WO2017029891A1 - パターン形成方法、電子デバイスの製造方法、及びレジスト組成物 - Google Patents
パターン形成方法、電子デバイスの製造方法、及びレジスト組成物 Download PDFInfo
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- WO2017029891A1 WO2017029891A1 PCT/JP2016/069537 JP2016069537W WO2017029891A1 WO 2017029891 A1 WO2017029891 A1 WO 2017029891A1 JP 2016069537 W JP2016069537 W JP 2016069537W WO 2017029891 A1 WO2017029891 A1 WO 2017029891A1
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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
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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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
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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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
- G03F7/20—Exposure; Apparatus therefor
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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
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
Definitions
- the present invention provides a developer containing an organic solvent that is suitably used in ultra microlithography processes such as manufacturing of large LSIs (Large Scale Integrated Circuits) and high-capacity microchips and other photofabrication processes.
- the present invention relates to a pattern forming method, an electronic device manufacturing method, and a resist composition. More specifically, a pattern forming method using a developer containing an organic solvent, which can be suitably used for microfabrication of a semiconductor element using an electron beam or EUV light (Extreme Ultra Violet, extreme ultraviolet, wavelength: around 13 nm),
- the present invention relates to an electronic device manufacturing method and a resist composition.
- a pattern is generally formed by using a resin that is hardly soluble or insoluble in an alkali developer and solubilizing an exposed portion in the alkali developer by exposure.
- a resin is soluble in an alkali developer and a pattern is formed by making an exposed portion insoluble or insoluble in an alkali developer by exposure.
- an actinic ray-sensitive or radiation-sensitive resin composition suitable for such a lithographic process a chemically amplified positive resist composition mainly utilizing an acid-catalyzed reaction has been studied from the viewpoint of high sensitivity.
- a chemically amplified positive resist composition comprising a resin that is insoluble or hardly soluble in an alkali developer and is soluble in an alkali developer by the action of an acid, and an acid generator is effectively used.
- Patent Documents 1 to 3 A chemically amplified positive resist composition comprising a resin that is insoluble or hardly soluble in an alkali developer and is soluble in an alkali developer by the action of an acid, and an acid generator is effectively used.
- a very fine pattern for example, a line-and-space pattern with a line width of 50 nm or less, a dot pattern with a diameter of 50 nm or less
- a very fine pattern is caused by swelling due to penetration of a developer containing an organic solvent into the pattern.
- pattern collapse occurred, and sufficient resolving power was not obtained.
- an object of the present invention is to provide a pattern forming method, an electronic device manufacturing method, and a resist having high sensitivity and high resolving power when forming an extremely fine pattern (for example, a dot pattern having a diameter of 50 nm or less). It is to provide a composition.
- the present inventors have used a resist composition in which a resin having a highly polar repeating unit, a compound capable of generating an acid upon irradiation with actinic rays or radiation, and a solvent are used, and includes an organic solvent. It has been found that the above object can be achieved by a method of forming a pattern by developing with a developer. That is, the above problem can be solved by the following means.
- a resin represented by the following general formula (1) which contains a repeating unit having a ClogP value of 2.2 or less and whose solubility in a developer containing an organic solvent is reduced by the action of an acid; and (B) activity
- a pattern forming method A pattern forming method.
- R 1 represents a hydrogen atom, an alkyl group, or a halogen atom
- R 2 and R 3 each independently represent a hydrogen atom, an alkyl group, or a carboxyl group
- L represents a single bond or a divalent group.
- R 2 or R 3 and L may combine with each other to form a ring, in which case either R 2 or R 3 represents a divalent linking group, and L represents a trivalent linking group.
- Ar represents an aromatic group.
- R 4 represents a substituent, and n represents an integer of 0 or more. If R 4 there are a plurality, the plurality of R 4 may be different and the same.
- R 1 represents a hydrogen atom, an alkyl group, or a halogen atom
- R 2 and R 3 each independently represent a hydrogen atom, an alkyl group, or a carboxyl group
- L represents a single bond or a divalent group.
- R 2 or R 3 and L may combine with each other to form a ring, in which case either R 2 or R 3 represents a divalent linking group, and L represents a trivalent linking group.
- R 4 represents a substituent
- n 2 represents an integer of 0 to 4. If R 4 there are a plurality, the plurality of R 4 may be different and the same.
- R 1 represents a hydrogen atom, an alkyl group, or a halogen atom
- L represents a single bond or a divalent linking group.
- R 4 represents a substituent.
- n 2 represents an integer of 0 to 4. If R 4 there are a plurality, the plurality of R 4 may be different and the same. [6] The pattern forming method according to any one of [1] to [4], wherein the general formula (1) is represented by the following general formula (4).
- A represents a single bond or a divalent linking group.
- R 4 represents a substituent.
- n 3 represents an integer of 0 to 4. If R 4 there are a plurality, the plurality of R 4 may be different and the same.
- R 4 represents a substituent. p represents an integer of 0 to 4, and n 3 represents an integer of 0 to 4. If R 4 there are a plurality, the plurality of R 4 may be different and the same.
- R 4 is represented by a hydroxyl group, a hydroxyalkyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an alkoxy group, an acyl group, a group represented by the following general formula (N1), or a following general formula (N2).
- R N1 and R N2 each independently represent a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring.
- R N3 represents a substituent
- R N4 represents a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring.
- R S1 represents a substituent. * Represents a bond bonded to the benzene ring.
- R S4 represents a substituent
- R S5 represents a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring.
- R 4 is a hydroxyl group, a hydroxymethyl group, a carboxyl group, a group represented by the above general formula (S1), or a group represented by the above general formula (S2).
- A represents a single bond or a divalent linking group.
- R 4 represents a substituent.
- n 3 represents an integer of 0 to 4. If R 4 there are a plurality, the plurality of R 4 may be different and the same.
- R 4 represents a substituent. p represents an integer of 0 to 4, and n 3 represents an integer of 0 to 4. If R 4 there are a plurality, the plurality of R 4 may be different and the same.
- R 4 is represented by a hydroxyl group, a hydroxyalkyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an alkoxy group, an acyl group, a group represented by the following general formula (N1), or a following general formula (N2).
- R N1 and R N2 each independently represent a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring.
- R N3 represents a substituent
- R N4 represents a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring.
- R S1 represents a substituent. * Represents a bond bonded to the benzene ring.
- R S4 represents a substituent
- R S5 represents a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring.
- a very fine pattern for example, a line-and-space pattern with a line width of 50 nm or less, a dot pattern with a diameter of 50 nm or less
- a pattern forming method with high sensitivity and high resolving power and a method for manufacturing an electronic device And a resist composition can be provided.
- a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- active light or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays, X-rays, electron beams and the like.
- light means actinic rays or radiation.
- exposure in the present specification includes not only exposure with an emission line spectrum of a mercury lamp, deep ultraviolet rays represented by excimer laser, X-rays, extreme ultraviolet rays (EUV light), but also EB (electron beam). ) And drawing with a particle beam such as an ion beam are also included in the exposure.
- group atomic group
- substitution or non-substitution includes what has a substituent in addition to what does not have a substituent.
- the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- “(meth) acrylate” and “(meth) acrylic acid” mean “at least one of acrylate and methacrylate” and “at least one of acrylic acid and methacrylic acid”, respectively.
- the weight average molecular weight of the resin is a polystyrene equivalent value measured by a GPC (gel permeation chromatography) method.
- GPC uses HLC-8120 (manufactured by Tosoh Corporation), TSK gel Multipore HXL-M (Tosoh Corporation, 7.8 mm ID ⁇ 30.0 cm) as a column, and THF (tetrahydrofuran) as an eluent. You can follow the same method.
- the pattern forming method of the present invention comprises: (A) a resin represented by the following general formula (1), which contains a repeating unit having a ClogP value of 2.2 or less and whose solubility in a developer containing an organic solvent is reduced by the action of an acid; and (B) activity A step (1) of forming a film using an actinic ray-sensitive or radiation-sensitive resin composition containing a compound that generates an acid upon irradiation with light or radiation, and (C) a solvent; A step (2) of exposing the film using actinic rays or radiation, and a step of developing the film exposed in the step (2) using a developer containing an organic solvent to form a negative pattern ( 3) having a pattern forming method.
- a resin represented by the following general formula (1) which contains a repeating unit having a ClogP value of 2.2 or less and whose solubility in a developer containing an organic solvent is reduced by the action of an acid
- B activity
- R 1 represents a hydrogen atom, an alkyl group, or a halogen atom
- R 2 and R 3 each independently represent a hydrogen atom, an alkyl group, or a carboxyl group
- L represents a single bond or a divalent group.
- R 2 or R 3 and L may combine with each other to form a ring, in which case either R 2 or R 3 represents a divalent linking group, and L represents a trivalent linking group.
- Ar represents an aromatic group.
- R 4 represents a substituent, and n represents an integer of 0 or more. If R 4 there are a plurality, the plurality of R 4 may be different and the same.
- the pattern forming method of the present invention has high sensitivity and high resolving power when forming an extremely fine pattern (for example, a dot pattern having a diameter of 50 nm or less). The reason is not clear, but is estimated as follows.
- the actinic ray-sensitive or radiation-sensitive resin composition used in the pattern forming method of the present invention has a negative development (when exposed, the solubility in the developer decreases, the exposed area remains as a pattern, Development for removing the exposed portion).
- the actinic ray-sensitive or radiation-sensitive resin composition used in the pattern forming method of the present invention is an actinic ray-sensitive or radiation-sensitive material for organic solvent development used in development using a developer containing an organic solvent. It is a resin composition.
- the term “for organic solvent development” means an application that is used in a step of developing using a developer containing at least an organic solvent.
- the actinic ray-sensitive or radiation-sensitive resin composition is typically a resist composition, and preferably a chemically amplified resist composition.
- the actinic ray-sensitive or radiation-sensitive resin composition used in the pattern forming method of the present invention includes (A) a repeating unit represented by the following general formula (1) and having a ClogP value of 2.2 or less, It contains a resin whose solubility in a developer containing an organic solvent is reduced by the action of an acid, (B) a compound that generates an acid upon irradiation with actinic rays or radiation, and (C) a solvent.
- Additional components that can be contained in the actinic ray-sensitive or radiation-sensitive resin composition used in the present invention include resins other than the resin (A), basic compounds, crosslinking agents, surfactants, organic carboxylic acids, and carboxylic acids.
- An onium salt is mentioned. Hereafter, each component mentioned above is demonstrated in order.
- the resin (A) contains a repeating unit represented by the following general formula (1) and has a ClogP value of 2.2 or less, and the solubility in a developer containing an organic solvent is reduced by the action of an acid. Resin.
- R 1 represents a hydrogen atom, an alkyl group, or a halogen atom
- R 2 and R 3 each independently represent a hydrogen atom, an alkyl group, or a carboxyl group
- L represents a single bond or a divalent group.
- R 2 or R 3 and L may combine with each other to form a ring, in which case either R 2 or R 3 represents a divalent linking group, and L represents a trivalent linking group.
- Ar represents an aromatic group.
- R 4 represents a substituent, and n represents an integer of 0 or more. If R 4 there are a plurality, the plurality of R 4 may be different and the same.
- R 1 represents a hydrogen atom, an alkyl group, or a halogen atom.
- the alkyl group for R 1 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and most preferably a methyl group.
- Examples of the halogen atom for R 1 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- R 1 is preferably a hydrogen atom or a methyl group.
- L represents a single bond or a divalent linking group.
- L represents a single bond, -COO -, - CONH -, - O -, - OCO -, - NHCO -, - COOCH 2 -, - COOCH 2 CH 2 -, - CONHCH 2 -, or -CONHCH 2 CH 2 - Is preferably represented.
- L may combine with R 2 or R 3 to form a ring, and in this case, L represents a trivalent linking group.
- the trivalent linking group in this case, the divalent removing 1 comprising group a hydrogen atom from the connecting group.
- -CONH-L A - (L A represents a divalent linking group It is preferably a group formed by removing one hydrogen atom from a divalent linking group represented by the general formula (LA) described later).
- R 2 and R 3 each independently represents a hydrogen atom, an alkyl group or a carboxyl group.
- R 2 and R 3 represent an alkyl group, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is more preferable.
- R 2 or R 3 and L may be linked to each other to form a ring, in which case R 2 or R 3 represents a divalent linking group.
- the divalent linking group is preferably a carbonyl group, an alkylene group, —O—, —NH—, or a divalent linking group formed by a combination thereof, such as a carbonyl group, an alkylene group, —CONH—, or A divalent linking group formed by combining these is more preferable, and a carbonyl group is still more preferable.
- R 2 and R 3 are preferably the case where they are linked to a hydrogen atom or L to form a ring.
- Ar represents an aromatic group.
- the aromatic group represented by Ar include an aromatic hydrocarbon ring optionally having a substituent having 6 to 18 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, and a phenanthrene ring.
- an aromatic heterocycle such as a thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, thiazole ring, etc.
- Ar is more preferably a benzene ring or a naphthalene ring, and most preferably a benzene ring.
- R 4 represents a substituent, and at least one is preferably a hydroxyl group.
- R 4 is a hydroxyl group, a hydroxyalkyl group, a carboxyl group, a sulfonic acid group, an alkyl group, an alkoxy group, an acyl group, a group represented by the following general formula (N1), a group represented by the following general formula (N2), It is preferable to represent a group represented by the following general formula (S1) or a group represented by the following general formula (S2).
- S1 a hydroxyl group, a hydroxyalkyl group, a carboxyl group, an alkyl group.
- R N1 and R N2 each independently represent a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring.
- R N3 represents a substituent
- R N4 represents a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring.
- R S1 represents a substituent. * Represents a bond bonded to the benzene ring.
- R S4 represents a substituent
- R S5 represents a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring.
- R N1 and R N2 each independently represent a hydrogen atom or a substituent, and preferably represent a hydrogen atom or a methyl group.
- R N3 represents a substituent, and preferably represents a methyl group.
- RN4 represents a hydrogen atom or a substituent, and preferably represents a hydrogen atom.
- R S1 represents a substituent, and preferably represents a methoxy group or an amino group. When R S1 represents an amino group, the general formula (S1) is represented by the following general formula (S3).
- R S2 and R S3 each independently represent a hydrogen atom or a substituent. * Represents a bond bonded to the benzene ring.
- R S2 and R S3 each independently represent a hydrogen atom or a substituent, and preferably represent a hydrogen atom or a methyl group.
- R S4 represents a substituent, and preferably represents a methyl group.
- R S5 represents a hydrogen atom or a substituent, and preferably represents a hydrogen atom.
- an alkyl group as R 1 , an alkyl group as R 2 and R 3 , a divalent linking group as R 4 and L, and Ar each may have a substituent.
- substituents include an alkyl group (which may be linear or branched, preferably 1 to 12 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms), an alkynyl group (2 to 12 carbon atoms). ), A cycloalkyl group (monocyclic or polycyclic, preferably having 3 to 12 carbon atoms), an aryl group (preferably having 6 to 18 carbon atoms), a hydroxy group, an alkoxy group, alkyl or aryl.
- Preferable examples include an alkyl group, a cycloalkyl group, a halogen atom, a haloalkyl group, a hydroxy group, an alkoxy group, an aryloxy group, an alkyl and aryloxycarbonyl group, an aryl group, and more preferable examples include an alkyl group, A halogen atom, a hydroxy group, and an alkoxy group are mentioned. Examples of the halogen atom are the same as those described for R 1 above.
- the substituent may further have a substituent.
- substituents examples include a hydroxyl group, a halogen atom (for example, a fluorine atom), an alkyl group, a cycloalkyl group, an alkoxy group, a carboxyl group, and an alkoxy group.
- substituents include a carbonyl group, an aryl group, an alkoxyalkyl group, and a group in which these are combined.
- N represents an integer of 0 or more, preferably an integer of 1 to 3.
- the general formula (1) is preferably represented by the following general formula (2).
- R 1 represents a hydrogen atom, an alkyl group, or a halogen atom
- R 2 and R 3 each independently represent a hydrogen atom, an alkyl group, or a carboxyl group
- L represents a single bond or a divalent group.
- R 2 or R 3 and L may combine with each other to form a ring, in which case either R 2 or R 3 represents a divalent linking group, and L represents a trivalent linking group.
- R 4 represents a substituent
- n 2 represents an integer of 0 to 4. If R 4 there is a plurality, the plurality of R 4 may be different and the same.
- R 1, R 2, R 3, R 4 and the L has the general formula (1) is R 1, R 2, R 3, same meanings as R 4 and L, specific examples and The preferable range is also the same.
- n 2 represents an integer of 0 to 4, preferably represents an integer of 0 to 2, and more preferably represents 1 or 2.
- the repeating unit represented by the general formula (1) is more preferably represented by the following general formula (3) or (4).
- R 1 represents a hydrogen atom, an alkyl group, or a halogen atom
- L represents a single bond or a divalent linking group.
- R 4 represents a substituent.
- n 2 represents an integer of 0 to 4. If R 4 there are a plurality, the plurality of R 4 may be different and the same.
- A represents a single bond or a divalent linking group.
- R 4 represents a substituent.
- n 3 represents an integer of 0 to 4. If R 4 there are a plurality, the plurality of R 4 may be different and the same.
- R 1, R 4 and L has the general formula (1) have the same meanings as R 1, R 4 and L are the same also specific examples and preferred ranges.
- n 2 have the same meanings as defined in formula (2) n 2 in, preferably 0 to 2, more preferably 1 or 2.
- R 4 has the same meaning as R 4 in the general formula (1), the same applies to specific examples and preferred ranges.
- n 3 represents an integer of 0 to 4, preferably 0 to 2.
- A represents a single bond or a divalent linking group, and A is preferably a single bond or a divalent linking group represented by the following general formula (LA).
- a 1 represents an alkylene group or an arylene group
- na represents an integer of 1 or more. If A 1 and A 2 there are a plurality, the plurality of A 1 and A 2 may be the same or different.
- * Represents a bond bonded to the nitrogen atom of maleimide.
- a 1 is preferably an alkylene group
- a 2 is preferably O, C ( ⁇ O) —O, O—C ( ⁇ O), or a single bond
- na is an integer of 1 to 4. It is preferable.
- the general formula (4) is preferably represented by the following general formula (4a).
- R 4 represents a substituent.
- p represents an integer of 0 to 4
- n 2 represents an integer of 0 to 4. If R 4 there are a plurality, the plurality of R 4 may be different and the same.
- R 4 has the same meaning as R 4 in General Formula (1), and specific examples and preferred ranges thereof are also the same.
- n 3 is the general formula (4) has the same meaning as n 3 of, preferably 0-2.
- p represents an integer of 0 to 4, and preferably represents an integer of 0 to 2.
- the resin (A) needs to have a ClogP value of 2.2 or less and 2.0 or less from the viewpoint of reducing the affinity with a developer containing an organic solvent and suppressing penetration into the pattern. It is preferable that it is 1.8 or less.
- the ClogP value is preferably ⁇ 0.2 or more, more preferably ⁇ 0.06 or more.
- the logP value can be obtained by actual measurement using n-octanol and water, but in the present invention, a distribution coefficient (ClogP value) calculated from a logP value estimation program is used.
- ClogP value in the present specification refers to a ClogP value obtained from “ChemBioDraw ultra ver.12”.
- the ClogP value of the repeating unit is a value calculated by the above method for a compound in which both ends of the repeating unit are methyl groups.
- the content of the repeating unit represented by the general formula (1), (2), (3), (4) or (4a) is a resin (A 2) to 70 mol%, more preferably 5 to 50 mol%, and particularly preferably 5 to 30 mol%, based on all repeating units contained in (1).
- the repeating unit represented by the general formula (1), (2), (3), (4) or (4a) contained in the resin (A) may be one type or two or more types. .
- Resin (A) is preferably nonionic from the viewpoint of ensuring sufficient developer solubility in the unexposed area.
- repeating unit represented by the general formula (1), (2), (3), (4) or (4a) include the following structures.
- required by the said method is appended to the example.
- Resin (A) may further contain a repeating unit having a ClogP value larger than 2.2, or may contain a repeating unit having a phenolic hydroxyl group having a ClogP value larger than 2.2.
- the content of the repeating unit having a ClogP value larger than 2.2 or the repeating unit having a phenolic hydroxyl group having a ClogP value larger than 2.2 is 0 to 50 mol% with respect to all repeating units in the resin (A). More preferably, it is 0 to 45 mol%, and still more preferably 0 to 40 mol%.
- Resin (A) is a resin whose solubility in a developer containing an organic solvent is reduced by the action of an acid.
- the resin (A) preferably contains a repeating unit having an acid-decomposable group, and preferably has a repeating unit having a group that decomposes by the action of an acid to generate a carboxyl group.
- the solubility with respect to an alkali developing solution will increase by the effect
- the repeating unit having a group that decomposes by the action of an acid to generate a carboxyl group is a repeating unit having a group in which a hydrogen atom of the carboxyl group is substituted with a group that decomposes and leaves by the action of an acid.
- R 36 to R 39 each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
- R 36 and R 37 may be bonded to each other to form a ring.
- R 01 and R 02 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
- a repeating unit having a group that decomposes by the action of an acid to generate a carboxyl group a repeating unit represented by the following general formula (AI) is preferable.
- Xa 1 represents a hydrogen atom or an alkyl group.
- T represents a single bond or a divalent linking group.
- Rx 1 to Rx 3 each independently represents an alkyl group (straight or branched) or a cycloalkyl group (monocyclic or polycyclic). However, when all of Rx 1 to Rx 3 are alkyl groups (linear or branched), at least two of Rx 1 to Rx 3 are preferably methyl groups. Two of Rx 1 to Rx 3 may combine to form a cycloalkyl group (monocyclic or polycyclic).
