WO2012023349A1 - Pattern-forming method and radiation-sensitive resin composition - Google Patents
Pattern-forming method and radiation-sensitive resin composition Download PDFInfo
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- WO2012023349A1 WO2012023349A1 PCT/JP2011/065120 JP2011065120W WO2012023349A1 WO 2012023349 A1 WO2012023349 A1 WO 2012023349A1 JP 2011065120 W JP2011065120 W JP 2011065120W WO 2012023349 A1 WO2012023349 A1 WO 2012023349A1
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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
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
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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
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
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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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
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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
- G03F7/2041—Exposure; Apparatus therefor in the presence of a fluid, e.g. immersion; using fluid cooling means
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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
- G03F7/325—Non-aqueous compositions
Definitions
- the present invention relates to a pattern forming method and a radiation sensitive resin composition.
- a fine resist pattern having a line width of about 90 nm can be formed by using, for example, an ArF excimer laser, but further fine pattern formation will be required in the future.
- immersion exposure it is said that even when a light source having the same exposure wavelength is used, the same high resolution as that when a light source having a shorter wavelength is used can be achieved. Therefore, immersion exposure is attracting attention as a technique for achieving high resolution while reducing an increase in cost in the manufacture of semiconductor elements that require a large capital investment.
- the resist film changes quality due to elution of substances contained in the resist into the immersion medium, etc., and its performance deteriorates, or the refractive index of the immersion medium changes locally due to the eluted substance.
- the lithographic properties are adversely affected due to contamination of the lens surface by the eluted substance (see WO 04/068242 pamphlet).
- it is necessary to change the resist composition and such a change usually tends to deteriorate the lithography characteristics.
- double exposure technology and double patterning technology are known as technologies for enhancing the resolution by using the characteristics of chemically amplified resist materials, but the technology for increasing the resolution without increasing the number of processes using existing equipment.
- a technique using an organic solvent having a polarity lower than that of an alkaline aqueous solution as a developing solution is disclosed (see JP-A-2000-199953). It is difficult to form a fine pattern due to poor optical contrast when forming a trench pattern or a hole pattern using an alkaline aqueous solution as a developer, but when an organic solvent is used, This is because a fine pattern can be formed because the optical contrast can be increased.
- the present invention has been made based on the above circumstances, and an object thereof is to provide a method for forming a trench pattern or a hole pattern excellent in lithography characteristics, and a radiation-sensitive resin composition.
- the invention made to solve the above problems is (1) a resist film forming step of applying a radiation sensitive resin composition on a substrate; (2) An exposure step of irradiating the resist film with radiation through a photomask, and (3) a trench pattern or hole pattern forming method including a development step of developing the exposed resist film,
- the radiation sensitive resin composition is [A] a polymer in which the content of the structural unit having an acid dissociable group is 10 mol% or less (hereinafter, also referred to as “[A] polymer”), [B] a polymer in which the content of the structural unit having an acid dissociable group exceeds 10 mol% (hereinafter, also referred to as “[B] polymer”), and [C] a radiation-sensitive acid generator, (3) A method for forming a trench pattern or a hole pattern, wherein the developer in the developing step contains 80% by mass or more of an organic solvent.
- the polymer has 10 mol% or less of a structural unit having an acid dissociable group, and even if all the acid dissociable groups are dissociated, the solubility of the [A] polymer in the developer is not impaired. Therefore, the occurrence of defects such as residues and bridges can be suppressed.
- the structural unit having an acid dissociable group refers to a structural unit in which a hydrogen atom of a polar group such as a carboxy group is substituted with an acid dissociable group.
- the [B] polymer has a structural unit having an acid dissociable group in excess of 10 mol%, and this acid dissociable group is dissociated by the action of an acid generated from the [C] radiation sensitive acid generator. To do.
- a developer containing an organic solvent having a polarity lower than that of an alkaline aqueous solution used for forming a positive chemically amplified resist as a developer in the development step (dissolves an unexposed portion of the resist film, A developer capable of forming a negative image is used, and this organic solvent has excellent affinity with the resist film surface, and as a result, developability can be improved. Therefore, a combination of such a specific composition and a characteristic pattern forming method enables pattern formation excellent in lithography properties such as sensitivity, cross-sectional shape, hole pattern circularity, and resolution.
- the fluorine content of the polymer is preferably higher than that of the [B] polymer.
- the fluorine content of the polymer is higher than that of the [B] polymer, the [A] polymer tends to be unevenly distributed near the resist film surface, and the acid generator or [D It is possible to suppress the acid diffusion control agent and the like from being eluted into the immersion medium. Further, the advancing contact angle between the resist film and the immersion medium can be controlled within a desired range, and the occurrence of bubble defects can be suppressed. Furthermore, the receding contact angle between the resist film and the immersion medium is increased, and high-speed scanning exposure is possible without leaving water droplets.
- the organic solvent contained in the developer is preferably at least one organic solvent selected from the group consisting of ether solvents, ketone solvents and ester solvents.
- an appropriate combination with a predetermined resist composition can be realized, and a pattern with more excellent lithography characteristics can be obtained.
- the polymer comprises at least one structural unit selected from the group consisting of the structural unit (I) represented by the following formula (1) and the structural unit (II) represented by the following formula (2). It is preferable to have.
- R 1 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
- R 2 is a linear or branched alkyl group having 1 to 6 carbon atoms or 4 carbon atoms. To 20 monovalent alicyclic hydrocarbon groups, provided that at least a part of the hydrogen atoms of the alkyl group and alicyclic hydrocarbon group are substituted with fluorine atoms.
- R 3 is a hydrogen atom, a methyl group or a trifluoromethyl group.
- R 4 is an (m + 1) -valent linking group.
- X is a divalent linking group having a fluorine atom.
- R 5 is a hydrogen atom or a monovalent organic group, m is an integer of 1 to 3, provided that when there are a plurality of m, the plurality of X and R 5 are the same as each other. May be different.
- the polymer has the above-mentioned specific structural unit, it has a fluorinated group in the structure, thereby improving the hydrophobicity of the resist film and being excellent in suppression of substance elution during immersion exposure.
- the receding contact angle between the resist film and the immersion liquid can be sufficiently increased, and there are effects such as no water droplets remaining when scanning exposure is performed at high speed, it is highly useful for immersion exposure.
- the acid dissociable group of the polymer preferably has a chain hydrocarbon group or a monocyclic or polycyclic alicyclic hydrocarbon group. [B] Since the acid-dissociable group of the polymer has the above specific group, the resist film can be made highly transparent with respect to an ArF excimer laser or the like, and a pattern with higher resolution can be formed.
- the radiation sensitive resin composition of the present invention (1) a resist film forming step of applying a radiation sensitive resin composition on a substrate; (2) An exposure step of irradiating the resist film with radiation through a photomask, and (3) a trench pattern or hole pattern forming method including a development step of developing the exposed resist film,
- the developer in the step (3) contains 80% by mass or more of an organic solvent,
- the radiation sensitive resin composition is [A] a polymer in which the content of the structural unit having an acid dissociable group is 10 mol% or less, [B] A polymer in which the content of the structural unit having an acid dissociable group exceeds 10 mol%, and [C] a radiation-sensitive acid generator.
- the present invention provides a method for forming a trench pattern or a hole pattern that is suitable for immersion exposure and has excellent lithography properties such as sensitivity, cross-sectional shape, circularity, and resolution, and a radiation-sensitive resin composition. Can do.
- the pattern forming method of the present invention comprises: (1) a resist film forming step of applying a radiation sensitive resin composition on a substrate; (2) An exposure step of irradiating the resist film with radiation through a photomask, and (3) a development step of developing the exposed resist film.
- a resist film forming step of applying a radiation sensitive resin composition on a substrate comprises: (1) a resist film forming step of applying a radiation sensitive resin composition on a substrate; (2) An exposure step of irradiating the resist film with radiation through a photomask, and (3) a development step of developing the exposed resist film.
- This step is a step of applying a radiation-sensitive resin composition of the present invention on a substrate to form a resist film.
- a substrate for example, a conventionally known substrate such as a silicon wafer or a wafer coated with aluminum can be used.
- An organic or inorganic antireflection film may be formed on the substrate.
- the thickness of the resist film to be formed is usually 0.01 ⁇ m to 1 ⁇ m, preferably 0.01 ⁇ m to 0.5 ⁇ m.
- the solvent in the coating film may be volatilized by pre-baking (PB) as necessary.
- PB pre-baking
- the heating conditions for PB are appropriately selected depending on the composition of the radiation sensitive resin composition, but are usually about 30 ° C. to 200 ° C., preferably 50 ° C. to 150 ° C.
- a protective film disclosed in, for example, Japanese Patent Laid-Open No. 5-188598 can be provided on the resist layer.
- an immersion protective film disclosed in, for example, Japanese Patent Application Laid-Open No. 2005-352384 can be provided on the resist layer.
- Step (2) This step is a step of irradiating the resist film formed in step (1) with radiation through a photomask. Further, exposure is performed by reducing and projecting through an immersion liquid as necessary.
- an isotrench pattern can be formed by performing reduced projection exposure on a desired region through an isoline pattern mask. Moreover, you may perform exposure twice or more with a desired pattern and a mask pattern. When performing exposure twice or more, it is preferable to perform exposure continuously. In the case of performing multiple exposures, for example, a first reduced projection exposure is performed on a desired area via a line and space pattern mask, and then the second is so that the line intersects the exposed portion where the first exposure has been performed. Reduced projection exposure is performed.
- the first exposure part and the second exposure part are preferably orthogonal. By being orthogonal, it becomes easy to form a circular contact hole pattern in the unexposed portion surrounded by the exposed portion.
- the immersion liquid used for exposure include water and a fluorine-based inert liquid.
- the immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient that is as small as possible so as to minimize distortion of the optical image projected onto the film.
- excimer laser light wavelength 193 nm
- an additive that decreases the surface tension of water and increases the surface activity may be added in a small proportion. This additive is preferably one that does not dissolve the resist layer on the wafer and can ignore the influence on the optical coating on the lower surface of the lens.
- the water used is preferably distilled water.
- the radiation used for exposure is appropriately selected according to the type of [C] radiation sensitive acid generator, and examples thereof include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams. Among these, far ultraviolet rays represented by ArF excimer laser light and KrF excimer laser light (wavelength 248 nm) are preferable, and ArF excimer laser light is more preferable.
- the exposure conditions such as the exposure amount are appropriately selected according to the blending composition of the radiation-sensitive resin composition, the type of additive, and the like.
- the exposure process may be performed a plurality of times, and the plurality of exposures may be performed using the same light source or different light sources, but ArF excimer laser light is used for the first exposure. Is preferably used.
- PEB post-exposure baking
- Step (3) This step is a step of developing the exposed resist film.
- the developer used for development is not particularly limited as long as it selectively dissolves and removes the low-exposed portion and the unexposed portion, and contains 80% by mass or more of an organic solvent.
- the organic solvent include at least one selected from the group consisting of alcohol solvents, ether solvents, ketone organic solvents, amide solvents, ester organic solvents, and hydrocarbon solvents.
- alcohol solvent examples include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol , Sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec -und
- ether solvents include diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, methoxybenzene, and the like.
- ketone solvent examples include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n- And ketone solvents such as hexyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, etc. .
- amide solvents include N, N′-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, Examples thereof include N-methylpropionamide and N-methylpyrrolidone.
- ester solvent examples include diethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, ⁇ -butyrolactone, ⁇ -valerolactone, n-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl acetate, sec -Butyl, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, acetoacetic acid Methyl, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate,
- hydrocarbon solvents examples include n-pentane, iso-pentane, n-hexane, iso-hexane, n-heptane, iso-heptane, 2,2,4-trimethylpentane, n-octane, iso-octane, cyclohexane , Aliphatic hydrocarbon solvents such as methylcyclohexane; Fragrances such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, iso-propylbenzene, diethylbenzene, iso-butylbenzene, triethylbenzene, di-iso-propylbenzene, n-amylnaphthalene Group hydrocarbon solvents and the like.
- the organic solvent is preferably at least one organic solvent selected from the group consisting of ether solvents, ketone solvents and ester solvents, and includes n-butyl acetate, isopropyl acetate, amyl acetate, Methyl ethyl ketone, methyl-n-butyl ketone, methyl-n-pentyl ketone, and anisole are more preferable.
- ether solvents preferably at least one organic solvent selected from the group consisting of ether solvents, ketone solvents and ester solvents, and includes n-butyl acetate, isopropyl acetate, amyl acetate, Methyl ethyl ketone, methyl-n-butyl ketone, methyl-n-pentyl ketone, and anisole are more preferable.
- these organic solvents may be used independently and may use 2 or more types together.
- a surfactant can be added to the developer as necessary.
- the surfactant include ionic and nonionic fluorine-based surfactants and silicon-based surfactants.
- 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 applying the developer while scanning the developer coating nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc.
- a rinsing liquid it is preferable to wash the resist film with a rinsing liquid after the development in the step (3).
- an organic solvent can be used also as the rinse liquid in the rinse process, and the generated scum can be efficiently washed.
- the rinsing liquid hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and the like are preferable. Of these, alcohol solvents and ester solvents are preferable, and monovalent alcohol solvents having 6 to 8 carbon atoms are more preferable.
- Examples of monohydric alcohols having 6 to 8 carbon atoms include linear, branched or cyclic monohydric alcohols such as 1-hexanol, 1-heptanol, 1-octanol, and 4-methyl-2-pentanol.
- 1-hexanol, 2-hexanol, 2-heptanol, and 4-methyl-2-pentanol are preferable.
- Each component of the rinse liquid may be used alone or in combination of two or more.
- the water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.
- the surfactant mentioned later can be added to the rinse liquid.
- a cleaning method for example, a method of continuously applying a rinse liquid onto a substrate rotating at a constant speed (rotary coating method), a method of immersing the substrate in a tank filled with the rinse liquid for a predetermined time (dip method) ), A method (spray method) of spraying a rinse liquid on the substrate surface, and the like.
- the radiation sensitive resin composition used in the present invention contains a [A] polymer, a [B] polymer, and a [C] radiation sensitive acid generator.
- [A] The polymer has 10 mol% or less of a structural unit having an acid dissociable group, and even if all the acid dissociable groups are dissociated, the solubility of the [A] polymer in the developer is not impaired. Therefore, the occurrence of defects such as residues and bridges can be suppressed.
- the structural unit having an acid dissociable group refers to a structural unit in which a hydrogen atom of a polar group such as a carboxy group is substituted with an acid dissociable group.
- the [B] polymer has a structural unit having an acid dissociable group in excess of 10 mol%, and this acid dissociable group is dissociated by the action of an acid generated from the [C] radiation sensitive acid generator.
- the polarity increases, the poor solubility of the [B] polymer in the exposed area increases, and the dissolution of the polymer in the resist film in the unexposed area in the developing solution is promoted.
- the said radiation sensitive resin composition may contain arbitrary components, unless the effect of this invention is impaired. Hereinafter, each component will be described in detail.
- a polymer is a polymer whose content rate of the structural unit which has an acid dissociable group is 10 mol% or less. Since the content ratio of the structural unit having an acid-dissociable group is 10 mol% or less, even if all the acid-dissociable groups are dissociated, the solubility in the developer is not impaired. Can be suppressed.
- Examples of the structural unit having an acid dissociable group include a structural unit (III) represented by the formula (5) described later.
- the fluorine content of the [A] polymer is preferably higher than that of the [B] polymer.
- the fluorine content of the polymer is higher than that of the [B] polymer, the [A] polymer tends to be unevenly distributed near the resist film surface, and the acid generator or [D It is possible to suppress the acid diffusion control agent and the like from being eluted into the immersion medium. Further, the advancing contact angle between the resist film and the immersion medium can be controlled within a desired range, and the occurrence of bubble defects can be suppressed. Furthermore, the receding contact angle between the resist film and the immersion medium is increased, and high-speed scanning exposure is possible without leaving water droplets.
- Examples of the [A] polymer containing a fluorine atom include (i) a structure in which a fluorinated alkyl group is bonded to the main chain, (ii) a structure in which a fluorinated alkyl group is bonded to a side chain, (iii) Examples include a structure in which a fluorinated alkyl group is bonded to a chain and a side chain.
- Examples of the monomer that gives the polymer having the structure (i) include an ⁇ -trifluoromethyl acrylate compound, a ⁇ -trifluoromethyl acrylate compound, an ⁇ , ⁇ -trifluoromethyl acrylate compound, and one or more types of vinyl moieties. And the like in which hydrogen is substituted with a fluorinated alkyl group such as a trifluoromethyl group.
- Examples of the monomer that gives a polymer having the structure (ii) include those in which the side chain of an alicyclic olefin compound such as norbornene is a fluorinated alkyl group, a fluorinated alkyl ester compound of acrylic acid or methacrylic acid, One or more olefin side chains (sites not containing a double bond) are fluorinated alkyl groups or derivatives thereof.
- Examples of the monomer that gives a polymer having the structure (iii) include fluorinated side chains such as ⁇ -trifluoromethylacrylic acid, ⁇ -trifluoromethylacrylic acid, ⁇ , ⁇ -trifluoromethylacrylic acid, etc.
- An ester compound of an alkyl group or a derivative thereof a compound in which the side chain of a compound in which hydrogen at one or more vinyl sites is substituted with a fluorinated alkyl group such as a trifluoromethyl group, or the like is substituted with a fluorinated alkyl group or a derivative thereof;
- Examples include those in which hydrogen bonded to the double bond of more than one kind of alicyclic olefin compound is substituted with a fluorinated alkyl group such as a trifluoromethyl group and the side chain is a fluorinated alkyl group or a derivative thereof. It is done.
- an alicyclic olefin compound shows the compound in which a part of ring is a double bond.
- the polymer comprises at least one structural unit selected from the group consisting of the structural unit (I) represented by the formula (1) and the structural unit (II) represented by the formula (2). It is preferable to have.
- the polymer may have “another structural unit” other than the structural unit (I) and the structural unit (II).
- a polymer may have 2 or more types of each structural unit. Hereinafter, each structural unit will be described in detail.
- the structural unit (I) is a structural unit represented by the above formula (1).
- R ⁇ 1 > is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.
- R 2 is a linear or branched alkyl group having 1 to 6 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms. However, at least a part of the hydrogen atoms of the alkyl group and the alicyclic hydrocarbon group are substituted with fluorine atoms.
- Examples of the linear or branched alkyl group having 1 to 6 carbon atoms represented by R 2 include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group.
- Examples of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by R 2 include a cyclopentyl group, a cyclopentylpropyl group, a cyclohexyl group, a cyclohexylmethyl group, a cycloheptyl group, a cyclooctyl group, and a cyclooctyl group.
- a methyl group etc. are mentioned.
- structural unit (I) structural units represented by the following formulas (1-1) and (1-2) are preferable.
- R 1 has the same meaning as in the above formula (1).
- Examples of the monomer that gives the structural unit (I) include trifluoromethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro n-propyl ( (Meth) acrylate, perfluoro i-propyl (meth) acrylate, perfluoro n-butyl (meth) acrylate, perfluoro i-butyl (meth) acrylate, perfluoro t-butyl (meth) acrylate, perfluorocyclohexyl (meth) Acrylate, 2- (1,1,1,3,3,3-hexafluoro) propyl (meth) acrylate, 1- (2,2,3,3,4,4,5,5-octafluoro) pentyl ( (Meth) acrylate, 1- (2,2,3,3,4,4,5,5-octafluoro) hex (Met
- the content of the structural unit (I) in the polymer is preferably 30 mol% to 100 mol% with respect to the total structural units.
- the structural unit (II) is a structural unit represented by the above formula (2).
- R 3 is a hydrogen atom, a methyl group or a trifluoromethyl group.
- R 4 is a (m + 1) -valent linking group.
- X is a divalent linking group having a fluorine atom.
- R 5 is a hydrogen atom or a monovalent organic group.
- m is an integer of 1 to 3. However, when m is plural, the plural X and R 5 may be the same or different.
- Examples of the (m + 1) -valent linking group represented by R 4 include a linear or branched hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 30 carbon atoms, and a carbon number. 6-30 aromatic hydrocarbon groups, or these groups combined with one or more groups selected from the group consisting of oxygen atom, sulfur atom, ether group, ester group, carbonyl group, imino group and amide group Groups and the like.
- the (m + 1) -valent linking group may have a substituent.
- linear or branched hydrocarbon group having 1 to 30 carbon atoms examples include hydrocarbon groups such as methane, ethane, propane, butane, pentane, hexane, heptane, decane, icosane and triacontane (m + 1). And a group excluding individual hydrogen atoms.
- Examples of the alicyclic hydrocarbon group having 3 to 30 carbon atoms include monocyclic saturated hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, methylcyclohexane, and ethylcyclohexane; Monocyclic unsaturated hydrocarbons such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclopentadiene, cyclohexadiene, cyclooctadiene, cyclodecadiene; Bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 2,6 ] decane, tricyclo [3.3.1.1 3,7 ] decane, Tetracycl
- aromatic hydrocarbon group having 6 to 30 carbon atoms examples include (m + 1) from aromatic hydrocarbon groups such as benzene, naphthalene, phenanthrene, anthracene, tetracene, pentacene, pyrene, picene, toluene, xylene, ethylbenzene, mesitylene, cumene and the like. ) Groups from which a single hydrogen atom is removed.
- Examples of the substituent that the (m + 1) -valent linking group may have include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, 1- Examples thereof include alkyl groups such as methylpropyl group, t-butyl group and cyclohexyl group, hydroxy group, cyano group, hydroxyalkyl group having 1 to 10 carbon atoms, carboxy group, carbonyl group and the like.
- Examples of the divalent linking group having a fluorine atom represented by X include a C 1-20 divalent linear hydrocarbon group having a fluorine atom.
- Examples of the divalent linear hydrocarbon group having 1 to 20 carbon atoms having a fluorine atom include groups represented by the following formulas (X-1) to (X-6).
- X is preferably a group represented by the above formula (X-1) or (X-2).
- Examples of the monovalent organic group represented by R 5 include linear or branched hydrocarbon groups having 1 to 30 carbon atoms, alicyclic hydrocarbon groups having 3 to 30 carbon atoms, and 6 to 6 carbon atoms. 30 aromatic hydrocarbon groups, or a combination of these groups and one or more groups selected from the group consisting of oxygen, sulfur, ether, ester, carbonyl, imino and amide groups, etc. Is mentioned.
- the group represented by R 5 is preferably a hydrogen atom from the viewpoint of improving the solubility of the [A] polymer in the developer.
- Examples of the structural unit (II) include structural units represented by the following formulas (2-1) and (2-2).
- R 4 is a divalent linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms.
- R 3 , X and R 5 are as defined in the above formula (2).
- R 3 , X, R 5 and m are as defined in the above formula (2).
- m is plural, the plural X and R 5 may be the same or different.
- the structural unit (II) is preferably a structural unit represented by the following formula.
- R ⁇ 3 > is synonymous with the said Formula (2).
- Examples of the monomer that gives structural unit (II) include (meth) acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-3-propyl) ester, (meth) acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-butyl) ester, (meth) acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy -5-pentyl) ester, (meth) acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-pentyl) ester, (meth) acrylic acid 2- ⁇ [5- ( 1 ′, 1 ′, 1′-trifluoro-2′-trifluoromethyl-2′-hydroxy) propyl] bicyclo [2.2.1] heptyl ⁇ ester and the like.
- the content ratio of the structural unit (II) in the polymer is preferably 30 mol% to 100 mol% with respect to the total structural units.
- the polymer is further divided into “other structural units” as a structural unit having a lactone structure to control the dissolution rate in the developer, a structural unit having a cyclic carbonate structure, and an alicyclic ring to increase etching resistance. You may have a structural unit etc. which have a formula structure.
- Examples of the structural unit having a lactone structure and the structural unit having a cyclic carbonate structure include a structural unit represented by the following formula.
- the group having a lactone structure refers to a cyclic group containing one ring (lactone ring) containing an —O—C (O) — structure.
- the lactone ring is counted as the first ring, and when it is only the lactone ring, it is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of the structure.
- R L1 is a hydrogen atom, a methyl group or a trifluoromethyl group.
- Examples of the monomer that gives a structural unit having a lactone structure include a compound represented by the following formula (L-1).
- monomers described in International Publication No. 2007/116664 pamphlet are preferable.
- Examples of the structural unit having an alicyclic structure include a structural unit represented by the following formula (4).
- R 6 is a hydrogen atom, a methyl group or a trifluoromethyl group.
- X 2 is an alicyclic hydrocarbon group having 4 to 20 carbon atoms.
- Examples of the alicyclic hydrocarbon group having 4 to 20 carbon atoms include cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, and tricyclo [5.2.1]. .0 2,6] decane, tetracyclo [6.2.1.1 3,6. 0 2,7 ] dodecane, tricyclo [3.3.1.1 3,7 ] decane and the like. These alicyclic hydrocarbon groups having 4 to 20 carbon atoms may have a substituent.
- substituents include those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group and t-butyl group.
- substituents include those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group and t-butyl group.
- substituent include those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group and t-butyl group.
