrocarbon group may be bonded to this ring structure.
- These ring structures may be spiro rings. When two R 9 forming the ring structure is attached to the same carbon atom are spiro ring is formed.
- Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R b include the same groups as the monovalent hydrocarbon group exemplified as R a .
- a hydrogen atom and a chain hydrocarbon group are preferable, a hydrogen atom and an alkyl group are more preferable, a hydrogen atom, a methyl group, and an ethyl group are further preferable, and a hydrogen atom is particularly preferable.
- Examples of the group in which some or all of the hydrogen atoms in the group or ring structure are substituted with at least one selected from the group consisting of a hydroxy group and a halogen atom include the chain hydrocarbon group and the alicyclic ring.
- Formula hydrocarbon group, the above aromatic hydrocarbon group, the above ring structure, or between these groups or the carbon-carbon of the ring structure —O—, —COO—, —SO 2 O—, —NR b SO 2 and —NR a group in which part or all of the hydrogen atoms of the group containing at least one selected from the group consisting of b CO— are substituted with a hydroxy group or a halogen atom, and the like.
- R 9 is preferably the above ring structure, more preferably a cyclobutane structure, a cyclopentane structure or a cyclohexane structure, and —O—, —CO—, —COO—, —SO 2 O between the carbon and carbon of these ring structures.
- a group containing at least one selected from the group consisting of —, —NR b SO 2 and —NR b CO—, and a part or all of the hydrogen atoms of these ring structures are selected from the group consisting of a hydroxy group and a halogen atom More preferably a group substituted by at least one kind, a group containing —O— between the carbon-carbons of these ring structures, and a group in which some of the hydrogen atoms of these ring structures are substituted with hydroxy groups.
- Particularly preferred are an oxacyclopentane structure and a hydroxy-containing cyclohexane structure.
- Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R 10 include the same groups as the monovalent hydrocarbon group exemplified as Ra above. Among these, a hydrogen atom and a chain hydrocarbon group are preferable, a hydrogen atom and an alkyl group are more preferable, a hydrogen atom, a methyl group, and an ethyl group are further preferable, and a hydrogen atom is particularly preferable.
- R 10 is preferably a hydrogen atom or a chain hydrocarbon group, more preferably a hydrogen atom or an alkyl group, still more preferably a hydrogen atom, a methyl group or an ethyl group, and particularly preferably a hydrogen atom.
- Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R 11 and R 12 include the same groups as the monovalent hydrocarbon groups exemplified as Ra above. Among these, a hydrogen atom and a chain hydrocarbon group are preferable, a hydrogen atom and an alkyl group are more preferable, a hydrogen atom, a methyl group, and an ethyl group are further preferable, and a hydrogen atom is particularly preferable.
- R 11 and R 12 are preferably a hydrogen atom or a chain hydrocarbon group, more preferably a hydrogen atom or an alkyl group, still more preferably a hydrogen atom, a methyl group or an ethyl group, and particularly preferably a hydrogen atom.
- Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R 13 and R 14 include the same groups as those exemplified as the monovalent hydrocarbon group represented by Ra above. .
- a chain hydrocarbon group is preferable, an alkyl group is more preferable, a methyl group, an ethyl group, an n-propyl group, and an i-propyl group are more preferable, and an i-propyl group is particularly preferable.
- Examples of the ring structure having 3 to 10 ring members formed together with the nitrogen atom to which R 13 and R 14 are bonded to each other include, for example, a nitrogen atom to which R 6 and R 7 are bonded to each other Examples of the ring structure formed together with the ring structure exemplified above.
- monocyclic azacycloalkane structure and azaoxacycloalkane structure are preferable, azacyclopentane structure, azacyclohexane structure and azaoxacyclohexane structure are more preferable, azacyclohexane structure and 1,4-azaoxacyclohexane structure (A morpholine structure) is more preferable.
- Examples of the compound (2) include compounds represented by the following formulas (ii-1) to (ii-13) (hereinafter also referred to as “compounds (ii-1) to (ii-13)”). It is done.
- the compounds (ii-1) to (ii-4) are preferable, and the compound (ii-1) and the compound (ii-2) are preferable.
- R 1 is a hydrocarbon group having a monovalent alicyclic structure having 3 to 30 carbon atoms, and —O—, —CO—, —COO—, —SO 2 O—, —B—
- a group containing at least one selected from the group consisting of NR a SO 2 — and —NR a CO—, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or part or all of the hydrogen atoms of these groups Is a group substituted with at least one selected from the group consisting of a hydroxy group and a halogen atom.
- R a is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
- R 2 and R 3 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and at least one of R 2 and R 3 is a monovalent hydrocarbon having 1 to 10 carbon atoms. It is a hydrocarbon group.
- R 4 and R 5 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- R 6 and R 7 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a ring with a nitrogen atom to which R 6 and R 7 are bonded to each other.
- a ring structure having 3 to 10 members is formed.
- R 8 is a group which forms an (n + 2) -valent monocyclic heterocyclic group having 5 to 8 ring members together with the carbon atom to which the ester group and R 10 are bonded.
- n is an integer of 1 to 6.
- R 9 is a monovalent hydrocarbon group having 1 to 20 carbon atoms when n is an integer of 1 to 6, and when n is 2 or more, two or more of a plurality of R 9 are bonded to each other Ring structures having 3 to 10 ring members, or —O—, —CO—, —COO—, —SO 2 O—, —NR b SO 2 and —NR between carbon and carbon of these groups or ring structures b
- a group containing at least one selected from the group consisting of CO—, or a part or all of hydrogen atoms of these groups or ring structures are substituted with at least one selected from the group consisting of a hydroxy group and a halogen atom.
- R b is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- R 10 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- R 11 and R 12 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
- R 13 and R 14 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a ring with a nitrogen atom to which R 13 and R 14 are bonded to each other.
- a ring structure having 3 to 10 members is formed.
- the compound represented by the above formula (1) or formula (2) is obtained by reacting with the amine compound in a solvent such as toluene in the presence of a base such as piperidine.
- R 3 and R 10 are preferably hydrogen atoms.
- the reaction of the above scheme can be more easily proceeded, and as a result, the above compound can be obtained with high yield.
- compound (I) can be easily synthesized from an acrylate-based compound or ⁇ -methylene lactone compound and an amine compound, it is easy to obtain raw materials and is advantageous in terms of production cost. is there.
- the radiation-sensitive resin composition includes a polymer having an acid dissociable group (hereinafter also referred to as “[A] polymer”), an acid generator (hereinafter also referred to as “[B] acid generator”), and An acid diffusion control agent (hereinafter also referred to as “[C] acid diffusion control agent”) is contained.
- the radiation-sensitive resin composition has a suitable component as an acid diffusion control agent [D] [C] acid diffusion control agent (hereinafter referred to as “[D] other acid diffusion control agent”).
- [E] a fluorine atom-containing polymer and a [F] solvent may be further contained, and other optional components may be contained within a range not impairing the effects of the present invention.
- each component will be described.
- the polymer is a polymer having an acid dissociable group.
- the polymer is at least one selected from the group consisting of a lactone structure, a cyclic carbonate structure and a sultone structure, in addition to a structural unit containing an acid dissociable group (hereinafter also referred to as “structural unit (I)”). It is preferable to further include a structural unit (II) containing a polar group and / or a structural unit (III) having a polar group, and may further include other structural units other than these structural units.
- the polymer may have one or more of each structural unit. Hereinafter, each structural unit will be described.
- the structural unit (I) is a structural unit containing an acid dissociable group.
- the “acid-dissociable group” refers to a group that substitutes a hydrogen atom of an acidic group such as a carboxy group or a hydroxy group and dissociates by the action of an acid.
- Examples of the structural unit (I) include a structural unit (I-1) represented by the following formula (3).
- RA is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.
- R p is a monovalent acid dissociable group represented by the following formula (p).
- R p1 , R p2 and R p3 are each independently an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 4 to 20 carbon atoms. However, R p2 and R p3 may be bonded to each other to form a cycloalkanediyl group having 4 to 20 carbon atoms together with the carbon atom to which they are bonded.
- structural unit (I-1) structural units represented by the following formulas (3-1) to (3-4) are preferable.
- R A has the same meaning as in the above formula (3).
- R p1 , R p2 and R p3 have the same meaning as in the above formula (p).
- i and j are each independently an integer of 1 to 4.
- Examples of the structural unit represented by the above formula (3) and the above formulas (3-1) to (3-4) include a structural unit represented by the following formula.
- R A has the same meaning as in the above formula (3).
- the structural unit (I) is preferably a structural unit represented by the above formula (3-1) or a structural unit represented by the formula (3-2), and is derived from 1-alkyl-1-cyclopentyl (meth) acrylate. More preferred are structural units derived from 2-alkyl-2-adamantyl (meth) acrylate, more preferred are structural units derived from 1-ethyl-1-cyclopentyl (meth) acrylate, 2-ethyl-2-adamantyl (meta More preferred are structural units derived from acrylates.
- the content ratio of the structural unit (I) is preferably 10% by mole to 100% by mole, more preferably 20% by mole to 80% by mole, and more preferably 30% by mole with respect to all the structural units constituting the [A] polymer. More preferred is ⁇ 70 mol%.
- the structural unit (II) is a structural unit containing at least one selected from the group consisting of a lactone structure, a cyclic carbonate structure, and a sultone structure.
- the polymer further has the structural unit (II), whereby the solubility in the developer can be adjusted. Moreover, the adhesiveness of the resist pattern formed from the said radiation sensitive resin composition and a board
- Examples of the structural unit (II) include a structural unit represented by the following formula.
- R L1 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
- a structural unit containing a lactone structure and a structural unit containing a sultone structure are preferred, a structural unit containing a lactone structure is more preferred, and a structural unit containing a norbornane lactone structure is more preferred, A structural unit derived from norbornanelactone-yl (meth) acrylate is particularly preferred.
- the content ratio of the structural unit (II) is preferably 0 to 80 mol%, more preferably 20 to 80 mol%, more preferably 30 mol% with respect to all the structural units constituting the [A] polymer. More preferred is ⁇ 70 mol%.
- the structural unit (III) is a structural unit having a polar group (except for those corresponding to the structural unit (II)).
- the polymer further has the structural unit (III), whereby the solubility in the developer can be adjusted.
- Examples of the polar group include a hydroxy group, a carboxy group, a cyano group, a nitro group, and a sulfonamide group. Among these, a hydroxy group and a carboxy group are preferable, and a hydroxy group is more preferable.
- Examples of the structural unit (III) include a structural unit represented by the following formula.
- R B is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
- the content ratio of the structural unit (III) is preferably 0 mol% to 80 mol%, more preferably 20 mol% to 75 mol%, more preferably 40 mol%, based on all structural units constituting the [A] polymer. More preferred is ⁇ 70 mol%.
- the polymer may have other structural units other than the structural units (I) to (III).
- the other structural units include structural units having a non-dissociable alicyclic hydrocarbon group.
- a content rate of the said other structural unit it is 30 mol% or less normally with respect to all the structural units which comprise a [A] polymer, and 20 mol% or less is preferable.
- the pattern formation property of the said radiation sensitive resin composition may fall.
- the content of the polymer is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 85% by mass or more based on the total solid content of the radiation-sensitive resin composition.
- the polymer can be synthesized, for example, by polymerizing a monomer giving each structural unit in a suitable solvent using a radical polymerization initiator.
- radical polymerization initiator examples include azobisisobutyronitrile (AIBN), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-cyclopropylpropylene). Pionitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), azo radical initiators such as dimethyl 2,2′-azobisisobutyrate; benzoyl peroxide, t-butyl hydroperoxide, And peroxide radical initiators such as cumene hydroperoxide. Of these, AIBN and dimethyl 2,2'-azobisisobutyrate are preferable, and AIBN is more preferable. These radical initiators can be used alone or in combination of two or more.
- Examples of the solvent used for the polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane; Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; Halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide, chlorobenzene; Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate and methyl propionate; Ketones such as acetone, 2-butanone, 4-methyl-2-p
- the reaction temperature in the above polymerization is usually preferably 40 ° C to 150 ° C and 50 ° C to 120 ° C.
- the reaction time is usually preferably 1 hour to 48 hours and 1 hour to 24 hours.
- the weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer is not particularly limited, but is preferably 1,000 or more and 50,000 or less, more preferably 2,000 or more and 30,000 or less. Preferably, 3,000 or more and 20,000 or less are more preferable, and 5,000 or more and 15,000 are particularly preferable. [A] If the Mw of the polymer is less than the lower limit, the heat resistance of the resulting resist film may be lowered. [A] If the Mw of the polymer exceeds the above upper limit, the developability of the resist film may deteriorate.
- the ratio (Mw / Mn) of Mw to the number average molecular weight (Mn) in terms of polystyrene by GPC of the polymer is usually from 1 to 5, preferably from 1 to 3, more preferably from 1 to 2.5. preferable.
- Mw and Mn of the polymer in this specification are values measured using gel permeation chromatography (GPC) under the following conditions.
- GPC column 2 G2000HXL, 1 G3000HXL, 1 G4000HXL (above, manufactured by Tosoh) Column temperature: 40 ° C
- Elution solvent Tetrahydrofuran (Wako Pure Chemical Industries)
- Flow rate 1.0 mL / min
- Sample concentration 1.0% by mass
- Sample injection volume 100 ⁇ L
- Detector Differential refractometer Standard material: Monodisperse polystyrene
- the content of the low molecular weight part (refers to a part having a molecular weight of less than 1,000) in the polymer is preferably 0.5% by mass or less, more preferably 0.2% by mass or less, and 0.1% by mass. % Or less is more preferable.
- the content of the low molecular weight portion in the polymer within the above range, the rectangularity, LWR performance, resolution and depth of focus of the cross-sectional shape of the radiation-sensitive resin composition can be further improved. it can.
- the content of the low molecular weight portion of the polymer in the present specification was determined by using a HPLC column (Intersil ODS-25 ⁇ m column (4.6 mm ⁇ ⁇ 250 mm), manufactured by GL Sciences) by high performance liquid chromatography (HPLC). It is a value measured by conditions.
- Elution solvent Acrylonitrile / 0.1% by mass phosphoric acid aqueous solution
- Flow rate 1.0 mL / min
- Sample concentration 1.0% by mass
- Sample injection volume 100 ⁇ L
- Detector Differential refractometer
- the acid generator is a substance that generates an acid upon exposure. This acid dissociates the acid dissociable group in the [A] polymer to form a polar group such as a carboxy group, and as a result, the solubility of the [A] polymer in the developer changes.
- the contained form of the [B] acid generator in the radiation-sensitive resin composition may be a low molecular compound form (hereinafter also referred to as “[B] acid generator” as appropriate), as described later. It may be in the form of an acid generating group incorporated as a part, or in both forms.
- Examples of the acid generator include onium salt compounds, N-sulfonyloxyimide compounds, halogen-containing compounds, and diazoketone compounds.
- onium salt compounds examples include sulfonium salts, tetrahydrothiophenium salts, iodonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like.
- sulfonium salt examples include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo [2.2.1] hept- 2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1-difluoroethanesulfonate, triphenylsulfonium camphorsulfonate, 4 -Cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate,
- tetrahydrothiophenium salt examples include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nona.
- iodonium salt examples include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl- 1,1,2,2-tetrafluoroethanesulfonate, diphenyliodonium camphorsulfonate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium nonafluoro-n-butanesulfonate, Bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium 2-bic
- N-sulfonyloxyimide compounds include N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy).