- the alkyl group represented by Xa 1 may have a substituent, and examples thereof include a methyl group or a group represented by —CH 2 —R 11 .
- R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms and an acyl group having 5 or less carbon atoms, preferably 3 or less carbon atoms. And more preferably a methyl group.
- Xa 1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, a hydroxymethyl group, or the like.
- Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, and the like.
- Rt represents an alkylene group or a cycloalkylene group.
- T is preferably a single bond or a —COO—Rt— group.
- Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH 2 — group, — (CH 2 ) 2 — group, or — (CH 2 ) 3 — group.
- the alkyl group of Rx 1 to Rx 3 is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group.
- Examples of the cycloalkyl group of Rx 1 to Rx 3 include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group.
- Examples of the cycloalkyl group formed by combining two of Rx 1 to Rx 3 include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group
- a monocyclic cycloalkyl group such as a group is preferred.
- a monocyclic cycloalkyl group having 5 to 6 carbon atoms is particularly preferred.
- the cycloalkyl group formed by combining two of Rx 1 to Rx 3 is, for example, a group in which one of the methylene groups constituting the ring has a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group. It may be replaced.
- the repeating unit represented by the general formula (AI) preferably has, for example, an embodiment in which Rx 1 is a methyl group or an ethyl group, and Rx 2 and Rx 3 are bonded to form the above-described cycloalkyl group.
- Each of the above groups may have a substituent.
- substituents include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, an alkoxy group.
- substituents include carbonyl groups (having 2 to 6 carbon atoms), and those having 8 or less carbon atoms are preferred.
- the repeating unit represented by formula (AI) is preferably an acid-decomposable (meth) acrylic acid tertiary alkyl ester-based repeating unit (Xa 1 represents a hydrogen atom or a methyl group, and T is a single bond. Is a repeating unit). More preferably, Rx 1 to Rx 3 are each independently a repeating unit representing a linear or branched alkyl group, and more preferably, Rx 1 to Rx 3 are each independently a repeating unit representing a linear alkyl group. Unit.
- Rx represents a hydrogen atom, CH 3 , CF 3 , or CH 2 OH.
- Rxa and Rxb each represents an alkyl group having 1 to 4 carbon atoms.
- Z represents a substituent containing a polar group, and when there are a plurality of them, each is independent.
- p represents 0 or a positive integer.
- Examples of the substituent containing a polar group represented by Z include a linear or branched alkyl group having a hydroxyl group, a cyano group, an amino group, an alkylamide group, or a sulfonamide group, and a cycloalkyl group. Is an alkyl group having a hydroxyl group. As the branched alkyl group, an isopropyl group is particularly preferable.
- the content of the repeating unit having a group capable of decomposing by the action of an acid to generate a carboxyl group is preferably 20 to 90 mol%, more preferably 25 to 80 mol%, based on all repeating units in the resin (A). More preferably, it is 30 to 75 mol%.
- the resin (A) may contain a repeating unit represented by the following general formula (VI).
- R 61 , R 62 and R 63 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
- R 62 may be bonded to Ar 6 to form a ring, and R 62 in this case represents a single bond or an alkylene group.
- X 6 represents a single bond, —COO—, or —CONR 64 —.
- R 64 represents a hydrogen atom or an alkyl group.
- L 6 represents a single bond or an alkylene group.
- Ar 6 represents an (n + 1) -valent aromatic ring group, and represents an (n + 2) -valent aromatic ring group when bonded to R 62 to form a ring.
- Y 2 independently represents a hydrogen atom or a group capable of leaving by the action of an acid when n ⁇ 2. However, at least one of Y 2 represents a group capable of leaving by the action of an acid.
- n represents an integer of 1 to 4.
- a structure represented by the following general formula (VI-A) is more preferable.
- L 1 and L 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined.
- M represents a single bond or a divalent linking group.
- Q represents an alkyl group, a cycloalkyl group which may contain a hetero atom, an aryl group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group. At least two of Q, M, and L 1 may combine to form a ring (preferably a 5-membered or 6-membered ring).
- the repeating unit represented by the general formula (VI) is preferably a repeating unit represented by the following general formula (13).
- Ar 3 represents an aromatic ring group.
- R 3 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, or a heterocyclic group.
- M 3 represents a single bond or a divalent linking group.
- Q 3 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. At least two of Q 3 , M 3 and R 3 may be bonded to form a ring.
- the aromatic ring group represented by Ar 3 is the same as Ar 6 in the general formula (VI) when n in the general formula (VI) is 1, more preferably a phenylene group or a naphthylene group, A phenylene group is preferred.
- repeating unit represented by the general formula (VI) are shown below, but the present invention is not limited thereto.
- Resin (A) also preferably contains a repeating unit represented by the following general formula (15).
- R 41 , R 42 and R 43 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
- R 42 may be bonded to L 4 to form a ring, and R 42 in this case represents an alkylene group.
- L 4 represents a single bond or a divalent linking group, and in the case of forming a ring with R 42 , represents a trivalent linking group.
- R 44 and R 45 represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group, or a heterocyclic group.
- M 4 represents a single bond or a divalent linking group.
- Q 4 represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. At least two of Q 4 , M 4 and R 44 may be bonded to form a ring.
- R 41 , R 42 and R 43 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
- R 42 may be bonded to L 4 to form a ring, and R 42 in this case represents an alkylene group.
- L 4 represents a single bond or a divalent linking group, and in the case of forming a ring with R 42 , represents a trivalent linking group.
- R 44 and R 45 have the same meaning as R 3 in the general formula (13), and the preferred range is also the same.
- M 4 has the same meaning as M 3 in the general formula (13), and the preferred range is also the same.
- Q 4 has the same meaning as Q 3 in the general formula (13), and the preferred range is also the same.
- Examples of the ring formed by combining at least two of Q 4 , M 4 and R 44 include rings formed by combining at least two of Q 3 , M 3 and R 3 , and the preferred range is the same. It is.
- the alkyl group of R 41 to R 43 in the general formula (15) is preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, which may have a substituent, Examples thereof include alkyl groups having 20 or less carbon atoms such as hexyl group, 2-ethylhexyl group, octyl group and dodecyl group, more preferably alkyl groups having 8 or less carbon atoms, and particularly preferably alkyl groups having 3 or less carbon atoms.
- the alkyl group contained in the alkoxycarbonyl group the same alkyl groups as those described above for R 41 to R 43 are preferable.
- the cycloalkyl group may be monocyclic or polycyclic. Preferred examples include a monocyclic cycloalkyl group having 3 to 10 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group, which may have a substituent.
- the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.
- Preferred substituents in each of the above groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyls.
- the alkylene group is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group or an octylene group. Groups. An alkylene group having 1 to 4 carbon atoms is more preferable, and an alkylene group having 1 to 2 carbon atoms is particularly preferable.
- the ring formed by combining R 42 and L 4 is particularly preferably a 5- or 6-membered ring.
- R 41 and R 43 are more preferably a hydrogen atom, an alkyl group, or a halogen atom.
- a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF 3 ), a hydroxymethyl group (—CH 2 —OH), A chloromethyl group (—CH 2 —Cl) and a fluorine atom (—F) are particularly preferred.
- R 42 is more preferably a hydrogen atom, an alkyl group, a halogen atom, or an alkylene group (forming a ring with L 4 ), a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (—CF 3 ), a hydroxymethyl group Particularly preferred are (—CH 2 —OH), chloromethyl group (—CH 2 —Cl), fluorine atom (—F), methylene group (forms a ring with L 4 ), and ethylene group (forms a ring with L 4 ). .
- L 1 represents an alkylene group, a cycloalkylene group, a divalent aromatic ring group, or a group in which an alkylene group and a divalent aromatic ring group are combined.
- L 4 is preferably a single bond, a group represented by —COO—L 1 —, or a divalent aromatic ring group.
- L 1 is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene or propylene group.
- examples of the trivalent linking group represented by L 4 from the embodiment described above of the divalent linking group represented by L 4 1 single Preferable examples include groups formed by removing any hydrogen atom.
- the resin (A) may contain a repeating unit represented by the following general formula (BZ).
- AR represents an aryl group.
- Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
- Rn and AR may be bonded to each other to form a non-aromatic ring.
- R 1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkyloxycarbonyl group.
- repeating unit represented by the general formula (BZ) are shown below, but are not limited thereto.
- the above repeating unit having an acid-decomposable group may be one type or a combination of two or more types.
- the content of the repeating unit having an acid-decomposable group in the resin (A) (when there are a plurality of types) is 20 mol% or more and 90 mol% or less with respect to all repeating units in the resin (A). It is preferably 25 mol% or more and 80 mol% or less, more preferably 25 mol% or more and 75 mol% or less.
- the resin (A) preferably further contains a repeating unit having a lactone group.
- the lactone group any group can be used as long as it contains a lactone structure, but a group containing a 5- to 7-membered ring lactone structure is preferred, and a bicyclo structure is added to the 5- to 7-membered ring lactone structure, Those in which other ring structures are condensed to form a spiro structure are preferred. It is more preferable to have a repeating unit having a group having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). Further, a group having a lactone structure may be directly bonded to the main chain.
- Preferred lactone structures are groups represented by general formulas (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), and (LC1-14).
- the lactone structure moiety may or may not have have a substituent (Rb 2).
- Preferred substituents (Rb 2 ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxyl group. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like.
- n 2 represents an integer of 0 to 4. When n 2 is 2 or more, a plurality of Rb 2 may be the same or different, and a plurality of Rb 2 may be bonded to form a ring.
- Examples of the repeating unit having a group having a lactone structure represented by any of the general formulas (LC1-1) to (LC1-17) include a repeating unit represented by the following general formula (AI). Can do.
- Rb 0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
- substituents that the alkyl group of Rb 0 may have include a hydroxyl group and a halogen atom.
- the halogen atom for Rb 0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- Rb 0 is preferably a hydrogen atom or a methyl group.
- Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group obtained by combining these. To express. Preferably, it is a single bond or a linking group represented by —Ab 1 —CO 2 —.
- Ab 1 is a linear, branched alkylene group, monocyclic or polycyclic cycloalkylene group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.
- V represents a group represented by any one of the general formulas (LC1-1) to (LC1-17).
- the repeating unit having a group having a lactone structure usually has an optical isomer, but any optical isomer may be used.
- One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used.
- the optical purity (ee) thereof is preferably 90 or more, more preferably 95 or more.
- repeating unit having a group having a lactone structure examples include:
- the content of the repeating unit having a lactone group is preferably from 1 to 30 mol%, more preferably from 5 to 25 mol%, still more preferably from 5 to 20 mol%, based on all repeating units in the resin (A). .
- the resin (A) may further have a repeating unit containing an organic group having a polar group, particularly a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group.
- a repeating unit containing an organic group having a polar group particularly a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group.
- the alicyclic hydrocarbon structure of the alicyclic hydrocarbon structure substituted with a polar group is preferably an adamantyl group, a diamantyl group, or a norbornane group.
- the polar group is preferably a hydroxyl group or a cyano group. Specific examples of the repeating unit having a polar group are listed below, but the present invention is not limited thereto.
- the content thereof is preferably 1 to 30 mol%, more preferably 5%, based on all repeating units in the resin (A). It is ⁇ 25 mol%, more preferably 5 to 20 mol%.
- a repeating unit having a group capable of generating an acid (photoacid generating group) upon irradiation with actinic rays or radiation can also be included.
- the repeating unit having this photoacid-generating group corresponds to the compound (B) that generates an acid upon irradiation with actinic rays or radiation described later.
- Examples of such a repeating unit include a repeating unit represented by the following general formula (14).
- R 41 represents a hydrogen atom or a methyl group.
- L 41 represents a single bond or a divalent linking group.
- L 42 represents a divalent linking group.
- R 40 represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain.
- examples of the repeating unit represented by the general formula (14) include repeating units described in paragraphs [0094] to [0105] of JP-A No. 2014-041327.
- the content of the repeating unit having a photoacid-generating group is preferably 1 to 40 mol% with respect to all the repeating units in the resin (A). More preferably, it is 5 to 35 mol%, and still more preferably 5 to 30 mol%.
- the resin (A) may contain a repeating unit represented by the following general formula (V-1) or the following general formula (V-2).
- R 6 and R 7 are each independently a hydrogen atom, a hydroxy group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group or an acyloxy group, a cyano group, a nitro group, an amino group, It represents a halogen atom, an ester group (—OCOR or —COOR: R is an alkyl group having 1 to 6 carbon atoms or a fluorinated alkyl group), or a carboxyl group.
- n 3 represents an integer of 0 to 6.
- n 4 represents an integer of 0 to 4.
- X 4 is a methylene group, an oxygen atom or a sulfur atom.
- Specific examples of the repeating unit represented by the general formula (V-1) or (V-2) are shown below, but are not limited thereto.
- Resin (A) containing the repeating unit represented by the general formula (1) is, for example, “5th edition, Experimental Chemistry Course” page 42, “Macromolecules”, 46, (2013), This method can be synthesized with reference to the method described on pages 8882-8887 or “Bioorganic and Medicinal Chemistry Letters”, 20, (2010) pages 74-77.
- Resin (A) can be synthesized according to a conventional method (for example, radical polymerization).
- a conventional method for example, radical polymerization
- a monomer polymerization method in which a monomer species and an initiator are dissolved in a solvent and polymerization is performed by heating, and a solution of the monomer species and the initiator is dropped into the heating solvent over 1 to 10 hours.
- the dropping polymerization method is added, and the dropping polymerization method is preferable.
- reaction solvent examples include ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate; amide solvents such as dimethylformamide and dimethylacetamide; And a solvent that dissolves the actinic ray-sensitive or radiation-sensitive composition in the present invention, such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone.
- ethers such as tetrahydrofuran, 1,4-dioxane and diisopropyl ether
- ketones such as methyl ethyl ketone and methyl isobutyl ketone
- ester solvents such as ethyl acetate
- amide solvents such as dimethylformamide and dimethylacetamide
- the polymerization is carried out using the same solvent as that used in the actinic ray-sensitive or radiation-sensitive composition of the present invention. Thereby, generation
- the polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.
- a polymerization initiator a commercially available radical initiator (azo initiator, peroxide, etc.) is used to initiate the polymerization.
- azo initiator an azo initiator is preferable, and an azo initiator having an ester group, a cyano group, or a carboxyl group is preferable.
- Preferable initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, dimethyl 2,2′-azobis (2-methylpropionate) and the like.
- an initiator is added or added in portions, and after completion of the reaction, it is put into a solvent and a desired polymer is recovered by a method such as powder or solid recovery.
- concentration of the reaction is 5 to 50% by mass, preferably 10 to 30% by mass.
- the reaction temperature is usually 10 ° C. to 150 ° C., preferably 30 ° C. to 120 ° C., more preferably 60 to 100 ° C.
- Purification can be accomplished by using a liquid-liquid extraction method that removes residual monomers and oligomer components by washing with water or an appropriate solvent, and a purification method in a solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less.
- the weight average molecular weight of the resin (A) is preferably from 1,000 to 200,000, more preferably from 3,000 to 30,000, and most preferably from 5,000 to 20,000 as a polystyrene-converted value by the GPC method. 000.
- the weight average molecular weight is preferably from 1,000 to 200,000, more preferably from 3,000 to 30,000, and most preferably from 5,000 to 20,000 as a polystyrene-converted value by the GPC method. 000.
- Another particularly preferable form of the weight average molecular weight of the resin (A) is 5,000 to 15,000 in terms of polystyrene by GPC method.
- the degree of dispersion is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. .
- the smaller the degree of dispersion the better the resolution and pattern shape, the smoother the sidewall of the resist pattern, and the better the roughness.
- the content of the resin (A) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass in the total solid content. .
- the resin (A) may be used alone or in combination.
- the actinic ray-sensitive or radiation-sensitive composition used in the pattern forming method of the present invention is a compound that generates an acid upon irradiation with an actinic ray or radiation (“photoacid generator ⁇ PAG: Photo Acid Generator” ”or“ Compound (B) ").
- the photoacid generator may be in the form of a low molecular compound or may be incorporated in a part of the polymer. Further, the form of the low molecular compound and the form incorporated in a part of the polymer may be used in combination.
- the photoacid generator is in the form of a low molecular compound
- the molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.
- the photoacid generator is in a form incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) or may be incorporated in a resin different from the resin (A).
- the photoacid generator is preferably in the form of a low molecular compound.
- the photoacid generator is not particularly limited as long as it is a known one, but upon irradiation with actinic rays or radiation, preferably electron beams or extreme ultraviolet rays, an organic acid such as sulfonic acid, bis (alkylsulfonyl) imide, or Compounds that generate at least one of tris (alkylsulfonyl) methides are preferred.
- the photoacid generator is preferably a sulfonium salt. More preferable examples of the photoacid generator include compounds represented by the following general formulas (ZI), (ZII), and (ZIII).
- R 201 , R 202 and R 203 each independently represents an organic group.
- the organic group as R 201 , R 202 and R 203 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
- Two of R 201 to R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
- Examples of the group formed by combining two members out of R 201 to R 203 include an alkylene group (eg, butylene group, pentylene group).
- Z ⁇ represents a non-nucleophilic anion (an anion having an extremely low ability to cause a nucleophilic reaction).
- Non-nucleophilic anions include, for example, sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphor sulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyls). Carboxylate anion, etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.
- the aliphatic moiety in the aliphatic sulfonate anion and aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number. Examples include 3 to 30 cycloalkyl groups.
- the aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.
- the alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. Specific examples thereof include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms).
- an alkylthio group preferably having 1 to 15 carbon atoms
- an alkylsulfonyl group preferably having 1 to 15 carbon atoms
- an alkyliminosulfonyl group preferably having 1 to 15 carbon atoms
- an aryloxysulfonyl group preferably having carbon atoms Number 6 to 20
- alkylaryloxysulfonyl group preferably having 7 to 20 carbon atoms
- cycloalkylary Examples thereof include an oxysulfonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like.
- examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 15).
- aralkyl group in the aralkyl carboxylate anion preferably an aralkyl group having 7 to 12 carbon atoms such as benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylbutyl group and the like can be mentioned.
- Examples of the sulfonylimide anion include saccharin anion.
- the alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms.
- substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like.
- a fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
- the alkyl groups in the bis (alkylsulfonyl) imide anion may be bonded to each other to form a ring structure. This increases the acid strength.
- non-nucleophilic anions examples include fluorinated phosphorus (eg, PF 6 ⁇ ), fluorinated boron (eg, BF 4 ⁇ ), fluorinated antimony (eg, SbF 6 ⁇ ), and the like. .
- non-nucleophilic anion examples include an aliphatic sulfonate anion in which at least ⁇ -position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group having a fluorine atom And a tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom.
- the non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (more preferably 4 to 8 carbon atoms), a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, or perfluorooctane.
- the pKa of the generated acid is preferably ⁇ 1 or less in order to improve sensitivity.
- an anion represented by the following general formula (AN1) can be mentioned as a preferred embodiment.
- Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
- R 1 and R 2 each independently represent a hydrogen atom, a fluorine atom or an alkyl group, and when there are a plurality of R 1 and R 2 , they may be the same or different.
- L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
- A represents a cyclic organic group.
- x represents an integer of 1 to 20
- y represents an integer of 0 to 10
- z represents an integer of 0 to 10.
- the alkyl group in the alkyl group substituted with the fluorine atom of Xf preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms.
- the alkyl group substituted with a fluorine atom of Xf is preferably a perfluoroalkyl group.
- Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.
- Xf include fluorine atom, CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , CH 2 CF 3 , CH 2 CH 2 CF 3 , CH 2 C 2 F 5 , CH 2 CH 2 C 2 F 5 , CH 2 C 3 F 7 , CH 2 CH 2 C 3 F 7 , CH 2 C 4 F 9 , CH 2 CH 2 C 4 F 9 may be mentioned, among which a fluorine atom and CF 3 are preferable. In particular, it is preferable that both Xf are fluorine atoms.
- the alkyl group of R 1 and R 2 may have a substituent (preferably a fluorine atom), and preferably has 1 to 4 carbon atoms. More preferred is a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of the alkyl group having a substituent for R 1 and R 2 include CF 3 , C 2 F 5 , C 3 F 7 , C 4 F 9 , C 5 F 11 , C 6 F 13 , and C 7 F 15.
- R 1 and R 2 are preferably a fluorine atom or CF 3 .
- x is preferably from 1 to 10, and more preferably from 1 to 5.
- y is preferably 0 to 4, more preferably 0.
- z is preferably 0 to 5, and more preferably 0 to 3.
- the divalent linking group of L is not particularly limited, and is —COO—, —OCO—, —CO—, —O—, —S—, —SO—, —SO 2 —, an alkylene group, a cycloalkylene group, An alkenylene group or a linking group in which a plurality of these groups are linked can be exemplified, and a linking group having a total carbon number of 12 or less is preferred.
- —COO—, —OCO—, —CO—, and —O— are preferable, and —COO— and —OCO— are more preferable.
- the cyclic organic group of A is not particularly limited as long as it has a cyclic structure, and is not limited to alicyclic groups, aryl groups, and heterocyclic groups (not only those having aromaticity but also aromaticity). And the like).
- the alicyclic group may be monocyclic or polycyclic, and may be a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, or a cyclooctyl group, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, or a tetracyclododecane group.
- a polycyclic cycloalkyl group such as a nyl group and an adamantyl group is preferred.