- substituent include those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group,
- Examples of the monomer that gives a structural unit containing an alicyclic compound include (meth) acrylic acid-bicyclo [2.2.1] hept-2-yl ester and (meth) acrylic acid-bicyclo [2.2. 2] Oct-2-yl ester, (meth) acrylic acid-tricyclo [5.2.1.0 2,6 ] dec-7-yl ester, (meth) acrylic acid-tricyclo [3.3.1.1] 3,7 ] dec-1-yl ester, (meth) acrylic acid-tricyclo [3.3.1.1 3,7 ] dec-2-yl ester, and the like.
- the [A] polymer does not have a structural unit having an aromatic group.
- an ArF light source when used, it may cause a decrease in sensitivity.
- the polymer can be produced, for example, by polymerizing a monomer corresponding to each predetermined structural unit in a suitable solvent using a radical polymerization initiator.
- Examples of the solvent used for the polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane; Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; Halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide, chlorobenzene; Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate and methyl propionate; Ketones such as acetone, 2-butanone, 4-methyl-2-p
- the reaction temperature in the above polymerization is usually preferably 40 ° C to 150 ° C and 50 ° C to 120 ° C.
- the reaction time is usually preferably 1 hour to 48 hours and 1 hour to 24 hours.
- the weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer is preferably 1,000 to 50,000, more preferably 1,000 to 30,000, and 1,000. ⁇ 10,000 is particularly preferred.
- Mw weight average molecular weight
- GPC gel permeation chromatography
- the ratio (Mw / Mn) of the polymer Mw to the polystyrene-equivalent number average molecular weight (Mn) by GPC method is usually 1 to 3, preferably 1 to 2.
- Mw and Mn in this specification were measured on the following conditions using the GPC column (Tosoh Corp., 2 G2000HXL, 1 G3000HXL, 1 G4000HXL). Column temperature: 40 ° C Elution solvent: Tetrahydrofuran (Wako Pure Chemical Industries) Flow rate: 1.0 mL / min Sample concentration: 1.0 mass% Sample injection volume: 100 ⁇ L Detector: Differential refractometer Standard material: Monodisperse polystyrene
- the polymer is a polymer containing more than 10 mol% of a structural unit having an acid dissociable group.
- the [B] polymer is a polymer whose polarity is increased by the action of an acid and hardly or insoluble in a developer containing an organic solvent.
- R 7 is a hydrogen atom, a methyl group or a trifluoromethyl group.
- R p is an acid dissociable group.
- the acid dissociable group represented by R p is preferably a group represented by the following formula (6).
- R p1 is an alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms.
- R p2 and R p3 are each independently an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 4 to 20 carbon atoms.
- R p2 and R p3 may be bonded to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms together with the carbon atoms to which R p2 and R p3 are bonded.
- some or all of the hydrogen atoms of these groups may be substituted with a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.
- Examples of the alkyl group having 1 to 4 carbon atoms represented by R p1 , R p2 and R p3 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and 2-methylpropyl. Group, 1-methylpropyl group, t-butyl group and the like.
- Examples of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by R p1 , R p2 and R p3 include polycyclic alicyclic rings having a bridged skeleton such as an adamantane skeleton and a norbornane skeleton. A formula group; And monocyclic alicyclic groups having a cycloalkane skeleton such as cyclopentane and cyclohexane.
- R p1 is an alkyl group having 1 to 4 carbon atoms
- R p2 and R p3 are bonded to each other, and together with the carbon atom to which each is bonded, an adamantane skeleton or It is preferable to form a divalent group having a cycloalkane skeleton.
- Examples of the structural unit (III) include a structural unit represented by the following formula.
- R ⁇ 7 > is synonymous with the said Formula (5).
- the content of the structural unit (III) in the polymer is preferably 20 mol% to 60 mol% with respect to the total structural units.
- the [B] polymer may have 1 type, or 2 or more types of structural units (III).
- the polymer preferably has a structural unit (IV) that does not have a fluorine atom and is derived from an acrylate ester having a lactone structure. [B] Since the polymer has the structural unit (IV), the adhesion of the resist film to the substrate can be improved.
- a structural unit similar to the structural unit having a lactone structure as the “other structural unit” described above and having no fluorine atom can be applied.
- the content ratio of the structural unit (IV) in the polymer is preferably 30 mol% to 60 mol% with respect to the total structural units.
- the polymer may have other structural units different from the structural unit (III) and the structural unit (IV).
- Examples of the other structural unit include a structural unit represented by the following formula containing a polar group.
- R 8 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
- the content of the structural unit (V) in the polymer is preferably 0 mol% to 30 mol%, more preferably 0 mol% to 20 mol%.
- the polymer can be produced, for example, by polymerizing a monomer corresponding to each predetermined structural unit in a suitable solvent using a radical polymerization initiator.
- Examples of the solvent used for the polymerization include the same solvents as mentioned in the method for synthesizing [A] polymer.
- the reaction temperature in the polymerization is usually preferably 40 ° C. to 150 ° C. and 50 ° C. to 120 ° C.
- the reaction time is usually preferably 1 hour to 48 hours and 1 hour to 24 hours.
- the Mw of the polymer by GPC method is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and particularly preferably 1,000 to 30,000.
- the polymer has sufficient solubility in a resist solvent to be used as a resist, and the dry etching resistance and resist pattern cross-sectional shape are improved.
- the ratio of Mw to Mn (Mw / Mn) of the polymer is usually 1 to 3, and preferably 1 to 2.
- the radiation sensitive acid generator generates an acid upon exposure, and the acid dissociates an acid dissociable group present in the [B] polymer to generate an acid.
- the containing form of the [C] radiation sensitive acid generator in the radiation sensitive resin composition even in the form of a compound as described later (hereinafter also referred to as “[C] radiation sensitive acid generator” as appropriate) [B]
- the form may be contained as a structural unit of a polymer or other polymer, or may be a form in which both are combined.
- Examples of the radiation sensitive acid generator include onium salt compounds, sulfonimide compounds, halogen-containing compounds, diazoketone compounds and the like. Of these [C] radiation sensitive acid generators, onium salt compounds are preferred.
- onium salt compounds examples include sulfonium salts (including tetrahydrothiophenium salts), iodonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like.
- sulfonium salt examples include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo [2.2.1] hept- 2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium camphorsulfonate, 4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexyl Phenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-cyclohexylphen
- triphenylsulfonium trifluoromethanesulfonate triphenylsulfonium nonafluoro-n-butanesulfonate and triphenylphosphonium 1,1,2,2-tetrafluoro-6- (1-adamantane carbonyloxy) -hexane-1 Sulfonate is preferred.
- tetrahydrothiophenium salt examples include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nona.
- iodonium salt examples include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl- 1,1,2,2-tetrafluoroethanesulfonate, diphenyliodonium camphorsulfonate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium nonafluoro-n-butanesulfonate, Bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium 2-bic
- hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate bis (4-t- butylphenyl) iodonium camphorsulfonate, and the like.
- bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate is preferred.
- [C] radiation sensitive acid generators may be used alone or in combination of two or more.
- the amount used when the radiation-sensitive acid generator is an acid generator is usually 0 with respect to 100 parts by mass of the polymer [B] from the viewpoint of ensuring sensitivity and developability as a resist. .1 to 20 parts by mass, preferably 0.5 to 15 parts by mass.
- the usage-amount of a radiation sensitive acid generator is less than 0.1 mass part, there exists a tendency for a sensitivity and developability to fall.
- the amount of the [C] radiation sensitive acid generator used exceeds 15 parts by mass, the transparency to radiation tends to decrease, and it becomes difficult to obtain a desired resist pattern.
- the radiation sensitive resin composition includes [D] acid diffusion as an optional component within a range not impairing the effects of the present invention.
- a control body, [E] solvent, surfactant, alicyclic skeleton containing compound, sensitizer and the like can be contained.
- the acid diffusion controller controls the diffusion phenomenon in the resist coating film of the acid generated from the [C] radiation-sensitive acid generator by exposure, and has the effect of suppressing undesirable chemical reactions in non-exposed areas,
- the storage stability of the resulting radiation-sensitive resin composition is further improved, the resolution as a resist is further improved, and it is possible to suppress changes in the line width of the resist pattern due to fluctuations in the holding time from exposure to development processing. And a composition having excellent process stability can be obtained.
- the inclusion form of the acid diffusion controller in the radiation-sensitive resin composition may be a form of a free compound, a form contained as a structural unit of a polymer, or a combination of both.
- Examples of the acid diffusion controller include amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, and the like.
- Examples of the amine compound include mono (cyclo) alkylamines; di (cyclo) alkylamines; tri (cyclo) alkylamines; substituted alkylanilines or derivatives thereof; ethylenediamine, N, N, N ′, N′-tetra Methylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylamine, 2,2-bis (4 -Aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-amino) Phenyl) -2- (4-hydroxyphenyl) propane, 1 4-bis (1- (4-a
- amide group-containing compounds include Nt-butoxycarbonyl group-containing amino compounds, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, Examples thereof include benzamide, pyrrolidone, N-methylpyrrolidone, N-acetyl-1-adamantylamine, and isocyanuric acid tris (2-hydroxyethyl).
- urea compounds include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butylthiourea, etc. Is mentioned.
- nitrogen-containing heterocyclic compound examples include imidazoles; pyridines; piperazines; pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, piperidine ethanol, 3-piperidino-1,2-propanediol, morpholine, 4- Methylmorpholine, 1- (4-morpholinyl) ethanol, 4-acetylmorpholine, 3- (N-morpholino) -1,2-propanediol, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2 ] Octane etc. are mentioned.
- a photodegradable base that is exposed to light and generates a weak acid can be used as the [D] acid diffusion control agent.
- the photodegradable base generates an acid in the exposed portion to increase the insolubility of the [B] polymer in the developer, while the unexposed portion exhibits a high acid capturing function by an anion and functions as a quencher.
- As an example of the photodegradable base there is an onium salt compound that is decomposed by exposure and loses acid diffusion controllability.
- the onium salt compound include a sulfonium salt compound represented by the following formula (7), an iodonium salt compound represented by the following formula (8), and the like.
- R 18 ⁇ R 22 are each independently a hydrogen atom, an alkyl group, an alkoxy group, hydroxy group, a halogen atom, or -SO 2 -R C.
- R C is an alkyl group, a cycloalkyl group, an alkoxy group or an aryl group.
- Z ⁇ represents OH ⁇ , R 23 —COO ⁇ , R D —SO 2 —N ⁇ —R 23 , R 23 —SO 3 ⁇ , or the following formula (9)
- An anion represented by R 23 is a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an alkaryl group having 7 to 30 carbon atoms. .
- one part or all part of the hydrogen atom which the said alkyl group, cycloalkyl group, aryl group, and alkaryl group have may be substituted.
- R D is a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms. However, some or all of the hydrogen atoms of the alkyl group and cycloalkyl group may be substituted with fluorine atoms. However, when Z ⁇ is R 23 —SO 3 — , the fluorine atom is not bonded to the carbon atom to which SO 3 — is bonded.
- R 24 represents a linear or branched alkyl group having 1 to 12 carbon atoms, in which part or all of the hydrogen atoms may be substituted with fluorine atoms, or 1 to 12 carbon atoms. These are linear or branched alkoxyl groups. u is an integer of 0-2.
- the alkyl group represented by R 23, a methyl group, an ethyl group, a propyl group, i- propyl group, butyl group, i- butyl group, a t- butyl group and the like can be mentioned.
- the aryl group represented by R 23, a phenyl group, a naphthyl group, anthranyl group, and the like.
- alkyl group, cycloalkyl group, aryl group, and alkaryl group have include a hydroxyl group, a halogen atom, an alkoxy group, a lactone group, and an alkylcarbonyl group.
- Examples of the alkyl group represented by RD include a methyl group, an ethyl group, a propyl group, and a butyl group.
- Examples of the cycloalkyl group represented by RD include a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like.
- Examples of the photodegradable base include compounds represented by the following formulas.
- the acid diffusion controller may be used alone or in combination of two or more.
- the content of the acid diffusion controller is preferably less than 15 parts by mass with respect to 100 parts by mass of the [B] polymer. When the content exceeds 15 parts by mass, the sensitivity as a resist tends to decrease.
- the radiation sensitive resin composition usually contains a solvent.
- a solvent will not be specifically limited if said [A] polymer, [B] polymer, [C] radiation sensitive acid generator, and an arbitrary component can be melt
- the solvent include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, and mixed solvents thereof.
- the solvent include the same organic solvents listed in the pattern formation step (3) above. Of these, propylene glycol monomethyl ether acetate and cyclohexanone are preferred. These solvents may be used alone or in combination of two or more.
- Surfactants have the effect of improving coatability, striation, developability, and the like.
- the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol diacrylate.
- nonionic surfactants such as stearate, the following trade names are KP341 (Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no.
- the alicyclic skeleton-containing compound has an effect of improving dry etching resistance, pattern shape, adhesion to the substrate, and the like.
- the sensitizer exhibits an action of increasing the amount of [C] radiation-sensitive acid generator, and has an effect of improving the “apparent sensitivity” of the radiation-sensitive resin composition.
- the radiation-sensitive resin composition can be prepared, for example, by mixing [A] polymer, [B] polymer, [C] radiation-sensitive acid generator, and optional components in a predetermined ratio in an organic solvent. . Moreover, the said radiation sensitive resin composition can be prepared and used in the state melt
- the content of the polymer is preferably 1 part by mass to 15 parts by mass and more preferably 2 parts by mass to 10 parts by mass with respect to 100 parts by mass of the polymer [B].
- the polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After completion of the polymerization, the solution was cooled with water and cooled to 30 ° C. or lower. The reaction solution was transferred to a 1 L separatory funnel, and then the polymerization solution was uniformly diluted with 90 g of n-hexane, and 360 g of methanol was added. Mixed. Next, 20 g of distilled water was added, and the mixture was further stirred and allowed to stand for 30 minutes. Thereafter, the lower layer was recovered to obtain a propylene glycol monomethyl ether solution containing the polymer (A-1).
- Mw of the polymer (A-1) was 5,900, Mw / Mn was 1.58, and the yield was 68%.
- the content ratio of the structural unit (II) given by (M-1) and the structural unit (I) given by (M-4) was 31:69 (mol%).
- the 13 C-NMR analysis was measured using a nuclear magnetic resonance apparatus (JEOL Ltd., JNM-EX270).
- the polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time.
- the polymerization solution was cooled with water, cooled to 30 ° C. or lower, poured into 600 g of methanol, and the precipitated white powder was separated by filtration.
- the filtered white powder was washed twice with 150 g of methanol in the form of a slurry, then filtered again and dried at 50 ° C. for 17 hours to obtain a white powder (B-1) polymer.
- Mw of the polymer (B-1) was 6,900
- Mw / Mn was 1.35
- the yield was 80%.
- the content ratio of the structural unit (III) given by (M-11) and the structural unit (IV) given by (M-16) was 49:51 (mol%).
- the polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time.
- the polymerization solution was cooled with water, cooled to 30 ° C. or lower, poured into 600 g of methanol, and the precipitated white powder was separated by filtration.
- the filtered white powder was washed twice with 150 g of methanol in the form of a slurry, then filtered again and dried at 50 ° C. for 17 hours to obtain a white powder (B-3) polymer.
- Mw of the polymer (B-3) was 7,200, Mw / Mn was 1.41, and the yield was 75%.
- the content ratio of the structural unit (III) given by (M-13), the structural unit given by (M-14), and the structural unit (IV) given by (M-18) was 40: It was 10:50 (mol%).
- [Example 1] [A] 3 parts by mass of (A-1) as a polymer, [B] 100 parts by mass of (B-1) as a polymer, [C] (C-1) as a radiation-sensitive acid generator 8 parts by mass, (D) 4.3 parts by mass as an acid diffusion controller, (E-1) 2,185 parts by mass as an [E] solvent, (E-2) 935 parts by mass, (E-3) A radiation-sensitive resin composition was prepared by mixing 30 parts by mass.
- Example 2 to 13 and Comparative Examples 1 and 2 Each radiation-sensitive resin composition was prepared in the same manner as in Example 1 except that a predetermined amount of each component shown in Table 2 was blended.
- An organic antireflection film forming agent (Nissan Chemical Co., ARC66) was applied to the wafer surface using a spin coater (CLEAN TRACK Lithius Pro i, Tokyo Electron), and then heated at 205 ° C. for 60 seconds to give a film thickness of 105 nm. An organic antireflection film was formed. On the surface of this substrate, each radiation sensitive resin composition was applied by spin coating using a clean track (Tokyo Electron Co., Ltd., ACT12), and soft-baked on a hot plate at 100 ° C. for 60 seconds to obtain a film thickness. A 0.10 ⁇ m resist film was formed.
- the present invention provides a method for forming a trench pattern or a hole pattern that is suitable for immersion exposure and has excellent lithography properties such as sensitivity, cross-sectional shape, circularity, and resolution, and a radiation-sensitive resin composition. Can do.
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Abstract
The present invention is a trench pattern-forming or hole pattern-forming method comprising (1) a step for forming a resist film in which a radiation-sensitive resin composition is applied to a substrate, (2) an exposure step in which radiation is irradiated onto the resist film via a photomask, and (3) a development step in which the exposed resist film is developed, wherein the trench pattern-forming or hole pattern-forming method is characterized in that the radiation-sensitive resin composition comprises: [A] a polymer containing 10 mol% or less of structural units having acid-dissociating groups; [B] a polymer containing more than 10 mol% of structural units having acid-dissociating groups; and [C] a radiation-sensitive acid generator, and the development solution for the development step (3) comprises 80 mass% or more of an organic solvent.
Description
本発明は、パターン形成方法及び感放射線性樹脂組成物に関する。
The present invention relates to a pattern forming method and a radiation sensitive resin composition.
半導体デバイス、液晶デバイス等の各種電子デバイス構造の微細化に伴って、リソグラフィー工程におけるレジストパターンの微細化が要求されている。現在、例えばArFエキシマレーザーを用いて線幅90nm程度の微細なレジストパターンを形成することができるが、今後はさらに微細なパターン形成が要求される。
With the miniaturization of various electronic device structures such as semiconductor devices and liquid crystal devices, miniaturization of resist patterns in the lithography process is required. At present, a fine resist pattern having a line width of about 90 nm can be formed by using, for example, an ArF excimer laser, but further fine pattern formation will be required in the future.
一方、液浸露光によれば同じ露光波長の光源を用いても、より短波長の光源を用いた場合と同様の高解像性を達成できるとされている。そのため液浸露光は、多額な設備投資を必要とする半導体素子の製造において、コストの増大を低減しつつ高解像度を達成する技術として注目されている。
On the other hand, according to the immersion exposure, it is said that even when a light source having the same exposure wavelength is used, the same high resolution as that when a light source having a shorter wavelength is used can be achieved. Therefore, immersion exposure is attracting attention as a technique for achieving high resolution while reducing an increase in cost in the manufacture of semiconductor elements that require a large capital investment.
しかし、液浸露光においてはレジストに含まれる物質の液浸媒体中への溶出等によりレジスト膜が変質してその性能が低下したり、溶出した物質によって液浸媒体の屈折率が局所的に変化したり、溶出した物質がレンズ表面を汚染する等により、リソグラフィー特性に悪影響を与える不都合が考えられる(国際公開第04/068242号パンフレット参照)。かかる不都合に対して、レジスト膜の疎水性を高めることが考えられ、その為にはレジスト組成を変更する必要があり、このような変更は通常リソグラフィー特性を悪化させる傾向がある。また、化学増幅型レジスト材料の特徴を利用し解像力を高める技術としては、二重露光技術や二重パターニング技術が知られているが、既存の装置を用いて工程を増やすことなく解像力を高める技術としては、現像液にアルカリ水溶液よりも極性の低い有機溶媒を用いる技術が開示されている(特開2000-199953号公報参照)。これは、現像液にアルカリ水溶液を用いてトレンチパターンやホールパターンを形成する際には、光学コントラストが乏しいために微細パターンを形成することが困難であるが、有機溶媒を用いた場合には、光学コントラストを高くすることができるために、微細パターンを形成することができることによる。
However, in immersion exposure, the resist film changes quality due to elution of substances contained in the resist into the immersion medium, etc., and its performance deteriorates, or the refractive index of the immersion medium changes locally due to the eluted substance. In addition, there may be a disadvantage that the lithographic properties are adversely affected due to contamination of the lens surface by the eluted substance (see WO 04/068242 pamphlet). For such inconvenience, it is conceivable to increase the hydrophobicity of the resist film. For this purpose, it is necessary to change the resist composition, and such a change usually tends to deteriorate the lithography characteristics. In addition, double exposure technology and double patterning technology are known as technologies for enhancing the resolution by using the characteristics of chemically amplified resist materials, but the technology for increasing the resolution without increasing the number of processes using existing equipment. For example, a technique using an organic solvent having a polarity lower than that of an alkaline aqueous solution as a developing solution is disclosed (see JP-A-2000-199953). It is difficult to form a fine pattern due to poor optical contrast when forming a trench pattern or a hole pattern using an alkaline aqueous solution as a developer, but when an organic solvent is used, This is because a fine pattern can be formed because the optical contrast can be increased.
上述のような液浸露光によるレジストパターン、特にトレンチパターン又はホールパターンの形成において、最適な感放射線性樹脂組成物、使用する現像液及びそれらの組み合わせは今日まで見出されていない。
In the formation of a resist pattern by immersion exposure as described above, particularly a trench pattern or a hole pattern, an optimal radiation-sensitive resin composition, a developer to be used, and a combination thereof have not been found to date.
本発明は、以上のような事情に基づいてなされたものであり、その目的はリソグラフィー特性に優れるトレンチパターン又はホールパターンの形成方法、及び感放射線性樹脂組成物を提供することである。
The present invention has been made based on the above circumstances, and an object thereof is to provide a method for forming a trench pattern or a hole pattern excellent in lithography characteristics, and a radiation-sensitive resin composition.
上記課題を解決するためになされた発明は、
(1)基板上に感放射線性樹脂組成物を塗布するレジスト膜形成工程、
(2)上記レジスト膜にフォトマスクを介して放射線を照射する露光工程、及び
(3)上記露光されたレジスト膜を現像する現像工程
を含むトレンチパターン又はホールパターンの形成方法であって、
上記感放射線性樹脂組成物が、
[A]酸解離性基を有する構造単位の含有割合が10モル%以下である重合体(以下、「[A]重合体」とも称する)、
[B]酸解離性基を有する構造単位の含有割合が10モル%を超える重合体(以下、「[B]重合体」とも称する)、及び
[C]感放射線性酸発生体
を含有し、
上記(3)現像工程における現像液が、有機溶媒を80質量%以上含むこと
を特徴とするトレンチパターン又はホールパターンの形成方法である。 The invention made to solve the above problems is
(1) a resist film forming step of applying a radiation sensitive resin composition on a substrate;
(2) An exposure step of irradiating the resist film with radiation through a photomask, and (3) a trench pattern or hole pattern forming method including a development step of developing the exposed resist film,
The radiation sensitive resin composition is
[A] a polymer in which the content of the structural unit having an acid dissociable group is 10 mol% or less (hereinafter, also referred to as “[A] polymer”),
[B] a polymer in which the content of the structural unit having an acid dissociable group exceeds 10 mol% (hereinafter, also referred to as “[B] polymer”), and [C] a radiation-sensitive acid generator,
(3) A method for forming a trench pattern or a hole pattern, wherein the developer in the developing step contains 80% by mass or more of an organic solvent.
(1)基板上に感放射線性樹脂組成物を塗布するレジスト膜形成工程、
(2)上記レジスト膜にフォトマスクを介して放射線を照射する露光工程、及び
(3)上記露光されたレジスト膜を現像する現像工程
を含むトレンチパターン又はホールパターンの形成方法であって、
上記感放射線性樹脂組成物が、
[A]酸解離性基を有する構造単位の含有割合が10モル%以下である重合体(以下、「[A]重合体」とも称する)、
[B]酸解離性基を有する構造単位の含有割合が10モル%を超える重合体(以下、「[B]重合体」とも称する)、及び
[C]感放射線性酸発生体
を含有し、
上記(3)現像工程における現像液が、有機溶媒を80質量%以上含むこと
を特徴とするトレンチパターン又はホールパターンの形成方法である。 The invention made to solve the above problems is
(1) a resist film forming step of applying a radiation sensitive resin composition on a substrate;
(2) An exposure step of irradiating the resist film with radiation through a photomask, and (3) a trench pattern or hole pattern forming method including a development step of developing the exposed resist film,
The radiation sensitive resin composition is
[A] a polymer in which the content of the structural unit having an acid dissociable group is 10 mol% or less (hereinafter, also referred to as “[A] polymer”),
[B] a polymer in which the content of the structural unit having an acid dissociable group exceeds 10 mol% (hereinafter, also referred to as “[B] polymer”), and [C] a radiation-sensitive acid generator,
(3) A method for forming a trench pattern or a hole pattern, wherein the developer in the developing step contains 80% by mass or more of an organic solvent.