- the acid generator is preferably an onium salt compound, more preferably a sulfonium salt, and triphenylsulfonium 2- (adamantan-1-ylcarbonyloxy) -1,1,3,3,3- More preferred is pentafluoropropane-1-sulfonate.
- [B] As the content of the acid generator, when the [B] acid generator is a [B] acid generator, from the viewpoint of ensuring the sensitivity and developability of the radiation-sensitive resin composition, [A] 0.1 mass part or more and 30 mass parts or less are preferable with respect to 100 mass parts of unification, 0.5 mass part or more and 20 mass parts or less are more preferable, and 1 mass part or more and 15 mass parts or less are more preferable. [B] By making content of an acid generator into the said range, the sensitivity and developability of the said radiation sensitive resin composition improve. [B] 1 type (s) or 2 or more types can be used for an acid generator.
- the acid diffusion controller is the acid diffusion controller (I) of the present invention.
- the radiation-sensitive resin composition contains the acid diffusion control agent (I) in addition to the [A] polymer and the [B] acid generator, so that the LWR performance, the resolution, and the rectangular shape of the cross-sectional shape. And excellent depth of focus.
- the acid diffusion control agent is described in the above-mentioned section of acid diffusion control agent (I).
- [C] 1 type (s) or 2 or more types can be used for an acid diffusion controlling agent.
- the content of the acid diffusion controller is preferably from 1 mol% to 100 mol%, more preferably from 3 mol% to 70 mol%, more preferably from 5 mol% to 50 mol, relative to the [B] acid generator. % Is more preferable.
- the content of an acid diffusion control agent is preferably 0.1 parts by mass or more and 20 parts by mass or less, and 0.5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the [A] polymer. Is more preferable, and 1 mass part or more and 10 mass parts or less are still more preferable.
- the radiation-sensitive resin composition may contain [D] another acid diffusion controller as necessary.
- the radiation sensitive resin composition further includes [D] another acid diffusion controller, so that LWR performance, resolution, rectangularity of the cross-sectional shape, and focus The depth can be further improved.
- [D] The reason why the above effect can be further improved by further containing another acid diffusion controller is not necessarily clear, but, for example, the degree of diffusion of the entire compound constituting the acid diffusion controller is determined. It can be considered that it can be adjusted.
- the content of the other acid diffusion controller in the radiation-sensitive resin composition may be a form of an acid diffusion controller that is a low molecular compound as described later (hereinafter referred to as “[D] Other acid diffusion May be in the form of an acid diffusion control group incorporated as part of the polymer, or both.
- Other acid diffusion control agents include, for example, a compound represented by the following formula (4) (hereinafter also referred to as “nitrogen-containing compound (I)”), a compound having two nitrogen atoms in the same molecule (Hereinafter also referred to as “nitrogen-containing compound (II)”), compounds having three nitrogen atoms (hereinafter also referred to as “nitrogen-containing compound (III)”), amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds Etc.
- nitrogen-containing compound (I) a compound represented by the following formula (4)
- nitrogen-containing compound (II) a compound having two nitrogen atoms in the same molecule
- nitrogen-containing compound (III) compounds having three nitrogen atoms
- amide group-containing compounds amide group-containing compounds
- urea compounds nitrogen-containing heterocyclic compounds Etc.
- R 15 , R 16 and R 17 are each independently a hydrogen atom, an optionally substituted linear, branched or cyclic alkyl group, aryl group or aralkyl group. .
- nitrogen-containing compound (I) examples include monoalkylamines such as n-hexylamine; dialkylamines such as di-n-butylamine; trialkylamines such as triethylamine; aromatic amines such as aniline and the like. Can be mentioned.
- nitrogen-containing compound (II) examples include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, and the like.
- nitrogen-containing compound (III) examples include polyamine compounds such as polyethyleneimine and polyallylamine; and polymers such as dimethylaminoethylacrylamide.
- amide group-containing compound examples include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone and the like. Can be mentioned.
- urea compound examples include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tributylthiourea and the like.
- nitrogen-containing heterocyclic compound examples include pyridines such as pyridine and 2-methylpyridine, pyrazine, pyrazole and the like.
- nitrogen-containing organic compound a compound having an acid dissociable group can also be used.
- nitrogen-containing organic compounds having an acid-dissociable group include N- (t-butoxycarbonyl) piperidine, N- (t-butoxycarbonyl) imidazole, N- (t-butoxycarbonyl) benzimidazole, N -(T-butoxycarbonyl) -2-phenylbenzimidazole, N- (t-butoxycarbonyl) di-n-octylamine, N- (t-butoxycarbonyl) diethanolamine, N- (t-butoxycarbonyl) dicyclohexylamine, N- (t-butoxycarbonyl) diphenylamine, N- (t-butoxycarbonyl) -4-hydroxypiperidine and the like can be mentioned.
- a photodegradable base that is exposed to light and generates a weak acid upon exposure can also be used.
- the photodegradable base include an onium salt compound that decomposes upon exposure and loses acid diffusion controllability.
- the onium salt compound include a sulfonium salt compound represented by the following formula (5-1), an iodonium salt compound represented by the following formula (5-2), and the like.
- R 18 to R 22 are each independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, or a halogen atom.
- E ⁇ and Q ⁇ are each independently OH ⁇ , R ⁇ —COO ⁇ , R ⁇ —SO 3 — or an anion represented by the following formula (6-3).
- R ⁇ is an alkyl group, an aryl group or an aralkyl group.
- R 23 represents a linear or branched alkyl group having 1 to 12 carbon atoms, in which part or all of the hydrogen atoms may be substituted with fluorine atoms, or 1 carbon atom 12 to 12 linear or branched alkoxyl groups.
- u is an integer of 0-2.
- the content of the other acid diffusion controller is as follows: [D] When the other acid diffusion controller is [D] another acid diffusion controller, it is 0 mole relative to the [B] acid generator. % To 300 mol%, preferably 5 mol% to 250 mol%, more preferably 10 mol% to 200 mol%. [D] By setting the content of other acid diffusion control agents in the above range, the sensitivity, LWR performance, resolution, rectangularity of the cross-sectional shape, and depth of focus of the radiation-sensitive resin composition are further improved. Can do. [D] When the content of the other acid diffusion control agent exceeds the upper limit, the sensitivity of the radiation-sensitive resin composition may decrease. [D] The content of the other acid diffusion control agent is preferably 0 to 10 parts by mass, more preferably 0.1 to 8 parts by mass with respect to 100 parts by mass of the polymer [A]. More preferred is 0.3 to 5 parts by mass.
- the radiation-sensitive resin composition may contain [E] fluorine atom-containing polymer (excluding those corresponding to [A] polymer).
- the radiation sensitive resin composition contains the [E] fluorine atom-containing polymer, when the resist film is formed, due to the oil repellency characteristics of the [E] fluorine atom-containing polymer in the resist film, The distribution tends to be unevenly distributed in the vicinity of the resist film surface, and it is possible to suppress the elution of the acid generator, the acid diffusion controller, and the like during the immersion exposure into the immersion medium.
- the advancing contact angle between the resist film and the immersion medium can be controlled within a desired range, and the occurrence of bubble defects can be suppressed. Furthermore, the receding contact angle between the resist film and the immersion medium is increased, and high-speed scanning exposure is possible without leaving water droplets.
- the resist film suitable for an immersion exposure method can be formed.
- the fluorine atom-containing polymer is not particularly limited as long as it is a polymer having a fluorine atom, but the fluorine atom content (mass%) than the [A] polymer in the radiation-sensitive resin composition. ) Is preferably high.
- the fluorine atom content is higher than that of the polymer, the degree of uneven distribution described above becomes higher, and characteristics such as water repellency and elution suppression of the resulting resist film are improved.
- the fluorine atom content of the fluorine atom-containing polymer is preferably 1% by mass or more, more preferably 2% by mass to 60% by mass, further preferably 4% by mass to 40% by mass, and more preferably 7% by mass to 30% by mass. Mass% is particularly preferred.
- the fluorine atom content of the fluorine atom-containing polymer is less than the lower limit, the hydrophobicity of the resist film surface may be lowered.
- the fluorine atom content (% by mass) of the polymer can be calculated from the structure of the polymer obtained by 13 C-NMR spectrum measurement.
- the fluorine atom-containing polymer preferably has at least one selected from the group consisting of the following structural unit (Ea) and structural unit (Eb).
- the fluorine atom-containing polymer may have one or more structural units (Ea) and structural units (Eb).
- the structural unit (Ea) is a structural unit represented by the following formula (6a).
- a fluorine atom containing polymer can adjust a fluorine atom content rate by having a structural unit (Ea).
- R C represents a hydrogen atom, a methyl group or a trifluoromethyl group.
- G is a single bond, an oxygen atom, a sulfur atom, —CO—O—, —SO 2 —O—NH—, —CO—NH— or —O—CO—NH—.
- R D represents a monovalent chain hydrocarbon group having 1 to 6 carbon atoms having at least one fluorine atom or a monovalent aliphatic cyclic hydrocarbon group having 4 to 20 carbon atoms having at least one fluorine atom. It is.
- Examples of the chain hydrocarbon group having 1 to 6 carbon atoms and having at least one fluorine atom represented by RD include, for example, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, and perfluoroethyl.
- 2,2,3,3,3-pentafluoropropyl group 1,1,1,3,3,3-hexafluoropropyl group, perfluoro n-propyl group, perfluoro i-propyl group, perfluoro Examples thereof include n-butyl group, perfluoro i-butyl group, perfluoro t-butyl group, 2,2,3,3,4,4,5,5-octafluoropentyl group, perfluorohexyl group and the like.
- trifluoromethyl group 2,2,2-trifluoroethyl group, 1,1,1,3,3,3-hexafluoropropyl group are preferable, and 2,2,2-trifluoroethyl group Is more preferable.
- Examples of the aliphatic cyclic hydrocarbon group having 4 to 20 carbon atoms and having at least one fluorine atom represented by RD include a monofluorocyclopentyl group, a difluorocyclopentyl group, a perfluorocyclopentyl group, and a monofluorocyclohexyl group. , Difluorocyclopentyl group, perfluorocyclohexylmethyl group, fluoronorbornyl group, fluoroadamantyl group, fluorobornyl group, fluoroisobornyl group, fluorotricyclodecyl group, fluorotetracyclodecyl group and the like.
- Examples of the monomer that gives the structural unit (Ea) include trifluoromethyl (meth) acrylic acid ester, 2,2,2-trifluoroethyl (meth) acrylic acid ester, and perfluoroethyl (meth) acrylic acid.
- trifluoromethyl (meth) acrylate 2,2,2-trifluoroethyl (meth) acrylate, 2- (1,1,1,3,3,3-hexafluoropropyl) (Meth) acrylic acid esters are preferred, and 2,2,2-trifluoroethyl (meth) acrylic acid esters are more preferred.
- the content ratio of the structural unit (Ea) is preferably 5 mol% to 80 mol%, more preferably 10 mol% to 60 mol%, based on all structural units constituting the [E] fluorine atom-containing polymer. More preferably, it is 15 mol% to 40 mol%.
- the structural unit (Eb) is a structural unit represented by the following formula (6b). [E] Since the fluorine atom-containing polymer has a structural unit (Eb) and thus becomes more hydrophobic, it can further improve the dynamic contact angle of the resist film surface formed from the radiation-sensitive resin composition. it can.
- R E is a hydrogen atom, a methyl group or a trifluoromethyl group.
- R 24 is a (s + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and an oxygen atom, a sulfur atom, —NR′—, a carbonyl group, —CO—O—, or a terminal at the R 25 side of R 24 Also includes a structure in which —CO—NH— is bonded.
- R ′ is a hydrogen atom or a monovalent organic group.
- R 25 is a single bond, a divalent chain hydrocarbon group having 1 to 10 carbon atoms, or a divalent aliphatic cyclic hydrocarbon group having 4 to 20 carbon atoms.
- X 2 is a C 1-20 divalent chain hydrocarbon group having at least one fluorine atom.
- a 1 is an oxygen atom, —NR ′′ —, —CO—O— *, or —SO 2 —O— *.
- R ′′ is a hydrogen atom or a monovalent organic group. * Indicates a binding site that binds to R 26.
- R 26 represents a hydrogen atom or a monovalent organic group.
- s is an integer of 1 to 3. However, when s is 2 or 3, a plurality of R 25 , X 2 , A 1 and R 26 may be the same or different.
- R 26 is a hydrogen atom in that the solubility of the [E] fluorine atom-containing polymer in an alkali developer can be improved.
- Examples of the monovalent organic group represented by R 26 include an acid dissociable group, an alkali dissociable group, or a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.
- Examples of the structural unit (Eb) include structural units represented by the following formulas (6b-1) to (6b-3).
- R 24 ′ is a divalent linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms.
- R E , X 2 , R 26 and s are as defined in the above formula (6b). When s is 2 or 3, the plurality of X 2 and R 26 may be the same or different.
- the content ratio of the structural unit (Eb) is preferably 0 mol% to 90 mol%, more preferably 0 mol% to 80 mol%, based on all structural units constituting the [E] fluorine atom-containing polymer. 10 mol% to 70 mol% is more preferable.
- the fluorine atom-containing polymer has a structural unit containing an acid-dissociable group (hereinafter also referred to as “structural unit (Ec)”). (However, those corresponding to the structural unit (Eb) are excluded).
- structural unit (Ec) Since the fluorine atom-containing polymer has the structural unit (Ec), it is possible to suppress undissolved residue of the [E] fluorine atom-containing polymer in the resist film in the developer, and as a result, Occurrence of development defects in the resist pattern can be suppressed.
- the structural unit (Ec) include the structural unit (I) in the above-described [A] polymer.
- the content ratio of the structural unit (Ec) is preferably 10 mol% to 90 mol%, more preferably 20 mol% to 85 mol%, based on all structural units constituting the [E] fluorine atom-containing polymer. More preferably, it is 25 mol% to 80 mol%. If the content ratio of the structural unit (Ec) is less than the lower limit, development defects in the resist pattern may not be sufficiently suppressed. When the content ratio of the structural unit (Ec) exceeds the above upper limit, the hydrophobicity of the resulting resist film surface may be lowered.
- the [E] fluorine atom-containing polymer has, for example, at least one structure selected from the group consisting of a structural unit containing an alkali-soluble group, a lactone structure, a cyclic carbonate structure, and a sultone structure.
- alkali-soluble group a carboxy group, a sulfonamide group, a sulfo group etc. are mentioned, for example.
- Examples of the structural unit having at least one structure selected from the group consisting of a lactone structure, a cyclic carbonate structure and a sultone structure include the structural unit (II) in the above-mentioned [A] polymer.
- the content ratio of the other structural units is usually 30 mol% or less and preferably 20 mol% or less with respect to all the structural units constituting the [E] fluorine atom-containing polymer.
- the content rate of said other structural unit exceeds the said upper limit, the pattern formation property of the said radiation sensitive resin composition may fall.
- the content of the [E] fluorine atom-containing polymer in the radiation-sensitive resin composition is preferably 0 to 20 parts by mass, and 0.5 to 15 parts by mass with respect to 100 parts by mass of the [A] polymer. Mass parts are more preferred, and 1 to 10 parts by mass are even more preferred. [E] If the content of the fluorine atom-containing polymer exceeds the above upper limit, the pattern-forming property of the radiation-sensitive resin composition may be lowered.
- the radiation-sensitive resin composition usually contains a [F] solvent.