- an alicyclic group having a bulky structure having 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, or the like is present in the film in the post-exposure heating step. Diffusivity can be suppressed, which is preferable from the viewpoint of improving MEEF.
- Examples of the aryl group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.
- Examples of the heterocyclic group include those derived from a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Of these, those derived from a furan ring, a thiophene ring and a pyridine ring are preferred.
- examples of the cyclic organic group also include a lactone structure, and specific examples include lactone structures represented by the above-described general formulas (LC1-1) to (LC1-17).
- the cyclic organic group may have a substituent, and examples of the substituent include an alkyl group (which may be linear, branched or cyclic, preferably having 1 to 12 carbon atoms), cyclo Alkyl group (which may be monocyclic, polycyclic or spiro ring, preferably having 3 to 20 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), hydroxy group, alkoxy group, ester group, amide Group, urethane group, ureido group, thioether group, sulfonamide group, sulfonic acid ester group and the like.
- the carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.
- Examples of the organic group for R 201 , R 202, and R 203 include an aryl group, an alkyl group, and a cycloalkyl group.
- R 201 , R 202 and R 203 at least one is preferably an aryl group, more preferably all three are aryl groups.
- aryl group in addition to a phenyl group, a naphthyl group, and the like, a heteroaryl group such as an indole residue and a pyrrole residue can be used.
- Preferred examples of the alkyl group and cycloalkyl group represented by R 201 to R 203 include a straight-chain or branched alkyl group having 1 to 10 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms. More preferable examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. More preferable examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
- These groups may further have a substituent.
- substituents include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7) and the like, but are not limited thereto.
- R 204 to R 207 each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
- the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 are the same as the aryl group described as the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 in the aforementioned compound (ZI).
- the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may have a substituent. Examples of this substituent include those that the aryl group, alkyl group, and cycloalkyl group of R 201 to R 203 in the aforementioned compound (ZI) may have.
- Z ⁇ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ⁇ in formula (ZI).
- the photoacid generator has a volume of 130 to 3 or more by irradiation with an electron beam or extreme ultraviolet rays from the viewpoint of suppressing the diffusion of the acid generated by exposure to the non-exposed portion and improving the resolution.
- the compound generate an acid (more preferably sulfonic acid) having a size of more than 1, more preferably a compound that generates an acid having a volume of 190 3 or more (more preferably sulfonic acid).
- more preferably 270 ⁇ 3 (more preferably sulfonic acid) or a size of the acid is a compound that generates, be (more preferably sulfonic acid) acid volume 400 ⁇ 3 or more in size is a compound capable of generating an Particularly preferred.
- the volume is preferably 2000 3 or less, and more preferably 1500 3 or less.
- the volume value was determined using “WinMOPAC” manufactured by Fujitsu Limited. That is, first, the chemical structure of the acid according to each example is input, and then the most stable conformation of each acid is determined by molecular force field calculation using the MM3 method with this structure as the initial structure. By performing molecular orbital calculation using the PM3 method for these most stable conformations, the “accessible volume” of each acid can be calculated.
- the calculated value of the volume is appended to a part of the example (unit 3 3 ).
- required here is a volume value of the acid which the proton couple
- One foot is 1 ⁇ 10 ⁇ 10 m.
- a photo-acid generator can be used individually by 1 type or in combination of 2 or more types.
- the content of the photoacid generator in the actinic ray-sensitive or radiation-sensitive composition is preferably 0.1 to 50% by mass, more preferably 5 to 50% by mass, based on the total solid content of the composition. More preferably, it is 8 to 40% by mass.
- the content of the photoacid generator is preferably high, more preferably 10 to 40% by mass, and most preferably 10 to 35% by mass.
- the actinic ray-sensitive or radiation-sensitive composition used in the pattern forming method of the present invention contains a solvent (C).
- This solvent comprises (M1) propylene glycol monoalkyl ether carboxylate and (M2) propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate. It is preferable that at least one of at least one selected from the group is included.
- this solvent may further contain components other than component (M1) and (M2).
- Component (M1) is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate is particularly preferable.
- the component (M2) the following are preferable.
- propylene glycol monoalkyl ether propylene glycol monomethyl ether or propylene glycol monoethyl ether is preferable.
- lactic acid ester ethyl lactate, butyl lactate or propyl lactate is preferable.
- acetate ester methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate is preferable.
- butyl butyrate is also preferred.
- alkoxypropionate methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferable.
- chain ketones include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, Acetonyl acetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, or methyl amyl ketone are preferred.
- cyclic ketone methylcyclohexanone, isophorone, or cyclohexanone is preferable.
- lactone ⁇ -butyrolactone is preferable.
- alkylene carbonate propylene carbonate is preferable.
- Component (M2) is more preferably propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, pentyl acetate, ⁇ -butyrolactone or propylene carbonate.
- an ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, more preferably 7 to 10) and a hetero atom number of 2 or less.
- ester solvents having 7 or more carbon atoms and 2 or less heteroatoms include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, and butyl propionate. , Isobutyl isobutyrate, heptyl propionate, butyl butanoate and the like, and it is particularly preferable to use isoamyl acetate.
- component (M2) one having a flash point (hereinafter also referred to as fp) of 37 ° C. or higher is preferably used.
- component (M2) include propylene glycol monomethyl ether (fp: 47 ° C.), ethyl lactate (fp: 53 ° C.), ethyl 3-ethoxypropionate (fp: 49 ° C.), methyl amyl ketone (fp: 42 ° C), cyclohexanone (fp: 44 ° C), pentyl acetate (fp: 45 ° C), methyl 2-hydroxyisobutyrate (fp: 45 ° C), ⁇ -butyrolactone (fp: 101 ° C) or propylene carbonate (fp: 132 ° C) ) Is preferred.
- propylene glycol monoethyl ether, ethyl lactate, pentyl acetate, or cyclohexanone is more preferred, and propylene glycol monoethyl ether or ethyl lactate is particularly preferred.
- flash point means a value described in a reagent catalog of Tokyo Chemical Industry Co., Ltd. or Sigma Aldrich.
- the solvent preferably contains the component (M1). It is more preferable that the solvent consists essentially of the component (M1) or a mixed solvent of the component (M1) and other components. In the latter case, it is more preferable that the solvent contains both the component (M1) and the component (M2).
- the mass ratio of the component (M1) and the component (M2) is preferably in the range of 100: 0 to 15:85, more preferably in the range of 100: 0 to 40:60, and 100: More preferably, it is in the range of 0 to 60:40. That is, it is preferable that a solvent consists only of a component (M1) or contains both a component (M1) and a component (M2), and those mass ratios are as follows. That is, in the latter case, the mass ratio of the component (M1) to the component (M2) is preferably 15/85 or more, more preferably 40/60 or more, and further preferably 60/40 or more. preferable. Employing such a configuration makes it possible to further reduce the number of development defects.
- mass ratio of the component (M1) with respect to a component (M2) shall be 99/1 or less, for example.
- the solvent may further contain components other than the components (M1) and (M2).
- the content of components other than the components (M1) and (M2) is preferably in the range of 5% by mass to 30% by mass with respect to the total amount of the solvent.
- the content of the solvent in the actinic ray-sensitive or radiation-sensitive composition is preferably determined so that the solid content concentration of all components is 0.5 to 30% by mass, and is preferably 1 to 20% by mass. More preferably, it is determined. If it carries out like this, the applicability
- the actinic ray-sensitive or radiation-sensitive composition of the present invention preferably contains a basic compound in order to reduce the change in performance over time from exposure to heating.
- Preferred examples of the basic compound include compounds having a structure represented by the following formulas (A) to (E).
- R 200 , R 201 and R 202 may be the same or different, and are a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), a cycloalkyl group (preferably a carbon atom). 3 to 20) or an aryl group (preferably having 6 to 20 carbon atoms), wherein R 201 and R 202 may be bonded to each other to form a ring.
- the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.
- R 203 , R 204 , R 205 and R 206 may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.
- the alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.
- Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate Examples thereof include a compound having a structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond.
- Examples of the compound having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole and the like.
- Examples of the compound having a diazabicyclo structure include 1,4-diazabicyclo [2,2,2] octane, 1,5-diazabicyclo [4,3,0] non-5-ene, and 1,8-diazabicyclo [5,4,0. And undeca-7-ene.
- Examples of the compound having an onium hydroxide structure include triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically, triphenylsulfonium hydroxide, tris (t-butylphenyl) sulfonium.
- Examples thereof include hydroxide, bis (t-butylphenyl) iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide.
- the compound having an onium carboxylate structure is a compound having an onium hydroxide structure in which the anion moiety is converted to a carboxylate, and examples thereof include acetate, adamantane-1-carboxylate, and perfluoroalkylcarboxylate.
- Examples of the compound having a trialkylamine structure include tri (n-butyl) amine and tri (n-octyl) amine.
- aniline compounds include 2,6-diisopropylaniline, N, N-dimethylaniline, N, N-dibutylaniline, N, N-dihexylaniline and the like.
- alkylamine derivative having a hydroxyl group and / or an ether bond examples include ethanolamine, diethanolamine, triethanolamine, and tris (methoxyethoxyethyl) amine.
- aniline derivatives having a hydroxyl group and / or an ether bond examples include N, N-bis (hydroxyethyl) aniline.
- Preferred examples of the basic compound further include an amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group.
- amine compound a primary, secondary or tertiary amine compound can be used, and an amine compound in which at least one alkyl group is bonded to a nitrogen atom is preferable.
- the amine compound is more preferably a tertiary amine compound.
- the amine compound has an cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 3 to 20 carbon atoms).
- 6 to 12 carbon atoms may be bonded to the nitrogen atom.
- the amine compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed.
- the number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6.
- an oxyethylene group (—CH 2 CH 2 O—) or an oxypropylene group (—CH (CH 3 ) CH 2 O— or —CH 2 CH 2 CH 2 O—) is preferable, and more preferably an oxyalkylene group Ethylene group.
- ammonium salt compound a primary, secondary, tertiary, or quaternary ammonium salt compound can be used, and an ammonium salt compound in which at least one alkyl group is bonded to a nitrogen atom is preferable.
- the ammonium salt compound may be a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group, provided that at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to the nitrogen atom. (Preferably having 6 to 12 carbon atoms) may be bonded to a nitrogen atom.
- the ammonium salt compound preferably has an oxygen atom in the alkyl chain and an oxyalkylene group is formed.
- the number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6.
- an oxyethylene group (—CH 2 CH 2 O—) or an oxypropylene group (—CH (CH 3 ) CH 2 O— or —CH 2 CH 2 CH 2 O—) is preferable, and more preferably an oxyalkylene group Ethylene group.
- the anion of the ammonium salt compound include halogen atoms, sulfonates, borates, and phosphates. Among them, halogen atoms and sulfonates are preferable.
- the halogen atom is particularly preferably chloride, bromide or iodide
- the sulfonate is particularly preferably an organic sulfonate having 1 to 20 carbon atoms.
- the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates.
- the alkyl group of the alkyl sulfonate may have a substituent, and examples of the substituent include fluorine, chlorine, bromine, alkoxy groups, acyl groups, and aryl groups.
- alkyl sulfonate examples include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate.
- aryl group of the aryl sulfonate include a benzene ring, a naphthalene ring, and an anthracene ring.
- the benzene ring, naphthalene ring and anthracene ring may have a substituent, and the substituent is preferably a linear or branched alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms.
- the linear or branched alkyl group and cycloalkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl, cyclohexyl and the like.
- the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.
- An amine compound having a phenoxy group and an ammonium salt compound having a phenoxy group are those having a phenoxy group at the terminal opposite to the nitrogen atom of the alkyl group of the amine compound or ammonium salt compound.
- the phenoxy group may have a substituent.
- the substituent of the phenoxy group include an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group.
- the substitution position of the substituent may be any of the 2-6 positions.
- the number of substituents may be any in the range of 1 to 5.
- oxyalkylene group between the phenoxy group and the nitrogen atom.
- the number of oxyalkylene groups is one or more in the molecule, preferably 3 to 9, and more preferably 4 to 6.
- an oxyethylene group (—CH 2 CH 2 O—) or an oxypropylene group (—CH (CH 3 ) CH 2 O— or —CH 2 CH 2 CH 2 O—) is preferable, and more preferably an oxyalkylene group Ethylene group.
- the amine compound having a phenoxy group is prepared by reacting a primary or secondary amine having a phenoxy group with a haloalkyl ether by heating, and then adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. It can be obtained by extraction with an organic solvent such as ethyl acetate or chloroform.
- an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide, or tetraalkylammonium is added, and then ethyl acetate, It can be obtained by extraction with an organic solvent such as chloroform.
- the actinic ray-sensitive or radiation-sensitive composition according to the present invention has a proton acceptor functional group as a basic compound, and is decomposed by irradiation with actinic rays or radiation to decrease the proton acceptor property. It may further contain a compound that generates a compound that has disappeared or changed from proton acceptor properties to acidic properties (hereinafter also referred to as compound (PA)).
- the proton acceptor functional group is a group that can interact electrostatically with a proton or a functional group having an electron.
- a functional group having a macrocyclic structure such as a cyclic polyether or a ⁇ -conjugated group. It means a functional group having a nitrogen atom with an unshared electron pair that does not contribute.
- the nitrogen atom having an unshared electron pair that does not contribute to ⁇ conjugation is, for example, a nitrogen atom having a partial structure represented by the following general formula.
- Examples of a preferable partial structure of the proton acceptor functional group include a crown ether, an azacrown ether, a primary to tertiary amine, a pyridine, an imidazole, and a pyrazine structure.
- the compound (PA) is decomposed by irradiation with actinic rays or radiation to generate a compound whose proton acceptor property is lowered, disappeared, or changed from proton acceptor property to acidity.
- the decrease or disappearance of the proton acceptor property or the change from the proton acceptor property to the acid is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group.
- a proton adduct is formed from a compound having a proton acceptor functional group (PA) and a proton, the equilibrium constant in the chemical equilibrium is reduced.
- Specific examples of the compound (PA) include the following compounds. Furthermore, as specific examples of the compound (PA), for example, those described in paragraphs 0421 to 0428 of JP2014-41328A and paragraphs 0108 to 0116 of JP2014-134686A can be used. The contents of which are incorporated herein.
- the amount of the basic compound used is usually 0.001 to 10% by mass, preferably 0.01 to 5% by mass, based on the solid content of the actinic ray-sensitive or radiation-sensitive composition.
- the molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until post-exposure heat treatment.
- the acid generator / basic compound (molar ratio) is more preferably from 5.0 to 200, still more preferably from 7.0 to 150.
- the actinic ray-sensitive or radiation-sensitive composition used in the pattern forming method of the present invention may have a hydrophobic resin different from the resin (A) separately from the resin (A).
- Hydrophobic resins are preferably designed to be unevenly distributed on the surface of the membrane, but unlike surfactants, it is not always necessary to have hydrophilic groups in the molecule, and polar / nonpolar substances should be mixed uniformly. It does not have to contribute to Examples of the effects of adding the hydrophobic resin include control of a static / dynamic contact angle of the film surface with respect to water, suppression of outgassing, and the like.
- the hydrophobic resin has at least one of “fluorine atom”, “silicon atom”, and “CH 3 partial structure contained in the side chain portion of the resin” from the viewpoint of uneven distribution in the film surface layer. It is preferable to have two or more types.
- the hydrophobic resin preferably contains a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on the side chain.
- the fluorine atom and / or silicon atom in the hydrophobic resin may be contained in the main chain of the resin or in the side chain. It may be.
- the hydrophobic resin when it contains a fluorine atom, it may be a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom.
- the alkyl group having a fluorine atom preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms
- the cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.
- the aryl group having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group or a naphthyl group is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.
- Examples of the repeating unit having a fluorine atom or a silicon atom include those exemplified in paragraph 0519 of US2012 / 0251948A1.
- the hydrophobic resin preferably includes a CH 3 partial structure in the side chain portion.
- the CH 3 partial structure contained in the side chain portion of the hydrophobic resin is intended to encompass CH 3 partial structure an ethyl group, and a propyl group having.
- methyl groups directly bonded to the main chain of the hydrophobic resin (for example, ⁇ -methyl groups of repeating units having a methacrylic acid structure) contribute to the uneven distribution of the surface of the hydrophobic resin due to the influence of the main chain. Since it is small, it is not included in the CH 3 partial structure in the present invention.
- hydrophobic resin those described in JP 2011-248019 A, JP 2010-175859 A, and JP 2012-032544 A can also be preferably used.
- the actinic ray-sensitive or radiation-sensitive composition used in the present invention may further contain a surfactant.
- a surfactant By containing a surfactant, when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less, is used, it is possible to form a pattern with less adhesion and development defects with good sensitivity and resolution. Become.
- the surfactant it is particularly preferable to use a fluorine-based and / or silicon-based surfactant. Examples of the fluorine-based and / or silicon-based surfactant include surfactants described in [0276] of US Patent Application Publication No. 2008/0248425.
- F top EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Florard FC430, 431 or 4430 (manufactured by Sumitomo 3M Co., Ltd.); Megafac F171, F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC Corporation); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by Asahi Glass Co., Ltd.); Troisol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by Toa Synthetic Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.); 01 (manufactured by Gemco); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA); or
- the surfactant is a fluoroaliphatic compound produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method). You may synthesize. Specifically, a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as a surfactant. This fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-90991. Further, surfactants other than fluorine-based and / or silicon-based surfactants described in [0280] of US Patent Application Publication No. 2008/0248425 may be used.
- surfactants may be used alone or in combination of two or more.
- the actinic ray-sensitive or radiation-sensitive composition used in the present invention contains a surfactant
- the content thereof is preferably 0 to 2% by mass, more preferably based on the total solid content of the composition. Is 0.0001 to 2 mass%, more preferably 0.0005 to 1 mass%.
- the actinic ray-sensitive or radiation-sensitive composition used in the present invention is a compound that promotes solubility in a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a developer (for example, It may further contain a phenol compound having a molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxy group.
- the actinic ray-sensitive or radiation-sensitive composition used in the present invention may further contain a dissolution inhibiting compound.
- the “dissolution inhibiting compound” is a compound having a molecular weight of 3000 or less, which decomposes by the action of an acid and decreases the solubility in a developer.
- the developer of the present invention can also be suitably applied to a non-chemical amplification resist composition.
- a non-chemical amplification resist composition for example, Resist materials whose solubility changes when the main chain is cleaved by irradiation with g-line, h-line, i-line, KrF, ArF, EB, EUV or the like and the molecular weight is reduced (for example, JP 2013-210411 A [0025] ] To [0029], [0056] and copolymers of ⁇ -chloroacrylate ester compounds and ⁇ -methylstyrene compounds described in US Patent Publications 2015/0008211 [0032] to [0036], [0063] A resist material mainly composed of Hydrogen silsesquioxane (HSQ) with silanol condensation reaction generated by g-line, h-line, i-line, KrF, ArF, EB or EUV, calixarene substituted with chlorine, Metal complexes that
- Step (1) is a step of forming a film using the actinic ray-sensitive or radiation-sensitive composition, and can be performed, for example, by the following method.
- the resin (A) and the compound (B) are dissolved in a solvent (C) and the actinic ray-sensitive or radiation-sensitive composition is formed.
- the composition is prepared, filtered as necessary, and then applied onto the substrate.
- the filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon having a pore size of 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and still more preferably 0.03 ⁇ m or less.
- a film active light sensitive or radiation sensitive film, typically a resist film, chemically amplified
- a topcoat layer may be formed on the actinic ray-sensitive or radiation-sensitive film using a topcoat composition.
- the thickness of this film is generally 200 nm or less, preferably 10 to 100 nm.
- the film thickness of the top coat layer is preferably 10 to 200 nm, more preferably 20 to 100 nm, and particularly preferably 40 to 80 nm.
- the film thickness of the formed film is preferably 50 nm or less. If the film thickness is 50 nm or less, pattern collapse is less likely to occur when a development process described later is applied, and better resolution performance is obtained. More preferably, the film thickness ranges from 15 nm to 45 nm. If the film thickness is 15 nm or more, sufficient etching resistance can be obtained. More preferably, the film thickness ranges from 15 nm to 40 nm. When the film thickness is in this range, etching resistance and better resolution performance can be satisfied at the same time.
- an actinic ray-sensitive or radiation-sensitive composition is used on a substrate (eg, silicon / silicon dioxide coating) used in the manufacture of precision integrated circuit elements, such as a spinner or a coater.
- the film is formed by applying and drying by an appropriate application method.
- Various known base films inorganic films, organic films, antireflection films
- spin coating is preferable, and the rotation speed is preferably 1000 to 3000 rpm.
- the top coat composition can be applied to the upper layer of the film by the same means as in the film forming method and dried to form the top coat layer. It is preferable that the top coat is not mixed with a film made of an actinic ray-sensitive or radiation-sensitive composition and can be uniformly applied to the upper layer of the film. Before forming the topcoat layer, it is preferable to dry the film. Further, the top coat preferably contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond and an ester bond. However, a conventionally known top coat can be formed by a conventionally known method.
- the top coat can be formed based on the description in paragraphs 0072 to 0082 of JP-A-2014-059543.
- a top coat containing a basic compound as described in JP2013-61648A is preferably formed on the film.
- Specific examples of the basic compound that can be contained in the top coat are the same as those described above.
- a method of drying by heating is generally used. Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.
- the heating temperature is preferably 80 to 150 ° C., more preferably 80 to 140 ° C., and still more preferably 80 to 130 ° C.
- the heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.