[A]重合体は、酸解離性基を有する構造単位を10モル%以下有しており、全ての酸解離性基が解離しても現像液に対する[A]重合体の溶解性を損なわない為、残渣やブリッジ等の欠陥発生を抑制できる。ここで、酸解離性基を有する構造単位とは、カルボキシ基等の極性基の水素原子が酸解離性基で置換された構造単位をいう。一方、[B]重合体は、酸解離性基を有する構造単位を10モル%を超えて有し、この酸解離性基は[C]感放射線性酸発生体から発生した酸の作用により解離する。結果として、極性が増大し、露光部における[B]重合体の難溶性が増大し、未露光部におけるレジスト膜中の重合体の現像液に対する溶解を促進する。また、当該パターン形成方法においては、現像工程における現像液としてポジ型化学増幅レジストの形成に用いられるアルカリ水溶液よりも極性の低い有機溶媒を含有する現像液(レジスト膜の未露光部を溶解し、ネガ型の像を形成することが可能な現像液)を用いており、この有機溶媒は上記レジスト膜表面との親和性に優れ、結果として現像性を向上できる。従って、このような特定の組成物と特徴的なパターン形成方法の組み合わせによって、感度、断面形状、ホールパターンの円形性、解像性等のリソグラフィー特性に優れたパターン形成を可能としている。
[A] The polymer has 10 mol% or less of a structural unit having an acid dissociable group, and even if all the acid dissociable groups are dissociated, the solubility of the [A] polymer in the developer is not impaired. Therefore, the occurrence of defects such as residues and bridges can be suppressed. Here, the structural unit having an acid dissociable group refers to a structural unit in which a hydrogen atom of a polar group such as a carboxy group is substituted with an acid dissociable group. On the other hand, the [B] polymer has a structural unit having an acid dissociable group in excess of 10 mol%, and this acid dissociable group is dissociated by the action of an acid generated from the [C] radiation sensitive acid generator. To do. As a result, the polarity increases, the poor solubility of the [B] polymer in the exposed area increases, and the dissolution of the polymer in the resist film in the unexposed area in the developing solution is promoted. Further, in the pattern forming method, a developer containing an organic solvent having a polarity lower than that of an alkaline aqueous solution used for forming a positive chemically amplified resist as a developer in the development step (dissolves an unexposed portion of the resist film, A developer capable of forming a negative image is used, and this organic solvent has excellent affinity with the resist film surface, and as a result, developability can be improved. Therefore, a combination of such a specific composition and a characteristic pattern forming method enables pattern formation excellent in lithography properties such as sensitivity, cross-sectional shape, hole pattern circularity, and resolution.
[A]重合体のフッ素含有率は、[B]重合体よりも高いことが好ましい。[A]重合体のフッ素含有率が、[B]重合体よりも高い場合、[A]重合体がレジスト膜表面近傍で偏在化する傾向があり、液浸露光時における酸発生剤や[D]酸拡散制御剤等が液浸媒体に溶出することを抑制できる。また、レジスト膜と液浸媒体との前進接触角が所望の範囲に制御でき、バブル欠陥の発生を抑制できる。さらに、レジスト膜と液浸媒体との後退接触角が高くなり、水滴が残らずに高速でのスキャン露光が可能となる。
[A] The fluorine content of the polymer is preferably higher than that of the [B] polymer. [A] When the fluorine content of the polymer is higher than that of the [B] polymer, the [A] polymer tends to be unevenly distributed near the resist film surface, and the acid generator or [D It is possible to suppress the acid diffusion control agent and the like from being eluted into the immersion medium. Further, the advancing contact angle between the resist film and the immersion medium can be controlled within a desired range, and the occurrence of bubble defects can be suppressed. Furthermore, the receding contact angle between the resist film and the immersion medium is increased, and high-speed scanning exposure is possible without leaving water droplets.
上記現像液に含有される有機溶媒は、エーテル系溶媒、ケトン系溶媒及びエステル系溶媒からなる群より選択される少なくとも1種の有機溶媒であることが好ましい。上記特定の有機溶媒を使用することで、所定のレジスト組成物との適切な組み合わせを実現でき、よりリソグラフィー特性に優れたパターンを得ることができる。
The organic solvent contained in the developer is preferably at least one organic solvent selected from the group consisting of ether solvents, ketone solvents and ester solvents. By using the specific organic solvent, an appropriate combination with a predetermined resist composition can be realized, and a pattern with more excellent lithography characteristics can be obtained.
[A]重合体は、下記式(1)で表される構造単位(I)及び下記式(2)で表される構造単位(II)からなる群より選択される少なくとも1種の構造単位を有することが好ましい。
[A] The polymer comprises at least one structural unit selected from the group consisting of the structural unit (I) represented by the following formula (1) and the structural unit (II) represented by the following formula (2). It is preferable to have.
[A]重合体が上記の特定構造単位を有することで、構造中にフッ素化された基を有することとなりレジスト膜の疎水性を向上し、液浸露光時の物質溶出抑制に優れる。また、レジスト膜と液浸液との後退接触角を十分に高くでき、高速でスキャン露光した場合に水滴が残らない等の効果を奏する為、液浸露光用としての有用性が高い。
[A] When the polymer has the above-mentioned specific structural unit, it has a fluorinated group in the structure, thereby improving the hydrophobicity of the resist film and being excellent in suppression of substance elution during immersion exposure. In addition, since the receding contact angle between the resist film and the immersion liquid can be sufficiently increased, and there are effects such as no water droplets remaining when scanning exposure is performed at high speed, it is highly useful for immersion exposure.
[B]重合体の酸解離性基は、鎖状の炭化水素基、又は単環若しくは多環の脂環式炭化水素基を有することが好ましい。[B]重合体の酸解離性基が上記特定の基を有することで、レジスト膜のArFエキシマレーザー等に対する透明性を高くでき、より解像性に優れたパターンを形成できる。
[B] The acid dissociable group of the polymer preferably has a chain hydrocarbon group or a monocyclic or polycyclic alicyclic hydrocarbon group. [B] Since the acid-dissociable group of the polymer has the above specific group, the resist film can be made highly transparent with respect to an ArF excimer laser or the like, and a pattern with higher resolution can be formed.
本発明の感放射線性樹脂組成物は、、
(1)基板上に感放射線性樹脂組成物を塗布するレジスト膜形成工程、
(2)上記レジスト膜にフォトマスクを介して放射線を照射する露光工程、及び
(3)上記露光されたレジスト膜を現像する現像工程
を含むトレンチパターン又はホールパターンの形成方法であって、
上記工程(3)における現像液が、有機溶媒を80質量%以上含み、
上記感放射線性樹脂組成物が、
[A]酸解離性基を有する構造単位の含有割合が10モル%以下である重合体、
[B]酸解離性基を有する構造単位の含有割合が10モル%を超える重合体、及び
[C]感放射線性酸発生体
を含有することを特徴とする。 The radiation sensitive resin composition of the present invention,
(1) a resist film forming step of applying a radiation sensitive resin composition on a substrate;
(2) An exposure step of irradiating the resist film with radiation through a photomask, and (3) a trench pattern or hole pattern forming method including a development step of developing the exposed resist film,
The developer in the step (3) contains 80% by mass or more of an organic solvent,
The radiation sensitive resin composition is
[A] a polymer in which the content of the structural unit having an acid dissociable group is 10 mol% or less,
[B] A polymer in which the content of the structural unit having an acid dissociable group exceeds 10 mol%, and [C] a radiation-sensitive acid generator.
(1)基板上に感放射線性樹脂組成物を塗布するレジスト膜形成工程、
(2)上記レジスト膜にフォトマスクを介して放射線を照射する露光工程、及び
(3)上記露光されたレジスト膜を現像する現像工程
を含むトレンチパターン又はホールパターンの形成方法であって、
上記工程(3)における現像液が、有機溶媒を80質量%以上含み、
上記感放射線性樹脂組成物が、
[A]酸解離性基を有する構造単位の含有割合が10モル%以下である重合体、
[B]酸解離性基を有する構造単位の含有割合が10モル%を超える重合体、及び
[C]感放射線性酸発生体
を含有することを特徴とする。 The radiation sensitive resin composition of the present invention,
(1) a resist film forming step of applying a radiation sensitive resin composition on a substrate;
(2) An exposure step of irradiating the resist film with radiation through a photomask, and (3) a trench pattern or hole pattern forming method including a development step of developing the exposed resist film,
The developer in the step (3) contains 80% by mass or more of an organic solvent,
The radiation sensitive resin composition is
[A] a polymer in which the content of the structural unit having an acid dissociable group is 10 mol% or less,
[B] A polymer in which the content of the structural unit having an acid dissociable group exceeds 10 mol%, and [C] a radiation-sensitive acid generator.
本発明は、液浸露光用として好適で、かつ感度、断面形状、円形性、解像性等のリソグラフィー特性に優れるトレンチパターン又はホールパターンの形成方法、及び感放射線性樹脂組成物を提供することができる。
The present invention provides a method for forming a trench pattern or a hole pattern that is suitable for immersion exposure and has excellent lithography properties such as sensitivity, cross-sectional shape, circularity, and resolution, and a radiation-sensitive resin composition. Can do.
<パターン形成方法>
本発明のパターン形成方法は、
(1)基板上に感放射線性樹脂組成物を塗布するレジスト膜形成工程、
(2)上記レジスト膜にフォトマスクを介して放射線を照射する露光工程、及び
(3)上記露光されたレジスト膜を現像する現像工程
を含む。以下、各工程を詳述する。 <Pattern formation method>
The pattern forming method of the present invention comprises:
(1) a resist film forming step of applying a radiation sensitive resin composition on a substrate;
(2) An exposure step of irradiating the resist film with radiation through a photomask, and (3) a development step of developing the exposed resist film. Hereinafter, each process is explained in full detail.
本発明のパターン形成方法は、
(1)基板上に感放射線性樹脂組成物を塗布するレジスト膜形成工程、
(2)上記レジスト膜にフォトマスクを介して放射線を照射する露光工程、及び
(3)上記露光されたレジスト膜を現像する現像工程
を含む。以下、各工程を詳述する。 <Pattern formation method>
The pattern forming method of the present invention comprises:
(1) a resist film forming step of applying a radiation sensitive resin composition on a substrate;
(2) An exposure step of irradiating the resist film with radiation through a photomask, and (3) a development step of developing the exposed resist film. Hereinafter, each process is explained in full detail.
[工程(1)]
本工程は、本発明の感放射線性樹脂組成物を基板上に塗布し、レジスト膜を形成する工程である。基板としては、例えばシリコンウェハ、アルミニウムで被覆されたウェハ等の従来公知の基板を使用できる。また、有機系又は無機系の反射防止膜を基板上に形成しても良い。 [Step (1)]
This step is a step of applying a radiation-sensitive resin composition of the present invention on a substrate to form a resist film. As the substrate, for example, a conventionally known substrate such as a silicon wafer or a wafer coated with aluminum can be used. An organic or inorganic antireflection film may be formed on the substrate.
本工程は、本発明の感放射線性樹脂組成物を基板上に塗布し、レジスト膜を形成する工程である。基板としては、例えばシリコンウェハ、アルミニウムで被覆されたウェハ等の従来公知の基板を使用できる。また、有機系又は無機系の反射防止膜を基板上に形成しても良い。 [Step (1)]
This step is a step of applying a radiation-sensitive resin composition of the present invention on a substrate to form a resist film. As the substrate, for example, a conventionally known substrate such as a silicon wafer or a wafer coated with aluminum can be used. An organic or inorganic antireflection film may be formed on the substrate.
塗布方法としては、例えば回転塗布(スピンコーティング)、流延塗布、ロール塗布等が挙げられる。なお、形成されるレジスト膜の膜厚としては、通常0.01μm~1μmであり、0.01μm~0.5μmが好ましい。
Examples of the application method include spin coating, spin coating, roll coating, and the like. The thickness of the resist film to be formed is usually 0.01 μm to 1 μm, preferably 0.01 μm to 0.5 μm.
当該感放射線性樹脂組成物を塗布した後、必要に応じてプレベーク(PB)によって塗膜中の溶媒を揮発させてもよい。PBの加熱条件としては、当該感放射線性樹脂組成物の配合組成によって適宜選択されるが、通常30℃~200℃程度であり、50℃~150℃が好ましい。
After applying the radiation sensitive resin composition, the solvent in the coating film may be volatilized by pre-baking (PB) as necessary. The heating conditions for PB are appropriately selected depending on the composition of the radiation sensitive resin composition, but are usually about 30 ° C. to 200 ° C., preferably 50 ° C. to 150 ° C.
環境雰囲気中に含まれる塩基性不純物等の影響を防止するために、例えば特開平5-188598号公報等に開示されている保護膜をレジスト層上に設けることもできる。さらに、レジスト層からの酸発生剤等の流出を防止するために、例えば特開2005-352384号公報等に開示されている液浸用保護膜をレジスト層上に設けることもできる。なお、これらの技術は併用できる。
In order to prevent the influence of basic impurities contained in the ambient atmosphere, a protective film disclosed in, for example, Japanese Patent Laid-Open No. 5-188598 can be provided on the resist layer. Further, in order to prevent the acid generator and the like from flowing out of the resist layer, an immersion protective film disclosed in, for example, Japanese Patent Application Laid-Open No. 2005-352384 can be provided on the resist layer. These techniques can be used in combination.
[工程(2)]
本工程は、工程(1)で形成した上記レジスト膜にフォトマスクを介して放射線を照射する工程である。また、必要に応じて液浸液を介して縮小投影することにより露光を行う。例えば、所望の領域にアイソラインパターンマスクを介して縮小投影露光を行うことにより、アイソトレンチパターンを形成できる。また、露光は所望のパターンとマスクパターンによって2回以上行ってもよい。2回以上露光を行う場合、露光は連続して行うことが好ましい。複数回露光する場合、例えば所望の領域にラインアンドスペースパターンマスクを介して第1の縮小投影露光を行い、続けて第1の露光を行った露光部に対してラインが交差するように第2の縮小投影露光を行う。第1の露光部と第2の露光部とは直交することが好ましい。直交することにより、露光部で囲まれた未露光部において円形状のコンタクトホールパターンが形成しやすくなる。なお、露光の際に用いられる液浸液としては水やフッ素系不活性液体等が挙げられる。液浸液は、露光波長に対して透明であり、かつ膜上に投影される光学像の歪みを最小限に留めるよう屈折率の温度係数ができる限り小さい液体が好ましいが、特に露光光源がArFエキシマレーザー光(波長193nm)である場合、上述の観点に加えて、入手の容易さ、取り扱いのし易さといった点から水を用いるのが好ましい。水を用いる場合、水の表面張力を減少させるとともに、界面活性力を増大させる添加剤を僅かな割合で添加しても良い。この添加剤は、ウェハ上のレジスト層を溶解させず、かつレンズの下面の光学コートに対する影響が無視できるものが好ましい。使用する水としては蒸留水が好ましい。 [Step (2)]
This step is a step of irradiating the resist film formed in step (1) with radiation through a photomask. Further, exposure is performed by reducing and projecting through an immersion liquid as necessary. For example, an isotrench pattern can be formed by performing reduced projection exposure on a desired region through an isoline pattern mask. Moreover, you may perform exposure twice or more with a desired pattern and a mask pattern. When performing exposure twice or more, it is preferable to perform exposure continuously. In the case of performing multiple exposures, for example, a first reduced projection exposure is performed on a desired area via a line and space pattern mask, and then the second is so that the line intersects the exposed portion where the first exposure has been performed. Reduced projection exposure is performed. The first exposure part and the second exposure part are preferably orthogonal. By being orthogonal, it becomes easy to form a circular contact hole pattern in the unexposed portion surrounded by the exposed portion. Examples of the immersion liquid used for exposure include water and a fluorine-based inert liquid. The immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient that is as small as possible so as to minimize distortion of the optical image projected onto the film. In the case of excimer laser light (wavelength 193 nm), it is preferable to use water from the viewpoints of availability and easy handling in addition to the above-described viewpoints. When water is used, an additive that decreases the surface tension of water and increases the surface activity may be added in a small proportion. This additive is preferably one that does not dissolve the resist layer on the wafer and can ignore the influence on the optical coating on the lower surface of the lens. The water used is preferably distilled water.
本工程は、工程(1)で形成した上記レジスト膜にフォトマスクを介して放射線を照射する工程である。また、必要に応じて液浸液を介して縮小投影することにより露光を行う。例えば、所望の領域にアイソラインパターンマスクを介して縮小投影露光を行うことにより、アイソトレンチパターンを形成できる。また、露光は所望のパターンとマスクパターンによって2回以上行ってもよい。2回以上露光を行う場合、露光は連続して行うことが好ましい。複数回露光する場合、例えば所望の領域にラインアンドスペースパターンマスクを介して第1の縮小投影露光を行い、続けて第1の露光を行った露光部に対してラインが交差するように第2の縮小投影露光を行う。第1の露光部と第2の露光部とは直交することが好ましい。直交することにより、露光部で囲まれた未露光部において円形状のコンタクトホールパターンが形成しやすくなる。なお、露光の際に用いられる液浸液としては水やフッ素系不活性液体等が挙げられる。液浸液は、露光波長に対して透明であり、かつ膜上に投影される光学像の歪みを最小限に留めるよう屈折率の温度係数ができる限り小さい液体が好ましいが、特に露光光源がArFエキシマレーザー光(波長193nm)である場合、上述の観点に加えて、入手の容易さ、取り扱いのし易さといった点から水を用いるのが好ましい。水を用いる場合、水の表面張力を減少させるとともに、界面活性力を増大させる添加剤を僅かな割合で添加しても良い。この添加剤は、ウェハ上のレジスト層を溶解させず、かつレンズの下面の光学コートに対する影響が無視できるものが好ましい。使用する水としては蒸留水が好ましい。 [Step (2)]
This step is a step of irradiating the resist film formed in step (1) with radiation through a photomask. Further, exposure is performed by reducing and projecting through an immersion liquid as necessary. For example, an isotrench pattern can be formed by performing reduced projection exposure on a desired region through an isoline pattern mask. Moreover, you may perform exposure twice or more with a desired pattern and a mask pattern. When performing exposure twice or more, it is preferable to perform exposure continuously. In the case of performing multiple exposures, for example, a first reduced projection exposure is performed on a desired area via a line and space pattern mask, and then the second is so that the line intersects the exposed portion where the first exposure has been performed. Reduced projection exposure is performed. The first exposure part and the second exposure part are preferably orthogonal. By being orthogonal, it becomes easy to form a circular contact hole pattern in the unexposed portion surrounded by the exposed portion. Examples of the immersion liquid used for exposure include water and a fluorine-based inert liquid. The immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient that is as small as possible so as to minimize distortion of the optical image projected onto the film. In the case of excimer laser light (wavelength 193 nm), it is preferable to use water from the viewpoints of availability and easy handling in addition to the above-described viewpoints. When water is used, an additive that decreases the surface tension of water and increases the surface activity may be added in a small proportion. This additive is preferably one that does not dissolve the resist layer on the wafer and can ignore the influence on the optical coating on the lower surface of the lens. The water used is preferably distilled water.
露光に使用される放射線としては、[C]感放射線性酸発生体の種類に応じて適宜選択されるが、例えば紫外線、遠紫外線、X線、荷電粒子線等が挙げられる。これらのうち、ArFエキシマレーザー光やKrFエキシマレーザー光(波長248nm)に代表される遠紫外線が好ましく、ArFエキシマレーザー光がより好ましい。露光量等の露光条件は、当該感放射線性樹脂組成物の配合組成や添加剤の種類等に応じて適宜選択される。本発明のパターン形成方法においては、露光工程を複数回有してもよく複数回の露光は同じ光源を用いても、異なる光源を用いても良いが、1回目の露光にはArFエキシマレーザー光を用いることが好ましい。
The radiation used for exposure is appropriately selected according to the type of [C] radiation sensitive acid generator, and examples thereof include ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams. Among these, far ultraviolet rays represented by ArF excimer laser light and KrF excimer laser light (wavelength 248 nm) are preferable, and ArF excimer laser light is more preferable. The exposure conditions such as the exposure amount are appropriately selected according to the blending composition of the radiation-sensitive resin composition, the type of additive, and the like. In the pattern forming method of the present invention, the exposure process may be performed a plurality of times, and the plurality of exposures may be performed using the same light source or different light sources, but ArF excimer laser light is used for the first exposure. Is preferably used.
また、露光後にポストエクスポージャーベーク(PEB)を行なうことが好ましい。PEBを行なうことにより、当該感放射線性樹脂組成物中の酸解離性基の解離反応を円滑に進行できる。PEBの加熱条件としては、通常30℃~200℃であり、50℃~170℃が好ましい。
Moreover, it is preferable to perform post-exposure baking (PEB) after exposure. By performing PEB, the dissociation reaction of the acid dissociable group in the radiation sensitive resin composition can proceed smoothly. The heating conditions for PEB are usually 30 ° C. to 200 ° C., preferably 50 ° C. to 170 ° C.
[工程(3)]
本工程は、上記露光されたレジスト膜を現像する工程である。露光後に有機溶媒を含有する。現像に用いられる現像液は、低露光部及び未露光部を選択的に溶解・除去させるものであって、有機溶媒を80質量%以上含むものであれば特に限定されない。有機溶媒としては、例えばアルコール系溶媒、エーテル系溶媒、ケトン系有機溶媒、アミド系溶媒、エステル系有機溶媒及び炭化水素系溶媒からなる群より選択される少なくとも1種が挙げられる。 [Step (3)]
This step is a step of developing the exposed resist film. Contains organic solvent after exposure. The developer used for development is not particularly limited as long as it selectively dissolves and removes the low-exposed portion and the unexposed portion, and contains 80% by mass or more of an organic solvent. Examples of the organic solvent include at least one selected from the group consisting of alcohol solvents, ether solvents, ketone organic solvents, amide solvents, ester organic solvents, and hydrocarbon solvents.
本工程は、上記露光されたレジスト膜を現像する工程である。露光後に有機溶媒を含有する。現像に用いられる現像液は、低露光部及び未露光部を選択的に溶解・除去させるものであって、有機溶媒を80質量%以上含むものであれば特に限定されない。有機溶媒としては、例えばアルコール系溶媒、エーテル系溶媒、ケトン系有機溶媒、アミド系溶媒、エステル系有機溶媒及び炭化水素系溶媒からなる群より選択される少なくとも1種が挙げられる。 [Step (3)]
This step is a step of developing the exposed resist film. Contains organic solvent after exposure. The developer used for development is not particularly limited as long as it selectively dissolves and removes the low-exposed portion and the unexposed portion, and contains 80% by mass or more of an organic solvent. Examples of the organic solvent include at least one selected from the group consisting of alcohol solvents, ether solvents, ketone organic solvents, amide solvents, ester organic solvents, and hydrocarbon solvents.
アルコール系溶媒としては、例えば
メタノール、エタノール、n-プロパノール、iso-プロパノール、n-ブタノール、iso-ブタノール、sec-ブタノール、tert-ブタノール、n-ペンタノール、iso-ペンタノール、2-メチルブタノール、sec-ペンタノール、tert-ペンタノール、3-メトキシブタノール、n-ヘキサノール、2-メチルペンタノール、sec-ヘキサノール、2-エチルブタノール、sec-ヘプタノール、3-ヘプタノール、n-オクタノール、2-エチルヘキサノール、sec-オクタノール、n-ノニルアルコール、2,6-ジメチル-4-ヘプタノール、n-デカノール、sec-ウンデシルアルコール、トリメチルノニルアルコール、sec-テトラデシルアルコール、sec-ヘプタデシルアルコール、フルフリルアルコール、フェノール、シクロヘキサノール、メチルシクロヘキサノール、3,3,5-トリメチルシクロヘキサノール、ベンジルアルコール、ジアセトンアルコール等のモノアルコール系溶媒;
エチレングリコール、1,2-プロピレングリコール、1,3-ブチレングリコール、2,4-ペンタンジオール、2-メチル-2,4-ペンタンジオール、2,5-ヘキサンジオール、2,4-ヘプタンジオール、2-エチル-1,3-ヘキサンジオール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、トリプロピレングリコール等の多価アルコール系溶媒;
エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノヘキシルエーテル、エチレングリコールモノフェニルエーテル、エチレングリコールモノ-2-エチルブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノプロピルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノヘキシルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル等の多価アルコール部分エーテル系溶媒等が挙げられる。 Examples of the alcohol solvent include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol , Sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec -Monoalcohol solvents such as heptadecyl alcohol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol;
Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2 Polyhydric alcohol solvents such as ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, polyhydric alcohol partial ether solvents such as dipropylene glycol monopropyl ether.