- [F] Solvent can dissolve or disperse at least [A] polymer, [B] acid generator and [C] acid diffusion controller, and [D] other acid diffusion controller contained as desired. If it is a solvent, it will not specifically limit.
- Solvents include, for example, alcohol solvents, ether solvents, ketone organic solvents, amide solvents, ester organic solvents, hydrocarbon solvents, and the like.
- an alcohol solvent for example, Methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec-pentanol, tert- Pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol, sec-octanol, n- Nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptan
- ether solvent for example, Dialkyl ether solvents such as diethyl ether, dipropyl ether, dibutyl ether; Cyclic ether solvents such as tetrahydrofuran and tetrahydropyran; Aromatic ring-containing ether solvents such as diphenyl ether and anisole (methylphenyl ether) are exemplified.
- ketone solvents include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, 2-heptanone (methyl-n-pentyl ketone), ethyl-n-butyl ketone.
- Chain ketone solvents such as methyl-n-hexyl ketone, di-iso-butyl ketone and trimethylnonanone: Cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone and methylcyclohexanone: Examples include 2,4-pentanedione, acetonylacetone, acetophenone, and the like.
- amide solvent examples include cyclic amide solvents such as N, N′-dimethylimidazolidinone and N-methylpyrrolidone; Examples thereof include chain amide solvents such as N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, and N-methylpropionamide.
- cyclic amide solvents such as N, N′-dimethylimidazolidinone and N-methylpyrrolidone
- chain amide solvents such as N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, and N-methylpropionamide.
- ester solvents include: Methyl acetate, ethyl acetate, n-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl acetate, sec-butyl acetate, n-pentyl acetate, i-pentyl acetate, sec-pentyl acetate, 3-methoxy acetate
- Acetate solvents such as butyl, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether
- hydrocarbon solvents examples include n-pentane, iso-pentane, n-hexane, iso-hexane, n-heptane, iso-heptane, 2,2,4-trimethylpentane, n-octane, iso-octane, cyclohexane , Aliphatic hydrocarbon solvents such as methylcyclohexane; Fragrances such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, iso-propylbenzene, diethylbenzene, iso-butylbenzene, triethylbenzene, di-iso-propylbenzene, n-amylnaphthalene Group hydrocarbon solvents and the like.
- ester solvents and ketone solvents are preferable, polyhydric alcohol partial ether acetate solvents and cyclic ketone solvents are more preferable, and propylene glycol monomethyl ether acetate and cyclohexanone are more preferable.
- the radiation-sensitive resin composition may contain one or more [F] solvents.
- the radiation sensitive resin composition may contain other optional components in addition to the above [A] to [F].
- the other optional components include uneven distribution accelerators, surfactants, alicyclic skeleton-containing compounds, and sensitizers. Each of these other optional components may be used alone or in combination of two or more.
- the uneven distribution accelerator has the effect of segregating the [E] fluorine atom-containing polymer more efficiently on the resist film surface.
- the amount of the [E] fluorine atom-containing polymer added can be reduced by adding this uneven distribution accelerator to the radiation sensitive resin composition. Therefore, elution of components from the resist film to the immersion liquid is further suppressed without impairing the cross-sectional rectangularity, LWR performance, resolution, depth of focus, and other characteristics, and high-speed scanning makes immersion exposure faster.
- the hydrophobicity of the resist film surface that suppresses immersion-derived defects such as watermark defects can be improved.
- Examples of such an uneven distribution promoter include low molecular compounds having a relative dielectric constant of 30 or more and 200 or less and a boiling point at 1 atm of 100 ° C. or more.
- Specific examples of such compounds include lactone compounds, carbonate compounds, nitrile compounds, and polyhydric alcohols.
- lactone compound examples include ⁇ -butyrolactone, valerolactone, mevalonic lactone, norbornane lactone, and the like.
- Examples of the carbonate compound include propylene carbonate, ethylene carbonate, butylene carbonate, vinylene carbonate, and the like.
- Examples of the nitrile compound include succinonitrile.
- Examples of the polyhydric alcohol include glycerin.
- the ubiquitous promoter is preferably a lactone compound, and more preferably ⁇ -butyrolactone.
- the content of the uneven distribution accelerator in the radiation-sensitive resin composition is preferably 10 parts by mass to 500 parts by mass, more preferably 15 parts by mass to 300 parts by mass with respect to 100 parts by mass of the total amount of the polymer. More preferred is 20 to 100 parts by mass.
- Surfactant Surfactants have the effect of improving coatability, striation, developability, and the like.
- the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol diacrylate.
- Nonionic surfactants such as stearate; commercially available products include KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no.
- the alicyclic skeleton-containing compound has an effect of improving dry etching resistance, pattern shape, adhesion to the substrate, and the like.
- Examples of the alicyclic skeleton-containing compound include adamantane derivatives such as 1-adamantanecarboxylic acid, 2-adamantanone, and 1-adamantanecarboxylic acid t-butyl; Deoxycholic acid esters such as t-butyl deoxycholic acid, t-butoxycarbonylmethyl deoxycholic acid, 2-ethoxyethyl deoxycholic acid; Lithocholic acid esters such as tert-butyl lithocholic acid, tert-butoxycarbonylmethyl lithocholic acid, 2-ethoxyethyl lithocholic acid; 3- [2-hydroxy-2,2-bis (trifluoromethyl) ethyl] tetracyclo [4.4.0.1 2,5 .
- adamantane derivatives such as 1-adamantanecarboxylic acid, 2-adamantanone, and 1-adamantanecarboxylic acid t-butyl
- Deoxycholic acid esters such
- sensitizer exhibits the effect
- sensitizer examples include carbazoles, acetophenones, benzophenones, naphthalenes, phenols, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines, and the like. These sensitizers may be used alone or in combination of two or more. As content of the sensitizer in the said radiation sensitive resin composition, it is 2 mass parts or less normally with respect to 100 mass parts of [A] polymers.
- the radiation-sensitive resin composition includes, for example, a predetermined ratio of [A] polymer, [B] acid generator, [C] acid diffusion controller, optional component contained as necessary, and [F] solvent. Can be prepared by mixing.
- the radiation-sensitive resin composition is preferably filtered after mixing with, for example, a filter having a pore size of about 0.2 ⁇ m.
- the solid content concentration of the radiation-sensitive resin composition is usually 0.1% by mass to 50% by mass, preferably 0.5% by mass to 30% by mass, and more preferably 1% by mass to 20% by mass.
- the method for forming a resist pattern according to the present invention includes: Using the radiation sensitive resin composition, a step of forming a resist film (hereinafter also referred to as “resist film forming step”), A step of exposing the resist film (hereinafter also referred to as “exposure step”), and a step of developing the exposed resist film (hereinafter also referred to as “development step”).
- resist film forming step a step of forming a resist film
- exposure step A step of exposing the resist film
- development step a step of developing the exposed resist film
- a resist pattern having a high LDO with a small LWR, excellent cross-sectional rectangularity, and high resolution while exhibiting a wide depth of focus. can be formed.
- each step will be described.
- a resist film is formed using the radiation sensitive resin composition.
- the substrate on which the resist film is formed include a silicon wafer, silicon dioxide, a wafer coated with an antireflection film, and the like.
- the method for applying the radiation sensitive resin composition include methods such as spin coating, cast coating, and roll coating. It is preferable to evaporate and remove the solvent in the coating film by pre-baking (PB) the coating film formed by the above application.
- PB temperature is usually 60 ° C to 140 ° C, preferably 80 ° C to 120 ° C.
- the PB time is usually 5 seconds to 600 seconds, and preferably 10 seconds to 300 seconds.
- the resist film formed in the resist film forming step is exposed.
- This exposure is performed by irradiating exposure light through a photomask or the like (in some cases through an immersion medium such as water).
- exposure light include electromagnetic waves such as visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and ⁇ rays; and charged particle beams such as electron beams and ⁇ -rays, depending on the line width of the target pattern. Can be mentioned.
- ArF excimer laser light (wavelength 193 nm), KrF excimer laser light (wavelength 248 nm), EUV (13.5 nm), and electron beams are more preferable, and ArF excimer laser light.
- An electron beam is more preferable.
- PEB post-exposure baking
- This PEB can surely cause a difference in solubility in the developer between the exposed portion (exposed portion) and the unexposed portion (unexposed portion).
- the PEB temperature is usually 50 ° C. to 180 ° C., preferably 80 ° C. to 130 ° C.
- the PEB time is usually 5 to 600 seconds, and preferably 10 to 300 seconds.
- a protective film for immersion that is insoluble in immersion liquid may be provided on the resist film before the exposure process in order to protect the direct contact between the immersion liquid and the resist film.
- the immersion protective film include a solvent peeling type protective film that peels off with a solvent before the developing process (see, for example, JP-A-2006-227632), and a developer peeling type protective film that peels off simultaneously with development in the developing process (for example, Any of WO 2005-069076 and WO 2006-035790 may be used.
- a developer peeling type immersion protective film it is preferable to use a developer peeling type immersion protective film.
- the development process In the development process, the resist film exposed in the exposure process is developed. Thereby, a predetermined resist pattern is formed.
- the development method may be alkali development or organic solvent development. Usually, a positive resist pattern is formed by alkali development, and a negative resist pattern is formed by organic solvent development. After the development, it is common to wash with water or a rinse solution such as alcohol and dry.
- alkali development for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine , Ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4 .3.0] -5-nonene, an alkaline aqueous solution in which at least one alkaline compound is dissolved, and the like.
- TMAH tetramethylammonium hydroxide
- a TMAH aqueous solution is preferable, and a 2.38 mass% TMAH aqueous solution is more preferable.
- organic solvents such as hydrocarbon solvents, ether solvents, ester solvents, ketone solvents, alcohol solvents, etc., or solvents containing organic solvents can be mentioned.
- the 1 type (s) or 2 or more types of the solvent enumerated as [F] solvent of the above-mentioned radiation sensitive resin composition are mentioned, for example.
- ester solvents and ketone solvents are preferable.
- the ester solvent an acetate solvent is preferable, and n-butyl acetate is more preferable.
- the ketone solvent is preferably a chain ketone, more preferably 2-heptanone.
- the compounds of the present invention are compound (1) and compound (2). Since the compound has the above-described properties, it can be suitably used as an acid diffusion control agent.
- the radiation-sensitive resin composition containing the compound has LWR performance, resolution, rectangularity of the cross-sectional shape, and depth of focus. Excellent.
- the compound is described in the section of the acid diffusion controller (I).
- the method for producing the compound of the present invention comprises: A process for producing a compound (1) comprising a step of reacting a compound represented by the above formula (ia) with an amine compound represented by the above formula (ib); And a method for producing a compound (2) comprising a step of reacting a compound represented by the above formula (ii-a) with an amine compound represented by the above formula (ii-b).
- compound (I) can be manufactured simply.
- the method for producing the compound is described in the section of the acid diffusion controller (I).
- Mw and Mn of the polymer were measured by gel permeation chromatography (GPC) using GPC columns (2 G2000HXL, 1 G3000HXL, 1 G4000HXL, manufactured by Tosoh Corporation) under the following conditions.
- the degree of dispersion (Mw / Mn) was calculated from the measurement results of Mw and Mn.
- [Low molecular weight partial content] [A] The content (% by mass) of a low molecular weight portion (referring to a portion having a molecular weight of less than 1,000) in the polymer was determined by HPLC using an HPLC column (Intersil ODS-25 ⁇ m column (4. 6 mm ⁇ ⁇ 250 mm), manufactured by GL Sciences Inc., and measurement was performed under the following conditions. Elution solvent: Acetonitrile / 0.1% by mass phosphoric acid aqueous solution Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass Sample injection volume: 100 ⁇ L Detector: Differential refractometer
- R 1 is a cyclohexyl group, 1-adamantatil group, 8-tricyclodecyl group, 3-hydroxy-1-adamantyl group, norbornanelactone-yl group, norbornane sultone-yl group, norbornanelactone-yloxycarbonylmethyl group, 2 -I-propyl-2-adamantyl group, 2-methyl-2-adamantyl group, 1-i-propyl-1-cyclopentyl group, 1,3-dioxa-2,2-dimethylcyclopentan-5-ylmethyl group, 7 A-(1,3-dioxa-2,2-dimethylcyclopentan-4-yl) -3,3-dimethyl-2,4,8-trioxabicyclo [3,3,0] octane-6-yl group or 7- (1,3-Dioxa-spiro [adamantane-2,2 ′] cyclopentan-4-y
- R 2 is a methyl group.
- R 4 and R 5 are hydrogen atoms.
- R 6 and R 7 are ethyl groups, or together with the nitrogen atom to which R 6 and R 7 are bonded to each other, they form a piperidine structure, a morpholine structure, or a decahydroquinoline structure.
- R 8 is a group that forms a butyrolactone-triyl group or a butyrolactone-tetrayl group together with the ester group and the carbon atom at the ⁇ -position thereof.
- R 9 is a cyclohexane-1,1-diyl group, a 2-methyl-1-oxacyclopentane-3,3-diyl group or an adamantane-2,2-diyl group.
- R 11 and R 12 are a hydrogen atom or a methyl group.
- R 13 and R 14 are bonded to each other to form a piperidine structure together with the nitrogen atom to which they are bonded.
- Example 1 Into a 100 mL eggplant flask, 16.8 g (100 mmol) of cyclohexyl methacrylate, 25.6 g (300 mmol) of piperidine and 20 g of toluene were charged, and the reaction was performed by heating and stirring at 65 ° C. for 36 hours. After completion of the reaction, water was added to the reaction solution, and the organic layer was washed with water seven times by a liquid separation operation. The organic layer was then dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain a pale yellow oil. The oil was purified by column chromatography to obtain 18.4 g (yield: 72.8%) of a compound represented by the following formula (i-1) as a colorless oil.
- Example 2 In Example 1, each (meth) acrylic acid ester or ⁇ -methylenebutyrolactone was used instead of cyclohexyl methacrylate, and each amine compound was used instead of piperidine.
- the dripping start was set as the polymerization reaction start time, and the polymerization reaction was carried out for 6 hours.
- the polymerization reaction solution was cooled with water and cooled to 30 ° C. or lower.
- the cooled polymerization reaction liquid was put into 400 g of methanol, and the precipitated white powder was separated by filtration.
- the filtered white powder was washed twice with 80 g of methanol, filtered, and dried at 50 ° C. for 17 hours to synthesize a white powdery polymer (A-1) (15.6 g, yield). 78%).
- Mw of the polymer (A-1) was 7,200, and Mw / Mn was 1.52.
- the content ratios of the structural unit derived from (M-1) and the structural unit derived from (M-2) were 50.2 mol% and 49.8 mol%, respectively.
- the content of the low molecular weight portion in this polymer (A-1) was 0.04% by mass.
- Mw of the polymer (A-2) was 10,000, and Mw / Mn was 2.1.
- the content ratios of the structural unit derived from p-hydroxystyrene and the structural unit derived from the compound (M-5) were 65.4 mol% and 34.6 mol%, respectively.
- the content of the low molecular weight portion in this polymer (A-2) was 0.05% by mass.
- the dripping start was set as the polymerization reaction start time, and the polymerization reaction was carried out for 6 hours.
- the polymerization reaction solution was cooled with water and cooled to 30 ° C. or lower.
- the polymerization reaction liquid was uniformly diluted with 150 g of n-hexane, and 600 g of methanol was added and mixed.
- 30 g of distilled water was added, and the mixture was further shaken and allowed to stand for 30 minutes.