- Step (2) is a step of exposing the film, and can be performed, for example, by the following method.
- the film formed as described above is irradiated with actinic rays or radiation through a predetermined mask.
- actinic light or radiation For example, they are KrF excimer laser, ArF excimer laser, extreme ultraviolet (EUV, Extreme Ultra Violet), an electron beam (EB, Electron Beam), etc., and extreme ultraviolet rays or an electron beam is especially preferable.
- the exposure may be immersion exposure.
- baking is preferably performed after exposure and before development.
- the reaction of the exposed part is promoted by baking, and the sensitivity and pattern shape become better.
- the heating temperature is preferably 80 to 150 ° C, more preferably 80 to 140 ° C, and still more preferably 80 to 130 ° C.
- the heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds. Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like.
- Step (3) is a step of developing the film exposed in step (2) with a developer containing an organic solvent.
- the developer used in the present invention contains an organic solvent.
- a developer containing an organic solvent is also referred to as an “organic developer”.
- the content of the organic solvent in the organic developer is preferably from 50% by mass to 100% by mass, more preferably from 70% by mass to 100% by mass, based on the total amount of the developer. 90 mass% or more and 100 mass% or less is more preferable, and 95 mass% or more and 100 mass% or less is particularly preferable.
- the organic solvent contained in the developer is not particularly limited, but at least one selected from the group consisting of ester solvents, ketone solvents, alcohol solvents, ether solvents, amide solvents, and hydrocarbon solvents. The organic solvent is preferable.
- An ester solvent is a solvent having an ester bond in the molecule
- a ketone solvent is a solvent having a ketone group in the molecule
- an alcohol solvent is a solvent having an alcoholic hydroxyl group in the molecule.
- the amide solvent is a solvent having an amide bond in the molecule
- the ether solvent is a solvent having an ether bond in the molecule.
- diethylene glycol monomethyl ether is applicable to both alcohol solvents and ether solvents in the above classification.
- ester solvent examples include methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, propyl acetate, isopropyl acetate, amyl acetate (pentyl acetate), isoamyl acetate (isopentyl acetate, 3-methylbutyl acetate), acetic acid 2 -Methylbutyl, 1-methylbutyl acetate, hexyl acetate, isohexyl acetate, heptyl acetate, octyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), ethylene glycol mono Ethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol
- butyl acetate, amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, heptyl propionate, and butyl butanoate are preferably used, and isoamyl acetate is particularly preferable. Preferably used.
- ketone solvent examples include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, cyclohexanone, methyl And cyclohexanone, phenylacetone, methyl ethyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate, ⁇ -butyrolactone, etc. preferable.
- the ketone solvent may have a branched alkyl group.
- the cycloaliphatic ketone solvent having a branched alkyl group include 2-isopropylcyclohexanone, 3-isopropylcyclohexanone, 4-isopropylcyclohexanone, 2-isopropylcycloheptanone, 3-isopropylcycloheptanone, 4-isopropylcyclohexane.
- Examples include heptanone and 2-isopropylcyclooctanone.
- Examples of the acyclic aliphatic ketone solvent having a branched alkyl group include diisohexyl ketone, methyl isopentyl ketone, ethyl isopentyl ketone, propyl isopentyl ketone, diisopentyl ketone, methyl isobutyl ketone, and ethyl isobutyl ketone.
- Propylisobutylketone, diisobutylketone, diisopropylketone, ethylisopropylketone, methylisopropylketone and the like, and diisobutylketone is particularly preferred.
- cyclic aliphatic ether solvent having a branched alkyl group examples include cyclopentyl isopropyl ether, cyclopentyl sec-butyl ether, cyclopentyl tert-butyl ether, cyclohexyl isopropyl ether, cyclohexyl sec-butyl ether, and cyclohexyl tert-butyl ether.
- Examples of the acyclic aliphatic ether solvent having a branched alkyl group include diisohexyl ether, methyl isopentyl ether, ethyl isopentyl ether, propyl isopentyl ether, diisopentyl ether, methyl isobutyl ether, ethyl isobutyl ether.
- alcohol solvents include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1 -Hexanol, 1-heptanol, 1-octanol, 1-decanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, 3-methyl-3-pen Tanol, cyclopentanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-2- Pentanol, 3-methyl-3-pentanol, 4-methyl- -Pentanol, 4-methyl-3-pentanol,
- ether solvents include glycol ether solvents that contain hydroxyl groups, glycol ether solvents that do not contain hydroxyl groups such as propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether, anisole, and phenetole.
- aromatic ether solvents dioxane, tetrahydrofuran, tetrahydropyran, perfluoro-2-butyltetrahydrofuran, perfluorotetrahydrofuran, 1,4-dioxane and the like.
- an glycol ether solvent or an aromatic ether solvent such as anisole is used.
- amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like. Can be used.
- hydrocarbon solvent examples include pentane, hexane, octane, nonane, decane, dodecane, undecane, hexadecane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, perfluorohexane, perfluoroheptane.
- Aliphatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene, dipropylbenzene, etc.
- aromatic hydrocarbon solvents such as octene, nonene, decene, undecene, dodecene, hexadecene, and the like.
- the unsaturated hydrocarbon solvent may have a plurality of double bonds and triple bonds, and may be present at any position of the hydrocarbon chain. Cis and trans isomers having a double bond may be mixed.
- the content of the other solvent is preferably 40% by mass or less, more preferably 20% by mass or less, and still more preferably based on the total mass of the developer. It is 10 mass% or less, Most preferably, it is 5 mass% or less.
- the developer preferably contains a surfactant.
- a surfactant the same surfactants as those used in the actinic ray-sensitive or radiation-sensitive composition described later can be used.
- the surfactant content is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, based on the total mass of the developer. %, More preferably 0.01 to 0.5% by mass.
- the developer preferably contains an antioxidant. Thereby, generation
- amine-based antioxidants and phenol-based antioxidants are preferably used.
- amine antioxidants include 1-naphthylamine, phenyl-1-naphthylamine, p-octylphenyl-1-naphthylamine, p-nonylphenyl-1-naphthylamine, p-dodecylphenyl-1-naphthylamine, and phenyl-2.
- Naphthylamine antioxidants such as naphthylamine; N, N′-diisopropyl-p-phenylenediamine, N, N′-diisobutyl-p-phenylenediamine, N, N′-diphenyl-p-phenylenediamine, N, N ′ -Di- ⁇ -naphthyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-1,3-dimethylbutyl-N '-Phenyl-p-phenylenediamine, dioctyl-p-phenyle Phenylenediamine antioxidants such as diamine, phenylhexyl-p-phenylenediamine, phenyloctyl-p-phenylenediamine; dipyridy
- phenolic antioxidant examples include 2,6-di-tert-butylphenol (hereinafter, tertiary butyl is abbreviated as t-butyl), 2,6-di-t-butyl-p-cresol.
- the content of the antioxidant is not particularly limited, but is preferably 0.0001 to 1% by mass, more preferably 0.0001 to 0.1% by mass, and 0.0001 to 0% with respect to the total mass of the developer. More preferred is 0.01 mass%. When it is 0.0001% by mass or more, a more excellent antioxidant effect is obtained, and when it is 1% by mass or less, development residue tends to be suppressed.
- the developer preferably contains a basic compound.
- the basic compound include compounds exemplified as basic compounds that can be contained in the actinic ray-sensitive or radiation-sensitive composition described later.
- a nitrogen-containing compound can be preferably used.
- a developing method for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc.
- dip method a method in which a substrate is immersed in a tank filled with a developer for a certain period of time
- paddle a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time
- spray method a method of spraying the developer on the substrate surface
- the development time is not particularly limited as long as the resin in the unexposed area is sufficiently dissolved, and is usually 10 to 300 seconds, preferably 20 to 120 seconds.
- the temperature of the developer is preferably 0 to 50 ° C, more preferably 15 to 35 ° C.
- the developer it is preferable to use the developer described above.
- development with an alkaline developer may be performed in addition to the development using the developer described above.
- the rinsing step is a step of rinsing (rinsing) with a rinsing liquid after the developing step.
- the developed wafer is cleaned using the rinsing liquid described above.
- the method of the cleaning process is not particularly limited. For example, a method of continuously discharging the rinse liquid onto the substrate rotating at a constant speed (rotary discharge method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinsing liquid onto the substrate surface (spray method), and the like can be applied.
- a cleaning process is performed by a rotary discharge method, and after cleaning, the substrate is rotated at a speed of 2000 rpm to 4000 rpm. It is preferable to rotate and remove the rinse liquid from the substrate.
- the rinse time is not particularly limited, but is preferably 10 seconds to 300 seconds, more preferably 10 seconds to 180 seconds, and most preferably 20 seconds to 120 seconds.
- the temperature of the rinse liquid is preferably 0 to 50 ° C., more preferably 15 to 35 ° C.
- a process of removing the developing solution or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed.
- a heat treatment can be performed in order to remove the solvent remaining in the pattern.
- the heating temperature is not particularly limited as long as a good resist pattern can be obtained, and is usually 40 to 160 ° C.
- the heating temperature is preferably 50 to 150 ° C, and most preferably 50 to 110 ° C.
- the heating time is not particularly limited as long as a good resist pattern can be obtained, but it is usually 15 to 300 seconds, and preferably 15 to 180 seconds.
- the rinsing liquid it is preferable to use a rinsing liquid containing an organic solvent.
- the organic solvent the organic solvent contained in the developer (preferably an ester solvent, a ketone solvent, an alcohol solvent, an ether solvent) is used. , At least one organic solvent selected from the group consisting of amide solvents and hydrocarbon solvents).
- the organic solvent contained in the rinse liquid is preferably a hydrocarbon solvent.
- organic solvent contained in the rinsing liquid when using EUV light (Extreme Ultra Violet) or EB (Electron Beam) in the exposure step, it is preferable to use a hydrocarbon solvent among the above organic solvents, and aliphatic hydrocarbons. It is more preferable to use a system solvent.
- EUV light Extreme Ultra Violet
- EB Electro Beam
- an aliphatic hydrocarbon solvent having 5 or more carbon atoms for example, pentane, hexane, octane, decane, undecane, dodecane, Hexadecane, etc.
- aliphatic hydrocarbon solvents having 8 or more carbon atoms are preferred
- aliphatic hydrocarbon solvents having 10 or more carbon atoms are more preferred.
- the upper limit of the carbon atom number of the said aliphatic hydrocarbon solvent is not specifically limited, For example, 16 or less is mentioned, 14 or less is preferable and 12 or less is more preferable.
- an unsaturated hydrocarbon solvent can also be used as the hydrocarbon solvent contained in the rinse liquid, and examples thereof include unsaturated hydrocarbon solvents such as octene, nonene, decene, undecene, dodecene, hexadecene and the like.
- the number of double bonds and triple bonds of the unsaturated hydrocarbon solvent is not particularly limited, and the unsaturated hydrocarbon solvent may have any position in the hydrocarbon chain.
- an unsaturated hydrocarbon solvent has a double bond, cis body and trans body may be mixed.
- the mixed solvent of the said ester solvent and the said hydrocarbon solvent or the mixed solvent of the said ketone solvent and the said hydrocarbon solvent as an organic solvent contained in a rinse liquid.
- a hydrocarbon solvent as a main component.
- an ester solvent and a hydrocarbon solvent are used in combination, it is preferable to use butyl acetate or isoamyl acetate as the ester solvent.
- the hydrocarbon solvent it is preferable to use a saturated hydrocarbon solvent (for example, decane, dodecane, undecane, hexadecane, etc.) from the viewpoint that the above effect is further exhibited.
- 2-heptanone is preferably used as the ketone solvent.
- the hydrocarbon solvent it is preferable to use a saturated hydrocarbon solvent (for example, decane, dodecane, undecane, hexadecane, etc.) from the viewpoint that the above effect is further exhibited.
- an ester solvent and a hydrocarbon solvent are used in combination, or when a ketone solvent and a hydrocarbon solvent are used in combination, an unsaturated hydrocarbon solvent can be used as the hydrocarbon solvent.
- Examples thereof include unsaturated hydrocarbon solvents such as octene, nonene, decene, undecene, dodecene, hexadecene and the like.
- the number of double bonds and triple bonds of the unsaturated hydrocarbon solvent is not particularly limited, and the unsaturated hydrocarbon solvent may have any position in the hydrocarbon chain.
- an unsaturated hydrocarbon solvent has a double bond, cis body and trans body may be mixed.
- the organic solvent contained in the rinse liquid is an embodiment in which at least one selected from the group consisting of the ester solvent and the ketone solvent is used from the viewpoint of being particularly effective for reducing residues after development. May be.
- the rinsing liquid contains at least one selected from the group consisting of ester solvents and ketone solvents, butyl acetate, isopentyl acetate (isoamyl acetate), n-pentyl acetate, ethyl 3-ethoxypropionate (EEP, Ethyl-3-ethoxypropionate) and at least one solvent selected from the group consisting of 2-heptanone as a main component, preferably at least selected from the group consisting of butyl acetate and 2-heptanone It is particularly preferable to contain one solvent as a main component.
- the rinse liquid is selected from the group consisting of ester solvents, glycol ether solvents, ketone solvents, alcohol solvents. It is preferable that propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethyl acetate, ethyl lactate, methyl 3-methoxypropionate, cyclohexanone, methyl ethyl ketone, ⁇ - A solvent selected from the group consisting of butyrolactone, propanol, 3-methoxy-1-butanol, N-methylpyrrolidone and propylene carbonate is preferred.
- PMEA propylene glycol monomethyl ether acetate
- PGME propylene glycol monomethyl ether
- ethyl acetate propylene glycol monomethyl ether
- ethyl lactate ethyl acetate
- ethyl lactate ethyl acetate
- an ester solvent when used as the organic solvent, it is preferable to use two or more ester solvents from the viewpoint that the above effect is further exhibited.
- an ester solvent preferably butyl acetate
- an ester solvent preferably propylene glycol monomethyl ether acetate (PGMEA)
- PMEA propylene glycol monomethyl ether acetate
- a glycol ether solvent may be used in addition to the ester solvent (one type or two or more types) from the viewpoint that the above effect is further exhibited.
- Specific examples in this case include using an ester solvent (preferably butyl acetate) as a main component and a glycol ether solvent (preferably propylene glycol monomethyl ether (PGME)) as a subcomponent.
- a glycol ether solvent preferably propylene glycol monomethyl ether (PGME)
- PGME propylene glycol monomethyl ether
- an ester solvent and / or a glycol ether solvent is used in addition to the ketone solvent (one or two or more) from the viewpoint that the above effects are further exhibited. May be.
- Specific examples in this case include a ketone solvent (preferably 2-heptanone) as a main component, an ester solvent (preferably propylene glycol monomethyl ether acetate (PGMEA)) and / or a glycol ether solvent (preferably propylene).
- Glycol monomethyl ether (PGME) is used as an accessory component.
- the above “main component” means that the content of the organic solvent is 50 to 100% by mass, preferably 70 to 100% by mass, more preferably 80 to 100% by mass, More preferably, it is 90 to 100% by mass, and particularly preferably 95 to 100% by mass.
- the content of the auxiliary component is preferably 0.1 to 20% by mass with respect to the total mass (100% by mass) of the main component, and preferably 0.5 to 10%. More preferably, it is more preferably 1 to 5% by weight.
- the vapor pressure of the rinsing liquid is preferably 0.05 kPa or more and 5 kPa or less at 20 ° C., more preferably 0.1 kPa or more and 5 kPa or less, and most preferably 0.12 kPa or more and 3 kPa or less.
- the rinse liquid is a mixed solvent of a plurality of solvents, it is preferable that the vapor pressure as a whole is in the above range.
- the rinse liquid may contain a surfactant.
- a surfactant When the rinsing liquid contains a surfactant, wettability to the film is improved, rinsing properties are improved, and generation of foreign matters tends to be suppressed.
- the surfactant the same surfactants as those used in the actinic ray-sensitive or radiation-sensitive composition described later can be used.
- the rinsing liquid contains a surfactant
- the content of the surfactant is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass with respect to the total mass of the rinsing liquid. More preferably, the content is 0.01 to 0.5% by mass.
- the rinse solution may contain an antioxidant.
- the antioxidant that the rinsing solution may contain is the same as the antioxidant that the developing solution may contain.
- the content of the antioxidant is not particularly limited, but is preferably 0.0001 to 1% by mass, and preferably 0.0001 to 0.1% with respect to the total mass of the rinse liquid. % By mass is more preferable, and 0.0001 to 0.01% by mass is still more preferable.
- the actinic ray-sensitive or radiation-sensitive composition used in the pattern forming method of the present invention and various materials (for example, a solvent, a developer, a rinse solution, an antireflection film-forming composition, a topcoat-forming composition, etc. )
- various materials for example, a solvent, a developer, a rinse solution, an antireflection film-forming composition, a topcoat-forming composition, etc.
- impurities such as metals, metal salts containing halogen, acids and alkalis.
- the content of impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb or less, still more preferably 100 ppt or less, particularly preferably 10 ppt or less, and substantially free (below the detection limit of the measuring device). Is most preferable.
- Examples of the method for removing impurities such as metals from various materials include filtration using a filter.
- the pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less.
- a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable.
- the filter may be a composite material obtained by combining these materials and ion exchange media.
- a filter that has been washed in advance with an organic solvent may be used.
- a plurality of types of filters may be connected in series or in parallel. When using a plurality of types of filters, filters having different pore diameters and / or materials may be used in combination.
- various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.
- an apparatus that selects a raw material having a low metal content as a raw material constituting each material, and performs filter filtration on the raw material constituting each material. Examples thereof include a method of performing distillation under a condition in which the inside is lined with Teflon (registered trademark) and contamination is suppressed as much as possible.
- Teflon registered trademark
- the preferable conditions for filter filtration performed on the raw materials constituting the various materials are the same as those described above.
- impurities may be removed with an adsorbent, or a combination of filter filtration and adsorbent may be used.
- adsorbent known adsorbents can be used.
- inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
- an organic solvent also referred to as “organic processing solution” that can be used for the developer and the rinsing solution, it is stored in a container for storing an organic processing solution for patterning a chemically amplified or non-chemically amplified film having a storing portion. It is preferable to use those prepared.
- the inner wall of the container that comes into contact with the organic treatment liquid is a resin different from any of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or rust prevention / metal elution prevention treatment is performed. It is preferably a container for containing an organic processing solution for patterning a film, which is formed from an applied metal.
- An organic solvent that is to be used as an organic processing liquid for film patterning is stored in the storage part of the storage container, and the one discharged from the storage part at the time of film patterning can be used.
- the seal portion is also selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin. It is preferably formed from a resin different from one or more resins, or a metal that has been subjected to a rust prevention / metal elution prevention treatment.
- the seal part means a member capable of shutting off the accommodating part and the outside air, and can preferably include a packing, an O-ring and the like.
- the resin different from one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin is preferably a perfluoro resin.
- Perfluoro resins include tetrafluoroethylene resin (PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), tetrafluoride.
- PTFE tetrafluoroethylene resin
- PFA perfluoroalkyl vinyl ether copolymer
- FEP tetrafluoroethylene-hexafluoropropylene copolymer resin
- Ethylene-ethylene copolymer resin Ethylene-ethylene copolymer resin (ETFE), ethylene trifluoride-ethylene copolymer resin (ECTFE), vinylidene fluoride resin (PVDF), ethylene trifluoride chloride copolymer resin (PCTFE), vinyl fluoride resin ( PVF) and the like.
- Particularly preferable perfluoro resins include tetrafluoroethylene resin, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, and tetrafluoroethylene-hexafluoropropylene copolymer resin.
- Examples of the metal in the metal subjected to the rust prevention / metal elution prevention treatment include carbon steel, alloy steel, nickel chromium steel, nickel chromium molybdenum steel, chromium steel, chromium molybdenum steel, manganese steel and the like.
- film technology as rust prevention and metal elution prevention treatment.
- metal coating variable plating
- inorganic coating variable chemical conversion treatment, glass, concrete, ceramics, etc.
- organic coating rust prevention oil, paint, rubber, plastics.
- Preferred film technology includes surface treatment with a rust inhibitor oil, a rust inhibitor, a corrosion inhibitor, a chelate compound, a peelable plastic, and a lining agent.
- pretreatment is a stage before rust prevention treatment. It is also preferable to adopt.
- a treatment for removing various corrosion factors such as chlorides and sulfates existing on the metal surface by washing and polishing can be preferably mentioned.
- the storage container includes the following.
- FluoroPure PFA composite drum manufactured by Entegris (Wetted inner surface; PFA resin lining)
- JFE steel drums (wetted inner surface; zinc phosphate coating)
- Examples of the storage container that can be used in the present invention include the containers described in JP-A-11-021393 [0013] to [0030] and JP-A-10-45961 [0012] to [0024]. be able to.
- the organic processing solution of the present invention can be added with a conductive compound to prevent failure of chemical piping and various parts (filters, O-rings, tubes, etc.) due to electrostatic charging and subsequent electrostatic discharge.
- a conductive compound for example, methanol is mentioned.
- the good addition is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less from the viewpoint of maintaining preferable development characteristics.
- SUS stainless steel
- various pipes coated with antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) should be used. it can.
- polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) subjected to antistatic treatment can be used for the filter and O-ring.
- the developer and the rinsing liquid are stored in a waste liquid tank through a pipe after use.
- the solvent in which the resist dissolves again in order to prevent the resist dissolved in the developer from precipitating and adhering to the wafer back surface or piping side surface.