メタノール、エタノール、n-プロパノール、iso-プロパノール、n-ブタノール、iso-ブタノール、sec-ブタノール、tert-ブタノール、n-ペンタノール、iso-ペンタノール、2-メチルブタノール、sec-ペンタノール、tert-ペンタノール、3-メトキシブタノール、n-ヘキサノール、2-メチルペンタノール、sec-ヘキサノール、2-エチルブタノール、sec-ヘプタノール、3-ヘプタノール、n-オクタノール、2-エチルヘキサノール、sec-オクタノール、n-ノニルアルコール、2,6-ジメチル-4-ヘプタノール、n-デカノール、sec-ウンデシルアルコール、トリメチルノニルアルコール、sec-テトラデシルアルコール、sec-ヘプタデシルアルコール、フルフリルアルコール、フェノール、シクロヘキサノール、メチルシクロヘキサノール、3,3,5-トリメチルシクロヘキサノール、ベンジルアルコール、ジアセトンアルコール等のモノアルコール系溶媒;
エチレングリコール、1,2-プロピレングリコール、1,3-ブチレングリコール、2,4-ペンタンジオール、2-メチル-2,4-ペンタンジオール、2,5-ヘキサンジオール、2,4-ヘプタンジオール、2-エチル-1,3-ヘキサンジオール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、トリプロピレングリコール等の多価アルコール系溶媒;
エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノヘキシルエーテル、エチレングリコールモノフェニルエーテル、エチレングリコールモノ-2-エチルブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノプロピルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノヘキシルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル等の多価アルコール部分エーテル系溶媒等が挙げられる。 Examples of the alcohol solvent include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, n-pentanol, iso-pentanol, 2-methylbutanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, sec-heptanol, 3-heptanol, n-octanol, 2-ethylhexanol , Sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec -Monoalcohol solvents such as heptadecyl alcohol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, diacetone alcohol;
Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, 2 Polyhydric alcohol solvents such as ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, polyhydric alcohol partial ether solvents such as dipropylene glycol monopropyl ether.
エーテル系溶媒としては、例えばジエチルエーテル、ジプロピルエーテル、ジブチルエーテル、ジフェニルエーテル、メトキシベンゼン等が挙げられる。
Examples of ether solvents include diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, methoxybenzene, and the like.
ケトン系溶媒としては、例えばアセトン、メチルエチルケトン、メチル-n-プロピルケトン、メチル-n-ブチルケトン、ジエチルケトン、メチル-iso-ブチルケトン、メチル-n-ペンチルケトン、エチル-n-ブチルケトン、メチル-n-ヘキシルケトン、ジ-iso-ブチルケトン、トリメチルノナノン、シクロペンタノン、シクロヘキサノン、シクロヘプタノン、シクロオクタノン、メチルシクロヘキサノン、2,4-ペンタンジオン、アセトニルアセトン、アセトフェノン等のケトン系溶媒が挙げられる。
Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n- And ketone solvents such as hexyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, acetophenone, etc. .
アミド系溶媒としては、例えばN,N’-ジメチルイミダゾリジノン、N-メチルホルムアミド、N,N-ジメチルホルムアミド、N,N-ジエチルホルムアミド、アセトアミド、N-メチルアセトアミド、N,N-ジメチルアセトアミド、N-メチルプロピオンアミド、N-メチルピロリドン等が挙げられる。
Examples of amide solvents include N, N′-dimethylimidazolidinone, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, Examples thereof include N-methylpropionamide and N-methylpyrrolidone.
エステル系溶媒としては、例えばジエチルカーボネート、プロピレンカーボネート、酢酸メチル、酢酸エチル、γ-ブチロラクトン、γ-バレロラクトン、酢酸n-プロピル、酢酸iso-プロピル、酢酸n-ブチル、酢酸iso-ブチル、酢酸sec-ブチル、酢酸n-ペンチル、酢酸sec-ペンチル、酢酸3-メトキシブチル、酢酸メチルペンチル、酢酸2-エチルブチル、酢酸2-エチルヘキシル、酢酸ベンジル、酢酸シクロヘキシル、酢酸メチルシクロヘキシル、酢酸n-ノニル、アセト酢酸メチル、アセト酢酸エチル、酢酸エチレングリコールモノメチルエーテル、酢酸エチレングリコールモノエチルエーテル、酢酸ジエチレングリコールモノメチルエーテル、酢酸ジエチレングリコールモノエチルエーテル、酢酸ジエチレングリコールモノ-n-ブチルエーテル、酢酸プロピレングリコールモノメチルエーテル、酢酸プロピレングリコールモノエチルエーテル、酢酸プロピレングリコールモノプロピルエーテル、酢酸プロピレングリコールモノブチルエーテル、酢酸ジプロピレングリコールモノメチルエーテル、酢酸ジプロピレングリコールモノエチルエーテル、ジ酢酸グリコール、酢酸メトキシトリグリコール、プロピオン酸エチル、プロピオン酸n-ブチル、プロピオン酸iso-アミル、シュウ酸ジエチル、シュウ酸ジ-n-ブチル、乳酸メチル、乳酸エチル、乳酸n-ブチル、乳酸n-アミル、マロン酸ジエチル、フタル酸ジメチル、フタル酸ジエチル等が挙げられる。
Examples of the ester solvent include diethyl carbonate, propylene carbonate, methyl acetate, ethyl acetate, γ-butyrolactone, γ-valerolactone, n-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl acetate, sec -Butyl, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, acetoacetic acid Methyl, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene acetate Recall mono-n-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, diacetic acid Glycol, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, iso-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate , Diethyl malonate, dimethyl phthalate, diethyl phthalate and the like.
炭化水素系溶媒としては、例えば
n-ペンタン、iso-ペンタン、n-ヘキサン、iso-ヘキサン、n-ヘプタン、iso-ヘプタン、2,2,4-トリメチルペンタン、n-オクタン、iso-オクタン、シクロヘキサン、メチルシクロヘキサン等の脂肪族炭化水素系溶媒;
ベンゼン、トルエン、キシレン、メシチレン、エチルベンゼン、トリメチルベンゼン、メチルエチルベンゼン、n-プロピルベンゼン、iso-プロピルベンゼン、ジエチルベンゼン、iso-ブチルベンゼン、トリエチルベンゼン、ジ-iso-プロピルベンセン、n-アミルナフタレン等の芳香族炭化水素系溶媒等が挙げられる。 Examples of hydrocarbon solvents include n-pentane, iso-pentane, n-hexane, iso-hexane, n-heptane, iso-heptane, 2,2,4-trimethylpentane, n-octane, iso-octane, cyclohexane , Aliphatic hydrocarbon solvents such as methylcyclohexane;
Fragrances such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, iso-propylbenzene, diethylbenzene, iso-butylbenzene, triethylbenzene, di-iso-propylbenzene, n-amylnaphthalene Group hydrocarbon solvents and the like.
n-ペンタン、iso-ペンタン、n-ヘキサン、iso-ヘキサン、n-ヘプタン、iso-ヘプタン、2,2,4-トリメチルペンタン、n-オクタン、iso-オクタン、シクロヘキサン、メチルシクロヘキサン等の脂肪族炭化水素系溶媒;
ベンゼン、トルエン、キシレン、メシチレン、エチルベンゼン、トリメチルベンゼン、メチルエチルベンゼン、n-プロピルベンゼン、iso-プロピルベンゼン、ジエチルベンゼン、iso-ブチルベンゼン、トリエチルベンゼン、ジ-iso-プロピルベンセン、n-アミルナフタレン等の芳香族炭化水素系溶媒等が挙げられる。 Examples of hydrocarbon solvents include n-pentane, iso-pentane, n-hexane, iso-hexane, n-heptane, iso-heptane, 2,2,4-trimethylpentane, n-octane, iso-octane, cyclohexane , Aliphatic hydrocarbon solvents such as methylcyclohexane;
Fragrances such as benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, iso-propylbenzene, diethylbenzene, iso-butylbenzene, triethylbenzene, di-iso-propylbenzene, n-amylnaphthalene Group hydrocarbon solvents and the like.
これらのうち、有機溶媒としては、エーテル系溶媒、ケトン系溶媒及びエステル系溶媒からなる群より選択される少なくとも1種の有機溶媒であることが好ましく、酢酸n-ブチル、酢酸イソプロピル、酢酸アミル、メチルエチルケトン、メチル-n-ブチルケトン、メチル-n-ペンチルケトン、アニソールがより好ましい。上記特定の有機溶媒を使用することで、所定のレジスト組成物との適切な組み合わせを実現でき、よりリソグラフィー特性に優れたパターンを得ることができる。なお、これらの有機溶媒は、単独で使用してもよく2種以上を併用してもよい。
Among these, the organic solvent is preferably at least one organic solvent selected from the group consisting of ether solvents, ketone solvents and ester solvents, and includes n-butyl acetate, isopropyl acetate, amyl acetate, Methyl ethyl ketone, methyl-n-butyl ketone, methyl-n-pentyl ketone, and anisole are more preferable. By using the specific organic solvent, an appropriate combination with a predetermined resist composition can be realized, and a pattern with more excellent lithography characteristics can be obtained. In addition, these organic solvents may be used independently and may use 2 or more types together.
現像液には、必要に応じて界面活性剤を適当量添加することができる。界面活性剤としては例えば、イオン性や非イオン性のフッ素系界面活性剤、シリコン系界面活性剤等が挙げられる。
An appropriate amount of a surfactant can be added to the developer as necessary. Examples of the surfactant include ionic and nonionic fluorine-based surfactants and silicon-based surfactants.
現像方法としては、例えば現像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)、基板表面に現像液を表面張力によって盛り上げて一定時間静止することで現像する方法(パドル法)、基板表面に現像液を噴霧する方法(スプレー法)、一定速度で回転している基板上に一定速度で現像液塗出ノズルをスキャンしながら現像液を塗出しつづける方法(ダイナミックディスペンス法)等が挙げられる。
As 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 applying the developer while scanning the developer coating nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc.
当該パターン形成では、工程(3)の現像後にレジスト膜をリンス液により洗浄することが好ましい。また、リンス工程におけるリンス液としても有機溶媒を使用することができ、発生したスカムを効率よく洗浄することができる。リンス液としては、炭化水素系溶媒、ケトン系溶媒、エステル系溶媒、アルコール系溶媒、アミド系溶媒等が好ましい。これらのうちアルコール系溶媒、エステル系溶媒が好ましく、炭素数6~8の1価のアルコール系溶媒がより好ましい。炭素数6~8の1価のアルコールとしては直鎖状、分岐状又は環状の1価のアルコールが挙げられ、例えば1-ヘキサノール、1-ヘプタノール、1-オクタノール、4-メチル-2-ペンタノール、2-ヘキサノール、2-ヘプタノール、2-オクタノール、3-ヘキサノール、3-ヘプタノール、3-オクタノール、4-オクタノール、ベンジルアルコール等が挙げられる。これらのうち、1-ヘキサノール、2-ヘキサノール、2-ヘプタノール、4-メチル-2-ペンタノールが好ましい。
In the pattern formation, it is preferable to wash the resist film with a rinsing liquid after the development in the step (3). Moreover, an organic solvent can be used also as the rinse liquid in the rinse process, and the generated scum can be efficiently washed. As the rinsing liquid, hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and the like are preferable. Of these, alcohol solvents and ester solvents are preferable, and monovalent alcohol solvents having 6 to 8 carbon atoms are more preferable. Examples of monohydric alcohols having 6 to 8 carbon atoms include linear, branched or cyclic monohydric alcohols such as 1-hexanol, 1-heptanol, 1-octanol, and 4-methyl-2-pentanol. 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, benzyl alcohol and the like. Of these, 1-hexanol, 2-hexanol, 2-heptanol, and 4-methyl-2-pentanol are preferable.
上記リンス液の各成分は、単独で使用してもよく2種以上を併用してもよい。リンス液中の含水率は、10質量%以下が好ましく、さらにより好ましくは5質量%以下、特に好ましくは3質量%以下である。含水率を10質量%以下にすることで、良好な現像特性を得ることができる。なお、リンス液には後述する界面活性剤を添加できる。
Each component of the rinse liquid may be used alone or in combination of two or more. The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained. In addition, the surfactant mentioned later can be added to the rinse liquid.
洗浄処理の方法としては、例えば一定速度で回転している基板上にリンス液を塗出しつづける方法(回転塗布法)、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)等が挙げられる。
As a cleaning method, for example, a method of continuously applying a rinse liquid onto a substrate rotating at a constant speed (rotary coating method), a method of immersing the substrate in a tank filled with the rinse liquid for a predetermined time (dip method) ), A method (spray method) of spraying a rinse liquid on the substrate surface, and the like.
<感放射線性樹脂組成物>
本発明に用いられる感放射線性樹脂組成物は、[A]重合体、[B]重合体、及び[C]感放射線性酸発生体を含有する。[A]重合体は、酸解離性基を有する構造単位を10モル%以下有しており、全ての酸解離性基が解離しても現像液に対する[A]重合体の溶解性を損なわない為、残渣やブリッジ等の欠陥発生を抑制できる。ここで、酸解離性基を有する構造単位とは、カルボキシ基等の極性基の水素原子が酸解離性基で置換された構造単位をいう。一方、[B]重合体は、酸解離性基を有する構造単位を10モル%を超えて有し、この酸解離性基は[C]感放射線性酸発生体から発生した酸の作用により解離する。結果として、極性が増大し、露光部における[B]重合体の難溶性が増大し、未露光部におけるレジスト膜中の重合体の現像液に対する溶解を促進する。また、当該感放射線性樹脂組成物は、本発明の効果を損なわない限り任意成分を含有してもよい。以下、各成分を詳述する。 <Radiation sensitive resin composition>
The radiation sensitive resin composition used in the present invention contains a [A] polymer, a [B] polymer, and a [C] radiation sensitive acid generator. [A] The polymer has 10 mol% or less of a structural unit having an acid dissociable group, and even if all the acid dissociable groups are dissociated, the solubility of the [A] polymer in the developer is not impaired. Therefore, the occurrence of defects such as residues and bridges can be suppressed. Here, the structural unit having an acid dissociable group refers to a structural unit in which a hydrogen atom of a polar group such as a carboxy group is substituted with an acid dissociable group. On the other hand, the [B] polymer has a structural unit having an acid dissociable group in excess of 10 mol%, and this acid dissociable group is dissociated by the action of an acid generated from the [C] radiation sensitive acid generator. To do. As a result, the polarity increases, the poor solubility of the [B] polymer in the exposed area increases, and the dissolution of the polymer in the resist film in the unexposed area in the developing solution is promoted. Moreover, the said radiation sensitive resin composition may contain arbitrary components, unless the effect of this invention is impaired. Hereinafter, each component will be described in detail.
本発明に用いられる感放射線性樹脂組成物は、[A]重合体、[B]重合体、及び[C]感放射線性酸発生体を含有する。[A]重合体は、酸解離性基を有する構造単位を10モル%以下有しており、全ての酸解離性基が解離しても現像液に対する[A]重合体の溶解性を損なわない為、残渣やブリッジ等の欠陥発生を抑制できる。ここで、酸解離性基を有する構造単位とは、カルボキシ基等の極性基の水素原子が酸解離性基で置換された構造単位をいう。一方、[B]重合体は、酸解離性基を有する構造単位を10モル%を超えて有し、この酸解離性基は[C]感放射線性酸発生体から発生した酸の作用により解離する。結果として、極性が増大し、露光部における[B]重合体の難溶性が増大し、未露光部におけるレジスト膜中の重合体の現像液に対する溶解を促進する。また、当該感放射線性樹脂組成物は、本発明の効果を損なわない限り任意成分を含有してもよい。以下、各成分を詳述する。 <Radiation sensitive resin composition>
The radiation sensitive resin composition used in the present invention contains a [A] polymer, a [B] polymer, and a [C] radiation sensitive acid generator. [A] The polymer has 10 mol% or less of a structural unit having an acid dissociable group, and even if all the acid dissociable groups are dissociated, the solubility of the [A] polymer in the developer is not impaired. Therefore, the occurrence of defects such as residues and bridges can be suppressed. Here, the structural unit having an acid dissociable group refers to a structural unit in which a hydrogen atom of a polar group such as a carboxy group is substituted with an acid dissociable group. On the other hand, the [B] polymer has a structural unit having an acid dissociable group in excess of 10 mol%, and this acid dissociable group is dissociated by the action of an acid generated from the [C] radiation sensitive acid generator. To do. As a result, the polarity increases, the poor solubility of the [B] polymer in the exposed area increases, and the dissolution of the polymer in the resist film in the unexposed area in the developing solution is promoted. Moreover, the said radiation sensitive resin composition may contain arbitrary components, unless the effect of this invention is impaired. Hereinafter, each component will be described in detail.
<[A]重合体>
[A]重合体は、酸解離性基を有する構造単位の含有割合が10モル%以下の重合体である。酸解離性基を有する構造単位の含有割合を10モル%以下とすることで、全ての酸解離性基が解離しても現像液に対する溶解性を損なわない為、残渣やブリッジ等の欠陥発生を抑制できる。酸解離性基を有する構造単位としては後述する式(5)で表される構造単位(III)等が挙げられる。[A]重合体における酸解離性基を有する構造単位の含有割合としては、0モル%が好ましい。 <[A] polymer>
[A] A polymer is a polymer whose content rate of the structural unit which has an acid dissociable group is 10 mol% or less. Since the content ratio of the structural unit having an acid-dissociable group is 10 mol% or less, even if all the acid-dissociable groups are dissociated, the solubility in the developer is not impaired. Can be suppressed. Examples of the structural unit having an acid dissociable group include a structural unit (III) represented by the formula (5) described later. [A] As a content rate of the structural unit which has an acid dissociable group in a polymer, 0 mol% is preferable.
[A]重合体は、酸解離性基を有する構造単位の含有割合が10モル%以下の重合体である。酸解離性基を有する構造単位の含有割合を10モル%以下とすることで、全ての酸解離性基が解離しても現像液に対する溶解性を損なわない為、残渣やブリッジ等の欠陥発生を抑制できる。酸解離性基を有する構造単位としては後述する式(5)で表される構造単位(III)等が挙げられる。[A]重合体における酸解離性基を有する構造単位の含有割合としては、0モル%が好ましい。 <[A] polymer>
[A] A polymer is a polymer whose content rate of the structural unit which has an acid dissociable group is 10 mol% or less. Since the content ratio of the structural unit having an acid-dissociable group is 10 mol% or less, even if all the acid-dissociable groups are dissociated, the solubility in the developer is not impaired. Can be suppressed. Examples of the structural unit having an acid dissociable group include a structural unit (III) represented by the formula (5) described later. [A] As a content rate of the structural unit which has an acid dissociable group in a polymer, 0 mol% is preferable.
また、[A]重合体のフッ素含有率は、[B]重合体よりも高いことが好ましい。[A]重合体のフッ素含有率が、[B]重合体よりも高い場合、[A]重合体がレジスト膜表面近傍で偏在化する傾向があり、液浸露光時における酸発生剤や[D]酸拡散制御剤等が液浸媒体に溶出することを抑制できる。また、レジスト膜と液浸媒体との前進接触角が所望の範囲に制御でき、バブル欠陥の発生を抑制できる。さらに、レジスト膜と液浸媒体との後退接触角が高くなり、水滴が残らずに高速でのスキャン露光が可能となる。
Further, the fluorine content of the [A] polymer is preferably higher than that of the [B] polymer. [A] When the fluorine content of the polymer is higher than that of the [B] polymer, the [A] polymer tends to be unevenly distributed near the resist film surface, and the acid generator or [D It is possible to suppress the acid diffusion control agent and the like from being eluted into the immersion medium. Further, the advancing contact angle between the resist film and the immersion medium can be controlled within a desired range, and the occurrence of bubble defects can be suppressed. Furthermore, the receding contact angle between the resist film and the immersion medium is increased, and high-speed scanning exposure is possible without leaving water droplets.
フッ素原子を含有する[A]重合体の態様としては、例えば(i)主鎖にフッ素化アルキル基が結合した構造、(ii)側鎖にフッ素化アルキル基が結合した構造、(iii)主鎖と側鎖とにフッ素化アルキル基が結合した構造等が挙げられる。
Examples of the [A] polymer containing a fluorine atom include (i) a structure in which a fluorinated alkyl group is bonded to the main chain, (ii) a structure in which a fluorinated alkyl group is bonded to a side chain, (iii) Examples include a structure in which a fluorinated alkyl group is bonded to a chain and a side chain.
(i)の構造を有する重合体を与える単量体としては、例えばα-トリフルオロメチルアクリレート化合物、β-トリフルオロメチルアクリレート化合物、α,β-トリフルオロメチルアクリレート化合物、1種類以上のビニル部位の水素がトリフルオロメチル基等のフッ素化アルキル基で置換された化合物等が挙げられる。
Examples of the monomer that gives the polymer having the structure (i) include an α-trifluoromethyl acrylate compound, a β-trifluoromethyl acrylate compound, an α, β-trifluoromethyl acrylate compound, and one or more types of vinyl moieties. And the like in which hydrogen is substituted with a fluorinated alkyl group such as a trifluoromethyl group.
(ii)の構造を有する重合体を与える単量体としては、例えばノルボルネン等の脂環式オレフィン化合物の側鎖がフッ素化アルキル基であるもの、アクリル酸又はメタクリル酸のフッ素化アルキルエステル化合物、1種類以上のオレフィンの側鎖(二重結合を含まない部位)がフッ素化アルキル基やその誘導体であるもの等が挙げられる。
Examples of the monomer that gives a polymer having the structure (ii) include those in which the side chain of an alicyclic olefin compound such as norbornene is a fluorinated alkyl group, a fluorinated alkyl ester compound of acrylic acid or methacrylic acid, One or more olefin side chains (sites not containing a double bond) are fluorinated alkyl groups or derivatives thereof.
(iii)の構造を有する重合体を与える単量体としては、例えばα-トリフルオロメチルアクリル酸、β-トリフルオロメチルアクリル酸、α,β-トリフルオロメチルアクリル酸等の側鎖がフッ素化アルキル基やその誘導体のエステル化合物、1種類以上のビニル部位の水素がトリフルオロメチル基等のフッ素化アルキル基で置換された化合物の側鎖をフッ素化アルキル基やその誘導体で置換したもの、1種類以上の脂環式オレフィン化合物の二重結合に結合している水素をトリフルオロメチル基等のフッ素化アルキル基で置換し、かつ側鎖がフッ素化アルキル基やその誘導体であるもの等が挙げられる。なお、脂環式オレフィン化合物とは、環の一部が二重結合である化合物を示す。
Examples of the monomer that gives a polymer having the structure (iii) include fluorinated side chains such as α-trifluoromethylacrylic acid, β-trifluoromethylacrylic acid, α, β-trifluoromethylacrylic acid, etc. An ester compound of an alkyl group or a derivative thereof, a compound in which the side chain of a compound in which hydrogen at one or more vinyl sites is substituted with a fluorinated alkyl group such as a trifluoromethyl group, or the like is substituted with a fluorinated alkyl group or a derivative thereof; Examples include those in which hydrogen bonded to the double bond of more than one kind of alicyclic olefin compound is substituted with a fluorinated alkyl group such as a trifluoromethyl group and the side chain is a fluorinated alkyl group or a derivative thereof. It is done. In addition, an alicyclic olefin compound shows the compound in which a part of ring is a double bond.
[A]重合体は、上記式(1)で表される構造単位(I)及び上記式(2)で表される構造単位(II)からなる群より選択される少なくとも1種の構造単位を有することが好ましい。また、[A]重合体は、構造単位(I)及び構造単位(II)以外の「他の構造単位」を有してもよい。[A]重合体は、各構造単位を2種以上有してよい。以下、各構造単位を詳述する。
[A] The polymer comprises at least one structural unit selected from the group consisting of the structural unit (I) represented by the formula (1) and the structural unit (II) represented by the formula (2). It is preferable to have. [A] The polymer may have “another structural unit” other than the structural unit (I) and the structural unit (II). [A] A polymer may have 2 or more types of each structural unit. Hereinafter, each structural unit will be described in detail.
[構造単位(I)]
構造単位(I)は上記式(1)で表される構造単位である。上記式(1)中、R1は、水素原子、フッ素原子、メチル基又はトリフルオロメチル基である。R2は、炭素数1~6の直鎖状若しくは分岐状のアルキル基又は炭素数4~20の1価の脂環式炭化水素基である。但し、上記アルキル基及び脂環式炭化水素基が有する水素原子の少なくとも一部は、フッ素原子で置換されている。 [Structural unit (I)]
The structural unit (I) is a structural unit represented by the above formula (1). In said formula (1), R < 1 > is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R 2 is a linear or branched alkyl group having 1 to 6 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms. However, at least a part of the hydrogen atoms of the alkyl group and the alicyclic hydrocarbon group are substituted with fluorine atoms.
構造単位(I)は上記式(1)で表される構造単位である。上記式(1)中、R1は、水素原子、フッ素原子、メチル基又はトリフルオロメチル基である。R2は、炭素数1~6の直鎖状若しくは分岐状のアルキル基又は炭素数4~20の1価の脂環式炭化水素基である。但し、上記アルキル基及び脂環式炭化水素基が有する水素原子の少なくとも一部は、フッ素原子で置換されている。 [Structural unit (I)]
The structural unit (I) is a structural unit represented by the above formula (1). In said formula (1), R < 1 > is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R 2 is a linear or branched alkyl group having 1 to 6 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms. However, at least a part of the hydrogen atoms of the alkyl group and the alicyclic hydrocarbon group are substituted with fluorine atoms.
上記R2で表される炭素数1~6の直鎖状若しくは分岐状のアルキル基としては、例えばメチル基、エチル基、n-プロピル基、n-ブチル基等が挙げられる。
Examples of the linear or branched alkyl group having 1 to 6 carbon atoms represented by R 2 include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group.