- solvent substitution was performed to obtain a propylene glycol monomethyl ether acetate solution of polymer (E-1) (yield 60%).
- Mw of the obtained polymer (E-1) was 7,200, and Mw / Mn was 2.00.
- the content ratios of the structural unit derived from (M-1) and the structural unit derived from (M-3) were 71.1 mol% and 28.9 mol%, respectively.
- the content of the low molecular weight portion in this polymer (E-1) was 0.07% by mass.
- B-1 Triphenylsulfonium 2- (adamantan-1-ylcarbonyloxy) -1,1,3,3,3-pentafluoropropane-1-sulfonate (compound represented by the following formula (B-1))
- B-2 Triphenylsulfonium norbornane sultone-2-yl-oxycarbonyldifluoromethanesulfonate (compound represented by the following formula (B-2))
- B-3 Triphenylsulfonium 3- (piperidin-1-ylsulfonyl) -1,1,2,2,3,3-hexafluoropropane-1-sulfonate (compound represented by the following formula (B-3) )
- B-4 Triphenylsulfonium adamantane-1-yloxycarbonyldifluoromethanesulfonate (compound represented by the following formula (B-4))
- [Example 22] [A] 100 parts by mass of (A-1) as a polymer, [B] 8.5 parts by mass of (B-1) as an acid generator, [C] (i-1) 30 as an acid diffusion controller Mol% (molar ratio to [B] acid generator), [E] 3 parts by mass of (E-1) as a fluorine atom-containing polymer, 2,240 parts by mass of (F-1) as a [F] solvent, and A radiation-sensitive resin composition (J-1) was prepared by mixing 960 parts by weight of (F-2) and 30 parts by weight of (G-1) as a [G] uneven distribution accelerator.
- Example 23 to 57 and Comparative Examples 1 to 5 The radiation-sensitive resin compositions (J-2) to (J-57) and (CJ-1) to (CJ-1) to (C) are the same as Example 22 except that the components of the types and contents shown in Table 1 were used. CJ-5) was prepared.
- NSR-S610C ArF excimer laser immersion exposure apparatus
- each radiation-sensitive resin composition was evaluated by measuring each resist pattern formed.
- the exposure amount for forming the 40 nm 1L1S pattern by the exposure through the 40 nm 1L1S mask pattern was set as the optimum exposure amount (Eop).
- a scanning electron microscope (S-9380, manufactured by Hitachi High-Technologies) was used for measuring the length of the resist pattern formed by this method.
- examples 22 to 38 are comparative example 1
- examples 39 to 42 are comparative example 2
- examples 43 to 47 are comparative example 3
- examples Comparative Example 4 was used for 48-52
- Comparative Example 5 for Examples 53-57.
- the evaluation results are shown in Table 2. “-” In Table 2 indicates a criterion for evaluation.
- LWR performance The resist pattern formed in the Eop was observed from above the pattern using the scanning electron microscope. A total of 50 line widths were measured at arbitrary points, and a 3-sigma value was obtained from the distribution of the measured values, and this was defined as LWR performance (nm). LWR performance indicates that the smaller the value, the better. The LWR performance is 10% or more of the LWR performance improvement (meaning that the value of the LWR performance is 90% or less) compared to the comparative example, and “A” is 5% or more and less than 10%. The improvement in LWR performance was evaluated as “B”, and the improvement in LWR performance of less than 5% was evaluated as “C”.
- resolution The minimum resist pattern dimension resolved in the above Eop was defined as resolution (nm). The smaller the value, the better the resolution. The resolution was 10% or more in comparison with the comparative example (meaning that the resolution value is 90% or less), and “A” was 5% or more and 10%. When the improvement in LWR performance was less than 5%, “B” was evaluated, and when the resolution improvement was less than 5%, “C” was evaluated.
- Example 59 to 93 and Comparative Examples 6 to 10 The radiation-sensitive resin compositions (J-38) to (J-72) and (CJ-6) to (CJ) were used in the same manner as in Example 58 except that the components having the types and contents shown in Table 3 were used. -10) was prepared.
- the radiation-sensitive resin compositions of the examples had LWR performance, resolution, and cross-sectional shape as compared with the radiation-sensitive resin compositions of the comparative examples. It can be said that the rectangularity is excellent.
- the radiation-sensitive resin composition containing the acid diffusion-controlling agent, and the resist pattern forming method using the radiation-sensitive resin composition the LWR is small and the cross-sectional shape is exhibited while exhibiting a wide depth of focus. It is possible to form a resist pattern with excellent rectangularity and high resolution.
- the compound of this invention can be used suitably as the said acid diffusion controlling agent. Therefore, they can be suitably used for pattern formation in semiconductor device manufacturing, which is expected to become increasingly finer in the future.
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Abstract
Description
下記式(1)で表される化合物及び下記式(2)で表される化合物からなる群より選ばれる少なくとも1種からなる酸拡散制御剤である。
R1は、炭素数3~30の1価の脂環式構造を有する炭化水素基、この基の炭素-炭素間に-O-、-CO-、-COO-、-SO2O-、-NRaSO2-及び-NRaCO-からなる群より選ばれる少なくとも1種を含む基、若しくは炭素数6~30の芳香族炭化水素基、又はこれらの基が有する水素原子の一部若しくは全部をヒドロキシ基及びハロゲン原子からなる群より選ばれる少なくとも1種で置換した基である。Raは、水素原子又は炭素数1~10の炭化水素基である。
R2及びR3は、それぞれ独立して、水素原子又は炭素数1~10の1価の炭化水素基であり、R2及びR3のうちの少なくとも一方が、炭素数1~10の1価の炭化水素基である。
R4及びR5は、それぞれ独立して、水素原子又は炭素数1~10の1価の炭化水素基である。
R6及びR7は、それぞれ独立して、水素原子若しくは炭素数1~10の1価の炭化水素基であるか、又はR6及びR7が互いに結合してそれらが結合する窒素原子と共に環員数3~10の環構造を形成している。
式(2)中、
R8は、エステル基及びR10が結合する炭素原子と共に環員数5~8の(n+2)価の単環の複素環基を形成する基である。nは、1~6の整数である。
R9は、nが1~6の整数の場合、炭素数1~20の1価の炭化水素基、nが2以上の場合、複数のR9のうちの2つ以上が互いに結合して形成された環員数3~10の環構造、若しくはこれらの基若しくは環構造の炭素-炭素間に-O-、-CO-、-COO-、-SO2O-、-NRbSO2及び-NRbCO-からなる群より選ばれる少なくとも1種を含む基、又はこれらの基若しくは環構造が有する水素原子の一部若しくは全部をヒドロキシ基及びハロゲン原子からなる群より選ばれる少なくとも1種で置換した基である。Rbは、水素原子又は炭素数1~10の1価の炭化水素基である。
R10は、水素原子又は炭素数1~10の1価の炭化水素基である。
R11及びR12は、それぞれ独立して、水素原子又は炭素数1~10の1価の炭化水素基である。
R13及びR14は、それぞれ独立して、水素原子若しくは炭素数1~10の1価の炭化水素基であるか、又はR13及びR14が互いに結合してそれらが結合する窒素原子と共に環員数3~10の環構造を形成している。)
酸解離性基を有する重合体、
酸発生体、及び
当該酸拡散制御剤
を含有する。
当該感放射線性樹脂組成物を用い、レジスト膜を形成する工程、
上記レジスト膜を露光する工程、及び
上記露光されたレジスト膜を現像する工程
を有する。
R1は、炭素数3~30の1価の脂環式構造を有する炭化水素基、この基の炭素-炭素間に-O-、-CO-、-COO-、-SO2O-、-NRaSO2-及び-NRaCO-からなる群より選ばれる少なくとも1種を含む基、若しくは炭素数6~30の芳香族炭化水素基、又はこれらの基が有する水素原子の一部若しくは全部をヒドロキシ基及びハロゲン原子からなる群より選ばれる少なくとも1種で置換した基である。Raは、水素原子又は炭素数1~10の炭化水素基である。
R2及びR3は、それぞれ独立して、水素原子又は炭素数1~10の1価の炭化水素基であり、R2及びR3のうちの少なくとも一方が、炭素数1~10の1価の炭化水素基である。
R4及びR5は、それぞれ独立して、水素原子又は炭素数1~10の1価の炭化水素基である。
R6及びR7は、それぞれ独立して、水素原子若しくは炭素数1~10の1価の炭化水素基であるか、又はR6及びR7が互いに結合してそれらが結合する窒素原子と共に環員数3~10の環構造を形成している。)
R8は、エステル基及びR10が結合する炭素原子と共に環員数5~8の(n+2)価の単環の複素環基を形成する基である。nは、1~6の整数である。
R9は、nが1~6の整数の場合、炭素数1~20の1価の炭化水素基、nが2以上の場合、複数のR9のうちの2つ以上が互いに結合して形成された環員数3~10の環構造、若しくはこれらの基若しくは環構造の炭素-炭素間に-O-、-CO-、-COO-、-SO2O-、-NRbSO2及び-NRbCO-からなる群より選ばれる少なくとも1種を含む基、又はこれらの基若しくは環構造が有する水素原子の一部若しくは全部をヒドロキシ基及びハロゲン原子からなる群より選ばれる少なくとも1種で置換した基である。Rbは、水素原子又は炭素数1~10の1価の炭化水素基である。
R10は、水素原子又は炭素数1~10の1価の炭化水素基である。
R11及びR12は、それぞれ独立して、水素原子又は炭素数1~10の1価の炭化水素基である。
R13及びR14は、それぞれ独立して、水素原子若しくは炭素数1~10の1価の炭化水素基であるか、又はR13及びR14が互いに結合してそれらが結合する窒素原子と共に環員数3~10の環構造を形成している。)
下記式(i-a)で表される化合物と、下記式(i-b)で表されるアミン化合物とを反応させる工程を有する下記式(1)で表される化合物の製造方法である。