- a method of passing through the piping after cleaning with a rinsing liquid, cleaning the back and side surfaces of the substrate with a solvent that dissolves the resist, or passing the solvent through which the resist dissolves without contacting the resist. The method of flowing is mentioned.
- the solvent to be passed through the pipe is not particularly limited as long as it can dissolve the resist, and examples thereof include the organic solvents described above, such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl.
- PGMEA propylene glycol monomethyl ether acetate
- PGMEA propylene glycol monoethyl ether acetate
- propylene glycol monopropyl propylene glycol monopropyl.
- Ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), propylene glycol mono Ethyl ether, propylene glycol monopropyl ether, propylene Glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-heptanone, ethyl lactate, 1-propanol, acetone, or the like can be used.
- PGMEA, PGME, and cyclohexanone can be preferably used.
- a pattern obtained by the pattern forming method of the present invention as a mask a semiconductor fine circuit, an imprint mold structure, a photomask, and the like can be manufactured by appropriately performing etching treatment and ion implantation.
- the pattern formed by the above method can also be used for guide pattern formation in DSA (Directed Self-Assembly) (for example, refer to ACS Nano Vol. 4 No. 8 Page 4815-4823). Further, the pattern formed by the above method can be used as a core material (core) of a spacer process disclosed in, for example, JP-A-3-270227 and JP-A-2013-164509.
- DSA Directed Self-Assembly
- core core material of a spacer process disclosed in, for example, JP-A-3-270227 and JP-A-2013-164509.
- Japanese Patent No. 4109085 Japanese Patent Application Laid-Open No. 2008-162101, and “Nanoimprint Basics and Technology Development / Application Deployment” -Nanoimprint substrate technology and latest technology development-edited by Yoshihiko Hirai (Frontier Publishing) ".
- the photomask manufactured using the pattern forming method of the present invention is a light reflective mask used in reflective lithography using EUV light as a light source, even if it is a light transmissive mask used in an ArF excimer laser or the like. May be.
- the present invention also relates to an electronic device manufacturing method including the above-described pattern forming method of the present invention, and an electronic device manufactured by this manufacturing method.
- the electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitably mounted on an electric / electronic device (home appliance, OA (Office Appliance) / media-related device, optical device, communication device, etc.). is there.
- the present invention also relates to a resist composition containing a resin having a repeating unit represented by the general formula (4) or (4a). Specific examples and preferred ranges of the repeating unit represented by formula (4) or (4a) and the resin having this repeating unit in the resist composition of the present invention are as described above.
- the resist composition is a preferred embodiment of the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition, and each component and its content described in the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition, and others This matter can also be referred to in the resist composition.
- the weight average molecular weight by GPC was 12900, and the molecular weight dispersity (Mw / Mn) was 1.70.
- a resin having the following structure was synthesized in the same manner as in the synthesis example of Resin A-1, except that the monomer used was changed.
- the composition ratio (molar ratio) of the resin was calculated by 1 H-NMR or 13 C-NMR measurement.
- the weight average molecular weight (Mw: polystyrene conversion) and dispersity (Mw / Mn) of the resin were calculated by GPC (solvent: THF) measurement.
- Table 1 below shows the composition ratio (molar ratio) of repeating units, the weight average molecular weight, the degree of dispersion, and the ClogP value of repeating units for each resin.
- the ClogP value described in Table 1 below is the ClogP value of the repeating unit described at the leftmost among the repeating units contained in each resin.
- ⁇ Resist composition The components shown in Tables 2 to 4 below were dissolved in the solvents shown in Tables 2 to 4. This was filtered using a polyethylene filter having a pore size of 0.03 ⁇ m to obtain a resist composition.
- a resist pattern was formed by the following operation.
- a resist composition was applied on a 4-inch silicon wafer subjected to HMDS (hexamethyldisilazane) treatment, and baked at 120 ° C. for 60 seconds to form a resist film having a thickness of 40 nm. One inch is 25.4 mm.
- HMDS hexamethyldisilazane
- EUV exposure was performed by changing the exposure amount through a mask including a pattern for forming a 1: 1 line and space pattern having a line width of 50 nm.
- the rinse liquid (23 ° C.) shown in Table 5 was sprayed at a flow rate of 200 mL / min for a predetermined time while rotating the wafer at 50 rotations (rpm) to perform a rinsing process. Finally, the wafer was dried by rotating at a high speed of 2500 rpm (rpm) for 120 seconds.
- the obtained resist pattern was evaluated for sensitivity and resolving power by the following methods.
- the resist pattern was observed using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.). The results are shown in Table 5 below.
- sensitivity The optimum exposure amount when resolving a 1: 1 line and space pattern with a line width of 50 nm was defined as sensitivity (Eop1). The smaller this value, the better the performance.
- a resist pattern was formed by the following operation.
- a resist composition was applied on a 4-inch silicon wafer subjected to HMDS (hexamethyldisilazane) treatment, and baked at 120 ° C. for 60 seconds to form a resist film having a thickness of 40 nm. One inch is 25.4 mm.
- HMDS hexamethyldisilazane
- EUV exposure was performed by changing the exposure amount through a mask including a pattern for forming dots with a diameter of 30 nm at a pitch of 100 nm.
- the rinse liquid (23 ° C.) described in Table 6 was sprayed at a flow rate of 200 mL / min for a predetermined time while rotating the wafer at 50 rpm (rpm) to perform the rinse treatment. Finally, the wafer was dried by rotating at a high speed of 2500 rpm (rpm) for 120 seconds.
- sensitivity The optimum exposure amount when resolving a dot with a diameter of 30 nm was defined as sensitivity (Eop2).
- a resist pattern was formed by the following operation.
- An organic film DUV44 (manufactured by Brewer Science) was applied on a 6-inch silicon wafer and baked at 200 ° C. for 60 seconds to form an organic film having a thickness of 60 nm.
- a resist composition was applied thereon and baked at 120 ° C. for 60 seconds to form a resist film having a thickness of 40 nm.
- PEB Post-exposure bake
- the rinse liquid (23 ° C.) shown in Table 7 was sprayed at a flow rate of 200 mL / min for a predetermined time while rotating the wafer at 50 rpm (rpm) to perform the rinse treatment. Finally, the wafer was dried by rotating at a high speed of 2500 rpm (rpm) for 120 seconds.
- the resist pattern was evaluated in the same manner as the “EUV exposure evaluation line and space pattern” described above. The results are shown in Table 7. The resolving power was evaluated by creating line and space patterns having different half pitch sizes by drawing.
- a resist pattern was formed by the following operation.
- An organic film DUV44 (manufactured by Brewer Science) was applied on a 6-inch silicon wafer and baked at 200 ° C. for 60 seconds to form an organic film having a thickness of 60 nm.
- a resist composition was applied thereon and baked at 120 ° C. for 60 seconds to form a resist film having a thickness of 40 nm.
- the wafer on which the resist film was formed was subjected to EB exposure using an electron beam irradiation apparatus (JBX 6000FS / E manufactured by JEOL; acceleration voltage 50 keV). Specifically, EB exposure was performed while changing the exposure amount so that dots with a diameter of 30 nm were formed at a pitch of 100 nm.
- JBX 6000FS / E manufactured by JEOL acceleration voltage 50 keV.
- PEB Post-exposure bake
- the rinse liquid (23 ° C.) shown in Table 8 was sprayed at a flow rate of 200 mL / min for a predetermined time while rotating the wafer at 50 rpm (rpm) to perform the rinse treatment. Finally, the wafer was dried by rotating at a high speed of 2500 rpm (rpm) for 120 seconds.
- the resist pattern was evaluated in the same manner as the “EUV exposure evaluation dot pattern” described above. The results are shown in Table 8. The resolving power was evaluated by drawing so that the dot diameter was decreased from 30 nm.
- the pattern formed by the pattern forming method of the present invention was excellent in sensitivity and resolution.
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Abstract
Description
このようなリソグラフィープロセスに適した感活性光線性又は感放射線性樹脂組成物としては、高感度化の観点から主に酸触媒反応を利用した化学増幅型ポジ型レジスト組成物が検討され、主成分としてアルカリ現像液には不溶又は難溶性で、酸の作用によりアルカリ現像液に可溶となる性質を有する樹脂、及び酸発生剤からなる化学増幅型ポジ型レジスト組成物が有効に使用されている(例えば、特許文献1~3)。
超微細パターンの形成においては、解像力の向上、パターン形状の更なる改良のために、酸分解性樹脂をアルカリ現像液以外の現像液を用いて現像する方法も提案されている(たとえば、特許文献4~6参照)。
即ち、以下の手段により上記課題を解決できる。
(A)下記一般式(1)で表され、ClogP値が2.2以下である繰り返し単位を含有し、酸の作用により有機溶剤を含む現像液に対する溶解度が減少する樹脂と、(B)活性光線又は放射線の照射により酸を発生する化合物と、(C)溶剤とを含有する感活性光線性又は感放射線性樹脂組成物を用いて膜を形成する工程(1)、
上記膜を活性光線又は放射線を用いて露光する工程(2)、及び
上記工程(2)において露光された膜を有機溶剤を含む現像液を用いて現像し、ネガ型のパターンを形成する工程(3)を有する、パターン形成方法。
[2]
上記樹脂(A)が、酸分解性基を有する繰り返し単位を含む、[1]に記載のパターン形成方法。
[3]
上記一般式(1)中のR4の少なくとも一つがヒドロキシル基である、[1]又は[2]に記載のパターン形成方法。
[4]
上記一般式(1)が下記一般式(2)で表される、[1]~[3]のいずれか1項に記載のパターン形成方法。
[5]
上記一般式(1)が下記一般式(3)で表される、[1]~[4]のいずれか1項に記載のパターン形成方法。
[6]
上記一般式(1)が下記一般式(4)で表される、[1]~[4]のいずれか1項に記載のパターン形成方法。
[7]
上記一般式(4)が下記一般式(4a)で表される、[6]に記載のパターン形成方法。
[8]
上記R4が、ヒドロキシル基、ヒドロキシアルキル基、カルボキシル基、スルホン酸基、アルキル基、アルコキシ基、アシル基、下記一般式(N1)で表される基、下記一般式(N2)で表される基、下記一般式(S1)で表される基、又は下記一般式(S2)で表される基を表す、[1]~[7]のいずれか1項に記載のパターン形成方法。
一般式(N2)中、RN3は置換基を表し、RN4は水素原子又は置換基を表す。*はベンゼン環に結合する結合手を表す。
一般式(S2)中、RS4は置換基を表し、RS5は水素原子又は置換基を表す。*はベンゼン環に結合する結合手を表す。
[9]
上記R4が、ヒドロキシル基、ヒドロキシメチル基、カルボキシル基、上記一般式(S1)で表される基、又は上記一般式(S2)で表される基である、[1]~[8]のいずれか1項に記載のパターン形成方法。
[10]
上記n2が1又は2である、[4]又は[5]に記載のパターン形成方法。
[11]
上記n3が0~2の整数である、[6]又は[7]に記載のパターン形成方法。
[12]
上記化合物(B)がスルホニウム塩である、[1]~[11]のいずれか1項に記載のパターン形成方法。
[13]
上記化合物(B)は、発生する酸の体積が130Å3以上2000Å3以下である、[12]に記載のパターン形成方法。
[14]
上記樹脂(A)が、ラクトン基を有する繰り返し単位をさらに含む、[1]~[13]のいずれか1項に記載のパターン形成方法。
[15]
[1]~[14]のいずれか1項に記載のパターン形成方法を含む電子デバイスの製造方法。
[16]
下記一般式(4)で表される繰り返し単位を有する樹脂を含むレジスト組成物。
[17]
上記一般式(4)が下記一般式(4a)で表される、[16]に記載のレジスト組成物。
[18]
上記R4が、ヒドロキシル基、ヒドロキアルキル基、カルボキシル基、スルホン酸基、アルキル基、アルコキシ基、アシル基、下記一般式(N1)で表される基、下記一般式(N2)で表される基、下記一般式(S1)で表される基、又は下記一般式(S2)で表される基を表す、[16]又は[17]に記載のレジスト組成物。
一般式(N2)中、RN3は置換基を表し、RN4は水素原子又は置換基を表す。*はベンゼン環に結合する結合手を表す。
一般式(S2)中、RS4は置換基を表し、RS5は水素原子又は置換基を表す。*はベンゼン環に結合する結合手を表す。
なお、本明細書において「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
本発明において「活性光線」又は「放射線」とは、例えば、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線、X線、電子線等を意味する。また、本発明において「光」とは、活性光線又は放射線を意味する。本明細書中における「露光」とは、特に断らない限り、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、X線、極紫外線(EUV光)等による露光のみならず、EB(電子線)及びイオンビーム等の粒子線による描画も露光に含める。