上記R2で表される炭素数4~20の1価の脂環式炭化水素基としては、例えばシクロペンチル基、シクロペンチルプロピル基、シクロヘキシル基、シクロヘキシルメチル基、シクロヘプチル基、シクロオクチル基、シクロオクチルメチル基等が挙げられる。
Examples of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by R 2 include a cyclopentyl group, a cyclopentylpropyl group, a cyclohexyl group, a cyclohexylmethyl group, a cycloheptyl group, a cyclooctyl group, and a cyclooctyl group. A methyl group etc. are mentioned.
構造単位(I)としては、下記式(1-1)、式(1-2)で表される構造単位が好ましい。
As the structural unit (I), structural units represented by the following formulas (1-1) and (1-2) are preferable.
上記式(1-1)及び式(1-2)中、R1は、上記式(1)と同義である。
In the above formulas (1-1) and (1-2), R 1 has the same meaning as in the above formula (1).
構造単位(I)を与える単量体としては、例えばトリフルオロメチル(メタ)アクレート、2,2,2-トリフルオロエチル(メタ)アクリレート、パーフルオロエチル(メタ)アクリレート、パーフルオロn-プロピル(メタ)アクリレート、パーフルオロi-プロピル(メタ)アクリレート、パーフルオロn-ブチル(メタ)アクリレート、パーフルオロi-ブチル(メタ)アクリレート、パーフルオロt-ブチル(メタ)アクリレート、パーフルオロシクロヘキシル(メタ)アクリレート、2-(1,1,1,3,3,3-ヘキサフルオロ)プロピル(メタ)アクリレート、1-(2,2,3,3,4,4,5,5-オクタフルオロ)ペンチル(メタ)アクリレート、1-(2,2,3,3,4,4,5,5-オクタフルオロ)ヘキシル(メタ)アクリレート、パーフルオロシクロヘキシルメチル(メタ)アクリレート、1-(2,2,3,3,3-ペンタフルオロ)プロピル(メタ)アクリレート、1-(2,2,3,3,4,4,4-ヘプタフルオロ)ペンタ(メタ)アクリレート、1-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-ヘプタデカフルオロ)デシル(メタ)アクリレート、1-(5-トリフルオロメチル-3,3,4,4,5,6,6,6-オクタフルオロ)ヘキシル(メタ)アクリレート等が挙げられる。
Examples of the monomer that gives the structural unit (I) include trifluoromethyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro n-propyl ( (Meth) acrylate, perfluoro i-propyl (meth) acrylate, perfluoro n-butyl (meth) acrylate, perfluoro i-butyl (meth) acrylate, perfluoro t-butyl (meth) acrylate, perfluorocyclohexyl (meth) Acrylate, 2- (1,1,1,3,3,3-hexafluoro) propyl (meth) acrylate, 1- (2,2,3,3,4,4,5,5-octafluoro) pentyl ( (Meth) acrylate, 1- (2,2,3,3,4,4,5,5-octafluoro) hex (Meth) acrylate, perfluorocyclohexylmethyl (meth) acrylate, 1- (2,2,3,3,3-pentafluoro) propyl (meth) acrylate, 1- (2,2,3,3,4, 4,4-Heptafluoro) penta (meth) acrylate, 1- (3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10- Heptadecafluoro) decyl (meth) acrylate, 1- (5-trifluoromethyl-3,3,4,4,5,6,6,6-octafluoro) hexyl (meth) acrylate and the like.
[A]重合体における構造単位(I)の含有割合としては、全構造単位に対して30モル%~100モル%が好ましい。
[A] The content of the structural unit (I) in the polymer is preferably 30 mol% to 100 mol% with respect to the total structural units.
[構造単位(II)]
構造単位(II)は、上記式(2)で表される構造単位である。上記式(2)中、R3は、水素原子、メチル基又はトリフルオロメチル基である。R4は、(m+1)価の連結基である。Xは、フッ素原子を有する2価の連結基である。R5は、水素原子又は1価の有機基である。mは、1~3の整数である。但し、mが複数の場合、複数のX及びR5は、それぞれ同一であっても異なっていてもよい。 [Structural unit (II)]
The structural unit (II) is a structural unit represented by the above formula (2). In the above formula (2), R 3 is a hydrogen atom, a methyl group or a trifluoromethyl group. R 4 is a (m + 1) -valent linking group. X is a divalent linking group having a fluorine atom. R 5 is a hydrogen atom or a monovalent organic group. m is an integer of 1 to 3. However, when m is plural, the plural X and R 5 may be the same or different.
構造単位(II)は、上記式(2)で表される構造単位である。上記式(2)中、R3は、水素原子、メチル基又はトリフルオロメチル基である。R4は、(m+1)価の連結基である。Xは、フッ素原子を有する2価の連結基である。R5は、水素原子又は1価の有機基である。mは、1~3の整数である。但し、mが複数の場合、複数のX及びR5は、それぞれ同一であっても異なっていてもよい。 [Structural unit (II)]
The structural unit (II) is a structural unit represented by the above formula (2). In the above formula (2), R 3 is a hydrogen atom, a methyl group or a trifluoromethyl group. R 4 is a (m + 1) -valent linking group. X is a divalent linking group having a fluorine atom. R 5 is a hydrogen atom or a monovalent organic group. m is an integer of 1 to 3. However, when m is plural, the plural X and R 5 may be the same or different.
上記R4で表される(m+1)価の連結基としては、例えば炭素数1~30の直鎖状又は分岐状の炭化水素基、炭素数3~30の脂環式炭化水素基、炭素数6~30の芳香族炭化水素基、又はこれらの基と酸素原子、硫黄原子、エーテル基、エステル基、カルボニル基、イミノ基及びアミド基からなる群より選ばれる1種以上の基とを組み合わせた基等が挙げられる。また、上記(m+1)価の連結基は、置換基を有していてもよい。
Examples of the (m + 1) -valent linking group represented by R 4 include a linear or branched hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 30 carbon atoms, and a carbon number. 6-30 aromatic hydrocarbon groups, or these groups combined with one or more groups selected from the group consisting of oxygen atom, sulfur atom, ether group, ester group, carbonyl group, imino group and amide group Groups and the like. The (m + 1) -valent linking group may have a substituent.
上記炭素数1~30の直鎖状又は分岐状の炭化水素基としては、例えばメタン、エタン、プロパン、ブタン、ペンタン、ヘキサン、ヘプタン、デカン、イコサン、トリアコンタン等の炭化水素基から(m+1)個の水素原子を除いた基等が挙げられる。
Examples of the linear or branched hydrocarbon group having 1 to 30 carbon atoms include hydrocarbon groups such as methane, ethane, propane, butane, pentane, hexane, heptane, decane, icosane and triacontane (m + 1). And a group excluding individual hydrogen atoms.
上記炭素数3~30の脂環式炭化水素基としては、例えば
シクロプロパン、シクロブタン、シクロペンタン、シクロヘキサン、シクロヘプタン、シクロオクタン、シクロデカン、メチルシクロヘキサン、エチルシクロヘキサン等の単環式飽和炭化水素;
シクロブテン、シクロペンテン、シクロヘキセン、シクロヘプテン、シクロオクテン、シクロデセン、シクロペンタジエン、シクロヘキサジエン、シクロオクタジエン、シクロデカジエン等の単環式不飽和炭化水素;
ビシクロ[2.2.1]ヘプタン、ビシクロ[2.2.2]オクタン、トリシクロ[5.2.1.02,6]デカン、トリシクロ[3.3.1.13,7]デカン、テトラシクロ[6.2.1.13,6.02,7]ドデカン、アダマンタン等の多環式飽和炭化水素;
ビシクロ[2.2.1]ヘプテン、ビシクロ[2.2.2]オクテン、トリシクロ[5.2.1.02,6]デセン、トリシクロ[3.3.1.13,7]デセン、テトラシクロ[6.2.1.13,6.02,7]ドデセン等の多環式炭化水素基から(m+1)個の水素原子を除いた基等が挙げられる。 Examples of the alicyclic hydrocarbon group having 3 to 30 carbon atoms include monocyclic saturated hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, methylcyclohexane, and ethylcyclohexane;
Monocyclic unsaturated hydrocarbons such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclopentadiene, cyclohexadiene, cyclooctadiene, cyclodecadiene;
Bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 2,6 ] decane, tricyclo [3.3.1.1 3,7 ] decane, Tetracyclo [6.2.1.1 3,6 . 0 2,7 ] polycyclic saturated hydrocarbons such as dodecane and adamantane;
Bicyclo [2.2.1] heptene, bicyclo [2.2.2] octene, tricyclo [5.2.1.0 2,6 ] decene, tricyclo [3.3.1.1 3,7 ] decene, Tetracyclo [6.2.1.1 3,6 . And a group obtained by removing (m + 1) hydrogen atoms from a polycyclic hydrocarbon group such as 0 2,7 ] dodecene.
シクロプロパン、シクロブタン、シクロペンタン、シクロヘキサン、シクロヘプタン、シクロオクタン、シクロデカン、メチルシクロヘキサン、エチルシクロヘキサン等の単環式飽和炭化水素;
シクロブテン、シクロペンテン、シクロヘキセン、シクロヘプテン、シクロオクテン、シクロデセン、シクロペンタジエン、シクロヘキサジエン、シクロオクタジエン、シクロデカジエン等の単環式不飽和炭化水素;
ビシクロ[2.2.1]ヘプタン、ビシクロ[2.2.2]オクタン、トリシクロ[5.2.1.02,6]デカン、トリシクロ[3.3.1.13,7]デカン、テトラシクロ[6.2.1.13,6.02,7]ドデカン、アダマンタン等の多環式飽和炭化水素;
ビシクロ[2.2.1]ヘプテン、ビシクロ[2.2.2]オクテン、トリシクロ[5.2.1.02,6]デセン、トリシクロ[3.3.1.13,7]デセン、テトラシクロ[6.2.1.13,6.02,7]ドデセン等の多環式炭化水素基から(m+1)個の水素原子を除いた基等が挙げられる。 Examples of the alicyclic hydrocarbon group having 3 to 30 carbon atoms include monocyclic saturated hydrocarbons such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, methylcyclohexane, and ethylcyclohexane;
Monocyclic unsaturated hydrocarbons such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclopentadiene, cyclohexadiene, cyclooctadiene, cyclodecadiene;
Bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, tricyclo [5.2.1.0 2,6 ] decane, tricyclo [3.3.1.1 3,7 ] decane, Tetracyclo [6.2.1.1 3,6 . 0 2,7 ] polycyclic saturated hydrocarbons such as dodecane and adamantane;
Bicyclo [2.2.1] heptene, bicyclo [2.2.2] octene, tricyclo [5.2.1.0 2,6 ] decene, tricyclo [3.3.1.1 3,7 ] decene, Tetracyclo [6.2.1.1 3,6 . And a group obtained by removing (m + 1) hydrogen atoms from a polycyclic hydrocarbon group such as 0 2,7 ] dodecene.
炭素数6~30の芳香族炭化水素基としては、例えばベンゼン、ナフタレン、フェナントレン、アントラセン、テトラセン、ペンタセン、ピレン、ピセン、トルエン、キシレン、エチルベンゼン、メシチレン、クメン等の芳香族炭化水素基から(m+1)個の水素原子を除いた基等が挙げられる。
Examples of the aromatic hydrocarbon group having 6 to 30 carbon atoms include (m + 1) from aromatic hydrocarbon groups such as benzene, naphthalene, phenanthrene, anthracene, tetracene, pentacene, pyrene, picene, toluene, xylene, ethylbenzene, mesitylene, cumene and the like. ) Groups from which a single hydrogen atom is removed.
上記(m+1)価の連結基が有していてもよい置換基としては、例えばメチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、2-メチルプロピル基、1-メチルプロピル基、t-ブチル基、シクロヘキシル基等のアルキル基、ヒドロキシ基、シアノ基、炭素数1~10のヒドロキシアルキル基、カルボキシ基、カルボニル基等が挙げられる。
Examples of the substituent that the (m + 1) -valent linking group may have include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, 1- Examples thereof include alkyl groups such as methylpropyl group, t-butyl group and cyclohexyl group, hydroxy group, cyano group, hydroxyalkyl group having 1 to 10 carbon atoms, carboxy group, carbonyl group and the like.
上記Xで表されるフッ素原子を有する2価の連結基としては、フッ素原子を有する炭素数1~20の2価の直鎖状炭化水素基等が挙げられる。フッ素原子を有する炭素数1~20の2価の直鎖状炭化水素基としては、例えば下記式(X-1)~(X-6)で表される基等が挙げられる。
Examples of the divalent linking group having a fluorine atom represented by X include a C 1-20 divalent linear hydrocarbon group having a fluorine atom. Examples of the divalent linear hydrocarbon group having 1 to 20 carbon atoms having a fluorine atom include groups represented by the following formulas (X-1) to (X-6).
Xとしては、上記式(X-1)、式(X-2)で表される基が好ましい。
X is preferably a group represented by the above formula (X-1) or (X-2).
上記R5で表される1価の有機基としては、例えば炭素数1~30の直鎖状若しくは分岐状の炭化水素基、炭素数3~30の脂環式炭化水素基、炭素数6~30の芳香族炭化水素基、又はこれらの基と酸素原子、硫黄原子、エーテル基、エステル基、カルボニル基、イミノ基及びアミド基からなる群より選ばれる1種以上の基とを組み合わせた基等が挙げられる。
Examples of the monovalent organic group represented by R 5 include linear or branched hydrocarbon groups having 1 to 30 carbon atoms, alicyclic hydrocarbon groups having 3 to 30 carbon atoms, and 6 to 6 carbon atoms. 30 aromatic hydrocarbon groups, or a combination of these groups and one or more groups selected from the group consisting of oxygen, sulfur, ether, ester, carbonyl, imino and amide groups, etc. Is mentioned.
上記R5で表される基としては、[A]重合体の現像液に対する溶解性を向上させる観点から水素原子が好ましい。
The group represented by R 5 is preferably a hydrogen atom from the viewpoint of improving the solubility of the [A] polymer in the developer.
上記構造単位(II)としては、例えば下記式(2-1)、式(2-2)で表される構造単位等が挙げられる。
Examples of the structural unit (II) include structural units represented by the following formulas (2-1) and (2-2).
上記式(2-1)中、R4は、炭素数1~20の2価の直鎖状、分岐状若しくは環状の飽和若しくは不飽和の炭化水素基である。R3、X及びR5は、上記式(2)と同義である。上記式(2-2)中、R3、X、R5及びmは、上記式(2)と同義である。但し、mが複数の場合、複数のX及びR5は、それぞれ同一であっても異なっていてもよい。
In the above formula (2-1), R 4 is a divalent linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms. R 3 , X and R 5 are as defined in the above formula (2). In the above formula (2-2), R 3 , X, R 5 and m are as defined in the above formula (2). However, when m is plural, the plural X and R 5 may be the same or different.
構造単位(II)としては、下記式で表される構造単位が好ましい。
The structural unit (II) is preferably a structural unit represented by the following formula.
上記式中、R3は、上記式(2)と同義である。
In said formula, R < 3 > is synonymous with the said Formula (2).
構造単位(II)を与える単量体としては、例えば(メタ)アクリル酸(1,1,1-トリフルオロ-2-トリフルオロメチル-2-ヒドロキシ-3-プロピル)エステル、(メタ)アクリル酸(1,1,1-トリフルオロ-2-トリフルオロメチル-2-ヒドロキシ-4-ブチル)エステル、(メタ)アクリル酸(1,1,1-トリフルオロ-2-トリフルオロメチル-2-ヒドロキシ-5-ペンチル)エステル、(メタ)アクリル酸(1,1,1-トリフルオロ-2-トリフルオロメチル-2-ヒドロキシ-4-ペンチル)エステル、(メタ)アクリル酸2-{[5-(1’,1’,1’-トリフルオロ-2’-トリフルオロメチル-2’-ヒドロキシ)プロピル]ビシクロ[2.2.1]ヘプチル}エステル等が挙げられる。
Examples of the monomer that gives structural unit (II) include (meth) acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-3-propyl) ester, (meth) acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-butyl) ester, (meth) acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy -5-pentyl) ester, (meth) acrylic acid (1,1,1-trifluoro-2-trifluoromethyl-2-hydroxy-4-pentyl) ester, (meth) acrylic acid 2-{[5- ( 1 ′, 1 ′, 1′-trifluoro-2′-trifluoromethyl-2′-hydroxy) propyl] bicyclo [2.2.1] heptyl} ester and the like.
[A]重合体における構造単位(II)の含有割合としては、全構造単位に対して30モル%~100モル%が好ましい。
[A] The content ratio of the structural unit (II) in the polymer is preferably 30 mol% to 100 mol% with respect to the total structural units.
[他の構造単位]
[A]重合体は、さらに「他の構造単位」として、現像液への溶解速度を制御するためにラクトン構造を有する構造単位、環状カーボネート構造を有する構造単位、エッチング耐性を高めるために脂環式構造を有する構造単位等を有してもよい。 [Other structural units]
[A] The polymer is further divided into “other structural units” as a structural unit having a lactone structure to control the dissolution rate in the developer, a structural unit having a cyclic carbonate structure, and an alicyclic ring to increase etching resistance. You may have a structural unit etc. which have a formula structure.
[A]重合体は、さらに「他の構造単位」として、現像液への溶解速度を制御するためにラクトン構造を有する構造単位、環状カーボネート構造を有する構造単位、エッチング耐性を高めるために脂環式構造を有する構造単位等を有してもよい。 [Other structural units]
[A] The polymer is further divided into “other structural units” as a structural unit having a lactone structure to control the dissolution rate in the developer, a structural unit having a cyclic carbonate structure, and an alicyclic ring to increase etching resistance. You may have a structural unit etc. which have a formula structure.
ラクトン構造を有する構造単位及び環状カーボネート構造を有する構造単位としては、例えば下記式で表される構造単位等が挙げられる。ここで、ラクトン構造を有する基とは、-O-C(O)-構造を含むひとつの環(ラクトン環)を含有する環式基を示す。ラクトン環を1つめの環として数え、ラクトン環のみの場合は単環式基、さらに他の環構造を有する場合は、その構造に関わらず多環式基と称する。
Examples of the structural unit having a lactone structure and the structural unit having a cyclic carbonate structure include a structural unit represented by the following formula. Here, the group having a lactone structure refers to a cyclic group containing one ring (lactone ring) containing an —O—C (O) — structure. The lactone ring is counted as the first ring, and when it is only the lactone ring, it is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of the structure.
上記式中、RL1は、水素原子、メチル基又はトリフルオロメチル基である。
In the above formula, R L1 is a hydrogen atom, a methyl group or a trifluoromethyl group.
ラクトン構造を有する構造単位を与える単量体としては、例えば下記式(L-1)で表される化合物等が挙げられる。上記ラクトン構造を有する構造単位を与える単量体としては、国際公開2007/116664号パンフレットに記載の単量体が好ましい。
Examples of the monomer that gives a structural unit having a lactone structure include a compound represented by the following formula (L-1). As the monomer that gives the structural unit having a lactone structure, monomers described in International Publication No. 2007/116664 pamphlet are preferable.
脂環式構造を有する構造単位としては、例えば下記式(4)で表される構造単位等が挙げられる。
Examples of the structural unit having an alicyclic structure include a structural unit represented by the following formula (4).
上記式(4)中、R6は、水素原子、メチル基又はトリフルオロメチル基である。X2は、炭素数4~20の脂環式炭化水素基である。
In the formula (4), R 6 is a hydrogen atom, a methyl group or a trifluoromethyl group. X 2 is an alicyclic hydrocarbon group having 4 to 20 carbon atoms.
炭素数4~20の脂環式炭化水素基としては、例えばシクロブタン、シクロペンタン、シクロヘキサン、ビシクロ[2.2.1]ヘプタン、ビシクロ[2.2.2]オクタン、トリシクロ[5.2.1.02,6]デカン、テトラシクロ[6.2.1.13,6.02,7]ドデカン、トリシクロ[3.3.1.13,7]デカン等が挙げられる。これらの炭素数4~20の脂環式炭化水素基は、置換基を有していてもよい。置換基としては例えばメチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、2-メチルプロピル基、1-メチルプロピル基、t-ブチル基等の炭素数1~4の直鎖状、分岐状又は環状のアルキル基、ヒドロキシル基、シアノ基、炭素数1~10のヒドロキシアルキル基、カルボキシ基、酸素原子等が挙げられる。
Examples of the alicyclic hydrocarbon group having 4 to 20 carbon atoms include cyclobutane, cyclopentane, cyclohexane, bicyclo [2.2.1] heptane, bicyclo [2.2.2] octane, and tricyclo [5.2.1]. .0 2,6] decane, tetracyclo [6.2.1.1 3,6. 0 2,7 ] dodecane, tricyclo [3.3.1.1 3,7 ] decane and the like. These alicyclic hydrocarbon groups having 4 to 20 carbon atoms may have a substituent. Examples of the substituent include those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group and t-butyl group. Examples thereof include a linear, branched or cyclic alkyl group, a hydroxyl group, a cyano group, a hydroxyalkyl group having 1 to 10 carbon atoms, a carboxy group, and an oxygen atom.
脂環式化合物を含む構造単位を与える単量体としては、例えば(メタ)アクリル酸-ビシクロ[2.2.1]ヘプト-2-イルエステル、(メタ)アクリル酸-ビシクロ[2.2.2]オクタ-2-イルエステル、(メタ)アクリル酸-トリシクロ[5.2.1.02,6]デカ-7-イルエステル、(メタ)アクリル酸-トリシクロ[3.3.1.13,7]デカ-1-イルエステル、(メタ)アクリル酸-トリシクロ[3.3.1.13,7]デカ-2-イルエステル等が挙げられる。
Examples of the monomer that gives a structural unit containing an alicyclic compound include (meth) acrylic acid-bicyclo [2.2.1] hept-2-yl ester and (meth) acrylic acid-bicyclo [2.2. 2] Oct-2-yl ester, (meth) acrylic acid-tricyclo [5.2.1.0 2,6 ] dec-7-yl ester, (meth) acrylic acid-tricyclo [3.3.1.1] 3,7 ] dec-1-yl ester, (meth) acrylic acid-tricyclo [3.3.1.1 3,7 ] dec-2-yl ester, and the like.
なお、[A]重合体は芳香族基を有する構造単位を有さないことが好ましい。特にArF光源を用いる場合に、感度の低下の原因となる場合がある。
In addition, it is preferable that the [A] polymer does not have a structural unit having an aromatic group. In particular, when an ArF light source is used, it may cause a decrease in sensitivity.
<[A]重合体の合成方法>
[A]重合体は、例えば所定の各構造単位に対応する単量体を、ラジカル重合開始剤を使用し、適当な溶媒中で重合することにより製造できる。 <[A] Polymer Synthesis Method>
[A] The polymer can be produced, for example, by polymerizing a monomer corresponding to each predetermined structural unit in a suitable solvent using a radical polymerization initiator.
[A]重合体は、例えば所定の各構造単位に対応する単量体を、ラジカル重合開始剤を使用し、適当な溶媒中で重合することにより製造できる。 <[A] Polymer Synthesis Method>
[A] The polymer can be produced, for example, by polymerizing a monomer corresponding to each predetermined structural unit in a suitable solvent using a radical polymerization initiator.
上記重合に使用される溶媒としては、例えば
n-ペンタン、n-ヘキサン、n-ヘプタン、n-オクタン、n-ノナン、n-デカン等のアルカン類;
シクロヘキサン、シクロヘプタン、シクロオクタン、デカリン、ノルボルナン等のシクロアルカン類;
ベンゼン、トルエン、キシレン、エチルベンゼン、クメン等の芳香族炭化水素類;
クロロブタン類、ブロモヘキサン類、ジクロロエタン類、ヘキサメチレンジブロミド、クロロベンゼン等のハロゲン化炭化水素類;
酢酸エチル、酢酸n-ブチル、酢酸i-ブチル、プロピオン酸メチル等の飽和カルボン酸エステル類;
アセトン、2-ブタノン、4-メチル-2-ペンタノン、2-ヘプタノン等のケトン類;
テトラヒドロフラン、ジメトキシエタン類、ジエトキシエタン類等のエーテル類;
メタノール、エタノール、1-プロパノール、2-プロパノール、4-メチル-2-ペンタノール等のアルコール類等が挙げられる。これらの溶媒は、単独で使用してもよく2種以上を併用してもよい。 Examples of the solvent used for the polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane;
Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane;
Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene;
Halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide, chlorobenzene;
Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate and methyl propionate;
Ketones such as acetone, 2-butanone, 4-methyl-2-pentanone, 2-heptanone;
Ethers such as tetrahydrofuran, dimethoxyethanes, diethoxyethanes;
Examples thereof include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, and 4-methyl-2-pentanol. These solvents may be used alone or in combination of two or more.
n-ペンタン、n-ヘキサン、n-ヘプタン、n-オクタン、n-ノナン、n-デカン等のアルカン類;
シクロヘキサン、シクロヘプタン、シクロオクタン、デカリン、ノルボルナン等のシクロアルカン類;
ベンゼン、トルエン、キシレン、エチルベンゼン、クメン等の芳香族炭化水素類;
クロロブタン類、ブロモヘキサン類、ジクロロエタン類、ヘキサメチレンジブロミド、クロロベンゼン等のハロゲン化炭化水素類;
酢酸エチル、酢酸n-ブチル、酢酸i-ブチル、プロピオン酸メチル等の飽和カルボン酸エステル類;
アセトン、2-ブタノン、4-メチル-2-ペンタノン、2-ヘプタノン等のケトン類;
テトラヒドロフラン、ジメトキシエタン類、ジエトキシエタン類等のエーテル類;
メタノール、エタノール、1-プロパノール、2-プロパノール、4-メチル-2-ペンタノール等のアルコール類等が挙げられる。これらの溶媒は、単独で使用してもよく2種以上を併用してもよい。 Examples of the solvent used for the polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane;
Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane;
Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene;
Halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide, chlorobenzene;
Saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, i-butyl acetate and methyl propionate;
Ketones such as acetone, 2-butanone, 4-methyl-2-pentanone, 2-heptanone;
Ethers such as tetrahydrofuran, dimethoxyethanes, diethoxyethanes;
Examples thereof include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, and 4-methyl-2-pentanol. These solvents may be used alone or in combination of two or more.