R1は、炭素数3~30の1価の脂環式構造を有する炭化水素基、この基の炭素-炭素間に-O-、-CO-、-COO-、-SO2O-、-NRaSO2-及び-NRaCO-からなる群より選ばれる少なくとも1種を含む基、若しくは炭素数6~30の芳香族炭化水素基、又はこれらの基が有する水素原子の一部若しくは全部をヒドロキシ基及びハロゲン原子からなる群より選ばれる少なくとも1種で置換した基である。Raは、水素原子又は炭素数1~10の炭化水素基である。
R2及びR3は、それぞれ独立して、水素原子又は炭素数1~10の1価の炭化水素基であり、R2及びR3のうちの少なくとも一方が、炭素数1~10の1価の炭化水素基である。
R4及びR5は、それぞれ独立して、水素原子又は炭素数1~10の1価の炭化水素基である。
R6及びR7は、それぞれ独立して、水素原子若しくは炭素数1~10の1価の炭化水素基であるか、又はR6及びR7が互いに結合してそれらが結合する窒素原子と共に環員数3~10の環構造を形成している。)
下記式(ii-a)で表される化合物と、下記式(ii-b)で表されるアミン化合物とを反応させる工程を有する下記式(2)で表される化合物の製造方法である。
R8は、エステル基及びR10が結合する炭素原子と共に環員数5~8の(n+2)価の単環の複素環基を形成する基である。nは、1~6の整数である。
R9は、nが1~6の整数の場合、炭素数1~20の1価の炭化水素基、nが2以上の場合、複数のR9のうちの2つ以上が互いに結合して形成された環員数3~10の環構造、若しくはこれらの基若しくは環構造の炭素-炭素間に-O-、-CO-、-COO-、-SO2O-、-NRbSO2及び-NRbCO-からなる群より選ばれる少なくとも1種を含む基、又はこれらの基若しくは環構造が有する水素原子の一部若しくは全部をヒドロキシ基及びハロゲン原子からなる群より選ばれる少なくとも1種で置換した基である。Rbは、水素原子又は炭素数1~10の1価の炭化水素基である。
R10は、水素原子又は炭素数1~10の1価の炭化水素基である。
R11及びR12は、それぞれ独立して、水素原子又は炭素数1~10の1価の炭化水素基である。
R13及びR14は、それぞれ独立して、水素原子若しくは炭素数1~10の1価の炭化水素基であるか、又はR13及びR14が互いに結合してそれらが結合する窒素原子と共に環員数3~10の環構造を形成している。)
当該酸拡散制御剤(以下、「酸拡散制御剤(I)」ともいう)は、上記式(1)で表される化合物(以下、「化合物(1)」ともいう)及び下記式(2)で表される化合物(以下、「化合物(2)」ともいう)からなる群より選ばれる少なくとも1種(以下、「化合物(I)」ともいう)からなる。酸拡散制御剤(I)は、化合物(I)からなることで、これを含有する感放射線性樹脂組成物は、LWR性能、解像性、断面形状の矩形性及び焦点深度に優れる。酸拡散制御剤(I)が化合物(I)からなることで、上記効果を奏する理由については必ずしも明確ではないが、例えば、以下のように推察することができる。
化合物(I)は、酸と相互作用し得る窒素原子と共にエステル基を有し、このエステル基の近傍の環構造又はエステル基を含む環構造を有し、さらに、このエステル基の近傍に炭化水素基又はその誘導基である特定基を有する特定の構造を有している。化合物(I)は、このように、極性を有するエステル基、嵩高さを有する環構造及び立体的効果を発揮する特定基が互いに近傍に存在することで、これらの相乗効果が発揮されると考えられ、従来の窒素原子含有化合物に比べて、化合物(I)とレジスト膜を構成する重合体等との親和性が高くなると共に、昇華性が低減されかつ耐熱性に優れる。これにより、化合物(I)のレジスト膜中での拡散及び偏在が適度に抑制される。その結果、化合物(I)を含有する感放射線性樹脂組成物は、LWR性能、解像性、断面形状の矩形性及び焦点深度が優れる。
また、化合物(I)は、上記特定構造を有するので、アクリル酸エステル系化合物又はαメチレンラクトン化合物と、アミン化合物とから簡便に合成することができるので、原料の入手が容易であり、製造コスト的にも有利である。
以下、化合物(1)及び化合物(2)の順に説明する。
化合物(1)は、下記式(1)で表される。
R1は、炭素数3~30の1価の脂環式構造を有する炭化水素基、この基の炭素-炭素間に-O-、-CO-、-COO-、-SO2O-、-NRaSO2-及び-NRaCO-からなる群より選ばれる少なくとも1種を含む基、若しくは炭素数6~30の芳香族炭化水素基、又はこれらの基が有する水素原子の一部若しくは全部をヒドロキシ基及びハロゲン原子からなる群より選ばれる少なくとも1種で置換した基である。Raは、水素原子又は炭素数1~10の炭化水素基である。
R2及びR3は、それぞれ独立して、水素原子又は炭素数1~10の1価の炭化水素基であり、R2及びR3のうちの少なくとも一方が、炭素数1~10の1価の炭化水素基である。
R4及びR5は、それぞれ独立して、水素原子又は炭素数1~10の1価の炭化水素基である。
R6及びR7は、それぞれ独立して、水素原子若しくは炭素数1~10の1価の炭化水素基であるか、又はR6及びR7が互いに結合してそれらが結合する窒素原子と共に環員数3~10の環構造を形成している。
シクロプロピル基、シクロブチル基、シクロペンチル基、1-i-プロピルシクロペンタン-1-イル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロデシル基、2-メチルアダマンタン-2-イル基、2-i-プロピルアダマンタン-2-イル基等の単環のシクロアルキル基;
ノルボルニル基、アダマンチル基、トリシクロデシル基、テトラシクロドデシル基等の多環のシクロアルキル基;
シクロペンテニル基、シクロヘキセニル基等の単環のシクロアルケニル基;
ノルボルネニル基、トリシクロデセニル基等の多環のシクロアルケニル基などが挙げられる。
これらの中で単環のシクロアルキル基、多環のシクロアルキル基が好ましく、多環のシクロアルキル基がより好ましく、アダマンタン環を有する基、トリシクロデカン環を有する基がさらに好ましく、1-アダマンチル基、8-トリシクロデシル基が特に好ましい。
1-メチル-1-シクロペンチル基、1-エチル-1-シクロペンチル基、1-i-プロピル-1-シクロペンチル基、1-メチル-1-シクロヘキシル基等のアルキル基置換単環のシクロアルキル基;
2-メチル-2-アダマンチル基、2-エチル-2-アダマンチル基、2-i-イソプロピル-2-アダマンチル基、2-メチル-2-ノルボルニル基等のアルキル基置換多環のシクロアルキル基等;
2-シクロペンチル-2-プロピル基、2-シクロヘキシル-2-プロピル基、2-ノルボルニル-2-プロピル基、2-アダマンチル-2-プロピル基等のシクロアルキル基置換アルキル基等が挙げられる。
これらの中で、アルキル基置換単環のシクロアルキル基、アルキル基置換多環のシクロアルキル基が好ましく、1-アルキル-1-単環シクロアルキル基、2-アルキル-2-多環シクロアルキル基がより好ましく、1-アルキル-1-シクロペンチル基、2-アルキル-2-アダマンチル基がさらに好ましく、1-i-プロピル-1-シクロペンチル基、2-エチル-2-アダマンチル基、2-i-プロピル-2-アダマンチル基が特に好ましい。
R1が酸解離性の脂環式構造を有する炭化水素基であると、化合物(1)は、露光部において、酸発生体から発生した酸の作用により解離しカルボキシ基を生じる。その結果、化合物(1)のレジスト膜中における拡散がより適度に制御される。また、R1が酸の作用により解離することで、現像液に対する親和性が変化するため、当該酸拡散制御剤を含有する感放射線性樹脂組成物の溶解コントラストが向上する。具体的には、露光部において、アルカリ現像液に対しては溶解性が向上し、有機溶剤現像液に対しては溶解禁止効果が向上する。
オキサシクロペンチル基、オキサシクロヘキシル基等のオキサシクロアルカン構造を有する基;
1,3-ジオキサ-2,2-ジメチルシクロペンタン-5-イルメチル基、1,3-ジオキサシクロペンタン-5-イルメチル基等の環状アセタール環(環状ケタール環を含む)を有する基;
7-(1,3-ジオキサ-2,2-ジメチルシクロペンタン-4-イル)-3,3-ジメチル-2,4,8-トリオキサビシクロ[3,3,0]オクタン-6-イル基、7-(1,3-ジオキサ-スピロ[アダマンタン-2,2’]シクロペンタン-4-イル)-スピロ[アダマンタン-3,3’]-2,4,8-トリオキサビシクロ[3,3,0]オクタン-6-イル基等のオキサシクロアルカン構造及び環状アセタール環を有する基等が挙げられる。
これらの中で、環状アセタール環を有する基、オキサシクロアルカン構造及び環状アセタール環を有する基が好ましく、1,3-ジオキサ-2,2-ジメチルシクロペンタン-5-イルメチル基、7-(1,3-ジオキサ-2,2-ジメチルシクロペンタン-4-イル)-3,3-ジメチル-2,4,8-トリオキサビシクロ[3,3,0]オクタン-6-イル基、7-(1,3-ジオキサ-スピロ[アダマンタン-2,2’]シクロペンタン-4-イル)-スピロ[アダマンタン-3,3’]-2,4,8-トリオキサビシクロ[3,3,0]オクタン-6-イル基がより好ましい。
R1が環状アセタール環を有する基であると、化合物(1)は、露光部において、酸発生体から発生する酸の作用により、2個のヒドロキシ基を生じる。その結果、化合物(1)のレジスト膜中における拡散がより適度に制御される。また、酸発生体から発生した酸の作用により解離することで、現像液に対する親和性が変化するため、溶解コントラストが向上する。具体的には、露光部において、アルカリ現像液に対しては溶解性が向上し、有機溶剤現像液に対しては溶解禁止効果が向上する。
オキソシクロペンチル基、オキソシクロヘキシル基、オキソノルボルニル基、オキソアダマンチル基、ジオキソシクロペンチル基、ジオキソシクロヘキシル基、ジオキソノルボルニル基、ジオキソアダマンチル基等の環状ケトン基;
ノルボルニルカルボニルメチル基、アダマンチルカルボニルメチル基等の環状ケトン基を有する鎖状基等が挙げられる。
これらの中で、環状ケトン基を有する鎖状基が好ましく、ノルボルニルカルボニルメチル基がより好ましい。
ブチロラクトン-イル基、バレロラクトン-イル基、カプロラクトン-イル基、ノルボルナンラクトン-イル基、5-オキソ-4-オキサトリシクロ[4.3.1.13,8]ウンデカン-イル基等のラクトン構造を有する基;
ノルボルナンラクトン-イルオキシカルボニルメチル基、ブチロラクトン-イルオキシカルボニルメチル基等のラクトン-イルオキシカルボニルアルキル基等のラクトン構造を有する基を有するエステル基含有鎖状基等が挙げられる。
これらの中で、ノルボルナンラクトン-イル基、ノルボルナンラクトン-イルオキシカルボニルメチル基が好ましい。
これらの中で、ノルボルナンスルトン-イル基が好ましい。
これらの中で、ノルボルナンスルタム-イル基が好ましい。
これらの中で、カプロラクタム-イル基、ノルボルナンラクタム-イル基が好ましい。
メチル基、エチル基、プロピル基、ブチル基等のアルキル基;
エテニル基、プロペニル基、ブテニル基等のアルケニル基;
エチニル基、プロピニル基、ブチニル基等のアルキニル基等が挙げられる。
シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、ノルボルニル基、アダマンチル基、トリシクロデシル基等のシクロアルキル基;
シクロブテニル基、シクロペンテニル基、シクロヘキセニル基、ノルボルネニル基等のシクロアルケニル基等が挙げられる。
フェニル基、トリル基、キシリル基、メシチル基、ナフチル基等のアリール基;
ベンジル基、フェネチル基、フェニルプロピル基等のアラルキル基等が挙げられる。
フェニル基、トリル基、キシリル基、メシチル基、ナフチル基、メチルナフチル基、アントリル基、メチルアントリル基等のアリール基;
ベンジル基、フェネチル基、フェニルプロピル基、ナフチルメチル基等のアラルキル基等が挙げられる。
ヒドロキシシクロペンチル基、ヒドロキシシクロヘキシル基、ジヒドロキシシクロペンチル基、ジヒドロキシシクロヘキシル基等のヒドロキシ基置換単環のシクロアルキル基;
ヒドロキシノルボルニル基、ヒドロキシアダマンチル基、ジヒドロキシノルボルニル基、ジヒドロキシアダマンチル基等のヒドロキシ基置換多環のシクロアルキル基;
ヒドロキシフェニル基、ヒドロキシトリル基、ヒドロキシナフチル基、ヒドロキシアントリル基等のヒドロキシ基置換アリール基等が挙げられる。
これらの中で、ヒドロキシ基置換多環のシクロアルキル基が好ましく、ヒドロキシアダマンチル基がより好ましく、3-ヒドロキシ-1-アダマンチル基がさらに好ましい。
ハロシクロペンチル基、ハロシクロヘキシル基、ジハロシクロペンチル基、ジハロシクロヘキシル基等のハロゲン原子置換単環のシクロアルキル基;
ハロノルボルニル基、ハロアダマンチル基、ジハロノルボルニル基、ジハロアダマンチル基等のハロゲン原子置換多環のシクロアルキル基;
ハロフェニル基、ハロトリル基、ハロナフチル基、ハロアントリル基等のハロゲン原子置換アリール基等が挙げられる。
これらの中で、ハロゲン原子置換単環のシクロアルキル基が好ましく、パーフルオロシクロアルキル基がより好ましい。
アザシクロプロパン構造、アザシクロブタン構造、アザシクロペンタン構造(ピロリジン構造)、アザシクロヘキサン構造(ピペリジン構造)、アザシクロヘプタン構造、アザシクロオクタン構造、アザシクロデカン構造等の単環のアザシクロアルカン構造;
アザビシクロ[2.2.1]ヘプタン構造、アザビシクロ[2.2.2]オクタン構造、アザトリシクロ[3.3.1.13,7]デカン構造等の多環のアザシクロアルカン構造;
アザオキサシクロプロパン構造、アザオキサシクロヘキサン構造(モルホリン構造を含む)等のアザオキサシクロアルカン構造等が挙げられる。
これらの中で、単環のアザシクロアルカン構造、アザオキサシクロアルカン構造が好ましく、アザシクロペンタン構造、アザシクロヘキサン構造、アザオキサシクロヘキサン構造がより好ましく、アザシクロヘキサン構造、1,4-アザオキサシクロヘキサン構造(モルホリン構造)がさらに好ましい。
化合物(2)は、下記式(2)で表される。
R8は、エステル基及びR10が結合する炭素原子と共に環員数5~8の(n+2)価の単環の複素環基を形成する基である。nは、1~6の整数である。
R9は、nが1~6の整数の場合、炭素数1~20の1価の炭化水素基、nが2以上の場合、複数のR9のうちの2つ以上が互いに結合して形成された環員数3~10の環構造、若しくはこれらの基若しくは環構造の炭素-炭素間に-O-、-CO-、-COO-、-SO2O-、-NRbSO2及び-NRbCO-からなる群より選ばれる少なくとも1種を含む基、又はこれらの基若しくは環構造が有する水素原子の一部若しくは全部をヒドロキシ基及びハロゲン原子からなる群より選ばれる少なくとも1種で置換した基である。Rbは、水素原子又は炭素数1~10の1価の炭化水素基である。
R10は、水素原子又は炭素数1~10の1価の炭化水素基である。
R11及びR12は、それぞれ独立して、水素原子又は炭素数1~10の1価の炭化水素基である。
R13及びR14は、それぞれ独立して、水素原子若しくは炭素数1~10の1価の炭化水素基であるか、又はR13及びR14が互いに結合してそれらが結合する窒素原子と共に環員数3~10の環構造を形成している。
ブチロラクトン、バレロラクトン、カプロラクトン等の単環のラクトン;このラクトンのCH2-CH2間に-O-、-S-、-NR-(Rは、水素原子又は1価の炭化水素基である)、-CO-、-CS-又はこれらを組み合わせた基を含む化合物から(n+2)個の水素原子を除いた基等が挙げられる。
これらの中で、単環のラクトンから(n+2)個の水素原子を除いた基が好ましく、ブチロラクトン、バレロラクトン又はカプロラクトンから(n+2)個の水素原子を除いた基がより好ましく、ブチロラクトンから(n+2)個の水素原子を除いた基がさらに好ましい。
メチル基、エチル基、プロピル基、ブチル基、ヘキシル基、オクチル基、デシル基、ドデシル基、テトラデシル基、オクタデシル基、イコシル基等のアルキル基;
エテニル基、プロペニル基、ブテニル基、ヘキセニル基、オクテニル基、デセニル基、ドデセニル基、テトラデセニル基、オクタデセニル基、イコセニル基等のアルケニル基;
エチニル基、プロピニル基、ブチニル基、ヘキシニル基、オクチニル基、デシニル基、ドデシニル基、テトラデシニル基等のアルキニル基などが挙げられる。
シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、ノルボルニル基、アダマンチル基、トリシクロデシル基、テトラシクロドデシル基等のシクロアルキル基;
シクロブテニル基、シクロペンテニル基、シクロヘキセニル基、ノルボルネニル基、トリシクロデセニル基、テトラシクロドデセニル基等のシクロアルケニル基などが挙げられる。
フェニル基、トリル基、キシリル基、メシチル基、ナフチル基、メチルナフチル基、アントリル基、メチルアントリル基等のアリール基;
ベンジル基、フェネチル基、フェニルプロピル基、ナフチルメチル基、アントリルメチル基等のアラルキル基等が挙げられる。
シクロプロパン構造、シクロブタン構造、シクロペンタン構造、シクロヘキサン構造、ノルボルナン構造、アダマンタン構造等のシクロアルカン構造;
オキサシクロブタン構造、オキサシクロペンタン構造、オキサシクロヘキサン構造、オキサノルボルナン構造、オキサアダマンタン構造等のオキサシクロアルカン構造;
ベンゼン環構造、ナフタレン環構造等の芳香環構造等が挙げられる。
この環構造には、ヒドロキシ基、ハロゲン原子、炭化水素基等の置換基が結合していてもよい。
また、これらの環構造は、スピロ環であってもよい。上記環構造を形成する2つのR9が同一炭素原子に結合している場合には、スピロ環が形成される。
これらの中で、単環のアザシクロアルカン構造、アザオキサシクロアルカン構造が好ましく、アザシクロペンタン構造、アザシクロヘキサン構造、アザオキサシクロヘキサン構造がより好ましく、アザシクロヘキサン構造、1,4-アザオキサシクロヘキサン構造(モルホリン構造)がさらに好ましい。
R1は、炭素数3~30の1価の脂環式構造を有する炭化水素基、この基の炭素-炭素間に-O-、-CO-、-COO-、-SO2O-、-NRaSO2-及び-NRaCO-からなる群より選ばれる少なくとも1種を含む基、若しくは炭素数6~30の芳香族炭化水素基、又はこれらの基が有する水素原子の一部若しくは全部をヒドロキシ基及びハロゲン原子からなる群より選ばれる少なくとも1種で置換した基である。Raは、水素原子又は炭素数1~10の炭化水素基である。
R2及びR3は、それぞれ独立して、水素原子又は炭素数1~10の1価の炭化水素基であり、R2及びR3のうちの少なくとも一方が、炭素数1~10の1価の炭化水素基である。
R4及びR5は、それぞれ独立して、水素原子又は炭素数1~10の1価の炭化水素基である。
R6及びR7は、それぞれ独立して、水素原子若しくは炭素数1~10の1価の炭化水素基であるか、又はR6及びR7が互いに結合してそれらが結合する窒素原子と共に環員数3~10の環構造を形成している。
R8は、エステル基及びR10が結合する炭素原子と共に環員数5~8の(n+2)価の単環の複素環基を形成する基である。nは、1~6の整数である。
R9は、nが1~6の整数の場合、炭素数1~20の1価の炭化水素基、nが2以上の場合、複数のR9のうちの2つ以上が互いに結合して形成された環員数3~10の環構造、若しくはこれらの基若しくは環構造の炭素-炭素間に-O-、-CO-、-COO-、-SO2O-、-NRbSO2及び-NRbCO-からなる群より選ばれる少なくとも1種を含む基、又はこれらの基若しくは環構造が有する水素原子の一部若しくは全部をヒドロキシ基及びハロゲン原子からなる群より選ばれる少なくとも1種で置換した基である。Rbは、水素原子又は炭素数1~10の1価の炭化水素基である。
R10は、水素原子又は炭素数1~10の1価の炭化水素基である。
R11及びR12は、それぞれ独立して、水素原子又は炭素数1~10の1価の炭化水素基である。
R13及びR14は、それぞれ独立して、水素原子若しくは炭素数1~10の1価の炭化水素基であるか、又はR13及びR14が互いに結合してそれらが結合する窒素原子と共に環員数3~10の環構造を形成している。
当該感放射線性樹脂組成物は、酸解離性基を有する重合体(以下、「[A]重合体」ともいう)、酸発生体(以下、「[B]酸発生体」ともいう)及び当該酸拡散制御剤(以下、「[C]酸拡散制御剤」ともいう)を含有する。当該感放射線性樹脂組成物は、これらの成分以外にも、好適成分として、[D][C]酸拡散制御剤の酸拡散制御剤(以下、「[D]他の酸拡散制御剤」ともいう)、[E]フッ素原子含有重合体及び[F]溶媒をさらに含有してもよく、本発明の効果を損なわない範囲において、その他の任意成分を含有してもよい。以下、各成分について説明する。
[A]重合体は、酸解離性基を有する重合体である。[A]重合体は、酸解離性基を含む構造単位(以下、「構造単位(I)」ともいう)以外にも、ラクトン構造、環状カーボネート構造及びスルトン構造からなる群より選ばれる少なくとも1種を含む構造単位(II)及び/又は極性基を有する構造単位(III)をさらに有していることが好ましく、これらの構造単位以外のその他の構造単位をさらに有していてもよい。[A]重合体は、各構造単位をそれぞれ1種又は2種以上有していてもよい。以下、各構造単位について説明する。
構造単位(I)は、酸解離性基を含む構造単位である。「酸解離性基」とは、カルボキシ基、ヒドロキシ基等の酸性基の水素原子を置換する基であって、酸の作用により解離する基をいう。
構造単位(II)は、ラクトン構造、環状カーボネート構造及びスルトン構造からなる群より選ばれる少なくとも1種を含む構造単位である。[A]重合体は、構造単位(II)をさらに有することで、現像液への溶解性を調整することができる。また、当該感放射線性樹脂組成物から形成されるレジストパターンと基板との密着性を向上させることができる。
構造単位(III)は、極性基を有する構造単位である(但し、構造単位(II)に該当するものを除く)。[A]重合体は、構造単位(III)をさらに有することで、現像液への溶解性を調整することができる。
[A]重合体は、上記構造単位(I)~(III)以外のその他の構造単位を有していもよい。上記その他の構造単位としては、例えば、非解離性の脂環式炭化水素基を有する構造単位等が挙げられる。上記その他の構造単位の含有割合としては、[A]重合体を構成する全構造単位に対して、通常30モル%以下であり、20モル%以下が好ましい。上記その他の構造単位の含有割合が上記上限を超えると、当該感放射線性樹脂組成物のパターン形成性が低下する場合がある。
[A]重合体は、例えば、各構造単位を与える単量体を、ラジカル重合開始剤を用い、適当な溶媒中で重合することにより合成できる。
n-ペンタン、n-ヘキサン、n-ヘプタン、n-オクタン、n-ノナン、n-デカン等のアルカン類;
シクロヘキサン、シクロヘプタン、シクロオクタン、デカリン、ノルボルナン等のシクロアルカン類;
ベンゼン、トルエン、キシレン、エチルベンゼン、クメン等の芳香族炭化水素類;
クロロブタン類、ブロモヘキサン類、ジクロロエタン類、ヘキサメチレンジブロミド、クロロベンゼン等のハロゲン化炭化水素類;
酢酸エチル、酢酸n-ブチル、酢酸i-ブチル、プロピオン酸メチル等の飽和カルボン酸エステル類;
アセトン、2-ブタノン、4-メチル-2-ペンタノン、2-ヘプタノン等のケトン類;
テトラヒドロフラン、ジメトキシエタン類、ジエトキシエタン類等のエーテル類;
メタノール、エタノール、1-プロパノール、2-プロパノール、4-メチル-2-ペンタノール、プロピレングリコールモノメチルエーテル等のアルコール類などが挙げられる。
これらの中で、ケトン類、アルコール類が好ましく、2-ブタノン、プロピレングリコールモノメチルエーテルがより好ましい。これらの重合に使用される溶媒は、1種単独で又は2種以上を併用してもよい。
GPCカラム:G2000HXL 2本、G3000HXL 1本、G4000HXL 1本(以上、東ソー製)
カラム温度:40℃
溶出溶媒:テトラヒドロフラン(和光純薬工業製)
流速:1.0mL/分
試料濃度:1.0質量%
試料注入量:100μL
検出器:示差屈折計
標準物質:単分散ポリスチレン
溶出溶媒:アクリロニトリル/0.1質量%リン酸水溶液
流量:1.0mL/分
試料濃度:1.0質量%
試料注入量:100μL
検出器:示差屈折計
[B]酸発生体は、露光により酸を発生する物質である。この酸により[A]重合体中の酸解離性基が解離してカルボキシ基等の極性基が生成し、その結果[A]重合体の現像液への溶解性が変化する。当該感放射線性樹脂組成物における[B]酸発生体の含有形態としては、後述するような低分子化合物の形態(以下、適宜「[B]酸発生剤」ともいう)でも、重合体の一部として組み込まれた酸発生基の形態でも、これらの両方の形態でもよい。
[C]酸拡散制御剤は、本発明の酸拡散制御剤(I)である。当該感放射線性樹脂組成物は、[A]重合体及び[B]酸発生体に加えて、酸拡散制御剤(I)を含有することで、LWR性能、解像性、断面形状の矩形性及び焦点深度に優れる。[C]酸拡散制御剤については、上述の酸拡散制御剤(I)の項で説明している。[C]酸拡散制御剤は、1種又は2種以上を用いることができる。
また、[C]酸拡散制御剤の含有量としては、[A]重合体100質量部に対して、0.1質量部以上20質量部以下が好ましく、0.5質量部以上15質量部以下がより好ましく、1質量部以上10質量部以下がさらに好ましい。
[[D]他の酸拡散制御体]
当該感放射線性樹脂組成物は、必要に応じて、[D]他の酸拡散制御体を含有してもよい。当該感放射線性樹脂組成物は、[C]酸拡散制御剤に加えて、さらに[D]他の酸拡散制御体を含有することで、LWR性能、解像性、断面形状の矩形性及び焦点深度をより向上させることができる。[D]他の酸拡散制御体をさらに含有することで、上記効果をより向上させることができる理由については必ずしも明確ではないが、例えば、酸拡散制御剤を構成する化合物全体としての拡散度合いを調整することができること等が考えられる。[D]他の酸拡散制御体の当該感放射線性樹脂組成物における含有形態としては、後述するような低分子化合物である酸拡散制御剤の形態(以下、適宜「[D]他の酸拡散制御剤」ともいう)でも、重合体の一部として組み込まれた酸拡散制御基の形態でも、これらの両方の形態でもよい。
また、[D]他の酸拡散制御剤の含有量としては、[A]重合体100質量部に対して、0~10質量部が好ましく、0.1質量部~8質量部がより好ましく、0.3質量部~5質量部がさらに好ましい。
当該感放射線性樹脂組成物は、[E]フッ素原子含有重合体([A]重合体に該当するものを除く)を含有してもよい。当該感放射線性樹脂組成物が、[E]フッ素原子含有重合体を含有することで、レジスト膜を形成した際に、レジスト膜中の[E]フッ素原子含有重合体の撥油性的特徴により、その分布がレジスト膜表面近傍で偏在化する傾向があり、液浸露光時における酸発生剤や酸拡散制御剤等が液浸媒体に溶出することを抑制することができる。また、この[E]フッ素原子含有重合体の撥水性的特徴により、レジスト被膜と液浸媒体との前進接触角が所望の範囲に制御でき、バブル欠陥の発生を抑制できる。さらに、レジスト膜と液浸媒体との後退接触角が高くなり、水滴が残らずに高速でのスキャン露光が可能となる。このように当該感放射線性樹脂組成物が[E]フッ素原子含有重合体を含有することにより、液浸露光法に好適なレジスト被膜を形成することができる。
構造単位(Ea)は、下記式(6a)で表される構造単位である。[E]フッ素原子含有重合体は構造単位(Ea)を有することでフッ素原子含有率を調整することができる。
これらの中で、トリフルオロメチル(メタ)アクリル酸エステル、2,2,2-トリフルオロエチル(メタ)アクリル酸エステル、2-(1,1,1,3,3,3-ヘキサフルオロプロピル)(メタ)アクリル酸エステルが好ましく、2,2,2-トリフルオロエチル(メタ)アクリル酸エステルがより好ましい。
構造単位(Eb)は、下記式(6b)で表される構造単位である。[E]フッ素原子含有重合体は、構造単位(Eb)を有することで疎水性が上がるため、当該感放射線性樹脂組成物から形成されたレジスト膜表面の動的接触角をさらに向上させることができる。
[E]フッ素原子含有重合体は、上記構造単位(Ea)及び(Eb)以外にも、酸解離性基を含む構造単位(以下、「構造単位(Ec)」ともいう。)を有してもよい(但し、構造単位(Eb)に該当するものを除く)。[E]フッ素原子含有重合体が構造単位(Ec)を有することで、レジスト膜中の[E]フッ素原子含有重合体の現像液への溶け残りを抑制することができ、その結果、得られるレジストパターンの現像欠陥の発生を抑制することができる。構造単位(Ec)としては、上述した[A]重合体における構造単位(I)等が挙げられる。
また、[E]フッ素原子含有重合体は、上記構造単位以外にも、例えば、アルカリ可溶性基を含む構造単位、ラクトン構造、環状カーボネート構造及びスルトン構造からなる群より選ばれる少なくとも1種の構造を含む構造単位、非酸解離性の脂環式基を含む構造単位等の他の構造単位を有していてもよい。上記アルカリ可溶性基としては、例えば、カルボキシ基、スルホンアミド基、スルホ基等が挙げられる。ラクトン構造、環状カーボネート構造及びスルトン構造からなる群より選ばれる少なくとも1種の構造を有する構造単位としては、上述した[A]重合体における構造単位(II)等が挙げられる。
当該感放射線性樹脂組成物は、通常、[F]溶媒を含有する。[F]溶媒は、少なくとも[A]重合体、[B]酸発生体及び[C]酸拡散制御剤、並びに所望により含有される[D]他の酸拡散制御体等を溶解又は分散可能な溶媒であれば特に限定されない。
メタノール、エタノール、n-プロパノール、iso-プロパノール、n-ブタノール、iso-ブタノール、sec-ブタノール、tert-ブタノール、n-ペンタノール、iso-ペンタノール、2-メチルブタノール、sec-ペンタノール、tert-ペンタノール、3-メトキシブタノール、n-ヘキサノール、2-メチルペンタノール、sec-ヘキサノール、2-エチルブタノール、sec-ヘプタノール、3-ヘプタノール、n-オクタノール、2-エチルヘキサノール、sec-オクタノール、n-ノニルアルコール、2,6-ジメチル-4-ヘプタノール、n-デカノール、sec-ウンデシルアルコール、トリメチルノニルアルコール、sec-テトラデシルアルコール、sec-ヘプタデシルアルコール、フルフリルアルコール、フェノール、シクロヘキサノール、メチルシクロヘキサノール、3,3,5-トリメチルシクロヘキサノール、ベンジルアルコール、ジアセトンアルコール等のモノアルコール系溶媒;
エチレングリコール、1,2-プロピレングリコール、1,3-ブチレングリコール、2,4-ペンタンジオール、2-メチル-2,4-ペンタンジオール、2,5-ヘキサンジオール、2,4-ヘプタンジオール、2-エチル-1,3-ヘキサンジオール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、トリプロピレングリコール等の多価アルコール系溶媒;
エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノヘキシルエーテル、エチレングリコールモノフェニルエーテル、エチレングリコールモノ-2-エチルブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノプロピルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノヘキシルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル等の多価アルコール部分エーテル系溶媒等が挙げられる。
ジエチルエーテル、ジプロピルエーテル、ジブチルエーテル等のジアルキルエーテル系溶媒;
テトラヒドロフラン、テトラヒドロピラン等の環状エーテル系溶媒;
ジフェニルエーテル、アニソール(メチルフェニルエーテル)等の芳香環含有エーテル系溶媒等が挙げられる。
シクロペンタノン、シクロヘキサノン、シクロヘプタノン、シクロオクタノン、メチルシクロヘキサノン等の環状ケトン系溶媒:
2,4-ペンタンジオン、アセトニルアセトン、アセトフェノン等が挙げられる。
N-メチルホルムアミド、N,N-ジメチルホルムアミド、N,N-ジエチルホルムアミド、アセトアミド、N-メチルアセトアミド、N,N-ジメチルアセトアミド、N-メチルプロピオンアミド等の鎖状アミド系溶媒等が挙げられる。