なお、本明細書における基(原子団)の表記において、置換又は無置換を記していない表記は、置換基を有していないものに加え置換基を有するものをも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含するものである。
本明細書では、「(メタ)アクリル系モノマー」とは、「CH2=CH-CO-」又は「CH2=C(CH3)-CO-」の構造を有するモノマーの少なくとも1種を意味する。同様に「(メタ)アクリレート」及び「(メタ)アクリル酸」とは、それぞれ「アクリレート及びメタクリレートの少なくとも1種」並びに「アクリル酸及びメタクリル酸の少なくとも1種」を意味する。
本明細書において、樹脂の重量平均分子量は、GPC(ゲルパーミエーションクロマトグラフィー)法により測定したポリスチレン換算値である。GPCは、HLC-8120(東ソー(株)製)を用い、カラムとしてTSK gel Multipore HXL-M (東ソー(株)製、7.8mmID×30.0cm)を、溶離液としてTHF(テトラヒドロフラン)を用いた方法に準ずる事ができる。
まず、本発明のパターン形成方法を説明する。
本発明のパターン形成方法は、
(A)下記一般式(1)で表され、ClogP値が2.2以下である繰り返し単位を含有し、酸の作用により有機溶剤を含む現像液に対する溶解度が減少する樹脂と、(B)活性光線又は放射線の照射により酸を発生する化合物と、(C)溶剤とを含有する感活性光線性又は感放射線性樹脂組成物を用いて膜を形成する工程(1)、
上記膜を活性光線又は放射線を用いて露光する工程(2)、及び
上記工程(2)において露光された膜を有機溶剤を含む現像液を用いて現像し、ネガ型のパターンを形成する工程(3)を有する、パターン形成方法である。
以下、本発明のパターン形成方法に用いられる感活性光線性又は感放射線性樹脂組成物について説明する。
本発明のパターン形成方法に用いられる感活性光線性又は感放射線性樹脂組成物は、ネガ型の現像(露光されると現像液に対して溶解性が減少し、露光部がパターンとして残り、未露光部が除去される現像)に用いられる。また、本発明のパターン形成方法に用いられる感活性光線性又は感放射線性樹脂組成物は、有機溶剤を含む現像液を用いた現像に用いられる有機溶剤現像用の感活性光線性又は感放射線性樹脂組成物である。ここで、有機溶剤現像用とは、少なくとも、有機溶剤を含む現像液を用いて現像する工程に供される用途を意味する。
また上記感活性光線性又は感放射線性樹脂組成物は、典型的にはレジスト組成物であり、好ましくは化学増幅型のレジスト組成物である。
以下、上述した各成分について、順に説明する。
本発明において、樹脂(A)は、下記一般式(1)で表され、ClogP値が2.2以下である繰り返し単位を含有し、酸の作用により有機溶剤を含む現像液に対する溶解度が減少する樹脂である。
R1のアルキル基としては、炭素数1~6のアルキル基が好ましく、炭素数1~4のアルキル基がより好ましく、メチル基が最も好ましい。
R1のハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
R1は、水素原子又はメチル基であることが好ましい。
Lは、単結合、-COO-、-CONH-、-O-、-OCO-、-NHCO-、-COOCH2-、-COOCH2CH2-、-CONHCH2-、または-CONHCH2CH2-を表すことが好ましい。
LはR2又はR3と、互いに連結して環を形成してもよく、その場合のLは3価の連結基を表す。この場合の3価の連結基としては、上記2価の連結基から水素原子を1つ取り除いてなる基が挙げられ、特に、-CONH-LA-(LAは2価の連結基を表し、好ましくは後述する一般式(LA)で表される2価の連結基である)で表される2価の連結基から水素原子を1つ取り除いてなる基であることが好ましい。
R2及びR3が、アルキル基を表す場合、炭素数1~4のアルキル基が好ましく、メチル基がより好ましい。
R2又はR3とLは、互いに連結して環を形成してもよく、その場合はR2又はR3は2価の連結基を表す。この場合の2価の連結基としては、カルボニル基、アルキレン基、-O-、-NH-、又はこれらを組み合わせてなる2価の連結基が好ましく、カルボニル基、アルキレン基、-CONH-、又はこれらを組み合わせてなる2価の連結基がより好ましく、カルボニル基であることが更に好ましい。
R2及びR3は、好ましくは、水素原子またはLと連結して環を形成する場合である。
R4はヒドロキシル基、ヒドロキシアルキル基、カルボキシル基、スルホン酸基、アルキル基、アルコキシ基、アシル基、下記一般式(N1)で表される基、下記一般式(N2)で表される基、下記一般式(S1)で表される基、又は下記一般式(S2)で表される基を表すことが好ましく、ヒドロキシル基、ヒドロキシアルキル基、カルボキシル基、アルキル基、下記一般式(S1)で表される基、又は下記一般式(S2)で表される基を表すことがより好ましく、ヒドロキシル基、ヒドロキシアルキル基(好ましくはヒドロキシメチル基)、カルボキシル基、上記一般式(S1)で表される基、又は上記一般式(S2)で表される基を表すことが更に好ましく、ヒドロキシル基、カルボキシル基、又はヒドロキシメチル基を表すことが特に好ましい。
一般式(N2)中、RN3は置換基を表し、RN4は水素原子又は置換基を表す。*はベンゼン環に結合する結合手を表す。
一般式(S2)中、RS4は置換基を表し、RS5は水素原子又は置換基を表す。*はベンゼン環に結合する結合手を表す。
一般式(N2)中、RN3は置換基を表し、メチル基を表すことが好ましい。RN4は水素原子又は置換基を表し、水素原子を表すことが好ましい。
一般式(S1)中、RS1は置換基を表し、メトキシ基又はアミノ基を表すことが好ましい。RS1がアミノ基を表す場合、一般式(S1)は下記一般式(S3)で表される。
一般式(S3)中、RS2及びRS3は各々独立に、水素原子又は置換基を表し、水素原子又はメチル基を表すことが好ましい。
一般式(S2)中、RS4は置換基を表し、メチル基を表すことが好ましい。RS5は水素原子又は置換基を表し、水素原子を表すことが好ましい。
上記置換基は、さらに置換基を有していてもよく、その置換基としては、例えば、ヒドロキシル基、ハロゲン原子(例えば、フッ素原子)、アルキル基、シクロアルキル基、アルコキシ基、カルボキシル基、アルコキシカルボニル基、アリール基、アルコキシアルキル基、これらを組み合わせた基が挙げられ、炭素数8以下が好ましい。
樹脂(A)は、酸分解性基を有する繰り返し単位を含むことが好ましく、酸の作用により分解してカルボキシル基を生じる基を有する繰り返し単位を有することが好ましい。
なお、酸の作用により分解してカルボキシル基を有する繰り返し単位を有すると、酸の作用によりアルカリ現像液に対する溶解度が増大し、有機溶剤に対する溶解度が減少する。
式中、R36~R39は、各々独立に、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。R36とR37とは、互いに結合して環を形成してもよい。
R01及びR02は、各々独立に、水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基又はアルケニル基を表す。
Xa1は、水素原子、又はアルキル基を表す。
Tは、単結合又は2価の連結基を表す。
Rx1~Rx3は、各々独立に、アルキル基(直鎖若しくは分岐)又はシクロアルキル基(単環若しくは多環)を表す。ただし、Rx1~Rx3の全てがアルキル基(直鎖若しくは分岐)である場合、Rx1~Rx3のうち少なくとも2つはメチル基であることが好ましい。
Rx1~Rx3の2つが結合して、シクロアルキル基(単環若しくは多環)を形成してもよい。
Tの2価の連結基としては、アルキレン基、-COO-Rt-基、-O-Rt-基等が挙げられる。式中、Rtは、アルキレン基又はシクロアルキレン基を表す。
Tは、単結合又は-COO-Rt-基が好ましい。Rtは、炭素数1~5のアルキレン基が好ましく、-CH2-基、-(CH2)2-基、-(CH2)3-基がより好ましい。
Rx1~Rx3のシクロアルキル基としては、シクロペンチル基、シクロヘキシル基などの単環のシクロアルキル基、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、アダマンチル基などの多環のシクロアルキル基が好ましい。
Rx1~Rx3の2つが結合して形成されるシクロアルキル基としては、シクロペンチル基、シクロヘキシル基などの単環のシクロアルキル基、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、アダマンチル基などの多環のシクロアルキル基が好ましい。炭素数5~6の単環のシクロアルキル基が特に好ましい。
Rx1~Rx3の2つが結合して形成されるシクロアルキル基は、例えば、環を構成するメチレン基の1つが、酸素原子等のヘテロ原子、又は、カルボニル基等のヘテロ原子を有する基で置き換わっていてもよい。
一般式(AI)で表される繰り返し単位は、例えば、Rx1がメチル基又はエチル基であり、Rx2とRx3とが結合して上述のシクロアルキル基を形成している態様が好ましい。
具体例中、Rxは、水素原子、CH3、CF3、又はCH2OHを表す。Rxa、Rxbは各々炭素数1~4のアルキル基を表す。Zは、極性基を含む置換基を表し、複数存在する場合は各々独立である。pは0又は正の整数を表す。Zにより表される極性基を含む置換基としては、例えば、水酸基、シアノ基、アミノ基、アルキルアミド基又はスルホンアミド基を有する、直鎖又は分岐のアルキル基、シクロアルキル基が挙げられ、好ましくは、水酸基を有するアルキル基である。分岐状アルキル基としてはイソプロピル基が特に好ましい。
R61、R62及びR63は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基、又はアルコキシカルボニル基を表す。但し、R62はAr6と結合して環を形成していてもよく、その場合のR62は単結合又はアルキレン基を表す。
X6は、単結合、-COO-、又は-CONR64-を表す。R64は、水素原子又はアルキル基を表す。
L6は、単結合又はアルキレン基を表す。
Ar6は、(n+1)価の芳香環基を表し、R62と結合して環を形成する場合には(n+2)価の芳香環基を表す。
Y2は、n≧2の場合には各々独立に、水素原子、又は酸の作用により脱離する基を表す。但し、Y2の少なくとも1つは、酸の作用により脱離する基を表す。
nは、1~4の整数を表す。
酸の作用により脱離する基Y2としては、下記一般式(VI-A)で表される構造がより好ましい。
Mは、単結合又は2価の連結基を表す。
Qは、アルキル基、ヘテロ原子を含んでいてもよいシクロアルキル基、ヘテロ原子を含んでいてもよいアリール基、アミノ基、アンモニウム基、メルカプト基、シアノ基又はアルデヒド基を表す。
Q、M、L1の少なくとも2つが結合して環(好ましくは、5員若しくは6員環)を形成してもよい。
Ar3は、芳香環基を表す。
R3は、水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基、アルコキシ基、アシル基又はヘテロ環基を表す。
M3は、単結合又は2価の連結基を表す。
Q3は、アルキル基、シクロアルキル基、アリール基又はヘテロ環基を表す。
Q3、M3及びR3の少なくとも二つが結合して環を形成してもよい。
R41、R42及びR43は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルコキシカルボニル基を表す。R42はL4と結合して環を形成していてもよく、その場合のR42はアルキレン基を表す。
L4は、単結合又は2価の連結基を表し、R42と環を形成する場合には3価の連結基を表す。
R44およびR45は、水素原子、アルキル基、シクロアルキル基、アリール基、アラルキル基、アルコキシ基、アシル基又はヘテロ環基を表す。
M4は、単結合又は2価の連結基を表す。
Q4は、アルキル基、シクロアルキル基、アリール基又はヘテロ環基を表す。
Q4、M4及びR44の少なくとも二つが結合して環を形成してもよい。
R41、R42及びR43は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基、又はアルコキシカルボニル基を表す。R42はL4と結合して環を形成していてもよく、その場合のR42はアルキレン基を表す。
L4は、単結合又は2価の連結基を表し、R42と環を形成する場合には3価の連結基を表す。
R44およびR45は、前述の一般式(13)中のR3と同義であり、また好ましい範囲も同様である。
M4は、前述の一般式(13)中のM3と同義であり、また好ましい範囲も同様である。
Q4は、前述の一般式(13)中のQ3と同義であり、また好ましい範囲も同様である。Q4、M4及びR44の少なくとも二つが結合して形成される環としては、Q3、M3及びR3の少なくとも二つが結合して形成される環があげられ、また好ましい範囲も同様である。
アルコキシカルボニル基に含まれるアルキル基としては、上記R41~R43におけるアルキル基と同様のものが好ましい。
シクロアルキル基としては、単環型でも、多環型でもよい。好ましくは置換基を有していても良いシクロプロピル基、シクロペンチル基、シクロヘキシル基のような炭素数3~10個で単環型のシクロアルキル基が挙げられる。
ハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子が挙げられ、フッ素原子が特に好ましい。
L4は、単結合、-COO-L1-で表される基又は2価の芳香環基が好ましい。L1は炭素数1~5のアルキレン基が好ましく、メチレン、プロピレン基がより好ましい。2価の芳香環基としては、1,4-フェニレン基、1,3-フェニレン基、1,2-フェニレン基、1,4-ナフチレン基が好ましく、1,4-フェニレン基がより好ましい。
L4がR42と結合して環を形成する場合における、L4で表される3価の連結基としては、L4で表される2価の連結基の上記した具体例から1個の任意の水素原子を除してなる基を好適に挙げることができる。
R1は、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基又はアルキルオキシカルボニル基を表す。
ラクトン基としては、ラクトン構造を含有していればいずれの基でも用いることができるが、好ましくは5~7員環ラクトン構造を含有する基であり、5~7員環ラクトン構造にビシクロ構造、スピロ構造を形成する形で他の環構造が縮環しているものが好ましい。下記一般式(LC1-1)~(LC1-17)のいずれかで表されるラクトン構造を有する基を有する繰り返し単位を有することがより好ましい。また、ラクトン構造を有する基が主鎖に直接結合していてもよい。好ましいラクトン構造としては一般式(LC1-1)、(LC1-4)、(LC1-5)、(LC1-6)、(LC1-13)、(LC1-14)で表される基である。
Rb0のアルキル基が有していてもよい好ましい置換基としては、水酸基、ハロゲン原子が挙げられる。
Rb0のハロゲン原子としては、フッ素原子、塩素原子、臭素原子、沃素原子を挙げることができる。Rb0は、水素原子又はメチル基が好ましい。
Abは、単結合、アルキレン基、単環または多環の脂環炭化水素構造を有する2価の連結基、エーテル基、エステル基、カルボニル基、カルボキシル基、又はこれらを組み合わせた2価の基を表す。好ましくは、単結合、-Ab1-CO2-で表される連結基である。Ab1は、直鎖、分岐アルキレン基、単環または多環のシクロアルキレン基であり、好ましくは、メチレン基、エチレン基、シクロヘキシレン基、アダマンチレン基、ノルボルニレン基である。
Vは、一般式(LC1-1)~(LC1-17)のうちのいずれかで示される基を表す。
極性基を有する繰り返し単位の具体例を以下に挙げるが、本発明はこれらに限定されない。
このような繰り返し単位としては、例えば、下記一般式(14)で表される繰り返し単位が挙げられる。
R6及びR7は、それぞれ独立に、水素原子、ヒドロキシ基、炭素数1~10の直鎖状、分岐状又は環状のアルキル基、アルコキシ基又はアシロキシ基、シアノ基、ニトロ基、アミノ基、ハロゲン原子、エステル基(-OCOR又は-COOR:Rは炭素数1~6のアルキル基又はフッ素化アルキル基)、又はカルボキシル基を表す。
n3は0~6の整数を表す。
n4は0~4の整数を表す。
X4はメチレン基、酸素原子又は硫黄原子である。
一般式(V-1)又は(V-2)で表される繰り返し単位の具体例を下記に示すが、これらに限定されない。
反応溶媒としては、例えば、テトラヒドロフラン、1,4-ジオキサン、ジイソプロピルエーテルなどのエーテル類;メチルエチルケトン、メチルイソブチルケトンなどのケトン類;酢酸エチルなどのエステル溶媒;ジメチルホルムアミド、ジメチルアセトアミドなどのアミド溶剤;後述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、プロピレングリコールモノメチルエーテル、シクロヘキサノンなどの本発明における感活性光線性又は感放射線性組成物を溶解する溶媒;等が挙げられる。より好ましくは本発明の感活性光線性又は感放射線性組成物に用いられる溶剤と同一の溶剤を用いて重合することが好ましい。これにより保存時のパーティクルの発生が抑制できる。
精製は、水洗や適切な溶媒を組み合わせることにより残留単量体やオリゴマー成分を除去する液液抽出法、特定の分子量以下のもののみを抽出除去する限外ろ過等の溶液状態での精製方法や、樹脂溶液を貧溶媒へ滴下することで樹脂を貧溶媒中に凝固させることにより残留単量体等を除去する再沈殿法や、濾別した樹脂スラリーを貧溶媒で洗浄する等の固体状態での精製方法等の通常の方法を適用できる。
樹脂(A)の重量平均分子量の特に好ましい別の形態は、GPC法によるポリスチレン換算値で5,000~15,000である。重量平均分子量を5,000~15,000にすることにより、特にレジスト残渣(以降、「スカム」ともいう)が抑制され、より良好なパターンを形成することができる。
分散度(分子量分布)は、通常1~5であり、好ましくは1~3、更に好ましくは1.2~3.0、特に好ましくは1.2~2.0の範囲のものが使用される。分散度の小さいものほど、解像度、パターン形状が優れ、且つレジストパターンの側壁がスムーズであり、ラフネス性に優れる。
また、本発明における感活性光線性又は感放射線性組成物において、樹脂(A)は、1種で使用してもよいし、複数併用してもよい。
本発明のパターン形成方法に用いられる感活性光線性又は感放射線性組成物は、活性光線又は放射線の照射により酸を発生する化合物(「光酸発生剤《PAG:Photo Acid Generator》」、又は「化合物(B)」ともいう)を含有する。
光酸発生剤は、低分子化合物の形態であっても良く、重合体の一部に組み込まれた形態であっても良い。また、低分子化合物の形態と重合体の一部に組み込まれた形態を併用しても良い。
光酸発生剤が、低分子化合物の形態である場合、分子量が3000以下であることが好ましく、2000以下であることがより好ましく、1000以下であることが更に好ましい。
光酸発生剤が、重合体の一部に組み込まれた形態である場合、樹脂(A)の一部に組み込まれても良く、樹脂(A)とは異なる樹脂に組み込まれても良い。
本発明においては、光酸発生剤が、低分子化合物の形態であることが好ましい。
光酸発生剤としては、公知のものであれば特に限定されないが、活性光線又は放射線、好ましくは電子線又は極紫外線の照射により、有機酸、例えば、スルホン酸、ビス(アルキルスルホニル)イミド、又はトリス(アルキルスルホニル)メチドの少なくともいずれかを発生する化合物が好ましい。
光酸発生剤としてはスルホニウム塩であることが好ましい。
光酸発生剤としては、より好ましくは下記一般式(ZI)、(ZII)、(ZIII)で表される化合物を挙げることができる。
R201、R202及びR203は、各々独立に、有機基を表す。
R201、R202及びR203としての有機基の炭素数は、一般的に1~30、好ましくは1~20である。
また、R201~R203のうち2つが結合して環構造を形成してもよく、環内に酸素原子、硫黄原子、エステル結合、アミド結合、カルボニル基を含んでいてもよい。R201~R203の内の2つが結合して形成する基としては、アルキレン基(例えば、ブチレン基、ペンチレン基)を挙げることができる。
Z-は、非求核性アニオン(求核反応を起こす能力が著しく低いアニオン)を表す。
また、ビス(アルキルスルホニル)イミドアニオンにおけるアルキル基は、互いに結合して環構造を形成してもよい。これにより、酸強度が増加する。
Xfは、それぞれ独立に、フッ素原子、又は少なくとも1つのフッ素原子で置換されたアルキル基を表す。
R1、R2は、それぞれ独立に、水素原子、フッ素原子、又は、アルキル基を表し、複数存在する場合のR1、R2は、それぞれ同一でも異なっていてもよい。
Lは、二価の連結基を表し、複数存在する場合のLは同一でも異なっていてもよい。
Aは、環状の有機基を表す。
xは1~20の整数を表し、yは0~10の整数を表し、zは0~10の整数を表す。
Xfのフッ素原子で置換されたアルキル基におけるアルキル基としては、好ましくは炭素数1~10であり、より好ましくは炭素数1~4である。また、Xfのフッ素原子で置換されたアルキル基は、パーフルオロアルキル基であることが好ましい。
Xfとして好ましくは、フッ素原子又は炭素数1~4のパーフルオロアルキル基である。Xfの具体的としては、フッ素原子、CF3、C2F5、C3F7、C4F9、CH2CF3、CH2CH2CF3、CH2C2F5、CH2CH2C2F5、CH2C3F7、CH2CH2C3F7、CH2C4F9、CH2CH2C4F9が挙げられ、中でもフッ素原子、CF3が好ましい。特に、双方のXfがフッ素原子であることが好ましい。
R1、R2としては、好ましくはフッ素原子又はCF3である。
yは0~4が好ましく、0がより好ましい。
zは0~5が好ましく、0~3がより好ましい。
Lの2価の連結基としては特に限定されず、―COO-、-OCO-、-CO-、-O-、-S―、-SO―、―SO2-、アルキレン基、シクロアルキレン基、アルケニレン基又はこれらの複数が連結した連結基などを挙げることができ、総炭素数12以下の連結基が好ましい。このなかでも―COO-、-OCO-、-CO-、-O-が好ましく、―COO-、-OCO-がより好ましい。
脂環基としては、単環でも多環でもよく、シクロペンチル基、シクロヘキシル基、シクロオクチル基などの単環のシクロアルキル基、ノルボルニル基、トリシクロデカニル基、テトラシクロデカニル基、テトラシクロドデカニル基、アダマンチル基などの多環のシクロアルキル基が好ましい。中でも、ノルボルニル基、トリシクロデカニル基、テトラシクロデカニル基、テトラシクロドデカニル基、アダマンチル基等の炭素数7以上のかさ高い構造を有する脂環基が、露光後加熱工程での膜中拡散性を抑制でき、MEEF向上の観点から好ましい。
アリール基としては、ベンゼン環、ナフタレン環、フェナンスレン環、アントラセン環が挙げられる。
複素環基としては、フラン環、チオフェン環、ベンゾフラン環、ベンゾチオフェン環、ジベンゾフラン環、ジベンゾチオフェン環、ピリジン環由来のものが挙げられる。中でもフラン環、チオフェン環、ピリジン環由来のものが好ましい。
R201、R202及びR203のうち、少なくとも1つがアリール基であることが好ましく、三つ全てがアリール基であることがより好ましい。アリール基としては、フェニル基、ナフチル基などの他に、インドール残基、ピロール残基などのヘテロアリール基も可能である。R201~R203のアルキル基及びシクロアルキル基としては、好ましくは、炭素数1~10の直鎖又は分岐アルキル基、炭素数3~10のシクロアルキル基を挙げることができる。アルキル基として、より好ましくはメチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基等を挙げることができる。シクロアルキル基として、より好ましくは、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、シクロへプチル基等を挙げることができる。これらの基は更に置換基を有していてもよい。その置換基としては、ニトロ基、フッ素原子などのハロゲン原子、カルボキシル基、水酸基、アミノ基、シアノ基、アルコキシ基(好ましくは炭素数1~15)、シクロアルキル基(好ましくは炭素数3~15)、アリール基(好ましくは炭素数6~14)、アルコキシカルボニル基(好ましくは炭素数2~7)、アシル基(好ましくは炭素数2~12)、アルコキシカルボニルオキシ基(好ましくは炭素数2~7)等が挙げられるが、これらに限定されるものではない。
R204~R207は、各々独立に、アリール基、アルキル基又はシクロアルキル基を表す。
R204~R207のアリール基、アルキル基、シクロアルキル基は、置換基を有していてもよい。この置換基としても、前述の化合物(ZI)におけるR201~R203のアリール基、アルキル基、シクロアルキル基が有していてもよいものが挙げられる。
本発明においては、活性光線又は放射線の照射により以下に例示する酸を発生する光酸発生剤が好ましい。なお、例の一部には、体積の計算値を付記している(単位Å3)。なお、ここで求めた計算値は、アニオン部にプロトンが結合した酸の体積値である。
1Åは1×10-10mである。