上記重合における反応温度としては、通常40℃~150℃、50℃~120℃が好ましい。反応時間としては、通常1時間~48時間、1時間~24時間が好ましい。
The reaction temperature in the above polymerization is usually preferably 40 ° C to 150 ° C and 50 ° C to 120 ° C. The reaction time is usually preferably 1 hour to 48 hours and 1 hour to 24 hours.
[A]重合体のゲルパーミエーションクロマトグラフィ(GPC)法によるポリスチレン換算重量平均分子量(Mw)としては、1,000~50,000が好ましく、1,000~30,000がより好ましく、1,000~10,000が特に好ましい。[A]重合体のMwが1,000未満の場合、十分な前進接触角を得ることができない。一方、Mwが50,000を超えると、レジストとした際の現像性が低下する傾向にある。
[A] The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer is preferably 1,000 to 50,000, more preferably 1,000 to 30,000, and 1,000. ˜10,000 is particularly preferred. [A] When the Mw of the polymer is less than 1,000, a sufficient advancing contact angle cannot be obtained. On the other hand, when Mw exceeds 50,000, the developability of the resist tends to decrease.
[A]重合体のMwとGPC法によるポリスチレン換算数平均分子量(Mn)との比(Mw/Mn)としては、通常1~3であり、好ましくは1~2である。なお、本明細書におけるMw及びMnは、GPCカラム(東ソー社、G2000HXL 2本、G3000HXL 1本、G4000HXL 1本)を用い、以下の条件により測定した。
カラム温度:40℃
溶出溶媒:テトラヒドロフラン(和光純薬工業社)
流速:1.0mL/分
試料濃度:1.0質量%
試料注入量:100μL
検出器:示差屈折計
標準物質:単分散ポリスチレン [A] The ratio (Mw / Mn) of the polymer Mw to the polystyrene-equivalent number average molecular weight (Mn) by GPC method is usually 1 to 3, preferably 1 to 2. In addition, Mw and Mn in this specification were measured on the following conditions using the GPC column (Tosoh Corp., 2 G2000HXL, 1 G3000HXL, 1 G4000HXL).
Column temperature: 40 ° C
Elution solvent: Tetrahydrofuran (Wako Pure Chemical Industries)
Flow rate: 1.0 mL / min Sample concentration: 1.0 mass%
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene
カラム温度:40℃
溶出溶媒:テトラヒドロフラン(和光純薬工業社)
流速:1.0mL/分
試料濃度:1.0質量%
試料注入量:100μL
検出器:示差屈折計
標準物質:単分散ポリスチレン [A] The ratio (Mw / Mn) of the polymer Mw to the polystyrene-equivalent number average molecular weight (Mn) by GPC method is usually 1 to 3, preferably 1 to 2. In addition, Mw and Mn in this specification were measured on the following conditions using the GPC column (Tosoh Corp., 2 G2000HXL, 1 G3000HXL, 1 G4000HXL).
Column temperature: 40 ° C
Elution solvent: Tetrahydrofuran (Wako Pure Chemical Industries)
Flow rate: 1.0 mL / min Sample concentration: 1.0 mass%
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene
<[B]重合体>
[B]重合体は、酸解離性基を有する構造単位の含有が10モル%を超える重合体である。また、[B]重合体は、酸の作用により極性が増大し、有機溶媒を含有する現像液に対して難溶又は不溶となる重合体である。 <[B] polymer>
[B] The polymer is a polymer containing more than 10 mol% of a structural unit having an acid dissociable group. In addition, the [B] polymer is a polymer whose polarity is increased by the action of an acid and hardly or insoluble in a developer containing an organic solvent.
[B]重合体は、酸解離性基を有する構造単位の含有が10モル%を超える重合体である。また、[B]重合体は、酸の作用により極性が増大し、有機溶媒を含有する現像液に対して難溶又は不溶となる重合体である。 <[B] polymer>
[B] The polymer is a polymer containing more than 10 mol% of a structural unit having an acid dissociable group. In addition, the [B] polymer is a polymer whose polarity is increased by the action of an acid and hardly or insoluble in a developer containing an organic solvent.
[構造単位(III)]
酸解離性基を有する構造単位としては、例えば下記式(5)で表される構造単位(III)等が挙げられる。 [Structural unit (III)]
Examples of the structural unit having an acid dissociable group include structural unit (III) represented by the following formula (5).
酸解離性基を有する構造単位としては、例えば下記式(5)で表される構造単位(III)等が挙げられる。 [Structural unit (III)]
Examples of the structural unit having an acid dissociable group include structural unit (III) represented by the following formula (5).
上記式(5)中、R7は、水素原子、メチル基又はトリフルオロメチル基である。Rpは、酸解離性基である。
In the above formula (5), R 7 is a hydrogen atom, a methyl group or a trifluoromethyl group. R p is an acid dissociable group.
上記Rpで表される酸解離性基としては、下記式(6)で表される基が好ましい。
The acid dissociable group represented by R p is preferably a group represented by the following formula (6).
上記式(6)中、Rp1は、炭素数1~4のアルキル基又は炭素数4~20の1価の脂環式炭化水素基である。Rp2及びRp3は、それぞれ独立して炭素数1~4のアルキル基又は炭素数4~20の脂環式炭化水素基である。なお、Rp2及びRp3は相互に結合して、それぞれが結合している炭素原子と共に炭素数4~20の2価の脂環式炭化水素基を形成してもよい。但し、これらの基が有する水素原子の一部又は全部は、炭素数1~10の直鎖状、分岐状若しくは環状のアルキル基で置換されていてもよい。
In the above formula (6), R p1 is an alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms. R p2 and R p3 are each independently an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 4 to 20 carbon atoms. R p2 and R p3 may be bonded to each other to form a divalent alicyclic hydrocarbon group having 4 to 20 carbon atoms together with the carbon atoms to which R p2 and R p3 are bonded. However, some or all of the hydrogen atoms of these groups may be substituted with a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.
上記Rp1、Rp2及びRp3で表される炭素数1~4のアルキル基としては、例えばメチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、2-メチルプロピル基、1-メチルプロピル基、t-ブチル基等が挙げられる。
Examples of the alkyl group having 1 to 4 carbon atoms represented by R p1 , R p2 and R p3 include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and 2-methylpropyl. Group, 1-methylpropyl group, t-butyl group and the like.
上記Rp1、Rp2及びRp3で表される炭素数4~20の1価の脂環式炭化水素基としては、例えば
アダマンタン骨格、ノルボルナン骨格等の有橋式骨格を有する多環の脂環式基;
シクロペンタン、シクロヘキサン等のシクロアルカン骨格を有する単環の脂環式基が挙げられる。 Examples of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by R p1 , R p2 and R p3 include polycyclic alicyclic rings having a bridged skeleton such as an adamantane skeleton and a norbornane skeleton. A formula group;
And monocyclic alicyclic groups having a cycloalkane skeleton such as cyclopentane and cyclohexane.
アダマンタン骨格、ノルボルナン骨格等の有橋式骨格を有する多環の脂環式基;
シクロペンタン、シクロヘキサン等のシクロアルカン骨格を有する単環の脂環式基が挙げられる。 Examples of the monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms represented by R p1 , R p2 and R p3 include polycyclic alicyclic rings having a bridged skeleton such as an adamantane skeleton and a norbornane skeleton. A formula group;
And monocyclic alicyclic groups having a cycloalkane skeleton such as cyclopentane and cyclohexane.
Rpで表される酸解離性基としては、Rp1が炭素数1~4のアルキル基であり、Rp2及びRp3が相互に結合してそれぞれが結合している炭素原子とともにアダマンタン骨格又はシクロアルカン骨格を有する2価の基を形成することが好ましい。
As the acid dissociable group represented by R p , R p1 is an alkyl group having 1 to 4 carbon atoms, R p2 and R p3 are bonded to each other, and together with the carbon atom to which each is bonded, an adamantane skeleton or It is preferable to form a divalent group having a cycloalkane skeleton.
構造単位(III)としては、例えば下記式で表される構造単位等が挙げられる。
Examples of the structural unit (III) include a structural unit represented by the following formula.
上記式中、R7は、上記式(5)と同義である。
In said formula, R < 7 > is synonymous with the said Formula (5).
[B]重合体における構造単位(III)の含有割合としては、全構造単位に対して20モル%~60モル%が好ましい。なお、[B]重合体は構造単位(III)を1種、又は2種以上を有してもよい。
[B] The content of the structural unit (III) in the polymer is preferably 20 mol% to 60 mol% with respect to the total structural units. In addition, the [B] polymer may have 1 type, or 2 or more types of structural units (III).
[構造単位(IV)]
[B]重合体は、フッ素原子を有さず、かつラクトン構造を有するアクリル酸エステルから誘導される構造単位(IV)を有することが好ましい。[B]重合体が、構造単位(IV)を有することで、レジスト膜の基板への密着性を向上できる。構造単位(IV)としては、上述の「他の構造単位」としてのラクトン構造を有する構造単位と同様の構造単位であってフッ素原子を有さない構造単位が適用できる。 [Structural unit (IV)]
[B] The polymer preferably has a structural unit (IV) that does not have a fluorine atom and is derived from an acrylate ester having a lactone structure. [B] Since the polymer has the structural unit (IV), the adhesion of the resist film to the substrate can be improved. As the structural unit (IV), a structural unit similar to the structural unit having a lactone structure as the “other structural unit” described above and having no fluorine atom can be applied.
[B]重合体は、フッ素原子を有さず、かつラクトン構造を有するアクリル酸エステルから誘導される構造単位(IV)を有することが好ましい。[B]重合体が、構造単位(IV)を有することで、レジスト膜の基板への密着性を向上できる。構造単位(IV)としては、上述の「他の構造単位」としてのラクトン構造を有する構造単位と同様の構造単位であってフッ素原子を有さない構造単位が適用できる。 [Structural unit (IV)]
[B] The polymer preferably has a structural unit (IV) that does not have a fluorine atom and is derived from an acrylate ester having a lactone structure. [B] Since the polymer has the structural unit (IV), the adhesion of the resist film to the substrate can be improved. As the structural unit (IV), a structural unit similar to the structural unit having a lactone structure as the “other structural unit” described above and having no fluorine atom can be applied.
[B]重合体における構造単位(IV)の含有割合としては、全構造単位に対して30モル%~60モル%が好ましい。
[B] The content ratio of the structural unit (IV) in the polymer is preferably 30 mol% to 60 mol% with respect to the total structural units.
[その他の構造単位]
[B]重合体は、構造単位(III)及び構造単位(IV)とは異なるその他の構造単位を有していてもよい。その他の構造単位としては、例えば極性基を含む下記式で表される構造単位等が挙げられる。 [Other structural units]
[B] The polymer may have other structural units different from the structural unit (III) and the structural unit (IV). Examples of the other structural unit include a structural unit represented by the following formula containing a polar group.
[B]重合体は、構造単位(III)及び構造単位(IV)とは異なるその他の構造単位を有していてもよい。その他の構造単位としては、例えば極性基を含む下記式で表される構造単位等が挙げられる。 [Other structural units]
[B] The polymer may have other structural units different from the structural unit (III) and the structural unit (IV). Examples of the other structural unit include a structural unit represented by the following formula containing a polar group.
上記式中、R8は水素原子、フッ素原子、メチル基又はトリフルオロメチル基である。
In the above formula, R 8 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
[B]重合体における構造単位(V)の含有率としては、0モル%~30モル%が好ましく、0モル%~20モル%がより好ましい。
[B] The content of the structural unit (V) in the polymer is preferably 0 mol% to 30 mol%, more preferably 0 mol% to 20 mol%.
<[B]重合体の合成方法>
[B]重合体は、例えば所定の各構造単位に対応する単量体を、ラジカル重合開始剤を使用し、適当な溶媒中で重合することにより製造できる。 <[B] Polymer Synthesis Method>
[B] The polymer can be produced, for example, by polymerizing a monomer corresponding to each predetermined structural unit in a suitable solvent using a radical polymerization initiator.
[B]重合体は、例えば所定の各構造単位に対応する単量体を、ラジカル重合開始剤を使用し、適当な溶媒中で重合することにより製造できる。 <[B] Polymer Synthesis Method>
[B] The polymer can be produced, for example, by polymerizing a monomer corresponding to each predetermined structural unit in a suitable solvent using a radical polymerization initiator.
重合に使用される溶媒としては、例えば[A]重合体の合成方法で挙げたものと同様の溶媒が挙げられる。重合における反応温度としては、通常40℃~150℃、50℃~120℃が好ましい。反応時間としては、通常1時間~48時間、1時間~24時間が好ましい。
Examples of the solvent used for the polymerization include the same solvents as mentioned in the method for synthesizing [A] polymer. The reaction temperature in the polymerization is usually preferably 40 ° C. to 150 ° C. and 50 ° C. to 120 ° C. The reaction time is usually preferably 1 hour to 48 hours and 1 hour to 24 hours.
[B]重合体のGPC法によるMwとしては、1,000~100,000が好ましく、1,000~50,000がより好ましく、1,000~30,000が特に好ましい。[B]重合体のMwを上記特定範囲とすることで、レジストとして用いるのに充分なレジスト溶媒への溶解性があり、かつ耐ドライエッチング性やレジストパターン断面形状が良好となる。[B]重合体のMwとMnとの比(Mw/Mn)としては、通常1~3であり、好ましくは1~2である。
[B] The Mw of the polymer by GPC method is preferably 1,000 to 100,000, more preferably 1,000 to 50,000, and particularly preferably 1,000 to 30,000. [B] By setting the Mw of the polymer in the above specific range, the polymer has sufficient solubility in a resist solvent to be used as a resist, and the dry etching resistance and resist pattern cross-sectional shape are improved. [B] The ratio of Mw to Mn (Mw / Mn) of the polymer is usually 1 to 3, and preferably 1 to 2.
<[C]感放射線性酸発生体>
[C]感放射線性酸発生体は、露光により酸を発生し、その酸により[B]重合体中に存在する酸解離性基を解離させ酸を発生させる。当該感放射線性樹脂組成物における[C]感放射線性酸発生体の含有形態としては、後述するような化合物の形態(以下、適宜「[C]感放射線性酸発生剤」とも称する)でも、[B]重合体若しくはその他の重合体の構造単位として含有される形態でも、これらの両方を組み合わせた形態でもよい。 <[C] Radiation sensitive acid generator>
[C] The radiation sensitive acid generator generates an acid upon exposure, and the acid dissociates an acid dissociable group present in the [B] polymer to generate an acid. As the containing form of the [C] radiation sensitive acid generator in the radiation sensitive resin composition, even in the form of a compound as described later (hereinafter also referred to as “[C] radiation sensitive acid generator” as appropriate) [B] The form may be contained as a structural unit of a polymer or other polymer, or may be a form in which both are combined.
[C]感放射線性酸発生体は、露光により酸を発生し、その酸により[B]重合体中に存在する酸解離性基を解離させ酸を発生させる。当該感放射線性樹脂組成物における[C]感放射線性酸発生体の含有形態としては、後述するような化合物の形態(以下、適宜「[C]感放射線性酸発生剤」とも称する)でも、[B]重合体若しくはその他の重合体の構造単位として含有される形態でも、これらの両方を組み合わせた形態でもよい。 <[C] Radiation sensitive acid generator>
[C] The radiation sensitive acid generator generates an acid upon exposure, and the acid dissociates an acid dissociable group present in the [B] polymer to generate an acid. As the containing form of the [C] radiation sensitive acid generator in the radiation sensitive resin composition, even in the form of a compound as described later (hereinafter also referred to as “[C] radiation sensitive acid generator” as appropriate) [B] The form may be contained as a structural unit of a polymer or other polymer, or may be a form in which both are combined.
[C]感放射線性酸発生剤としては、例えばオニウム塩化合物、スルホンイミド化合物、ハロゲン含有化合物、ジアゾケトン化合物等が挙げられる。これらの[C]感放射線性酸発生剤のうち、オニウム塩化合物が好ましい。
[C] Examples of the radiation sensitive acid generator include onium salt compounds, sulfonimide compounds, halogen-containing compounds, diazoketone compounds and the like. Of these [C] radiation sensitive acid generators, onium salt compounds are preferred.
オニウム塩化合物としては、例えばスルホニウム塩(テトラヒドロチオフェニウム塩を含む)、ヨードニウム塩、ホスホニウム塩、ジアゾニウム塩、ピリジニウム塩等が挙げられる。
Examples of the onium salt compounds include sulfonium salts (including tetrahydrothiophenium salts), iodonium salts, phosphonium salts, diazonium salts, pyridinium salts, and the like.
スルホニウム塩としては、例えばトリフェニルスルホニウムトリフルオロメタンスルホネート、トリフェニルスルホニウムノナフルオロ-n-ブタンスルホネート、トリフェニルスルホニウムパーフルオロ-n-オクタンスルホネート、トリフェニルスルホニウム2-ビシクロ[2.2.1]ヘプト-2-イル-1,1,2,2-テトラフルオロエタンスルホネート、トリフェニルスルホニウムカンファースルホネート、4-シクロヘキシルフェニルジフェニルスルホニウムトリフルオロメタンスルホネート、4-シクロヘキシルフェニルジフェニルスルホニウムノナフルオロ-n-ブタンスルホネート、4-シクロヘキシルフェニルジフェニルスルホニウムパーフルオロ-n-オクタンスルホネート、4-シクロヘキシルフェニルジフェニルスルホニウム2-ビシクロ[2.2.1]ヘプト-2-イル-1,1,2,2-テトラフルオロエタンスルホネート、4-シクロヘキシルフェニルジフェニルスルホニウムカンファースルホネート、4-メタンスルホニルフェニルジフェニルスルホニウムトリフルオロメタンスルホネート、4-メタンスルホニルフェニルジフェニルスルホニウムノナフルオロ-n-ブタンスルホネート、4-メタンスルホニルフェニルジフェニルスルホニウムパーフルオロ-n-オクタンスルホネート、4-メタンスルホニルフェニルジフェニルスルホニウム2-ビシクロ[2.2.1]ヘプト-2-イル-1,1,2,2-テトラフルオロエタンスルホネート、4-メタンスルホニルフェニルジフェニルスルホニウムカンファースルホネート、トリフェニルホスホニウム1,1,2,2-テトラフルオロ-6-(1-アダマンタンカルボニロキシ)-ヘキサン-1-スルホネート等が挙げられる。これらのうち、トリフェニルスルホニウムトリフルオロメタンスルホネート、トリフェニルスルホニウムノナフルオロ-n-ブタンスルホネート及びトリフェニルホスホニウム1,1,2,2-テトラフルオロ-6-(1-アダマンタンカルボニロキシ)-ヘキサン-1-スルホネートが好ましい。
Examples of the sulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo [2.2.1] hept- 2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium camphorsulfonate, 4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexyl Phenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-cyclohexylphenyl diphe Rusulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium camphorsulfonate, 4-methanesulfonylphenyldiphenylsulfonium trifluoromethanesulfonate 4-methanesulfonylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium 2-bicyclo [2.2.1] hept- 2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium camphorsulfonate, trif Niruhosuhoniumu 1,1,2,2-tetrafluoro-6- (1-adamantanecarbonyloxy) - hexane-1-sulfonate, and the like. Of these, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate and triphenylphosphonium 1,1,2,2-tetrafluoro-6- (1-adamantane carbonyloxy) -hexane-1 Sulfonate is preferred.
テトラヒドロチオフェニウム塩としては、例えば1-(4-n-ブトキシナフタレン-1-イル)テトラヒドロチオフェニウムトリフルオロメタンスルホネート、1-(4-n-ブトキシナフタレン-1-イル)テトラヒドロチオフェニウムノナフルオロ-n-ブタンスルホネート、1-(4-n-ブトキシナフタレン-1-イル)テトラヒドロチオフェニウムパーフルオロ-n-オクタンスルホネート、1-(4-n-ブトキシナフタレン-1-イル)テトラヒドロチオフェニウム2-ビシクロ[2.2.1]ヘプト-2-イル-1,1,2,2-テトラフルオロエタンスルホネート、1-(4-n-ブトキシナフタレン-1-イル)テトラヒドロチオフェニウムカンファースルホネート、1-(6-n-ブトキシナフタレン-2-イル)テトラヒドロチオフェニウムトリフルオロメタンスルホネート、1-(6-n-ブトキシナフタレン-2-イル)テトラヒドロチオフェニウムノナフルオロ-n-ブタンスルホネート、1-(6-n-ブトキシナフタレン-2-イル)テトラヒドロチオフェニウムパーフルオロ-n-オクタンスルホネート、1-(6-n-ブトキシナフタレン-2-イル)テトラヒドロチオフェニウム2-ビシクロ[2.2.1]ヘプト-2-イル-1,1,2,2-テトラフルオロエタンスルホネート、1-(6-n-ブトキシナフタレン-2-イル)テトラヒドロチオフェニウムカンファースルホネート、1-(3,5-ジメチル-4-ヒドロキシフェニル)テトラヒドロチオフェニウムトリフルオロメタンスルホネート、1-(3,5-ジメチル-4-ヒドロキシフェニル)テトラヒドロチオフェニウムノナフルオロ-n-ブタンスルホネート、1-(3,5-ジメチル-4-ヒドロキシフェニル)テトラヒドロチオフェニウムパーフルオロ-n-オクタンスルホネート、1-(3,5-ジメチル-4-ヒドロキシフェニル)テトラヒドロチオフェニウム2-ビシクロ[2.2.1]ヘプト-2-イル-1,1,2,2-テトラフルオロエタンスルホネート、1-(3,5-ジメチル-4-ヒドロキシフェニル)テトラヒドロチオフェニウムカンファースルホネート等が挙げられる。これらのテトラヒドロチオフェニウム塩のうち、1-(4-n-ブトキシナフタレン-1-イル)テトラヒドロチオフェニウムノナフルオロ-n-ブタンスルホネート、1-(4-n-ブトキシナフタレン-1-イル)テトラヒドロチオフェニウムパーフルオロ-n-オクタンスルホネート及び1-(3,5-ジメチル-4-ヒドロキシフェニル)テトラヒドロチオフェニウムノナフルオロ-n-ブタンスルホネートが好ましい。
Examples of the tetrahydrothiophenium salt include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nona. Fluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiofe Nitro 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium camphorsulfonate , 1- (6-n-Butoxynaphthalen-2-yl Tetrahydrothiophenium trifluoromethanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothio Phenium perfluoro-n-octanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2, 2-tetrafluoroethanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium camphorsulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl- -Hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (3,5-dimethyl -4-hydroxyphenyl) tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (3,5-dimethyl-4- Hydroxyphenyl) tetrahydrothiophenium camphorsulfonate and the like. Of these tetrahydrothiophenium salts, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) Tetrahydrothiophenium perfluoro-n-octane sulfonate and 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butane sulfonate are preferred.
ヨードニウム塩としては、例えばジフェニルヨードニウムトリフルオロメタンスルホネート、ジフェニルヨードニウムノナフルオロ-n-ブタンスルホネート、ジフェニルヨードニウムパーフルオロ-n-オクタンスルホネート、ジフェニルヨードニウム2-ビシクロ[2.2.1]ヘプト-2-イル-1,1,2,2-テトラフルオロエタンスルホネート、ジフェニルヨードニウムカンファースルホネート、ビス(4-t-ブチルフェニル)ヨードニウムトリフルオロメタンスルホネート、ビス(4-t-ブチルフェニル)ヨードニウムノナフルオロ-n-ブタンスルホネート、ビス(4-t-ブチルフェニル)ヨードニウムパーフルオロ-n-オクタンスルホネート、ビス(4-t-ブチルフェニル)ヨードニウム2-ビシクロ[2.2.1]ヘプト-2-イル-1,1,2,2-テトラフルオロエタンスルホネート、ビス(4-t-ブチルフェニル)ヨードニウムカンファースルホネート等が挙げられる。これらのヨードニウム塩のうち、ビス(4-t-ブチルフェニル)ヨードニウムノナフルオロ-n-ブタンスルホネートが好ましい。
Examples of the iodonium salt include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl- 1,1,2,2-tetrafluoroethanesulfonate, diphenyliodonium camphorsulfonate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium nonafluoro-n-butanesulfonate, Bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium 2-bicyclo [2. .1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis (4-t- butylphenyl) iodonium camphorsulfonate, and the like. Of these iodonium salts, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate is preferred.