酢酸メチル、酢酸エチル、酢酸n-プロピル、酢酸iso-プロピル、酢酸n-ブチル、酢酸iso-ブチル、酢酸sec-ブチル、酢酸n-ペンチル、酢酸i-ペンチル、酢酸sec-ペンチル、酢酸3-メトキシブチル、酢酸メチルペンチル、酢酸2-エチルブチル、酢酸2-エチルヘキシル、酢酸ベンジル、酢酸シクロヘキシル、酢酸メチルシクロヘキシル、酢酸n-ノニル等の酢酸エステル系溶媒;
エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノ-n-ブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノエチルエーテルアセテート等の多価アルコール部分エーテルアセテート系溶媒;
ジエチルカーボネート等のカーボネート系溶媒;
ジ酢酸グリコール、酢酸メトキシトリグリコール、プロピオン酸エチル、プロピオン酸n-ブチル、プロピオン酸iso-アミル、シュウ酸ジエチル、シュウ酸ジ-n-ブチル、アセト酢酸メチル、アセト酢酸エチル、乳酸メチル、乳酸エチル、乳酸n-ブチル、乳酸n-アミル、マロン酸ジエチル、フタル酸ジメチル、フタル酸ジエチルなどが挙げられる。
n-ペンタン、iso-ペンタン、n-ヘキサン、iso-ヘキサン、n-ヘプタン、iso-ヘプタン、2,2,4-トリメチルペンタン、n-オクタン、iso-オクタン、シクロヘキサン、メチルシクロヘキサン等の脂肪族炭化水素系溶媒;
ベンゼン、トルエン、キシレン、メシチレン、エチルベンゼン、トリメチルベンゼン、メチルエチルベンゼン、n-プロピルベンゼン、iso-プロピルベンゼン、ジエチルベンゼン、iso-ブチルベンゼン、トリエチルベンゼン、ジ-iso-プロピルベンセン、n-アミルナフタレン等の芳香族炭化水素系溶媒等が挙げられる。
当該感放射線性樹脂組成物は、上記[A]~[F]以外にも、その他の任意成分を含有していてもよい。上記その他の任意成分としては、例えば、偏在化促進剤、界面活性剤、脂環式骨格含有化合物、増感剤等が挙げられる。これらのその他の任意成分は、それぞれ1種又は2種以上を併用してもよい。
偏在化促進剤は、[E]フッ素原子含有重合体を、より効率的にレジスト膜表面に偏析させる効果を有するものである。当該感放射線性樹脂組成物にこの偏在化促進剤を含有させることで[E]フッ素原子含有重合体の添加量を従来よりも少なくすることができる。従って断面形状の矩形性、LWR性能、解像性及び焦点深度等の特性を損なうことなく、レジスト膜から液浸液への成分の溶出をさらに抑制したり、高速スキャンにより液浸露光をより高速に行うことが可能になり、結果としてウォーターマーク欠陥等の液浸由来欠陥を抑制するレジスト膜表面の疎水性を向上させることができる。このような偏在化促進剤として用いることができるものとしては、比誘電率が30以上200以下で、1気圧における沸点が100℃以上の低分子化合物を挙げることができる。このような化合物としては、具体的には、ラクトン化合物、カーボネート化合物、ニトリル化合物、多価アルコール等が挙げられる。
上記多価アルコールとしては、例えば、グリセリン等が挙げられる。
界面活性剤は、塗布性、ストリエーション、現像性等を改良する効果を奏する。界面活性剤としては、例えばポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンn-オクチルフェニルエーテル、ポリオキシエチレンn-ノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート等のノニオン系界面活性剤;市販品としては、KP341(信越化学工業製)、ポリフローNo.75、同No.95(以上、共栄社化学製)、エフトップEF301、同EF303、同EF352(以上、トーケムプロダクツ製)、メガファックF171、同F173(以上、DIC製)、フロラードFC430、同FC431(以上、住友スリーエム製)、アサヒガードAG710、サーフロンS-382、同SC-101、同SC-102、同SC-103、同SC-104、同SC-105、同SC-106(以上、旭硝子製)等が挙げられる。当該感放射線性樹脂組成物における界面活性剤の含有量としては、[A]重合体100質量部に対して通常2質量部以下である。
脂環式骨格含有化合物は、ドライエッチング耐性、パターン形状、基板との接着性等を改善する効果を奏する。
1-アダマンタンカルボン酸、2-アダマンタノン、1-アダマンタンカルボン酸t-ブチル等のアダマンタン誘導体類;
デオキシコール酸t-ブチル、デオキシコール酸t-ブトキシカルボニルメチル、デオキシコール酸2-エトキシエチル等のデオキシコール酸エステル類;
リトコール酸t-ブチル、リトコール酸t-ブトキシカルボニルメチル、リトコール酸2-エトキシエチル等のリトコール酸エステル類;
3-〔2-ヒドロキシ-2,2-ビス(トリフルオロメチル)エチル〕テトラシクロ[4.4.0.12,5.17,10]ドデカン、2-ヒドロキシ-9-メトキシカルボニル-5-オキソ-4-オキサ-トリシクロ[4.2.1.03,7]ノナン等が挙げられる。当該感放射線性樹脂組成物における脂環式骨格含有化合物の含有量としては、[A]重合体100質量部に対して通常5質量部以下である。
増感剤は、[B]酸発生剤等からの酸の生成量を増加する作用を示すものであり、当該感放射線性樹脂組成物の「みかけの感度」を向上させる効果を奏する。
当該感放射線性樹脂組成物は、例えば、[A]重合体、[B]酸発生体、[C]酸拡散制御剤、必要に応じて含有される任意成分及び[F]溶媒を所定の割合で混合することにより調製できる。当該感放射線性樹脂組成物は、混合後に、例えば、孔径0.2μm程度のフィルター等でろ過することが好ましい。当該感放射線性樹脂組成物の固形分濃度としては、通常0.1質量%~50質量%であり、0.5質量%~30質量%が好ましく、1質量%~20質量%がより好ましい。
本発明のレジストパターンの形成方法は、
当該感放射線性樹脂組成物を用い、レジスト膜を形成する工程(以下、「レジスト膜形成工程」ともいう)、
上記レジスト膜を露光する工程(以下、「露光工程」ともいう)、及び
上記露光されたレジスト膜を現像する工程(以下、「現像工程」ともいう)
を有する。
本工程では、当該感放射線性樹脂組成物を用い、レジスト膜を形成する。レジスト膜を形成する基板としては、例えば、シリコンウェハ、二酸化シリコン、反射防止膜で被覆されたウェハ等が挙げられる。感放射線性樹脂組成物の塗布方法としては、例えば、回転塗布、流延塗布、ロール塗布等の方法が挙げられる。上記塗布により形成された塗膜をプレベーク(PB)することにより塗膜中の溶媒を蒸発除去することが好ましい。PB温度としては、通常60℃~140℃であり、80℃~120℃が好ましい。PB時間としては、通常5秒~600秒であり、10秒~300秒が好ましい。
本工程では、レジスト膜形成工程で形成されたレジスト膜を露光する。この露光は、フォトマスク等(場合によっては、水等の液浸媒体を介して)を介して露光光を照射して行う。露光光としては、目的とするパターンの線幅に応じて、例えば、可視光線、紫外線、遠紫外線、極端紫外線、X線、γ線等の電磁波;電子線、α線等の荷電粒子線などが挙げられる。これらの中でも、遠紫外線、極端紫外線、電子線が好ましく、ArFエキシマレーザー光(波長193nm)、KrFエキシマレーザー光(波長248nm)、EUV(13.5nm)、電子線がより好ましく、ArFエキシマレーザー光、電子線がさらに好ましい。
現像工程では、露光工程で露光されたレジスト膜を現像する。これにより、所定のレジストパターンが形成される。上記現像の方法としては、アルカリ現像でも、有機溶媒現像でもよい。通常、アルカリ現像によりポジ型のレジストパターンが、有機溶媒現像によって、ネガ型のレジストパターンが形成される。上記現像後は、水又はアルコール等のリンス液で洗浄し、乾燥することが一般的である。
アルカリ現像の場合、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、けい酸ナトリウム、メタけい酸ナトリウム、アンモニア水、エチルアミン、n-プロピルアミン、ジエチルアミン、ジ-n-プロピルアミン、トリエチルアミン、メチルジエチルアミン、エチルジメチルアミン、トリエタノールアミン、テトラメチルアンモニウムヒドロキシド(TMAH)、ピロール、ピペリジン、コリン、1,8-ジアザビシクロ-[5.4.0]-7-ウンデセン、1,5-ジアザビシクロ-[4.3.0]-5-ノネン等のアルカリ性化合物の少なくとも1種を溶解したアルカリ水溶液等が挙げられる。これらの中でも、TMAH水溶液が好ましく、2.38質量%TMAH水溶液がより好ましい。
また、有機溶媒現像の場合、炭化水素系溶媒、エーテル系溶媒、エステル系溶媒、ケトン系溶媒、アルコール系溶媒等の有機溶媒、又は有機溶媒を含有する溶媒が挙げられる。上記有機溶媒としては、例えば、上述の感放射線性樹脂組成物の[F]溶媒として列挙した溶媒の1種又は2種以上等が挙げられる。これらの中でも、エステル系溶媒、ケトン系溶媒が好ましい。エステル系溶媒としては、酢酸エステル系溶媒が好ましく、酢酸n-ブチルがより好ましい。ケトン系溶媒としては、鎖状ケトンが好ましく、2-ヘプタノンがより好ましい。
本発明の化合物は、化合物(1)及び化合物(2)である。当該化合物は、上述の性質を有するので、酸拡散制御剤として好適に用いることができ、これを含有する感放射線性樹脂組成物は、LWR性能、解像性、断面形状の矩形性及び焦点深度に優れる。当該化合物については、上記酸拡散制御剤(I)の項で説明している。
本発明の化合物の製造方法は、
上記式(i-a)で表される化合物と、上記式(i-b)で表されるアミン化合物とを反応させる工程を有する化合物(1)の製造方法、
及び上記式(ii-a)で表される化合物と、上記式(ii-b)で表されるアミン化合物とを反応させる工程を有する化合物(2)の製造方法である。
当該化合物の製造方法によれば、化合物(I)を簡便に製造することができる。当該化合物の製造方法については、上記酸拡散制御剤(I)の項で説明している。
重合体のMw及びMnは、ゲルパーミエーションクロマトグラフィー(GPC)によりGPCカラム(G2000HXL 2本、G3000HXL 1本、G4000HXL 1本、東ソー製)を使用し、以下の条件により測定した。また、分散度(Mw/Mn)は、Mw及びMnの測定結果より算出した。
溶出溶媒:テトラヒドロフラン
流量:1.0mL/分
試料濃度:1.0質量%
試料注入量:100μL
カラム温度:40℃
検出器:示差屈折計
標準物質:単分散ポリスチレン
[A]重合体中の低分子量部分(分子量1,000未満の部分をいう)の含有率(質量%)は、高速液体クロマトグラフィー(HPLC)により、HPLCカラム(Intersil ODS-25μmカラム(4.6mmφ×250mm)、ジーエルサイエンス製)を使用し、以下の条件により測定した。
溶出溶媒:アセトニトリル/0.1質量%リン酸水溶液
流量:1.0mL/分
試料濃度:1.0質量%
試料注入量:100μL
検出器:示差屈折計
重合体の各構成単位含有割合を求めるための13C-NMR分析は、核磁気共鳴装置(JNM-ECX400、日本電子製)を使用して測定した。
化合物(I)は、以下の反応スキームに従い、合成した。
R1は、シクロヘキシル基、1-アダマンタチル基、8-トリシクロデシル基、3-ヒドロキシ-1-アダマンチル基、ノルボルナンラクトン-イル基、ノルボルナンスルトン-イル基、ノルボルナンラクトン-イルオキシカルボニルメチル基、2-i-プロピル-2-アダマンタチル基、2-メチル-2-アダマンチル基、1-i-プロピル-1-シクロペンチル基、1,3-ジオキサ-2,2-ジメチルシクロペンタン-5-イルメチル基、7-(1,3-ジオキサ-2,2-ジメチルシクロペンタン-4-イル)-3,3-ジメチル-2,4,8-トリオキサビシクロ[3,3,0]オクタン-6-イル基又は7-(1,3-ジオキサ-スピロ[アダマンタン-2,2’]シクロペンタン-4-イル)-スピロ[アダマンタン-3,3’]-2,4,8-トリオキサビシクロ[3,3,0]オクタン-6-イル基である。
R2は、メチル基である。
R4及びR5は、水素原子である。
R6及びR7は、エチル基であるか、又はR6及びR7が互いに結合してそれらが結合する窒素原子と共に、ピペリジン構造、モルホリン構造若しくはデカヒドロキノリン構造を形成している。
R8は、エステル基及びそのα位の炭素原子と共にブチロラクトン-トリイル基又はブチロラクトン-テトライル基を形成する基である。
R9は、シクロヘキサン-1,1-ジイル基、2-メチル-1-オキサシクロペンタン-3,3-ジイル基又はアダマンタン-2,2-ジイル基である。
R11及びR12は、水素原子又はメチル基である。
R13及びR14は、互いに結合してそれらが結合する窒素原子と共に、ピペリジン構造を形成している。
100mLのナスフラスコに、シクロヘキシルメタクリレート16.8g(100mmol)、ピペリジン25.6g(300mmol)及びトルエン20gを仕込み、65℃で36時間加熱攪拌し、反応を行った。反応終了後、反応液に水を加え、分液操作によって有機層の水洗浄を7回行なった。次いで、有機層を無水硫酸ナトリウムで乾燥させた後、溶媒を留去することにより淡黄色油状物を得た。この油状物をカラムクロマトグラフィで精製することにより、下記式(i-1)で表される化合物を、無色油状物として18.4g(収率72.8%)得た。
実施例1において、シクロヘキシルメタクリレートの代わりに各(メタ)アクリル酸エステル又はαメチレンブチロラクトンを用い、ピペリジンの代わりに各アミン化合物を用いた以外は、実施例1と同様にして、下記式(i-2)~(i-17)で表される化合物及び下記式(ii-1)~(ii-4)で表される化合物をそれぞれ合成した。
[A]重合体、[E]フッ素原子含有重合体の合成に用いた各単量体を下記に示す。
[合成例1]
上記化合物(M-1)9.01g(50モル%)及び化合物(M-2)10.99g(50モル%)を2-ブタノン40gに溶解し、さらにラジカル開始剤としてのAIBN0.81g(上記化合物の合計モル数に対して5モル%)を溶解させて単量体溶液を調製した。20gの2-ブタノンを入れた100mLの三口フラスコを30分窒素パージした後、攪拌しながら80℃に加熱し、上記調製した単量体溶液を滴下漏斗を用い3時間かけて滴下した。滴下開始を重合反応の開始時間とし、重合反応を6時間実施した。重合反応終了後、重合反応液を水冷して30℃以下に冷却した。400gのメタノール中に冷却した重合反応液を投入し、析出した白色粉末をろ別した。ろ別した白色粉末を80gずつのメタノールで2回洗浄した後、ろ別し、50℃で17時間乾燥させて白色粉末状の重合体(A-1)を合成した(15.6g、収率78%)。重合体(A-1)のMwは7,200であり、Mw/Mnは1.52であった。13C-NMR分析の結果、(M-1)に由来する構造単位及び(M-2)に由来する構造単位の含有割合は、それぞれ50.2モル%及び49.8モル%であった。この重合体(A-1)における低分子量部分の含有率は0.04質量%であった。
上記化合物(M-4)55.0g及び化合物(M-5)45.0g、AIBN4g及び連鎖移動剤としてのt-ドデシルメルカプタン1gを、プロピレングリコールモノメチルエーテル100gに溶解した後、窒素雰囲気下、反応温度を70℃に保持して、16時間重合させた。重合反応終了後、重合反応液を1,000gのn-ヘキサン中に滴下して、生成重合体を凝固精製した。次いで、この重合体に、再度プロピレングリコールモノメチルエーテル150gを加えた後、さらに、メタノール150g、トリエチルアミン34g及び水6gを加えて、沸点にて還流させながら、8時間加水分解反応を行った。反応後、溶媒及びトリエチルアミンを減圧留去し、得られた重合体をアセトン150gに溶解した後、2,000gの水中に滴下して凝固させ、生成した白色粉末をろ別し、50℃で17時間乾燥させて白色粉末の重合体(A-2)を得た(65.7g、収率76.6%)。重合体(A-2)のMwは10,000であり、Mw/Mnは2.1であった。13C-NMR分析の結果、p-ヒドロキシスチレンに由来する構造単位及び化合物(M-5)に由来する構造単位の含有割合は、それぞれ65.4モル%及び34.6モル%であった。この重合体(A-2)における低分子量部分の含有率は、0.05質量%であった。
[合成例3]