光酸発生剤の感活性光線性又は感放射線性組成物中の含有量は、組成物の全固形分を基準として、0.1~50質量%が好ましく、より好ましくは5~50質量%、更に好ましくは8~40質量%である。特に、電子線や極紫外線露光の際に高感度化、高解像性を両立するには光酸発生剤の含有率は高いほうが好ましく、更に好ましくは10~40質量%、最も好ましくは10~35質量%である。
本発明のパターン形成方法に用いられる感活性光線性又は感放射線性組成物は、溶剤(C)を含む。この溶剤は、(M1)プロピレングリコールモノアルキルエーテルカルボキシレートと、(M2)プロピレングリコールモノアルキルエーテル、乳酸エステル、酢酸エステル、アルコキシプロピオン酸エステル、鎖状ケトン、環状ケトン、ラクトン、及びアルキレンカーボネートからなる群より選択される少なくとも1つとの少なくとも一方を含んでいることが好ましい。なお、この溶剤は、成分(M1)及び(M2)以外の成分を更に含んでいてもよい。
プロピレングリコールモノアルキルエーテルとしては、プロピレングリコールモノメチルエーテル又はプロピレングリコールモノエチルエーテルが好ましい。
乳酸エステルとしては、乳酸エチル、乳酸ブチル、又は乳酸プロピルが好ましい。
酢酸エステルとしては、酢酸メチル、酢酸エチル、酢酸ブチル、酢酸イソブチル、酢酸プロピル、酢酸イソアミル、蟻酸メチル、蟻酸エチル、蟻酸ブチル、蟻酸プロピル、又は酢酸3-メトキシブチルが好ましい。
酪酸ブチルも好ましい。
アルコキシプロピオン酸エステルとしては、3-メトキシプロピオン酸メチル(MMP)、又は、3-エトキシプロピオン酸エチル(EEP)が好ましい。
鎖状ケトンとしては、1-オクタノン、2-オクタノン、1-ノナノン、2-ノナノン、アセトン、4-ヘプタノン、1-ヘキサノン、2-ヘキサノン、ジイソブチルケトン、フェニルアセトン、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン、アセトニルアセトン、イオノン、ジアセトニルアルコール、アセチルカービノール、アセトフェノン、メチルナフチルケトン、又はメチルアミルケトンが好ましい。
環状ケトンとしては、メチルシクロヘキサノン、イソホロン、又はシクロヘキサノンが好ましい。
ラクトンとしては、γ-ブチロラクトンが好ましい。
アルキレンカーボネートとしては、プロピレンカーボネートが好ましい。
本発明の感活性光線性又は感放射線性組成物は、露光から加熱までの経時による性能変化を低減するために、塩基性化合物を含有することが好ましい。
塩基性化合物としては、好ましくは、下記式(A)~(E)で示される構造を有する化合物を挙げることができる。
R203、R204、R205及びR206は、同一でも異なってもよく、炭素数1~20個のアルキル基を表す。
これら一般式(A)及び(E)中のアルキル基は、無置換であることがより好ましい。
また、アミン化合物は、アルキル鎖中に、酸素原子を有し、オキシアルキレン基が形成されていることが好ましい。オキシアルキレン基の数は、分子内に1つ以上、好ましくは3~9個、さらに好ましくは4~6個である。オキシアルキレン基の中でもオキシエチレン基(-CH2CH2O-)もしくはオキシプロピレン基(-CH(CH3)CH2O-もしくは-CH2CH2CH2O-)が好ましく、さらに好ましくはオキシエチレン基である。
アンモニウム塩化合物は、アルキル鎖中に、酸素原子を有し、オキシアルキレン基が形成されていることが好ましい。オキシアルキレン基の数は、分子内に1つ以上、好ましくは3~9個、さらに好ましくは4~6個である。オキシアルキレン基の中でもオキシエチレン基(-CH2CH2O-)もしくはオキシプロピレン基(-CH(CH3)CH2O-もしくは-CH2CH2CH2O-)が好ましく、さらに好ましくはオキシエチレン基である。
アンモニウム塩化合物のアニオンとしては、ハロゲン原子、スルホネート、ボレート、フォスフェート等が挙げられるが、中でもハロゲン原子、スルホネートが好ましい。ハロゲン原子としてはクロライド、ブロマイド、アイオダイドが特に好ましく、スルホネートとしては、炭素数1~20の有機スルホネートが特に好ましい。有機スルホネートとしては、炭素数1~20のアルキルスルホネート、アリールスルホネートが挙げられる。アルキルスルホネートのアルキル基は置換基を有していてもよく、置換基としては例えばフッ素、塩素、臭素、アルコキシ基、アシル基、アリール基等が挙げられる。アルキルスルホネートとして、具体的にはメタンスルホネート、エタンスルホネート、ブタンスルホネート、ヘキサンスルホネート、オクタンスルホネート、ベンジルスルホネート、トリフルオロメタンスルホネート、ペンタフルオロエタンスルホネート、ノナフルオロブタンスルホネート等が挙げられる。アリールスルホネートのアリール基としてはベンゼン環、ナフタレン環、アントラセン環が挙げられる。ベンゼン環、ナフタレン環、アントラセン環は置換基を有していてもよく、置換基としては炭素数1~6の直鎖若しくは分岐アルキル基、炭素数3~6のシクロアルキル基が好ましい。直鎖若しくは分岐アルキル基、シクロアルキル基として、具体的には、メチル、エチル、n-プロピル、イソプロピル、n-ブチル、i-ブチル、t-ブチル、n-ヘキシル、シクロヘキシル等が挙げられる。他の置換基としては炭素数1~6のアルコキシ基、ハロゲン原子、シアノ、ニトロ、アシル基、アシルオキシ基等が挙げられる。
本発明に係る感活性光線性又は感放射線性組成物は、塩基性化合物として、プロトンアクセプター性官能基を有し、かつ、活性光線又は放射線の照射により分解してプロトンアクセプター性が低下、消失、又はプロトンアクセプター性から酸性に変化した化合物を発生する化合物〔以下、化合物(PA)ともいう〕を更に含んでいてもよい。
本発明のパターン形成方法に用いられる感活性光線性又は感放射線性組成物は、上記樹脂(A)とは別に樹脂(A)とは異なる疎水性樹脂を有していてもよい。
疎水性樹脂は膜の表面に偏在するように設計されることが好ましいが、界面活性剤とは異なり、必ずしも分子内に親水基を有する必要はなく、極性/非極性物質を均一に混合することに寄与しなくてもよい。
疎水性樹脂を添加することの効果として、水に対する膜表面の静的/動的な接触角の制御、アウトガスの抑制などを挙げることができる。
フッ素原子を有するアルキル基(好ましくは炭素数1~10、より好ましくは炭素数1~4)は、少なくとも1つの水素原子がフッ素原子で置換された直鎖又は分岐アルキル基であり、更にフッ素原子以外の置換基を有していてもよい。
フッ素原子を有するシクロアルキル基は、少なくとも1つの水素原子がフッ素原子で置換された単環又は多環のシクロアルキル基であり、更にフッ素原子以外の置換基を有していてもよい。
フッ素原子を有するアリール基としては、フェニル基、ナフチル基などのアリール基の少なくとも1つの水素原子がフッ素原子で置換されたものが挙げられ、更にフッ素原子以外の置換基を有していてもよい。
フッ素原子又は珪素原子を有する繰り返し単位の例としては、US2012/0251948A1の段落0519に例示されたものを挙げることが出来る。
ここで、疎水性樹脂中の側鎖部分が有するCH3部分構造には、エチル基、プロピル基等が有するCH3部分構造を包含するものである。
一方、疎水性樹脂の主鎖に直接結合しているメチル基(例えば、メタクリル酸構造を有する繰り返し単位のα-メチル基)は、主鎖の影響により疎水性樹脂の表面偏在化への寄与が小さいため、本発明におけるCH3部分構造に包含されないものとする。
本発明において用いられる感活性光線性又は感放射線性組成物は、界面活性剤を更に含んでいてもよい。界面活性剤を含有することにより、波長が250nm以下、特には220nm以下の露光光源を使用した場合に、良好な感度及び解像度で、密着性及び現像欠陥のより少ないパターンを形成することが可能となる。
界面活性剤としては、フッ素系及び/又はシリコン系界面活性剤を用いることが特に好ましい。
フッ素系及び/又はシリコン系界面活性剤としては、例えば、米国特許出願公開第2008/0248425号明細書の[0276]に記載の界面活性剤が挙げられる。また、エフトップEF301若しくはEF303(新秋田化成(株)製);フロラードFC430、431若しくは4430(住友スリーエム(株)製);メガファックF171、F173、F176、F189、F113、F110、F177、F120若しくはR08(DIC(株)製);サーフロンS-382、SC101、102、103、104、105若しくは106(旭硝子(株)製);トロイゾルS-366(トロイケミカル(株)製);GF-300若しくはGF-150(東亜合成化学(株)製)、サーフロンS-393(セイミケミカル(株)製);エフトップEF121、EF122A、EF122B、RF122C、EF125M、EF135M、EF351、EF352、EF801、EF802若しくはEF601((株)ジェムコ製);PF636、PF656、PF6320若しくはPF6520(OMNOVA社製);又は、FTX-204G、208G、218G、230G、204D、208D、212D、218D若しくは222D((株)ネオス製)を用いてもよい。なお、ポリシロキサンポリマーKP-341(信越化学工業(株)製)も、シリコン系界面活性剤として用いることができる。
また、米国特許出願公開第2008/0248425号明細書の[0280]に記載されているフッ素系及び/又はシリコン系以外の界面活性剤を使用してもよい。
本発明において用いられる感活性光線性又は感放射線性組成物は、溶解阻止化合物、染料、可塑剤、光増感剤、光吸収剤、及び/又は現像液に対する溶解性を促進させる化合物(例えば、分子量1000以下のフェノール化合物、又はカルボキシ基を含んだ脂環族若しくは脂肪族化合物)を更に含んでいてもよい。
非化学増幅系のレジスト組成物としては、例えば、
g線、h線、i線、KrF、ArF、EBあるいはEUV等の照射によって主鎖が切断し、分子量が低下することにより溶解性が変化するレジスト材料(例えば特開2013-210411号公報[0025]~[0029]、[0056]や米国特許公報2015/0008211[0032]~[0036]、[0063]に記載のα-クロロアクリル酸エステル系化合物とα-メチルスチレン系化合物との共重合体を主成分とするレジスト材料等)、
g線、h線、i線、KrF、ArF、EBあるいはEUV等によって生じたシラノール縮合反応を伴うハイドロゲンシルセスオキサン(HSQ)、塩素置換したカリックスアレーン、
g線、h線、i線、KrF、ArF、EBあるいはEUV等の光に対して吸収を有する金属錯体(マグネシウム、クロム、マンガン、鉄、コバルト、ニッケル、銅、亜鉛、銀、カドミウム、インジウム、錫、アンチモン、セシウム、ジルコニウム、ハフニウム等の錯体であり、チタン、ジルコニウム、ハフニウムがパターン形成性の観点から好ましい)を含み、配位子脱離や酸発生剤と併用して配位子交換過程を伴うレジスト材料(特開2015-075500[0017]~[0033]、[0037]~[0047]、特開2012-185485[0017]~[0032]、[0043]~[0044]、米国特許公報2012/0208125[0042]~[0051]、[0066]等に記載のレジスト材料)等が挙げられる。
また、レジスト組成物としては、特開2008-83384号公報に記載の[0010]~[0062]、[0129]~[0165]に記載のレジスト組成物も用いることができる。
工程(1)は、上記感活性光線性又は感放射線性組成物を用いて膜を形成する工程であり、例えば次の方法により行うことができる。
感活性光線性又は感放射線性組成物を用いて基板上に膜を形成するためには、上記樹脂(A)及び化合物(B)を溶剤(C)に溶解して感活性光線性又は感放射線性組成物を調製し、必要に応じてフィルター濾過した後、基板上に塗布する。フィルターとしては、ポアサイズ0.1μm以下、より好ましくは0.05μm以下、更に好ましくは0.03μm以下のポリテトラフロロエチレン製、ポリエチレン製、ナイロン製のものが好ましい。
膜厚の範囲としてより好ましくは、15nmから45nmの範囲である。膜厚が15nm以上であれば、十分なエッチング耐性が得られる。膜厚の範囲として更に好ましくは、15nmから40nmである。膜厚がこの範囲にあると、エッチング耐性とより優れた解像性能とを同時に満足させることができる。
基板上に感活性光線性又は感放射線性組成物を塗布する方法としては、スピン塗布が好ましく、その回転数は1000~3000rpmが好ましい。
また、トップコートは、エーテル結合、チオエーテル結合、ヒドロキシル基、チオール基、カルボニル結合及びエステル結合からなる群より選択される基又は結合を少なくとも一つ含む化合物を含むことが好ましいが、これらは特に限定されず、従来公知のトップコートを、従来公知の方法によって形成でき、例えば、特開2014-059543号公報の段落0072~0082の記載に基づいてトップコートを形成できる。
現像工程において、例えば、特開2013-61648号公報に記載されたような塩基性化合物を含有するトップコートを膜上に形成することが好ましい。トップコートが含み得る塩基性化合物の具体的な例は前述した塩基性化合物と同様である。
工程(2)は、膜を露光する工程であり、例えば次の方法により行うことができる。
上記のようにして形成した膜に、所定のマスクを通して活性光線又は放射線を照射する。なお、電子ビームの照射では、マスクを介さない描画(直描)が一般的である。
活性光線又は放射線としては特に限定されないが、例えばKrFエキシマレーザー、ArFエキシマレーザー、極紫外線(EUV、Extreme Ultra Violet)、電子線(EB、Electron Beam)等であり、極紫外線又は電子線が特に好ましい。露光は液浸露光であってもよい。
本発明のパターン形成方法においては、露光後、現像を行う前にベーク(加熱)を行うことが好ましい。ベークにより露光部の反応が促進され、感度やパターン形状がより良好となる。
加熱温度は80~150℃が好ましく、80~140℃がより好ましく、80~130℃が更に好ましい。
加熱時間は30~1000秒が好ましく、60~800秒がより好ましく、60~600秒が更に好ましい。
加熱は通常の露光・現像機に備わっている手段で行うことができ、ホットプレート等を用いて行ってもよい。
工程(3)は、工程(2)で露光された膜を有機溶剤を含む現像液によって現像する工程である。
本発明で用いられる現像液は有機溶剤を含有する。有機溶剤を含有する現像液を、「有機系現像液」ともいう。有機系現像液中の有機溶剤の含有量は、現像液の全量に対して、50質量%より大きく100質量%以下であることが好ましく、70質量%以上100質量%以下であることがより好ましく、90質量%以上100質量%以下であることがさらに好ましく、95質量%以上100質量%以下であることが特に好ましい。
現像液に含有される有機溶剤としては特に限定されないが、エステル系溶剤、ケトン系溶剤、アルコール系溶剤、エーテル系溶剤、アミド系溶剤、及び炭化水素系溶剤からなる群より選択される少なくとも1種の有機溶剤が好ましい。
分岐アルキル基を有する非環式脂肪族ケトン系溶剤としては、例えば、ジイソヘキシルケトン、メチルイソペンチルケトン、エチルイソペンチルケトン、プロピルイソペンチルケトン、ジイソペンチルケトン、メチルイソブチルケトン、エチルイソブチルケトン、プロピルイソブチルケトン、ジイソブチルケトン、ジイソプロピルケトン、エチルイソプロピルケトン、メチルイソプロピルケトンなどが挙げられ、特に好ましくは、ジイソブチルケトンである。
分岐アルキル基を有する環式脂肪族エーテル系溶剤としては、例えば、シクロペンチルイソプロピルエーテル、シクロペンチルsec-ブチルエーテル、シクロペンチルtert-ブチルエーテル、シクロヘキシルイソプロピルエーテル、シクロヘキシルsec-ブチルエーテル、シクロヘキシルtert-ブチルエーテルが挙げられる。
分岐アルキル基を有する非環式脂肪族エーテル系溶剤としては、例えば、ジイソヘキシルエーテル、メチルイソペンチルエーテル、エチルイソペンチルエーテル、プロピルイソペンチルエーテル、ジイソペンチルエーテル、メチルイソブチルエーテル、エチルイソブチルエーテル、プロピルイソブチルエーテル、ジイソブチルエーテル、ジイソプロピルエーテル、エチルイソプロピルエーテル、メチルイソプロピルエーテルなどが挙げられ、特に好ましくは、ジイソブチルエーテル又はジイソペンチルエーテルである。
不飽和炭化水素溶剤が有する二重結合、三重結合は複数でもよく、炭化水素鎖のどの位置に有しても良い。二重結合を有することによるCis、trans体が混合しても良い。
界面活性剤としては、後述する感活性光線又は感放射線性組成物に用いられる界面活性剤と同様のものを用いることができる。
現像液が界面活性剤を含有する場合、界面活性剤の含有量は、現像液の全質量に対して、0.001~5質量%であることが好ましく、より好ましくは0.005~2質量%であり、更に好ましくは0.01~0.5質量%である。
アミン系酸化防止剤としては、例えば、1-ナフチルアミン、フェニル-1-ナフチルアミン、p-オクチルフェニル-1-ナフチルアミン、p-ノニルフェニル-1-ナフチルアミン、p-ドデシルフェニル-1-ナフチルアミン、フェニル-2-ナフチルアミン等のナフチルアミン系酸化防止剤;N,N'-ジイソプロピル-p-フェニレンジアミン、N,N'-ジイソブチル-p-フェニレンジアミン、N,N'-ジフェニル-p-フェニレンジアミン、N,N'-ジ-β-ナフチル-p-フェニレンジアミン、N-フェニル-N'-イソプロピル-p-フェニレンジアミン、N-シクロヘキシル-N'-フェニル-p-フェニレンジアミン、N-1,3-ジメチルブチル-N'-フェニル-p-フェニレンジアミン、ジオクチル-p-フェニレンジアミン、フェニルヘキシル-p-フェニレンジアミン、フェニルオクチル-p-フェニレンジアミン等のフェニレンジアミン系酸化防止剤;ジピリジルアミン、ジフェニルアミン、p,p'-ジ-n-ブチルジフェニルアミン、p,p'-ジ-t-ブチルジフェニルアミン、p,p'-ジ-t-ペンチルジフェニルアミン、p,p'-ジオクチルジフェニルアミン、p,p'-ジノニルジフェニルアミン、p,p'-ジデシルジフェニルアミン、p,p'-ジドデシルジフェニルアミン、p,p'-ジスチリルジフェニルアミン、p,p'-ジメトキシジフェニルアミン、4,4'-ビス(4-α,α-ジメチルベンゾイル)ジフェニルアミン、p-イソプロポキシジフェニルアミン、ジピリジルアミン等のジフェニルアミン系酸化防止剤;フェノチアジン、N-メチルフェノチアジン、N-エチルフェノチアジン、3,7-ジオクチルフェノチアジン、フェノチアジンカルボン酸エステル、フェノセレナジン等のフェノチアジン系酸化防止剤が挙げられる。
フェノール系酸化防止剤としては、例えば、例えば、2,6-ジ-ターシャリブチルフェノール(以下、ターシャリブチルをt-ブチルと略記する。)、2,6-ジ-t-ブチル-p-クレゾール、2,6-ジ-t-ブチル-4-メチルフェノール、2,6-ジ-t-ブチル-4-エチルフェノール、2,4-ジメチル-6-t-ブチルフェノール、4,4’-メチレンビス(2,6-ジ-t-ブチルフェノール)、4,4’-ビス(2,6-ジ-t-ブチルフェノール)、4,4’-ビス(2-メチル-6-t-ブチルフェノール)、2,2’-メチレンビス(4-メチル-6-t-ブチルフェノール)、2,2’-メチレンビス(4-エチル-6-t-ブチルフェノール)、4,4’-ブチリデンビス(3-メチル-6-t-ブチルフェノール)、4,4’-イソプロピリデンビス(2,6-ジ-t-ブチルフェノール)、2,2’-メチレンビス(4-メチル-6-シクロヘキシルフェノール)、2,2’-メチレンビス(4-メチル-6-ノニルフェノール)、2,2’-イソブチリデンビス(4,6-ジメチルフェノール)、2,6-ビス(2’-ヒドロキシ-3’-t-ブチル-5’-メチルベンジル)-4-メチルフェノール、3-t-ブチル-4-ヒドロキシアニソール、2-t-ブチル-4-ヒドロキシアニソール、3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオン酸オクチル、3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオン酸ステアリル、3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオン酸オレイル、3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオン酸ドデシル、3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオン酸デシル、3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオン酸オクチル、テトラキス{3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオニルオキシメチル}メタン、3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオン酸グリセリンモノエステル、3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオン酸とグリセリンモノオレイルエーテルとのエステル、3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオン酸ブチレングリコールジエステル、3-(4-ヒドロキシ-3,5-ジ-t-ブチルフェニル)プロピオン酸チオジグリコールジエステル、4,4’-チオビス(3-メチル-6-t-ブチルフェノール)、4,4’-チオビス(2-メチル-6-t-ブチルフェノール)、2,2’-チオビス(4-メチル-6-t-ブチルフェノール)、2,6-ジ-t-ブチル-α-ジメチルアミノ-p-クレゾール、2,6-ジ-t-ブチル-4-(N,N’-ジメチルアミノメチルフェノール)、ビス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)サルファイド、トリス{(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオニル―オキシエチル}イソシアヌレート、トリス(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)イソシアヌレート、1,3,5-トリス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)イソシアヌレート、ビス{2-メチル-4-(3-n-アルキルチオプロピオニルオキシ)-5-t-ブチルフェニル}サルファイド、1,3,5-トリス(4-t-ブチル-3-ヒドロキシ-2,6―ジメチルベンジル)イソシアヌレート、テトラフタロイル―ジ(2,6-ジメチル-4-t-ブチル-3-ヒドロキシベンジルサルファイド)、6-(4-ヒドロキシ-3,5-ジ-t-ブチルアニリノ)-2,4-ビス(オクチルチオ)-1,3,5―トリアジン、2,2-チオ-{ジエチル-ビス-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)}プロピオネート、N,N’-ヘキサメチレンビス(3,5-ジ-t-ブチル-4-ヒドロキシ-ヒドロシナミド)、3,9-ビス〔1,1-ジメチル-2-{β-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ}エチル〕-2,4,8,10-テトラオキサスピロ[5,5]ウンデカン、1,1,3-トリス(2-メチル-4-ヒドロキシ-5-t-ブチルフェニル)ブタン、1,3,5-トリメチル-2,4,6-トリス(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)ベンゼン、ビス{3,3’-ビス-(4’-ヒドロキシ-3’-t-ブチルフェニル)ブチリックアシッド}グリコールエステル等が挙げられる。
現像液に含まれ得る塩基性化合物の中でも、含窒素化合物を好ましく用いることができる。
また、現像を行う工程の後に、他の溶媒に置換しながら、現像を停止する工程を実施してもよい。
現像時間は未露光部の樹脂が十分に溶解する時間であれば特に制限はなく、通常は10~300秒であり、好ましくは20~120秒である。
現像液の温度は0~50℃が好ましく、15~35℃がより好ましい。
リンス工程は、現像工程の後にリンス液によって洗浄(リンス)する工程である。
洗浄処理の方法は特に限定されないが、たとえば、一定速度で回転している基板上にリンス液を吐出しつづける方法(回転吐出法)、リンス液が満たされた槽中に基板を一定時間浸漬する方法(ディップ法)、基板表面にリンス液を噴霧する方法(スプレー法)、などを適用することができ、この中でも回転吐出方法で洗浄処理を行い、洗浄後に基板を2000rpm~4000rpmの回転数で回転させ、リンス液を基板上から除去することが好ましい。
リンス時間には特に制限はないが、好ましくは10秒~300秒であり、より好ましくは10秒~180秒であり、最も好ましくは20秒~120秒である。
リンス液の温度は0~50℃が好ましく、15~35℃が更に好ましい。
さらに、現像処理又はリンス処理又は超臨界流体による処理の後、パターン中に残存する溶剤を除去するために加熱処理を行うことができる。加熱温度は、良好なレジストパターンが得られる限り特に限定されるものではなく、通常40~160℃である。加熱温度は50~150℃が好ましく、50~110℃が最も好ましい。加熱時間に関しては良好なレジストパターンが得られる限り特に限定されないが、通常15~300秒であり、好ましくは、15~180秒である。