これらの[C]感放射線性酸発生剤は、単独で使用してもよく2種以上を併用してもよい。[C]感放射線性酸発生体が酸発生剤である場合の使用量としては、レジストとしての感度及び現像性を確保する観点から、[B]重合体100質量部に対して、通常、0.1質量部以上20質量部以下、好ましくは0.5質量部以上15質量部以下である。[C]感放射線性酸発生剤の使用量が0.1質量部未満では、感度及び現像性が低下する傾向がある。一方、[C]感放射線性酸発生剤の使用量が15質量部を超えると、放射線に対する透明性が低下して、所望のレジストパターンを得られ難くなる傾向がある。
These [C] radiation sensitive acid generators may be used alone or in combination of two or more. [C] The amount used when the radiation-sensitive acid generator is an acid generator is usually 0 with respect to 100 parts by mass of the polymer [B] from the viewpoint of ensuring sensitivity and developability as a resist. .1 to 20 parts by mass, preferably 0.5 to 15 parts by mass. [C] If the usage-amount of a radiation sensitive acid generator is less than 0.1 mass part, there exists a tendency for a sensitivity and developability to fall. On the other hand, when the amount of the [C] radiation sensitive acid generator used exceeds 15 parts by mass, the transparency to radiation tends to decrease, and it becomes difficult to obtain a desired resist pattern.
<任意成分>
当該感放射線性樹脂組成物は、[A]重合体、[B]重合体及び[C]感放射線性酸発生体に加え、本発明の効果を損なわない範囲で任意成分として[D]酸拡散制御体、[E]溶媒、界面活性剤、脂環式骨格含有化合物、増感剤等を含有できる。以下、各任意成分を詳述する。 <Optional component>
In addition to the [A] polymer, [B] polymer and [C] radiation sensitive acid generator, the radiation sensitive resin composition includes [D] acid diffusion as an optional component within a range not impairing the effects of the present invention. A control body, [E] solvent, surfactant, alicyclic skeleton containing compound, sensitizer and the like can be contained. Hereinafter, each optional component will be described in detail.
当該感放射線性樹脂組成物は、[A]重合体、[B]重合体及び[C]感放射線性酸発生体に加え、本発明の効果を損なわない範囲で任意成分として[D]酸拡散制御体、[E]溶媒、界面活性剤、脂環式骨格含有化合物、増感剤等を含有できる。以下、各任意成分を詳述する。 <Optional component>
In addition to the [A] polymer, [B] polymer and [C] radiation sensitive acid generator, the radiation sensitive resin composition includes [D] acid diffusion as an optional component within a range not impairing the effects of the present invention. A control body, [E] solvent, surfactant, alicyclic skeleton containing compound, sensitizer and the like can be contained. Hereinafter, each optional component will be described in detail.
[[D]酸拡散制御体]
[D]酸拡散制御体は、露光により[C]感放射線性酸発生体から生じる酸のレジスト塗膜中における拡散現象を制御し、非露光領域における好ましくない化学反応を抑制する効果を奏し、得られる感放射線性樹脂組成物の貯蔵安定性がさらに向上し、またレジストとしての解像度がさらに向上するとともに、露光から現像処理までの引き置き時間の変動によるレジストパターンの線幅変化を抑えることができ、プロセス安定性に極めて優れた組成物が得られる。[D]酸拡散制御体の当該感放射線性樹脂組成物における含有形態としては、遊離の化合物の形態でも、重合体の構造単位として含有される形態でも、これらの両方を組み合わせた形態でもよい。 [[D] Acid diffusion controller]
[D] The acid diffusion controller controls the diffusion phenomenon in the resist coating film of the acid generated from the [C] radiation-sensitive acid generator by exposure, and has the effect of suppressing undesirable chemical reactions in non-exposed areas, The storage stability of the resulting radiation-sensitive resin composition is further improved, the resolution as a resist is further improved, and it is possible to suppress changes in the line width of the resist pattern due to fluctuations in the holding time from exposure to development processing. And a composition having excellent process stability can be obtained. [D] The inclusion form of the acid diffusion controller in the radiation-sensitive resin composition may be a form of a free compound, a form contained as a structural unit of a polymer, or a combination of both.
[D]酸拡散制御体は、露光により[C]感放射線性酸発生体から生じる酸のレジスト塗膜中における拡散現象を制御し、非露光領域における好ましくない化学反応を抑制する効果を奏し、得られる感放射線性樹脂組成物の貯蔵安定性がさらに向上し、またレジストとしての解像度がさらに向上するとともに、露光から現像処理までの引き置き時間の変動によるレジストパターンの線幅変化を抑えることができ、プロセス安定性に極めて優れた組成物が得られる。[D]酸拡散制御体の当該感放射線性樹脂組成物における含有形態としては、遊離の化合物の形態でも、重合体の構造単位として含有される形態でも、これらの両方を組み合わせた形態でもよい。 [[D] Acid diffusion controller]
[D] The acid diffusion controller controls the diffusion phenomenon in the resist coating film of the acid generated from the [C] radiation-sensitive acid generator by exposure, and has the effect of suppressing undesirable chemical reactions in non-exposed areas, The storage stability of the resulting radiation-sensitive resin composition is further improved, the resolution as a resist is further improved, and it is possible to suppress changes in the line width of the resist pattern due to fluctuations in the holding time from exposure to development processing. And a composition having excellent process stability can be obtained. [D] The inclusion form of the acid diffusion controller in the radiation-sensitive resin composition may be a form of a free compound, a form contained as a structural unit of a polymer, or a combination of both.
[D]酸拡散制御剤としては、例えばアミン化合物、アミド基含有化合物、ウレア化合物、含窒素複素環化合物等が挙げられる。
[D] Examples of the acid diffusion controller include amine compounds, amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, and the like.
アミン化合物としては、例えばモノ(シクロ)アルキルアミン類;ジ(シクロ)アルキルアミン類;トリ(シクロ)アルキルアミン類;置換アルキルアニリン又はその誘導体;エチレンジアミン、N,N,N’,N’-テトラメチルエチレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン、4,4’-ジアミノジフェニルメタン、4,4’-ジアミノジフェニルエーテル、4,4’-ジアミノベンゾフェノン、4,4’-ジアミノジフェニルアミン、2,2-ビス(4-アミノフェニル)プロパン、2-(3-アミノフェニル)-2-(4-アミノフェニル)プロパン、2-(4-アミノフェニル)-2-(3-ヒドロキシフェニル)プロパン、2-(4-アミノフェニル)-2-(4-ヒドロキシフェニル)プロパン、1,4-ビス(1-(4-アミノフェニル)-1-メチルエチル)ベンゼン、1,3-ビス(1-(4-アミノフェニル)-1-メチルエチル)ベンゼン、ビス(2-ジメチルアミノエチル)エーテル、ビス(2-ジエチルアミノエチル)エーテル、1-(2-ヒドロキシエチル)-2-イミダゾリジノン、2-キノキサリノール、N,N,N’,N’-テトラキス(2-ヒドロキシプロピル)エチレンジアミン、N,N,N’,N’’N’’-ペンタメチルジエチレントリアミン等が挙げられる。
Examples of the amine compound include mono (cyclo) alkylamines; di (cyclo) alkylamines; tri (cyclo) alkylamines; substituted alkylanilines or derivatives thereof; ethylenediamine, N, N, N ′, N′-tetra Methylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylamine, 2,2-bis (4 -Aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-amino) Phenyl) -2- (4-hydroxyphenyl) propane, 1 4-bis (1- (4-aminophenyl) -1-methylethyl) benzene, 1,3-bis (1- (4-aminophenyl) -1-methylethyl) benzene, bis (2-dimethylaminoethyl) Ether, bis (2-diethylaminoethyl) ether, 1- (2-hydroxyethyl) -2-imidazolidinone, 2-quinoxalinol, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine N, N, N ′, N ″ N ″ -pentamethyldiethylenetriamine and the like.
アミド基含有化合物としては、例えばN-t-ブトキシカルボニル基含有アミノ化合物、ホルムアミド、N-メチルホルムアミド、N,N-ジメチルホルムアミド、アセトアミド、N-メチルアセトアミド、N,N-ジメチルアセトアミド、プロピオンアミド、ベンズアミド、ピロリドン、N-メチルピロリドン、N-アセチル-1-アダマンチルアミン、イソシアヌル酸トリス(2-ヒドロキシエチル)等が挙げられる。
Examples of amide group-containing compounds include Nt-butoxycarbonyl group-containing amino compounds, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, Examples thereof include benzamide, pyrrolidone, N-methylpyrrolidone, N-acetyl-1-adamantylamine, and isocyanuric acid tris (2-hydroxyethyl).
ウレア化合物としては、例えば尿素、メチルウレア、1,1-ジメチルウレア、1,3-ジメチルウレア、1,1,3,3-テトラメチルウレア、1,3-ジフェニルウレア、トリ-n-ブチルチオウレア等が挙げられる。
Examples of urea compounds include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butylthiourea, etc. Is mentioned.
含窒素複素環化合物としては、例えばイミダゾール類;ピリジン類;ピペラジン類;ピラジン、ピラゾール、ピリダジン、キノザリン、プリン、ピロリジン、ピペリジン、ピペリジンエタノール、3-ピペリジノ-1,2-プロパンジオール、モルホリン、4-メチルモルホリン、1-(4-モルホリニル)エタノール、4-アセチルモルホリン、3-(N-モルホリノ)-1,2-プロパンジオール、1,4-ジメチルピペラジン、1,4-ジアザビシクロ[2.2.2]オクタン等が挙げられる。
Examples of the nitrogen-containing heterocyclic compound include imidazoles; pyridines; piperazines; pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, piperidine ethanol, 3-piperidino-1,2-propanediol, morpholine, 4- Methylmorpholine, 1- (4-morpholinyl) ethanol, 4-acetylmorpholine, 3- (N-morpholino) -1,2-propanediol, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2 ] Octane etc. are mentioned.
また、[D]酸拡散制御剤として、露光により感光し弱酸を発生する光崩壊性塩基を用いることもできる。光崩壊性塩基は、露光部においては酸を発生して[B]重合体の現像液に対する不溶性を高める一方、未露光部ではアニオンによる高い酸捕捉機能が発揮されクエンチャーとして機能し、露光部から拡散する酸を捕捉する。光崩壊性塩基の一例として、露光により分解して酸拡散制御性を失うオニウム塩化合物がある。オニウム塩化合物としては、例えば下記式(7)で表されるスルホニウム塩化合物、下記式(8)で表されるヨードニウム塩化合物等が挙げられる。
Further, as the [D] acid diffusion control agent, a photodegradable base that is exposed to light and generates a weak acid can be used. The photodegradable base generates an acid in the exposed portion to increase the insolubility of the [B] polymer in the developer, while the unexposed portion exhibits a high acid capturing function by an anion and functions as a quencher. Captures acid that diffuses from As an example of the photodegradable base, there is an onium salt compound that is decomposed by exposure and loses acid diffusion controllability. Examples of the onium salt compound include a sulfonium salt compound represented by the following formula (7), an iodonium salt compound represented by the following formula (8), and the like.
上記式(7)及び式(8)中、R18~R22は、それぞれ独立して、水素原子、アルキル基、アルコキシ基、ヒドロキシ基、ハロゲン原子、又は-SO2-RCである。RCは、アルキル基、シクロアルキル基、アルコキシ基又はアリール基である。上記式(7)及び式(8)中、Z-は、OH-、R23-COO-、RD-SO2-N-―R23、R23-SO3
-、又は下記式(9)で表されるアニオンである。R23は、炭素数1~10の直鎖状若しくは分岐状のアルキル基、炭素数3~20のシクロアルキル基、炭素数6~30のアリール基、炭素数7~30のアルカリール基である。但し、上記アルキル基、シクロアルキル基、アリール基及びアルカリール基が有する水素原子の一部又は全部は置換されていてもよい。RDは、炭素数1~10の直鎖状若しくは分岐状のアルキル基又は炭素数3~20のシクロアルキル基である。但し、上記アルキル基及びシクロアルキル基が有する水素原子の一部又は全部は、フッ素原子で置換されていてもよい。但し、Z-がR23-SO3
-の場合、SO3
-が結合する炭素原子にフッ素原子が結合する場合はない。
The equation (7) and wherein (8), R 18 ~ R 22 are each independently a hydrogen atom, an alkyl group, an alkoxy group, hydroxy group, a halogen atom, or -SO 2 -R C. R C is an alkyl group, a cycloalkyl group, an alkoxy group or an aryl group. In the above formulas (7) and (8), Z − represents OH − , R 23 —COO − , R D —SO 2 —N − —R 23 , R 23 —SO 3 − , or the following formula (9) An anion represented by R 23 is a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an alkaryl group having 7 to 30 carbon atoms. . However, one part or all part of the hydrogen atom which the said alkyl group, cycloalkyl group, aryl group, and alkaryl group have may be substituted. R D is a linear or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms. However, some or all of the hydrogen atoms of the alkyl group and cycloalkyl group may be substituted with fluorine atoms. However, when Z − is R 23 —SO 3 — , the fluorine atom is not bonded to the carbon atom to which SO 3 — is bonded.
上記式(9)中、R24は、水素原子の一部又は全部がフッ素原子で置換されていてもよい炭素数1~12の直鎖状若しくは分岐状のアルキル基、又は炭素数1~12の直鎖状若しくは分岐状のアルコキシル基である。uは、0~2の整数である。
In the above formula (9), R 24 represents a linear or branched alkyl group having 1 to 12 carbon atoms, in which part or all of the hydrogen atoms may be substituted with fluorine atoms, or 1 to 12 carbon atoms. These are linear or branched alkoxyl groups. u is an integer of 0-2.
上記R23で表されるアルキル基としては、例えばメチル基、エチル基、プロピル基、i-プロピル基、ブチル基、i―ブチル基、t-ブチル基等が挙げられる。
The alkyl group represented by R 23, a methyl group, an ethyl group, a propyl group, i- propyl group, butyl group, i- butyl group, a t- butyl group and the like can be mentioned.
上記R23で表されるシクロアルキル基としては、例えばシクロペンチル基、シクロヘキシル基、ノルボルニル基、トリシクロデカニル基、テトラシクロドデカニル基、アダマンチル基等が挙げられる。
The cycloalkyl group represented by R 23, for example a cyclopentyl group, a cyclohexyl group, a norbornyl group, tricyclodecanyl group, tetracyclododecanyl group, and adamantyl.
上記R23で表されるアリール基としては、例えばフェニル基、ナフチル基、アントラニル基等が挙げられる。
The aryl group represented by R 23, a phenyl group, a naphthyl group, anthranyl group, and the like.
上記R23で表されるアルカリール基としては、例えば、ベンジル基、フェニルエチル基、フェニルプロピル基等が挙げられる。
The alkaryl group represented by R 23, for example, benzyl, phenylethyl group, phenylpropyl group and the like.
上記アルキル基、シクロアルキル基、アリール基及びアルカリール基が有する置換基としては、例えばヒドロキシル基、ハロゲン原子、アルコキシ基、ラクトン基、アルキルカルボニル基等が挙げられる。
Examples of the substituent that the alkyl group, cycloalkyl group, aryl group, and alkaryl group have include a hydroxyl group, a halogen atom, an alkoxy group, a lactone group, and an alkylcarbonyl group.
上記RDで表されるアルキル基としては、例えばメチル基、エチル基、プロピル基、ブチル基等が挙げられる。
Examples of the alkyl group represented by RD include a methyl group, an ethyl group, a propyl group, and a butyl group.
上記RDで表されるシクロアルキル基としては、例えばシクロペンチル基、シクロヘキシル基、ノルボルニル基、アダマンチル基等が挙げられる。
Examples of the cycloalkyl group represented by RD include a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like.
上記光崩壊性塩基としては、例えば下記式で表される化合物等が挙げられる。
Examples of the photodegradable base include compounds represented by the following formulas.
[D]酸拡散制御剤は、単独で使用してもよく2種以上を併用してもよい。[D]酸拡散制御剤の含有量としては、[B]重合体100質量部に対して、15質量部未満が好ましい。含有量が15質量部を超えると、レジストとしての感度が低下する傾向にある。
[D] The acid diffusion controller may be used alone or in combination of two or more. [D] The content of the acid diffusion controller is preferably less than 15 parts by mass with respect to 100 parts by mass of the [B] polymer. When the content exceeds 15 parts by mass, the sensitivity as a resist tends to decrease.
[[E]溶媒]
当該感放射線性樹脂組成物は通常溶媒を含有する。溶媒は少なくとも上記の[A]重合体、[B]重合体、[C]感放射線性酸発生体、及び任意成分を溶解できれば特に限定されない。溶媒としては、例えばアルコール系溶媒、エーテル系溶媒、ケトン系溶媒、アミド系溶媒、エステル系溶媒及びその混合溶媒等が挙げられる。 [[E] solvent]
The radiation sensitive resin composition usually contains a solvent. A solvent will not be specifically limited if said [A] polymer, [B] polymer, [C] radiation sensitive acid generator, and an arbitrary component can be melt | dissolved at least. Examples of the solvent include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, and mixed solvents thereof.
当該感放射線性樹脂組成物は通常溶媒を含有する。溶媒は少なくとも上記の[A]重合体、[B]重合体、[C]感放射線性酸発生体、及び任意成分を溶解できれば特に限定されない。溶媒としては、例えばアルコール系溶媒、エーテル系溶媒、ケトン系溶媒、アミド系溶媒、エステル系溶媒及びその混合溶媒等が挙げられる。 [[E] solvent]
The radiation sensitive resin composition usually contains a solvent. A solvent will not be specifically limited if said [A] polymer, [B] polymer, [C] radiation sensitive acid generator, and an arbitrary component can be melt | dissolved at least. Examples of the solvent include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, and mixed solvents thereof.
溶媒の具体例としては、上述のパターン形成工程(3)で列挙した有機溶媒と同様のものが挙げられる。これらのうち酢酸プロピレングリコールモノメチルエーテル、シクロヘキサノンが好ましい。これらの溶媒は単独で使用してもよく2種以上を併用してもよい。
Specific examples of the solvent include the same organic solvents listed in the pattern formation step (3) above. Of these, propylene glycol monomethyl ether acetate and cyclohexanone are preferred. These solvents may be used alone or in combination of two or more.
[界面活性剤]
界面活性剤は、塗布性、ストリエーション、現像性等を改良する効果を奏する。界面活性剤としては、例えばポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンn-オクチルフェニルエーテル、ポリオキシエチレンn-ノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート等のノニオン系界面活性剤の他、以下商品名でKP341(信越化学工業社)、ポリフローNo.75、同No.95(以上、共栄社化学社)、エフトップEF301、同EF303、同EF352(以上、トーケムプロダクツ社)、メガファックF171、同F173(以上、大日本インキ化学工業社)、フロラードFC430、同FC431(以上、住友スリーエム社)、アサヒガードAG710、サーフロンS-382、同SC-101、同SC-102、同SC-103、同SC-104、同SC-105、同SC-106(以上、旭硝子工業社)等が挙げられる。これらの界面活性剤は、単独で使用してもよく2種以上を併用してもよい。 [Surfactant]
Surfactants have the effect of improving coatability, striation, developability, and the like. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol diacrylate. In addition to nonionic surfactants such as stearate, the following trade names are KP341 (Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (above, Kyoeisha Chemical Co., Ltd.), F-Top EF301, EF303, EF352 (above, Tochem Products), MegaFuck F171, F173 (above, Dainippon Ink and Chemicals), Florard FC430, FC431 ( Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (above, Asahi Glass Industry) Company). These surfactants may be used alone or in combination of two or more.
界面活性剤は、塗布性、ストリエーション、現像性等を改良する効果を奏する。界面活性剤としては、例えばポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンn-オクチルフェニルエーテル、ポリオキシエチレンn-ノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート等のノニオン系界面活性剤の他、以下商品名でKP341(信越化学工業社)、ポリフローNo.75、同No.95(以上、共栄社化学社)、エフトップEF301、同EF303、同EF352(以上、トーケムプロダクツ社)、メガファックF171、同F173(以上、大日本インキ化学工業社)、フロラードFC430、同FC431(以上、住友スリーエム社)、アサヒガードAG710、サーフロンS-382、同SC-101、同SC-102、同SC-103、同SC-104、同SC-105、同SC-106(以上、旭硝子工業社)等が挙げられる。これらの界面活性剤は、単独で使用してもよく2種以上を併用してもよい。 [Surfactant]
Surfactants have the effect of improving coatability, striation, developability, and the like. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol diacrylate. In addition to nonionic surfactants such as stearate, the following trade names are KP341 (Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (above, Kyoeisha Chemical Co., Ltd.), F-Top EF301, EF303, EF352 (above, Tochem Products), MegaFuck F171, F173 (above, Dainippon Ink and Chemicals), Florard FC430, FC431 ( Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (above, Asahi Glass Industry) Company). These surfactants may be used alone or in combination of two or more.
[脂環式骨格含有化合物]
脂環式骨格含有化合物は、ドライエッチング耐性、パターン形状、基板との接着性等を改善する効果を奏する。 [Alicyclic skeleton-containing compound]
The alicyclic skeleton-containing compound has an effect of improving dry etching resistance, pattern shape, adhesion to the substrate, and the like.
脂環式骨格含有化合物は、ドライエッチング耐性、パターン形状、基板との接着性等を改善する効果を奏する。 [Alicyclic skeleton-containing compound]
The alicyclic skeleton-containing compound has an effect of improving dry etching resistance, pattern shape, adhesion to the substrate, and the like.
[増感剤]
増感剤は、[C]感放射線性酸発生体の生成量を増加する作用を示すものであり、当該感放射線性樹脂組成物の「みかけの感度」を向上させる効果を奏する。 [Sensitizer]
The sensitizer exhibits an action of increasing the amount of [C] radiation-sensitive acid generator, and has an effect of improving the “apparent sensitivity” of the radiation-sensitive resin composition.
増感剤は、[C]感放射線性酸発生体の生成量を増加する作用を示すものであり、当該感放射線性樹脂組成物の「みかけの感度」を向上させる効果を奏する。 [Sensitizer]
The sensitizer exhibits an action of increasing the amount of [C] radiation-sensitive acid generator, and has an effect of improving the “apparent sensitivity” of the radiation-sensitive resin composition.
<感放射線性樹脂組成物の調製>
当該感放射線性樹脂組成物は、例えば有機溶媒中で[A]重合体、[B]重合体、[C]感放射線性酸発生体、及び任意成分を所定の割合で混合することにより調製できる。また、当該感放射線性樹脂組成物は、適当な有機溶媒に溶解又は分散させた状態に調製され使用され得る。[A]重合体の含有割合としては、[B]重合体100質量部に対して、1質量部~15質量部が好ましく、2質量部~10質量部がより好ましい。 <Preparation of radiation-sensitive resin composition>
The radiation-sensitive resin composition can be prepared, for example, by mixing [A] polymer, [B] polymer, [C] radiation-sensitive acid generator, and optional components in a predetermined ratio in an organic solvent. . Moreover, the said radiation sensitive resin composition can be prepared and used in the state melt | dissolved or disperse | distributed to the appropriate organic solvent. [A] The content of the polymer is preferably 1 part by mass to 15 parts by mass and more preferably 2 parts by mass to 10 parts by mass with respect to 100 parts by mass of the polymer [B].
当該感放射線性樹脂組成物は、例えば有機溶媒中で[A]重合体、[B]重合体、[C]感放射線性酸発生体、及び任意成分を所定の割合で混合することにより調製できる。また、当該感放射線性樹脂組成物は、適当な有機溶媒に溶解又は分散させた状態に調製され使用され得る。[A]重合体の含有割合としては、[B]重合体100質量部に対して、1質量部~15質量部が好ましく、2質量部~10質量部がより好ましい。 <Preparation of radiation-sensitive resin composition>
The radiation-sensitive resin composition can be prepared, for example, by mixing [A] polymer, [B] polymer, [C] radiation-sensitive acid generator, and optional components in a predetermined ratio in an organic solvent. . Moreover, the said radiation sensitive resin composition can be prepared and used in the state melt | dissolved or disperse | distributed to the appropriate organic solvent. [A] The content of the polymer is preferably 1 part by mass to 15 parts by mass and more preferably 2 parts by mass to 10 parts by mass with respect to 100 parts by mass of the polymer [B].
以下に本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.