上記化合物(M-1)79.9g(70モル%)及び化合物(M-3)20.91g(30モル%)を、100gの2-ブタノンに溶解し、ラジカル重合開始剤としてのジメチル2,2’-アゾビスイソブチレート4.77gを溶解させて単量体溶液を調製した。100gの2-ブタノンを入れた1,000mLの三口フラスコを30分窒素パージした後、攪拌しながら80℃に加熱し、上記調製した単量体溶液を滴下漏斗を用い3時間かけて滴下した。滴下開始を重合反応の開始時間とし、重合反応を6時間実施した。重合反応終了後、重合反応液を水冷して30℃以下に冷却した。重合反応液を2L分液漏斗に移液した後、150gのn-ヘキサンでその重合反応液を均一に希釈し、600gのメタノールを投入して混合した。次いで、30gの蒸留水を投入し、さらに振とうして30分静置した。次いで、下層を回収した後、溶媒置換を行い、重合体(E-1)のプロピレングリコールモノメチルエーテルアセテート溶液を得た(収率60%)。得られた重合体(E-1)のMwは7,200であり、Mw/Mnは2.00であった。13C-NMR分析の結果、(M-1)に由来する構造単位及び(M-3)に由来する構造単位の含有割合は、それぞれ71.1モル%及び28.9モル%であった。この重合体(E-1)における低分子量部分の含有率は0.07質量%であった。
各感放射線性樹脂組成物の調製に用いた各成分を下記に示す。
B-1:トリフェニルスルホニウム2-(アダマンタン-1-イルカルボニルオキシ)-1,1,3,3,3-ペンタフルオロプロパン-1-スルホネート(下記式(B-1)で表される化合物)
B-2:トリフェニルスルホニウムノルボルナンスルトン-2-イル-オキシカルボニルジフルオロメタンスルホネート(下記式(B-2)で表される化合物)
B-3:トリフェニルスルホニウム3-(ピペリジン-1-イルスルホニル)-1,1,2,2,3,3-ヘキサフルオロプロパン-1-スルホネート(下記式(B-3)で表される化合物)
B-4:トリフェニルスルホニウムアダマンタン-1-イルオキシカルボニルジフルオロメタンスルホネート(下記式(B-4)で表される化合物)
上記式(i-1)~(i-17)で表される化合物、上記式(ii-1)~(ii-4)で表される化合物、並びに下記式(ci-1)、式(cii-1)、式(ciii-1)、式(civ-1)及び式(cv-1)で表される化合物
F-1:プロピレングリコールモノメチルエーテルアセテート
F-2:シクロヘキサノン
G-1:γ-ブチロラクトン
[A]重合体としての(A-1)100質量部、[B]酸発生剤としての(B-1)8.5質量部、[C]酸拡散制御剤としての(i-1)30モル%([B]酸発生剤に対するモル比)、[E]フッ素原子含有重合体としての(E-1)3質量部、[F]溶媒としての(F-1)2,240質量部及び(F-2)960質量部、並びに[G]偏在化促進剤としての(G-1)30質量部を混合し感放射線性樹脂組成物(J-1)を調製した。
表1に示す種類及び含有量の各成分を用いた以外は、実施例22と同様にして、感放射線性樹脂組成物(J-2)~(J-57)及び(CJ-1)~(CJ-5)を調製した。
[ArF露光の場合]
[アルカリ現像]
12インチのシリコンウェハ表面に、スピンコーター(CLEAN TRACK ACT12、東京エレクトロン製)を使用して、下層反射防止膜形成用組成物(ARC66、ブルワーサイエンス製)を塗布した後、205℃で60秒間加熱することにより膜厚105nmの下層反射防止膜を形成した。この下層反射防止膜上に、上記スピンコーターを使用して各感放射線性樹脂組成物を塗布し、90℃で60秒間PBを行った。その後23℃で30秒間冷却し、膜厚90nmのレジスト膜を形成した。次に、このレジスト膜を、ArFエキシマレーザー液浸露光装置(NSR-S610C、NIKON製)を用い、NA=1.3、ダイポール(シグマ0.977/0.782)の光学条件にて、40nmラインアンドスペース(1L1S)マスクパターンを介して露光した。露光後、90℃で60秒間PEBを行った。その後、2.38質量%TMAH水溶液により現像し、水で洗浄、乾燥し、ポジ型のレジストパターンを形成した。
上記[アルカリ現像]によるレジストパターンの形成において、現像液としての2.38質量%TMAH水溶液の代わりに酢酸n-ブチルを用い、かつ水での洗浄を行わなかった以外は、上記[アルカリ現像]の場合と同様にして、ネガ型のレジストパターンを形成した。
上記アルカリ現像の場合及び有機溶媒現像の場合それぞれにおいて、形成した各レジストパターンの測定により、各感放射線性樹脂組成物の評価を行った。それぞれの場合において、上記40nm1L1Sマスクパターンを介した露光により、40nm1L1Sパターンを形成する露光量を最適露光量(Eop)とした。なお、この方法で形成したレジストパターンの測長には走査型電子顕微鏡(S-9380、日立ハイテクノロジーズ製)を用いた。下記評価において実施例と比較する「比較例」としては、実施例22~38については比較例1、実施例39~42については比較例2、実施例43~47については比較例3、実施例48~52については比較例4、実施例53~57については比較例5とした。評価結果を表2に示す。表2中の「-」は、評価の基準であることを示す。
上記Eopにおいて形成したレジストパターンを、上記走査型電子顕微鏡を用い、パターン上部から観察した。線幅を任意のポイントで計50点測定し、その測定値の分布から3シグマ値を求め、これをLWR性能(nm)とした。LWR性能は、その値が小さいほど良好であることを示す。LWR性能は、比較例と比べて、10%以上のLWR性能向上(LWR性能の値が90%以下になることをいう)が見られたものを「A」と、5%以上10%未満のLWR性能向上が見られたものを「B」と、5%未満のLWR性能向上であったものを「C」と評価した。
上記Eopにおいて解像される最小のレジストパターンの寸法を解像性(nm)とした。解像性は、その値が小さいほど良好であることを示す。解像性は、比較例と比べて、10%以上の解像性向上(解像性の値が90%以下になることをいう)が見られたものを「A」と、5%以上10%未満のLWR性能向上が見られたものを「B」と、5%未満の解像性向上であったものを「C」と評価した。
上記Eopにおいて解像されるレジストパターンの断面形状を観察し、レジストパターンの高さ方向の中間での線幅Lbと、レジスト膜の上部での線幅Laを測定した。断面形状の矩形性は、0.9≦(La/Lb)≦1.1である場合を「A」(良好)と、(La/Lb)<0.9又は1.1<(La/Lb)である場合を「B」(不良)と評価した。
上記Eopにおいて解像されるレジストパターンにおいて、深さ方向にフォーカスを変化させた際の寸法を測定し、ブリッジや残渣が無いままパターン寸法が基準の90%~110%に入る深さ方向の余裕度を焦点深度とした。焦点深度(nm)は、その値が大きいほど良好であることを示す。焦点深度は、比較例と比べて、10%以上の焦点深度向上(焦点深度の値が110%以上になることをいう)が見られたものを「A」と5%以上10%未満の焦点深度向上が見られたものを「B」と、5%未満の焦点深度向上であったものを「C」と評価した。
[電子線照射の場合]
[実施例58]
[A]重合体としての(A-2)100質量部、[B]酸発生剤としての(B-1)20質量部、[C]酸拡散制御剤としての(i-1)30モル%([B]酸発生剤に対するモル比)、並びに[F]溶媒としての(F-1)4,280質量部及び(F-2)1,830質量部を混合して感放射線性樹脂組成物(J-37)を調製した。
下記表3に示す種類及び含有量の各成分を用いた以外は実施例58と同様にして感放射線性樹脂組成物(J-38)~(J-72)及び(CJ-6)~(CJ-10)を調製した。
8インチのシリコンウェハ表面にスピンコーター(CLEAN TRACK ACT8、東京エレクトロン製)を使用して、下記表3に記載の各感放射線性樹脂組成物を塗布し、90℃で60秒間PBを行った。その後23℃で30秒間冷却し、膜厚50nmのレジスト膜を形成した。次に、このレジスト膜に、簡易型の電子線描画装置(HL800D、日立製作所製、出力;50KeV、電流密度;5.0アンペア/cm2)を用いて電子線を照射した。照射後、130℃で60秒間PEBを行った。その後、2.38質量%のTMAH水溶液を用いて23℃で30秒間現像し、水で洗浄、乾燥し、ポジ型のレジストパターンを形成した。
形成した各レジストパターンについて、上記[ArF露光]における評価のうち、LWR性能、解像性及び断面形状の矩形性について、上記同様の方法で測定を行い、感放射線性樹脂組成物の評価を行った。実施例と比較する「比較例」としては、実施例58~74については比較例6、実施例75~78については比較例7、実施例79~83については比較例8、実施例84~88については比較例9、実施例89~93については比較例10とした。評価結果を表3に合わせて示す。表3中の「-」は、評価の基準であることを示す。
Claims (8)
- 下記式(1)で表される化合物及び下記式(2)で表される化合物からなる群より選ばれる少なくとも1種からなる酸拡散制御剤。
R1は、炭素数3~30の1価の脂環式構造を有する炭化水素基、この基の炭素-炭素間に-O-、-CO-、-COO-、-SO2O-、-NRaSO2-及び-NRaCO-からなる群より選ばれる少なくとも1種を含む基、若しくは炭素数6~30の芳香族炭化水素基、又はこれらの基が有する水素原子の一部若しくは全部をヒドロキシ基及びハロゲン原子からなる群より選ばれる少なくとも1種で置換した基である。Raは、水素原子又は炭素数1~10の炭化水素基である。
R2及びR3は、それぞれ独立して、水素原子又は炭素数1~10の1価の炭化水素基であり、R2及びR3のうちの少なくとも一方が、炭素数1~10の1価の炭化水素基である。
R4及びR5は、それぞれ独立して、水素原子又は炭素数1~10の1価の炭化水素基である。
R6及びR7は、それぞれ独立して、水素原子若しくは炭素数1~10の1価の炭化水素基であるか、又はR6及びR7が互いに結合してそれらが結合する窒素原子と共に環員数3~10の環構造を形成している。
式(2)中、
R8は、エステル基及びR10が結合する炭素原子と共に環員数5~8の(n+2)価の単環の複素環基を形成する基である。nは、1~6の整数である。
R9は、nが1~6の整数の場合、炭素数1~20の1価の炭化水素基、nが2以上の場合、複数のR9のうちの2つ以上が互いに結合して形成された環員数3~10の環構造、若しくはこれらの基若しくは環構造の炭素-炭素間に-O-、-CO-、-COO-、-SO2O-、-NRbSO2及び-NRbCO-からなる群より選ばれる少なくとも1種を含む基、又はこれらの基若しくは環構造が有する水素原子の一部若しくは全部をヒドロキシ基及びハロゲン原子からなる群より選ばれる少なくとも1種で置換した基である。Rbは、水素原子又は炭素数1~10の1価の炭化水素基である。
R10は、水素原子又は炭素数1~10の1価の炭化水素基である。
R11及びR12は、それぞれ独立して、水素原子又は炭素数1~10の1価の炭化水素基である。
R13及びR14は、それぞれ独立して、水素原子若しくは炭素数1~10の1価の炭化水素基であるか、又はR13及びR14が互いに結合してそれらが結合する窒素原子と共に環員数3~10の環構造を形成している。) - 酸解離性基を有する重合体、
酸発生体、及び
請求項1に記載の酸拡散制御剤
を含有する感放射線性樹脂組成物。 - 上記酸拡散制御剤以外の酸拡散制御剤
をさらに含有する請求項2に記載の感放射線性樹脂組成物。 - 請求項2に記載の感放射線性樹脂組成物を用い、レジスト膜を形成する工程、
上記レジスト膜を露光する工程、及び
上記露光されたレジスト膜を現像する工程
を有するレジストパターン形成方法。 - 下記式(1)で表される化合物。
R1は、炭素数3~30の1価の脂環式構造を有する炭化水素基、この基の炭素-炭素間に-O-、-CO-、-COO-、-SO2O-、-NRaSO2-及び-NRaCO-からなる群より選ばれる少なくとも1種を含む基、若しくは炭素数6~30の芳香族炭化水素基、又はこれらの基が有する水素原子の一部若しくは全部をヒドロキシ基及びハロゲン原子からなる群より選ばれる少なくとも1種で置換した基である。Raは、水素原子又は炭素数1~10の炭化水素基である。
R2及びR3は、それぞれ独立して、水素原子又は炭素数1~10の1価の炭化水素基であり、R2及びR3のうちの少なくとも一方が、炭素数1~10の1価の炭化水素基である。
R4及びR5は、それぞれ独立して、水素原子又は炭素数1~10の1価の炭化水素基である。
R6及びR7は、それぞれ独立して、水素原子若しくは炭素数1~10の1価の炭化水素基であるか、又はR6及びR7が互いに結合してそれらが結合する窒素原子と共に環員数3~10の環構造を形成している。) - 下記式(2)で表される化合物。
R8は、エステル基及びR10が結合する炭素原子と共に環員数5~8の(n+2)価の単環の複素環基を形成する基である。nは、1~6の整数である。
R9は、nが1~6の整数の場合、炭素数1~20の1価の炭化水素基、nが2以上の場合、複数のR9のうちの2つ以上が互いに結合して形成された環員数3~10の環構造、若しくはこれらの基若しくは環構造の炭素-炭素間に-O-、-CO-、-COO-、-SO2O-、-NRbSO2及び-NRbCO-からなる群より選ばれる少なくとも1種を含む基、又はこれらの基若しくは環構造が有する水素原子の一部若しくは全部をヒドロキシ基及びハロゲン原子からなる群より選ばれる少なくとも1種で置換した基である。Rbは、水素原子又は炭素数1~10の1価の炭化水素基である。
R10は、水素原子又は炭素数1~10の1価の炭化水素基である。
R11及びR12は、それぞれ独立して、水素原子又は炭素数1~10の1価の炭化水素基である。
R13及びR14は、それぞれ独立して、水素原子若しくは炭素数1~10の1価の炭化水素基であるか、又はR13及びR14が互いに結合してそれらが結合する窒素原子と共に環員数3~10の環構造を形成している。) - 下記式(i-a)で表される化合物と、下記式(i-b)で表されるアミン化合物とを反応させる工程を有する下記式(1)で表される化合物の製造方法。
R1は、炭素数3~30の1価の脂環式構造を有する炭化水素基、この基の炭素-炭素間に-O-、-CO-、-COO-、-SO2O-、-NRaSO2-及び-NRaCO-からなる群より選ばれる少なくとも1種を含む基、若しくは炭素数6~30の芳香族炭化水素基、又はこれらの基が有する水素原子の一部若しくは全部をヒドロキシ基及びハロゲン原子からなる群より選ばれる少なくとも1種で置換した基である。Raは、水素原子又は炭素数1~10の炭化水素基である。
R2及びR3は、それぞれ独立して、水素原子又は炭素数1~10の1価の炭化水素基であり、R2及びR3のうちの少なくとも一方が、炭素数1~10の1価の炭化水素基である。
R4及びR5は、それぞれ独立して、水素原子又は炭素数1~10の1価の炭化水素基である。
R6及びR7は、それぞれ独立して、水素原子若しくは炭素数1~10の1価の炭化水素基であるか、又はR6及びR7が互いに結合してそれらが結合する窒素原子と共に環員数3~10の環構造を形成している。) - 下記式(ii-a)で表される化合物と、下記式(ii-b)で表されるアミン化合物とを反応させる工程を有する下記式(2)で表される化合物の製造方法。
R8は、エステル基及びR10が結合する炭素原子と共に環員数5~8の(n+2)価の単環の複素環基を形成する基である。nは、1~6の整数である。
R9は、nが1~6の整数の場合、炭素数1~20の1価の炭化水素基、nが2以上の場合、複数のR9のうちの2つ以上が互いに結合して形成された環員数3~10の環構造、若しくはこれらの基若しくは環構造の炭素-炭素間に-O-、-CO-、-COO-、-SO2O-、-NRbSO2及び-NRbCO-からなる群より選ばれる少なくとも1種を含む基、又はこれらの基若しくは環構造が有する水素原子の一部若しくは全部をヒドロキシ基及びハロゲン原子からなる群より選ばれる少なくとも1種で置換した基である。Rbは、水素原子又は炭素数1~10の1価の炭化水素基である。
R10は、水素原子又は炭素数1~10の1価の炭化水素基である。
R11及びR12は、それぞれ独立して、水素原子又は炭素数1~10の1価の炭化水素基である。
R13及びR14は、それぞれ独立して、水素原子若しくは炭素数1~10の1価の炭化水素基であるか、又はR13及びR14が互いに結合してそれらが結合する窒素原子と共に環員数3~10の環構造を形成している。)
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