リンス液が含む有機溶剤は、炭化水素系溶剤が好ましい。
なお、上記脂肪族炭化水素系溶剤の炭素原子数の上限値は特に限定されないが、例えば、16以下が挙げられ、14以下が好ましく、12以下がより好ましい。
上記脂肪族炭化水素系溶剤の中でも、特に好ましくは、デカン、ウンデカン、イソデカン、ドデカンであり、さらに好ましくはウンデカンである。
尚、リンス液に含まれる炭化水素系溶剤として不飽和炭化水素系溶剤も用いることができ、例えば、オクテン、ノネン、デセン、ウンデセン、ドデセン、ヘキサデセン等の不飽和炭化水素系溶剤が挙げられる。不飽和炭化水素溶剤が有する二重結合、三重結合の数は特に限定されず、また、炭化水素鎖のどの位置に有してもよい。また、不飽和炭化水素溶剤が二重結合を有する場合には、cis体及びtrans体が混在していてもよい。
このようにリンス液に含まれる有機溶剤として炭化水素系溶剤(特に脂肪族炭化水素系溶剤)を用いることで、現像後にわずかに膜に染み込んでいた現像液が洗い流されて、膨潤がより抑制され、パターン倒れが抑制されるという効果が一層発揮される。
エステル系溶剤と炭化水素系溶剤とを組み合わせて用いる場合には、エステル系溶剤として酢酸ブチル、酢酸イソアミルを用いることが好ましい。また、炭化水素系溶剤としては、上記効果が一層発揮されるという点から、飽和炭化水素溶剤(例えば、デカン、ドデカン、ウンデカン、ヘキサデカンなど)を用いることが好ましい。
ケトン系溶剤と炭化水素系溶剤とを組み合わせて用いる場合には、ケトン系溶剤として2-ヘプタノンを用いることが好ましい。また、炭化水素系溶剤としては、上記効果が一層発揮されるという点から、飽和炭化水素溶剤(例えば、デカン、ドデカン、ウンデカン、ヘキサデカンなど)を用いることが好ましい。
また、エステル系溶剤と炭化水素系溶剤とを組み合わせて用いる場合、ケトン系溶剤と炭化水素系溶剤とを組み合わせて用いる場合には、炭化水素系溶剤として不飽和炭化水素系溶剤も用いることができ、例えば、オクテン、ノネン、デセン、ウンデセン、ドデセン、ヘキサデセン等の不飽和炭化水素系溶剤が挙げられる。不飽和炭化水素溶剤が有する二重結合、三重結合の数は特に限定されず、また、炭化水素鎖のどの位置に有してもよい。
また、不飽和炭化水素溶剤が二重結合を有する場合には、cis体及びtrans体が混在していてもよい。
リンス液が、エステル系溶剤及びケトン系溶剤からなる群より選択される少なくとも1種を含有する場合、酢酸ブチル、酢酸イソペンチル(酢酸イソアミル)、酢酸n-ペンチル、3-エトキシプロピオン酸エチル(EEP、エチル-3-エトキシプロピオネート)、及び2-ヘプタノンからなる群より選択される少なくとも1種の溶剤を主成分として含有することが好ましく、酢酸ブチル及び2-ヘプタノンからなる群より選択される少なくとも1種の溶剤を主成分として含有することが特に好ましい。
また、リンス液が、エステル系溶剤及びケトン系溶剤からなる群より選択される少なくとも1種を含有する場合、エステル系溶剤、グリコールエーテル系溶剤、ケトン系溶剤、アルコール系溶剤からなる群より選択される溶剤を副成分として含有することが好ましく、中でも、プロピレングリコールモノメチルエーテルアセテート(PGMEA)、プロピレングリコールモノメチルエーテル(PGME)、酢酸エチル、乳酸エチル、3-メトキシプロピオン酸メチル、シクロヘキサノン、メチルエチルケトン、γ-ブチロラクトン、プロパノール、3-メトキシ-1-ブタノール、N-メチルピロリドン、プロピレンカーボネートからなる群より選択される溶剤が好ましい。
この中でも、有機溶剤としてエステル系溶剤を用いる場合には、上記効果が一層発揮されるという点から、2種以上のエステル系溶剤を用いることが好ましい。この場合の具体例としては、エステル系溶剤(好ましくは酢酸ブチル)を主成分として、これとは化学構造が異なるエステル系溶剤(好ましくは、プロピレングリコールモノメチルエーテルアセテート(PGMEA))を副成分として用いることが挙げられる。
また、有機溶剤としてエステル系溶剤を用いる場合には、上記効果が一層発揮されるという点から、エステル系溶剤(1種又は2種以上)に加えて、グリコールエーテル系溶剤を用いてもよい。この場合の具体例としては、エステル系溶剤(好ましくは、酢酸ブチル)を主成分として、グリコールエーテル系溶剤(好ましくはプロピレングリコールモノメチルエーテル(PGME))を副成分として用いることが挙げられる。
有機溶剤としてケトン系溶剤を用いる場合には、上記効果が一層発揮されるという点から、ケトン系溶剤(1種又は2種以上)に加えて、エステル系溶剤及び/又はグリコールエーテル系溶剤を用いてもよい。この場合の具体例としては、ケトン系溶剤(好ましくは2-ヘプタノン)を主成分として、エステル系溶剤(好ましくは、プロピレングリコールモノメチルエーテルアセテート(PGMEA))及び/又はグリコールエーテル系溶剤(好ましくはプロピレングリコールモノメチルエーテル(PGME))を副成分として用いることが挙げられる。
ここで、上記の「主成分」とは、有機溶剤の全質量に対する含有量が、50~100質量%であることをいい、好ましくは70~100質量%、より好ましくは80~100質量%、さらに好ましくは90~100質量%、特に好ましくは95~100質量%であることをいう。
また、副成分を含有する場合には、副成分の含有量は、主成分の全質量(100質量%)に対して、0.1~20質量%であることが好ましく、0.5~10質量%であることがより好ましく、1~5質量%であることがさらに好ましい。
界面活性剤としては、後述する感活性光線または感放射線性組成物に用いられる界面活性剤と同様のものを用いることができる。
リンス液が界面活性剤を含有する場合、界面活性剤の含有量は、リンス液の全質量に対して、0.001~5質量%が好ましく、より好ましくは0.005~2質量%であり、更に好ましくは0.01~0.5質量%である。
各種材料から金属等の不純物を除去する方法としては、例えば、フィルターを用いた濾過を挙げることができる。フィルター孔径としては、ポアサイズ10nm以下が好ましく、5nm以下がより好ましく、3nm以下が更に好ましい。フィルターの材質としては、ポリテトラフロロエチレン製、ポリエチレン製、ナイロン製のフィルターが好ましい。フィルターは、これらの材質とイオン交換メディアを組み合わせた複合材料であってもよい。フィルターは、有機溶剤であらかじめ洗浄したものを用いてもよい。フィルター濾過工程では、複数種類のフィルターを直列又は並列に接続して用いてもよい。複数種類のフィルターを使用する場合は、孔径及び/又は材質が異なるフィルターを組み合わせて使用しても良い。また、各種材料を複数回濾過してもよく、複数回濾過する工程が循環濾過工程であっても良い。
また、各種材料に含まれる金属等の不純物を低減する方法としては、各種材料を構成する原料として金属含有量が少ない原料を選択する、各種材料を構成する原料に対してフィルター濾過を行う、装置内をテフロン(登録商標)でライニングする等してコンタミネーションを可能な限り抑制した条件下で蒸留を行う等の方法を挙げることができる。各種材料を構成する原料に対して行うフィルター濾過における好ましい条件は、上記した条件と同様である。
フィルター濾過の他、吸着材による不純物の除去を行っても良く、フィルター濾過と吸着材を組み合わせて使用しても良い。吸着材としては、公知の吸着材を用いることができ、例えば、シリカゲル、ゼオライトなどの無機系吸着材、活性炭などの有機系吸着材を使用することができる。
現像液及びリンス液に使用し得る有機溶剤(「有機系処理液」ともいう)としては、収容部を有する、化学増幅型又は非化学増幅型膜のパターニング用有機系処理液の収容容器に保存されたものを使用することが好ましい。この収容容器としては、例えば、収容部の、有機系処理液に接触する内壁が、ポリエチレン樹脂、ポリプロピレン樹脂、及び、ポリエチレン-ポリプロピレン樹脂のいずれとも異なる樹脂、又は、防錆・金属溶出防止処理が施された金属から形成された、膜のパターニング用有機系処理液の収容容器であることが好ましい。この収容容器の上記収容部に、膜のパターニング用有機系処理液として使用される予定の有機溶剤を収容し、膜のパターニング時において、上記収容部から排出したものを使用することができる。
・JFE社製 鋼製ドラム缶(接液内面;燐酸亜鉛皮膜)
配管に通す溶剤としては、レジストを溶解し得るものであれば特に限定されず、例えば上述した有機溶媒が挙げられ、プロピレングリコールモノメチルエーテルアセテート(PGMEA)、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、プロピレングリコールモノメチルエーテルプロピオネート、プロピレングリコールモノエチルエーテルプロピオネート、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、プロピレングリコールモノメチルエーテル(PGME)、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、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、2-ヘプタノン、乳酸エチル、1-プロパノール、アセトン、等を用いることができる。中でも好ましくは、PGMEA,PGME,シクロヘキサノンを用いることができる。
本発明は、上記一般式(4)又は(4a)で表される繰り返し単位を有する樹脂を含むレジスト組成物にも関する。本発明のレジスト組成物における一般式(4)又は(4a)で表される繰り返し単位、及びこの繰り返し単位を有する樹脂の具体例及び好ましい範囲は前述のとおりである。
レジスト組成物は、前述の感活性光線性又は感放射線性樹脂組成物の好ましい態様であり、前述の感活性光線性又は感放射線性樹脂組成物において説明した、各成分及びその含有量、並びにその他の事項をレジスト組成物においても参照できる。
《モノマー(a1)の合成》
4-アミノフェノール30gをテトラヒドロフラン250mlに溶解し、この溶液に無水マレイン酸27gを過度に発熱しないよう注意深く加え、室温で3時間攪拌した。反応後、溶媒を留去し、得られた粗結晶を酢酸エチルで洗浄することにより、中間体(a1-1)56gを得た。
1H-NMR(nuclear magnetic resonance)(DMSO(Dimethyl sulfoxide)―d6:ppm)δ:13.67(br)、10.38(s)、9.35(s)、7.43(d)、6.74(d)、6.48(d)、6.30(d)
中間体(a1-1)56gをトルエン240mlに懸濁し、パラトルエンスルホン酸3.7gとN,N-ジメチルホルムアミド28mlを加え、ディーン・スターク管を備え、5時間加熱還流させた。室温まで放冷後、水3000mlにこの反応液を加え、粉体をろ過した。シリカゲルカラムクロマトグラフィー(溶離液:酢酸エチル/n-ヘキサン=1/1)で精製後、イソプロパノールで再結晶を行い、モノマー(a1)22gを得た。
1H-NMR(DMSO―d6:ppm)δ:9.68(s)、7.13(s)、7.08(d)、6.83(d)
5.1gのモノマー(a1)と、2.0gのモノマー(c1)と、t-ブチルメタクリレート7.7gと、0.48gの重合開始剤V-601(和光純薬工業(株)製)とを、54.5gのシクロヘキサノンに溶解させた。反応容器中に29.3gのシクロヘキサノンを入れ、窒素ガス雰囲気下、85℃の系中に4時間かけて滴下した。反応溶液を2時間に亘って加熱撹拌した後、これを室温まで放冷した。上記反応溶液を、990gの、n-ヘプタン及び酢酸エチルの混合溶液(n-ヘプタン/酢酸エチル=9/1(質量比))中に滴下し、ポリマーを沈殿させ、ろ過した。300gの、n-ヘプタン及び酢酸エチルの混合溶液(n-ヘプタン/酢酸エチル=9/1(質量比))を用いて、ろ過した固体のかけ洗いを行なった。得られたポリマーをシクロヘキサノン82gに溶解し、960gの、メタノール及び水の混合溶液(メタノール/水=4/6(質量比))中に滴下し、ポリマーを沈殿させ、ろ過した。290gの、メタノール及び水の混合溶液(メタノール/水=4/6(質量比))を用いて、ろ過した固体のかけ洗いを行なった。その後、洗浄後の固体を減圧乾燥に供して、12.3gの樹脂(A-1)を得た。GPCによる重量平均分子量は12900、分子量分散度(Mw/Mn)は1.70であった。
1H-NMR(DMSO―d6:ppm)δ:9.80、7.15-6.71、4.76-4.26、2.93―0.79(ピークはいずれもブロード)
酸発生剤としては、以下のものを用いた。
塩基性化合物としては、以下のものを用いた。
溶剤としては、以下のものを用いた。
C1:プロピレングリコールモノメチルエーテルアセテート
C2:プロピレングリコールモノメチルエーテル
C3:乳酸エチル
C4:シクロヘキサノン
現像液としては、以下のものを用いた。
SG-1:アニソール
SG-2:メチルアミルケトン
SG-3:酢酸イソアミル
リンス液としては、以下のものを用いた。
R-1:ウンデカン
R-2:イソデカン
R-3:デカン
R-4:4-メチル-2-ペンタノール
架橋剤としては、以下のものを用いた。
下記表2~4に示す各成分を、表2~4に示す溶剤に溶解させた。これを0.03μmのポアサイズを有するポリエチレンフィルターを用いてろ過して、レジスト組成物を得た。
レジスト組成物を用いて、以下の操作によりレジストパターンを形成した。
HMDS(ヘキサメチルジシラザン)処理を行った4インチシリコンウエハ上に、レジスト組成物を塗布し、120℃で60秒間ベークし、膜厚40nmのレジスト膜を形成した。
1インチは25.4mmである。
レジスト膜を形成したウエハに、NA(レンズ開口数、Numerical Aperture)0.3、ダイポール照明でEUV露光を行った。具体的には、線幅50nmの1:1ラインアンドスペースパターンを形成する為のパターンが含まれたマスクを介して、露光量を変えてEUV露光を行った。
露光後、ウエハをEUV露光装置から取り出し、ただちに、表5に示す温度の条件で60秒間ベークした。
その後、シャワー型現像装置(ACTES(株)製ADE3000S)を用いて、50回転(rpm)でウエハを回転しながら表5に記載の現像液(23℃)を、200mL/分の流量で、所定時間スプレー吐出して現像を行った。
その後、50回転(rpm)でウエハを回転しながら表5に記載のリンス液(23℃)を、200mL/分の流量で、所定時間スプレー吐出してリンス処理を行った。
最後に、2500回転(rpm)で120秒間高速回転してウエハを乾燥させた。
得られたレジストパターンについて下記の方法で、感度、解像力を評価した。レジストパターンは、走査型電子顕微鏡((株)日立製作所製S-9380II)を用いて観察した。結果を下記表5に示す。
線幅50nmの1:1ラインアンドスペースパターンを解像する時の最適露光量を感度(Eop1)とした。この値が小さいほど性能が良好であることを示す。
上記Eop1において、マスクを変更することによりハーフピッチサイズの異なるラインアンドスペースパターンを作成した。そのとき、分離している(1:1)のラインアンドスペースパターンが得られる最小のハーフピッチサイズを解像力とした。この値が小さいほど性能が良好であることを示す。
レジスト組成物を用いて、以下の操作によりレジストパターンを形成した。
HMDS(ヘキサメチルジシラザン)処理を行った4インチシリコンウエハ上に、レジスト組成物を塗布し、120℃で60秒間ベークし、膜厚40nmのレジスト膜を形成した。
1インチは25.4mmである。
レジスト膜を形成したウエハに、NA(レンズ開口数、Numerical Aperture)0.3、ダイポール照明でEUV露光を行った。具体的には、直径30nmのドットをピッチ100nmで形成する為のパターンが含まれたマスクを介して、露光量を変えてEUV露光を行った。
露光後、ウエハをEUV露光装置から取り出し、ただちに、表6に示す温度の条件で60秒間ベークした。
その後、シャワー型現像装置(ACTES(株)製ADE3000S)を用いて、50回転(rpm)でウエハを回転しながら表6に記載の現像液(23℃)を、200mL/分の流量で、所定時間スプレー吐出して現像を行った。
その後、50回転(rpm)でウエハを回転しながら表6に記載のリンス液(23℃)を、200mL/分の流量で、所定時間スプレー吐出してリンス処理を行った。
最後に、2500回転(rpm)で120秒間高速回転してウエハを乾燥させた。
得られたレジストパターンについて下記の方法で、解像力を評価した。レジストパターンは、走査型電子顕微鏡((株)日立製作所製S-9380II)を用いて観察した。結果を下記表6に示す。
直径30nmのドットを解像する時の最適露光量を感度(Eop2)とした。
上記Eop2において、マスクを変更することにより、ピッチ(ドットとドットの間隔)を100nmに維持した状態で、ドット径を30nmから小さくしていき、分離しているドットパターンの限界最小径を解像力とした。この値が小さいほど性能が良好であることを示す。
レジスト組成物を用いて、以下の操作によりレジストパターンを形成した。
6インチシリコンウエハ上に有機膜DUV44(Brewer Science社製)を塗布し、200℃で60秒間ベークして、膜厚60nmの有機膜を形成した。その上にレジスト組成物を塗布し、120℃で60秒間ベークし、膜厚40nmのレジスト膜を形成した。
レジスト膜を形成したウエハに、電子線照射装置((株)JEOL製 JBX6000FS/E;加速電圧50keV)を用いて、EB露光を行った。具体的には、線幅50nmの1:1ラインアンドスペースパターン(長さ方向0.12mm、描画本数20本)を、露光量を変えて露光した。
露光後、ウエハを電子線照射装置から取り出し、ただちに、表7に示す温度で60秒の条件でホットプレート上にて加熱した。
シャワー型現像装置(ACTES(株)製ADE3000S)を用いて、50回転(rpm)でウエハを回転しながら表7に記載の現像液(23℃)を、200mL/分の流量で、所定時間スプレー吐出して現像を行った。
その後、50回転(rpm)でウエハを回転しながら表7に記載のリンス液(23℃)を、200mL/分の流量で、所定時間スプレー吐出してリンス処理を行った。
最後に、2500回転(rpm)で120秒間高速回転してウエハを乾燥させた。
レジスト組成物を用いて、以下の操作によりレジストパターンを形成した。
6インチシリコンウエハ上に有機膜DUV44(Brewer Science社製)を塗布し、200℃で60秒間ベークして、膜厚60nmの有機膜を形成した。その上にレジスト組成物を塗布し、120℃で60秒間ベークし、膜厚40nmのレジスト膜を形成した。
レジスト膜を形成したウエハに、電子線照射装置((株)JEOL製 JBX6000FS/E;加速電圧50keV)を用いて、EB露光を行った。具体的には、直径30nmのドットをピッチ100nmで形成するように、露光量を変えてEB露光を行った。
露光後、ウエハを電子線照射装置から取り出し、ただちに、表8に示す温度で60秒の条件でホットプレート上にて加熱した。
シャワー型現像装置(ACTES(株)製ADE3000S)を用いて、50回転(rpm)でウエハを回転しながら表8に記載の現像液(23℃)を、200mL/分の流量で、所定時間スプレー吐出して現像を行った。
その後、50回転(rpm)でウエハを回転しながら表8に記載のリンス液(23℃)を、200mL/分の流量で、所定時間スプレー吐出してリンス処理を行った。
最後に、2500回転(rpm)で120秒間高速回転してウエハを乾燥させた。
Claims (18)
- (A)下記一般式(1)で表され、ClogP値が2.2以下である繰り返し単位を含有し、酸の作用により有機溶剤を含む現像液に対する溶解度が減少する樹脂と、(B)活性光線又は放射線の照射により酸を発生する化合物と、(C)溶剤と、を含有する感活性光線性又は感放射線性樹脂組成物を用いて膜を形成する工程(1)、
前記膜を活性光線又は放射線を用いて露光する工程(2)、及び
前記工程(2)において露光された膜を有機溶剤を含む現像液を用いて現像し、ネガ型のパターンを形成する工程(3)を有する、パターン形成方法。
一般式(1)中、R1は水素原子、アルキル基、又はハロゲン原子を表し、R2及びR3はそれぞれ独立に、水素原子、アルキル基又はカルボキシル基を表し、Lは単結合または2価の連結基を表す。R2又はR3とLは、互いに連結して環を形成してもよく、その場合はR2及びR3のどちらか一方が2価の連結基を表し、Lは3価の連結基を表す。Arは芳香族基を表す。R4は置換基を表し、nは0以上の整数を表す。R4が複数存在する場合、複数のR4は同一であっても異なっていてもよい。 - 前記樹脂(A)が、酸分解性基を有する繰り返し単位を含む、請求項1に記載のパターン形成方法。
- 前記一般式(1)中のR4の少なくとも一つがヒドロキシル基である、請求項1又は2に記載のパターン形成方法。
- 前記R4が、ヒドロキシル基、ヒドロキシアルキル基、カルボキシル基、スルホン酸基、アルキル基、アルコキシ基、アシル基、下記一般式(N1)で表される基、下記一般式(N2)で表される基、下記一般式(S1)で表される基、又は下記一般式(S2)で表される基を表す、請求項1~7のいずれか1項に記載のパターン形成方法。
一般式(N1)中、RN1及びRN2は各々独立に、水素原子又は置換基を表す。*はベンゼン環に結合する結合手を表す。
一般式(N2)中、RN3は置換基を表し、RN4は水素原子又は置換基を表す。*はベンゼン環に結合する結合手を表す。
一般式(S1)中、RS1は置換基を表す。*はベンゼン環に結合する結合手を表す。
一般式(S2)中、RS4は置換基を表し、RS5は水素原子又は置換基を表す。*はベンゼン環に結合する結合手を表す。 - 前記n2が1又は2である、請求項4又は5に記載のパターン形成方法。
- 前記n3が0~2の整数である、請求項6又は7に記載のパターン形成方法。
- 前記化合物(B)がスルホニウム塩である、請求項1~11のいずれか1項に記載のパターン形成方法。
- 前記化合物(B)は、発生する酸の体積が130Å3以上2000Å3以下である、請求項12に記載のパターン形成方法。
- 前記樹脂(A)が、ラクトン基を有する繰り返し単位をさらに含む、請求項1~13のいずれか1項に記載のパターン形成方法。
- 請求項1~14のいずれか1項に記載のパターン形成方法を含む電子デバイスの製造方法。
- 前記R4が、ヒドロキシル基、ヒドロキアルキル基、カルボキシル基、スルホン酸基、アルキル基、アルコキシ基、アシル基、下記一般式(N1)で表される基、下記一般式(N2)で表される基、下記一般式(S1)で表される基、又は下記一般式(S2)で表される基を表す、請求項16又は17に記載のレジスト組成物。
一般式(N1)中、RN1及びRN2は各々独立に、水素原子又は置換基を表す。*はベンゼン環に結合する結合手を表す。
一般式(N2)中、RN3は置換基を表し、RN4は水素原子又は置換基を表す。*はベンゼン環に結合する結合手を表す。
一般式(S1)中、RS1は置換基を表す。*はベンゼン環に結合する結合手を表す。
一般式(S2)中、RS4は置換基を表し、RS5は水素原子又は置換基を表す。*はベンゼン環に結合する結合手を表す。
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WO2018043255A1 (ja) * | 2016-08-31 | 2018-03-08 | 富士フイルム株式会社 | 感活性光線性又は感放射線性樹脂組成物、パターン形成方法及び電子デバイスの製造方法 |
WO2019131351A1 (ja) * | 2017-12-27 | 2019-07-04 | 富士フイルム株式会社 | レジスト組成物、レジスト膜、パターン形成方法、及び電子デバイスの製造方法 |
JP2019147857A (ja) * | 2018-02-26 | 2019-09-05 | 国立大学法人 東京大学 | ガロール基様側鎖を有する共重合体を含む接着剤組成物 |
WO2020066342A1 (ja) * | 2018-09-28 | 2020-04-02 | 富士フイルム株式会社 | 感活性光線性又は感放射線性樹脂組成物、レジスト膜、パターン形成方法、電子デバイスの製造方法 |
CN111902775A (zh) * | 2018-04-19 | 2020-11-06 | 富士胶片株式会社 | 图案的制造方法、光学滤波器的制造方法、固体摄像元件的制造方法、图像显示装置的制造方法、光固化性组合物及膜 |
WO2021171852A1 (ja) * | 2020-02-27 | 2021-09-02 | Jsr株式会社 | 感放射線性樹脂組成物、レジストパターン形成方法及び重合体 |
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TW201708271A (zh) | 2017-03-01 |
KR102104807B1 (ko) | 2020-04-27 |
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KR20180011193A (ko) | 2018-01-31 |
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TWI720995B (zh) | 2021-03-11 |
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