<[A]重合体の合成>
[合成例1]
下記式(M-1)で表される単量体10.4g(30mol%)及び式(M-4)で表される単量体19.6g(70mol%)を、メチルエチルケトン30gに溶解し、さらに2,2’-アゾビス(イソブチロニトリル)0.91gを投入した溶液を調製した。次に、30gのメチルエチルケトンを投入した200mLの三口フラスコを30分窒素パージした後、反応釜を攪拌しながら80℃に加熱し、事前に準備した単量体溶液を滴下漏斗を用いて3時間かけて滴下した。滴下開始を重合開始時間とし、重合反応を6時間実施した。重合終了後、溶液を水冷し30℃以下に冷却し、反応溶液を1L分液漏斗に移液した後、90gのn-ヘキサンでその重合溶液を均一に希釈し、360gのメタノールを投入して混合した。次いで、20gの蒸留水を投入し、さらに攪拌して30分静置した。その後、下層を回収し、重合体(A-1)を含む酢酸プロピレングリコールモノメチルエーテル溶液とした。重合体(A-1)のMwは5,900であり、Mw/Mnは1.58、収率は68%であった。13C-NMR分析の結果、(M-1)が与える構造単位(II)及び(M-4)が与える構造単位(I)の含有割合は、31:69(mol%)であった。なお、13C-NMR分析は、核磁気共鳴装置(日本電子社、JNM-EX270)を使用し測定した。 <[A] Synthesis of polymer>
[Synthesis Example 1]
10.4 g (30 mol%) of a monomer represented by the following formula (M-1) and 19.6 g (70 mol%) of a monomer represented by the formula (M-4) were dissolved in 30 g of methyl ethyl ketone, Further, a solution charged with 0.91 g of 2,2′-azobis (isobutyronitrile) was prepared. Next, a 200 mL three-necked flask charged with 30 g of methyl ethyl ketone was purged with nitrogen for 30 minutes, and then the reaction kettle was heated to 80 ° C. with stirring, and the monomer solution prepared in advance was added over 3 hours using a dropping funnel. And dripped. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After completion of the polymerization, the solution was cooled with water and cooled to 30 ° C. or lower. The reaction solution was transferred to a 1 L separatory funnel, and then the polymerization solution was uniformly diluted with 90 g of n-hexane, and 360 g of methanol was added. Mixed. Next, 20 g of distilled water was added, and the mixture was further stirred and allowed to stand for 30 minutes. Thereafter, the lower layer was recovered to obtain a propylene glycol monomethyl ether solution containing the polymer (A-1). Mw of the polymer (A-1) was 5,900, Mw / Mn was 1.58, and the yield was 68%. As a result of 13 C-NMR analysis, the content ratio of the structural unit (II) given by (M-1) and the structural unit (I) given by (M-4) was 31:69 (mol%). The 13 C-NMR analysis was measured using a nuclear magnetic resonance apparatus (JEOL Ltd., JNM-EX270).
[合成例1]
下記式(M-1)で表される単量体10.4g(30mol%)及び式(M-4)で表される単量体19.6g(70mol%)を、メチルエチルケトン30gに溶解し、さらに2,2’-アゾビス(イソブチロニトリル)0.91gを投入した溶液を調製した。次に、30gのメチルエチルケトンを投入した200mLの三口フラスコを30分窒素パージした後、反応釜を攪拌しながら80℃に加熱し、事前に準備した単量体溶液を滴下漏斗を用いて3時間かけて滴下した。滴下開始を重合開始時間とし、重合反応を6時間実施した。重合終了後、溶液を水冷し30℃以下に冷却し、反応溶液を1L分液漏斗に移液した後、90gのn-ヘキサンでその重合溶液を均一に希釈し、360gのメタノールを投入して混合した。次いで、20gの蒸留水を投入し、さらに攪拌して30分静置した。その後、下層を回収し、重合体(A-1)を含む酢酸プロピレングリコールモノメチルエーテル溶液とした。重合体(A-1)のMwは5,900であり、Mw/Mnは1.58、収率は68%であった。13C-NMR分析の結果、(M-1)が与える構造単位(II)及び(M-4)が与える構造単位(I)の含有割合は、31:69(mol%)であった。なお、13C-NMR分析は、核磁気共鳴装置(日本電子社、JNM-EX270)を使用し測定した。 <[A] Synthesis of polymer>
[Synthesis Example 1]
10.4 g (30 mol%) of a monomer represented by the following formula (M-1) and 19.6 g (70 mol%) of a monomer represented by the formula (M-4) were dissolved in 30 g of methyl ethyl ketone, Further, a solution charged with 0.91 g of 2,2′-azobis (isobutyronitrile) was prepared. Next, a 200 mL three-necked flask charged with 30 g of methyl ethyl ketone was purged with nitrogen for 30 minutes, and then the reaction kettle was heated to 80 ° C. with stirring, and the monomer solution prepared in advance was added over 3 hours using a dropping funnel. And dripped. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After completion of the polymerization, the solution was cooled with water and cooled to 30 ° C. or lower. The reaction solution was transferred to a 1 L separatory funnel, and then the polymerization solution was uniformly diluted with 90 g of n-hexane, and 360 g of methanol was added. Mixed. Next, 20 g of distilled water was added, and the mixture was further stirred and allowed to stand for 30 minutes. Thereafter, the lower layer was recovered to obtain a propylene glycol monomethyl ether solution containing the polymer (A-1). Mw of the polymer (A-1) was 5,900, Mw / Mn was 1.58, and the yield was 68%. As a result of 13 C-NMR analysis, the content ratio of the structural unit (II) given by (M-1) and the structural unit (I) given by (M-4) was 31:69 (mol%). The 13 C-NMR analysis was measured using a nuclear magnetic resonance apparatus (JEOL Ltd., JNM-EX270).
[合成例2~10]
表1に記載の単量体を所定量配合した以外は、合成例1と同様に操作して各重合体を合成した。また、得られた各重合体のMw、Mw/Mn、収率(%)及び各重合体における各単量体が与える構造単位の含有割合をあわせて表1に示す。なお、各[A]重合体の合成に使用した単量体を下記に示す。 [Synthesis Examples 2 to 10]
Each polymer was synthesized in the same manner as in Synthesis Example 1 except that a predetermined amount of the monomers listed in Table 1 were blended. In addition, Table 1 shows the Mw, Mw / Mn, yield (%), and the content ratio of the structural unit provided by each monomer in each polymer. In addition, the monomer used for the synthesis | combination of each [A] polymer is shown below.
表1に記載の単量体を所定量配合した以外は、合成例1と同様に操作して各重合体を合成した。また、得られた各重合体のMw、Mw/Mn、収率(%)及び各重合体における各単量体が与える構造単位の含有割合をあわせて表1に示す。なお、各[A]重合体の合成に使用した単量体を下記に示す。 [Synthesis Examples 2 to 10]
Each polymer was synthesized in the same manner as in Synthesis Example 1 except that a predetermined amount of the monomers listed in Table 1 were blended. In addition, Table 1 shows the Mw, Mw / Mn, yield (%), and the content ratio of the structural unit provided by each monomer in each polymer. In addition, the monomer used for the synthesis | combination of each [A] polymer is shown below.
<[B]重合体の合成>
[B]重合体の合成に使用した単量体を下記に示す。 <[B] Synthesis of polymer>
[B] Monomers used for polymer synthesis are shown below.
[B]重合体の合成に使用した単量体を下記に示す。 <[B] Synthesis of polymer>
[B] Monomers used for polymer synthesis are shown below.
[合成例11]
上記式(M-11)で表される単量体12.9g(50mol%)及び式(M-16)で表される単量体17.1g(50mol%)を、メチルエチルケトン60gに溶解し、さらにジメチルアゾビスイソブチロニトリル1.77gを投入した溶液を調製した。次に、30gのメチルエチルケトンを投入した200mLの三口フラスコを30分窒素パージした後、反応釜を攪拌しながら80℃に加熱し、事前に準備した単量体溶液を滴下漏斗を用いて3時間かけて滴下した。滴下開始を重合開始時間とし、重合反応を6時間実施した。重合終了後、重合溶液を水冷し30℃以下に冷却し、600gのメタノールへ投入して、析出した白色粉末を濾別した。濾別した白色粉末を150gのメタノールにて2度スラリー状で洗浄した後、再度濾別し、50℃にて17時間乾燥して白色粉末の(B-1)重合体を得た。重合体(B-1)のMwは6,900であり、Mw/Mnは1.35、収率は80%であった。13C-NMR分析の結果、(M-11)が与える構造単位(III)及び(M-16)が与える構造単位(IV)の含有割合は、49:51(mol%)であった。 [Synthesis Example 11]
12.9 g (50 mol%) of the monomer represented by the above formula (M-11) and 17.1 g (50 mol%) of the monomer represented by the formula (M-16) were dissolved in 60 g of methyl ethyl ketone, Further, a solution charged with 1.77 g of dimethylazobisisobutyronitrile was prepared. Next, a 200 mL three-necked flask charged with 30 g of methyl ethyl ketone was purged with nitrogen for 30 minutes, and then the reaction kettle was heated to 80 ° C. with stirring, and the monomer solution prepared in advance was added over 3 hours using a dropping funnel. And dripped. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After completion of the polymerization, the polymerization solution was cooled with water, cooled to 30 ° C. or lower, poured into 600 g of methanol, and the precipitated white powder was separated by filtration. The filtered white powder was washed twice with 150 g of methanol in the form of a slurry, then filtered again and dried at 50 ° C. for 17 hours to obtain a white powder (B-1) polymer. Mw of the polymer (B-1) was 6,900, Mw / Mn was 1.35, and the yield was 80%. As a result of 13 C-NMR analysis, the content ratio of the structural unit (III) given by (M-11) and the structural unit (IV) given by (M-16) was 49:51 (mol%).
上記式(M-11)で表される単量体12.9g(50mol%)及び式(M-16)で表される単量体17.1g(50mol%)を、メチルエチルケトン60gに溶解し、さらにジメチルアゾビスイソブチロニトリル1.77gを投入した溶液を調製した。次に、30gのメチルエチルケトンを投入した200mLの三口フラスコを30分窒素パージした後、反応釜を攪拌しながら80℃に加熱し、事前に準備した単量体溶液を滴下漏斗を用いて3時間かけて滴下した。滴下開始を重合開始時間とし、重合反応を6時間実施した。重合終了後、重合溶液を水冷し30℃以下に冷却し、600gのメタノールへ投入して、析出した白色粉末を濾別した。濾別した白色粉末を150gのメタノールにて2度スラリー状で洗浄した後、再度濾別し、50℃にて17時間乾燥して白色粉末の(B-1)重合体を得た。重合体(B-1)のMwは6,900であり、Mw/Mnは1.35、収率は80%であった。13C-NMR分析の結果、(M-11)が与える構造単位(III)及び(M-16)が与える構造単位(IV)の含有割合は、49:51(mol%)であった。 [Synthesis Example 11]
12.9 g (50 mol%) of the monomer represented by the above formula (M-11) and 17.1 g (50 mol%) of the monomer represented by the formula (M-16) were dissolved in 60 g of methyl ethyl ketone, Further, a solution charged with 1.77 g of dimethylazobisisobutyronitrile was prepared. Next, a 200 mL three-necked flask charged with 30 g of methyl ethyl ketone was purged with nitrogen for 30 minutes, and then the reaction kettle was heated to 80 ° C. with stirring, and the monomer solution prepared in advance was added over 3 hours using a dropping funnel. And dripped. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After completion of the polymerization, the polymerization solution was cooled with water, cooled to 30 ° C. or lower, poured into 600 g of methanol, and the precipitated white powder was separated by filtration. The filtered white powder was washed twice with 150 g of methanol in the form of a slurry, then filtered again and dried at 50 ° C. for 17 hours to obtain a white powder (B-1) polymer. Mw of the polymer (B-1) was 6,900, Mw / Mn was 1.35, and the yield was 80%. As a result of 13 C-NMR analysis, the content ratio of the structural unit (III) given by (M-11) and the structural unit (IV) given by (M-16) was 49:51 (mol%).
[合成例12]
上記式(M-12)で表される単量体12.57g(35mol%)、式(M-15)で表される単量体5.13g(15mol%)及び式(M-17)で表される単量体12.30g(50mol%)を、メチルエチルケトン60gに溶解し、さらにジメチルアゾビスイソブチロニトリル1.19gを投入した溶液を調製した。次に、30gのメチルエチルケトンを投入した200mLの三口フラスコを30分窒素パージした後、反応釜を攪拌しながら80℃に加熱し、事前に準備した単量体溶液を滴下漏斗を用いて3時間かけて滴下した。滴下開始を重合開始時間とし、重合反応を6時間実施した。重合終了後、重合溶液を水冷し30℃以下に冷却し、600gのメタノールへ投入して、析出した白色粉末を濾別した。濾別した白色粉末を150gのメタノールにて2度スラリー状で洗浄した後、再度濾別し、50℃にて17時間乾燥して白色粉末の(B-2)重合体を得た。重合体(B-2)のMwは5,800であり、Mw/Mnは1.37、収率は68%であった。13C-NMR分析の結果、(M-12)が与える構造単位(III)、(M-15)が与える構造単位、(M-17)が与える構造単位(IV)の含有割合は、33:16:51(mol%)であった。 [Synthesis Example 12]
In the above formula (M-12), 12.57 g (35 mol%) of the monomer represented by the formula (M-12), 5.13 g (15 mol%) of the monomer represented by the formula (M-15), and formula (M-17) A solution was prepared by dissolving 12.30 g (50 mol%) of the monomer represented in 60 g of methyl ethyl ketone and further adding 1.19 g of dimethylazobisisobutyronitrile. Next, a 200 mL three-necked flask charged with 30 g of methyl ethyl ketone was purged with nitrogen for 30 minutes, and then the reaction kettle was heated to 80 ° C. with stirring, and the monomer solution prepared in advance was added over 3 hours using a dropping funnel. And dripped. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After completion of the polymerization, the polymerization solution was cooled with water, cooled to 30 ° C. or lower, poured into 600 g of methanol, and the precipitated white powder was separated by filtration. The filtered white powder was washed twice with 150 g of methanol in the form of a slurry, then filtered again and dried at 50 ° C. for 17 hours to obtain a white powder (B-2) polymer. Mw of the polymer (B-2) was 5,800, Mw / Mn was 1.37, and the yield was 68%. As a result of 13 C-NMR analysis, the content ratio of the structural unit (III) given by (M-12), the structural unit given by (M-15), and the structural unit (IV) given by (M-17) was 33: 16:51 (mol%).
上記式(M-12)で表される単量体12.57g(35mol%)、式(M-15)で表される単量体5.13g(15mol%)及び式(M-17)で表される単量体12.30g(50mol%)を、メチルエチルケトン60gに溶解し、さらにジメチルアゾビスイソブチロニトリル1.19gを投入した溶液を調製した。次に、30gのメチルエチルケトンを投入した200mLの三口フラスコを30分窒素パージした後、反応釜を攪拌しながら80℃に加熱し、事前に準備した単量体溶液を滴下漏斗を用いて3時間かけて滴下した。滴下開始を重合開始時間とし、重合反応を6時間実施した。重合終了後、重合溶液を水冷し30℃以下に冷却し、600gのメタノールへ投入して、析出した白色粉末を濾別した。濾別した白色粉末を150gのメタノールにて2度スラリー状で洗浄した後、再度濾別し、50℃にて17時間乾燥して白色粉末の(B-2)重合体を得た。重合体(B-2)のMwは5,800であり、Mw/Mnは1.37、収率は68%であった。13C-NMR分析の結果、(M-12)が与える構造単位(III)、(M-15)が与える構造単位、(M-17)が与える構造単位(IV)の含有割合は、33:16:51(mol%)であった。 [Synthesis Example 12]
In the above formula (M-12), 12.57 g (35 mol%) of the monomer represented by the formula (M-12), 5.13 g (15 mol%) of the monomer represented by the formula (M-15), and formula (M-17) A solution was prepared by dissolving 12.30 g (50 mol%) of the monomer represented in 60 g of methyl ethyl ketone and further adding 1.19 g of dimethylazobisisobutyronitrile. Next, a 200 mL three-necked flask charged with 30 g of methyl ethyl ketone was purged with nitrogen for 30 minutes, and then the reaction kettle was heated to 80 ° C. with stirring, and the monomer solution prepared in advance was added over 3 hours using a dropping funnel. And dripped. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After completion of the polymerization, the polymerization solution was cooled with water, cooled to 30 ° C. or lower, poured into 600 g of methanol, and the precipitated white powder was separated by filtration. The filtered white powder was washed twice with 150 g of methanol in the form of a slurry, then filtered again and dried at 50 ° C. for 17 hours to obtain a white powder (B-2) polymer. Mw of the polymer (B-2) was 5,800, Mw / Mn was 1.37, and the yield was 68%. As a result of 13 C-NMR analysis, the content ratio of the structural unit (III) given by (M-12), the structural unit given by (M-15), and the structural unit (IV) given by (M-17) was 33: 16:51 (mol%).
[合成例13]
上記式(M-13)で表される単量体11.73g(40mol%)、式(M-14)で表される単量体2.62g(10mol%)及び式(M-18)で表される単量体15.66g(50mol%)を、メチルエチルケトン60gに溶解し、さらにジメチルアゾビスイソブチロニトリル0.92gを投入した溶液を調製した。次に、30gのメチルエチルケトンを投入した200mLの三口フラスコを30分窒素パージした後、反応釜を攪拌しながら80℃に加熱し、事前に準備した単量体溶液を滴下漏斗を用いて3時間かけて滴下した。滴下開始を重合開始時間とし、重合反応を6時間実施した。重合終了後、重合溶液を水冷し30℃以下に冷却し、600gのメタノールへ投入して、析出した白色粉末を濾別した。濾別した白色粉末を150gのメタノールにて2度スラリー状で洗浄した後、再度濾別し、50℃にて17時間乾燥して白色粉末の(B-3)重合体を得た。重合体(B-3)のMwは7,200であり、Mw/Mnは1.41、収率は75%であった。13C-NMR分析の結果、(M-13)が与える構造単位(III)、(M-14)が与える構造単位、(M-18)が与える構造単位(IV)の含有割合は、40:10:50(mol%)であった。 [Synthesis Example 13]
11.73 g (40 mol%) of the monomer represented by the above formula (M-13), 2.62 g (10 mol%) of the monomer represented by the formula (M-14), and (M-18) A solution was prepared by dissolving 15.66 g (50 mol%) of the monomer represented in 60 g of methyl ethyl ketone and further adding 0.92 g of dimethylazobisisobutyronitrile. Next, a 200 mL three-necked flask charged with 30 g of methyl ethyl ketone was purged with nitrogen for 30 minutes, and then the reaction kettle was heated to 80 ° C. with stirring, and the monomer solution prepared in advance was added over 3 hours using a dropping funnel. And dripped. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After completion of the polymerization, the polymerization solution was cooled with water, cooled to 30 ° C. or lower, poured into 600 g of methanol, and the precipitated white powder was separated by filtration. The filtered white powder was washed twice with 150 g of methanol in the form of a slurry, then filtered again and dried at 50 ° C. for 17 hours to obtain a white powder (B-3) polymer. Mw of the polymer (B-3) was 7,200, Mw / Mn was 1.41, and the yield was 75%. As a result of 13 C-NMR analysis, the content ratio of the structural unit (III) given by (M-13), the structural unit given by (M-14), and the structural unit (IV) given by (M-18) was 40: It was 10:50 (mol%).
上記式(M-13)で表される単量体11.73g(40mol%)、式(M-14)で表される単量体2.62g(10mol%)及び式(M-18)で表される単量体15.66g(50mol%)を、メチルエチルケトン60gに溶解し、さらにジメチルアゾビスイソブチロニトリル0.92gを投入した溶液を調製した。次に、30gのメチルエチルケトンを投入した200mLの三口フラスコを30分窒素パージした後、反応釜を攪拌しながら80℃に加熱し、事前に準備した単量体溶液を滴下漏斗を用いて3時間かけて滴下した。滴下開始を重合開始時間とし、重合反応を6時間実施した。重合終了後、重合溶液を水冷し30℃以下に冷却し、600gのメタノールへ投入して、析出した白色粉末を濾別した。濾別した白色粉末を150gのメタノールにて2度スラリー状で洗浄した後、再度濾別し、50℃にて17時間乾燥して白色粉末の(B-3)重合体を得た。重合体(B-3)のMwは7,200であり、Mw/Mnは1.41、収率は75%であった。13C-NMR分析の結果、(M-13)が与える構造単位(III)、(M-14)が与える構造単位、(M-18)が与える構造単位(IV)の含有割合は、40:10:50(mol%)であった。 [Synthesis Example 13]
11.73 g (40 mol%) of the monomer represented by the above formula (M-13), 2.62 g (10 mol%) of the monomer represented by the formula (M-14), and (M-18) A solution was prepared by dissolving 15.66 g (50 mol%) of the monomer represented in 60 g of methyl ethyl ketone and further adding 0.92 g of dimethylazobisisobutyronitrile. Next, a 200 mL three-necked flask charged with 30 g of methyl ethyl ketone was purged with nitrogen for 30 minutes, and then the reaction kettle was heated to 80 ° C. with stirring, and the monomer solution prepared in advance was added over 3 hours using a dropping funnel. And dripped. The polymerization start was carried out for 6 hours with the start of dropping as the polymerization start time. After completion of the polymerization, the polymerization solution was cooled with water, cooled to 30 ° C. or lower, poured into 600 g of methanol, and the precipitated white powder was separated by filtration. The filtered white powder was washed twice with 150 g of methanol in the form of a slurry, then filtered again and dried at 50 ° C. for 17 hours to obtain a white powder (B-3) polymer. Mw of the polymer (B-3) was 7,200, Mw / Mn was 1.41, and the yield was 75%. As a result of 13 C-NMR analysis, the content ratio of the structural unit (III) given by (M-13), the structural unit given by (M-14), and the structural unit (IV) given by (M-18) was 40: It was 10:50 (mol%).
<感放射線性樹脂組成物の調製>
当該感放射線性樹脂組成物の調製で使用した[C]感放射線性酸発生剤、酸拡散制御剤及び溶媒は下記のとおりである。 <Preparation of radiation-sensitive resin composition>
The [C] radiation sensitive acid generator, acid diffusion controller and solvent used in the preparation of the radiation sensitive resin composition are as follows.
当該感放射線性樹脂組成物の調製で使用した[C]感放射線性酸発生剤、酸拡散制御剤及び溶媒は下記のとおりである。 <Preparation of radiation-sensitive resin composition>
The [C] radiation sensitive acid generator, acid diffusion controller and solvent used in the preparation of the radiation sensitive resin composition are as follows.
<[C]感放射線性酸発生剤>
下記式で表される化合物 <[C] Radiation sensitive acid generator>
Compound represented by the following formula
下記式で表される化合物 <[C] Radiation sensitive acid generator>
Compound represented by the following formula
<[D]酸拡散制御剤>
下記式で表される化合物 <[D] Acid diffusion controller>
Compound represented by the following formula
下記式で表される化合物 <[D] Acid diffusion controller>
Compound represented by the following formula
<[E]溶媒>
E-1:酢酸プロピレングリコールモノメチルエーテル
E-2:シクロヘキサノン
E-3:γ-ブチロラクトン <[E] solvent>
E-1: Propylene glycol monomethyl ether acetate E-2: Cyclohexanone E-3: γ-butyrolactone
E-1:酢酸プロピレングリコールモノメチルエーテル
E-2:シクロヘキサノン
E-3:γ-ブチロラクトン <[E] solvent>
E-1: Propylene glycol monomethyl ether acetate E-2: Cyclohexanone E-3: γ-butyrolactone
[実施例1]
[A]重合体としての(A-1)3質量部、[B]重合体としての(B-1)100質量部、[C]感放射線性酸発生剤としての(C-1)10.8質量部、[D]酸拡散制御剤としての(D-1)4.3質量部、[E]溶媒としての(E-1)2,185質量部、(E-2)935質量部、(E-3)30質量部を混合して感放射線性樹脂組成物を調製した。 [Example 1]
[A] 3 parts by mass of (A-1) as a polymer, [B] 100 parts by mass of (B-1) as a polymer, [C] (C-1) as a radiation-sensitive acid generator 8 parts by mass, (D) 4.3 parts by mass as an acid diffusion controller, (E-1) 2,185 parts by mass as an [E] solvent, (E-2) 935 parts by mass, (E-3) A radiation-sensitive resin composition was prepared by mixing 30 parts by mass.
[A]重合体としての(A-1)3質量部、[B]重合体としての(B-1)100質量部、[C]感放射線性酸発生剤としての(C-1)10.8質量部、[D]酸拡散制御剤としての(D-1)4.3質量部、[E]溶媒としての(E-1)2,185質量部、(E-2)935質量部、(E-3)30質量部を混合して感放射線性樹脂組成物を調製した。 [Example 1]
[A] 3 parts by mass of (A-1) as a polymer, [B] 100 parts by mass of (B-1) as a polymer, [C] (C-1) as a radiation-sensitive acid generator 8 parts by mass, (D) 4.3 parts by mass as an acid diffusion controller, (E-1) 2,185 parts by mass as an [E] solvent, (E-2) 935 parts by mass, (E-3) A radiation-sensitive resin composition was prepared by mixing 30 parts by mass.
[実施例2~13及び比較例1~2]
表2に記載の各成分を所定量配合した以外は、実施例1と同様に操作して各感放射線性樹脂組成物を調製した。 [Examples 2 to 13 and Comparative Examples 1 and 2]
Each radiation-sensitive resin composition was prepared in the same manner as in Example 1 except that a predetermined amount of each component shown in Table 2 was blended.
表2に記載の各成分を所定量配合した以外は、実施例1と同様に操作して各感放射線性樹脂組成物を調製した。 [Examples 2 to 13 and Comparative Examples 1 and 2]
Each radiation-sensitive resin composition was prepared in the same manner as in Example 1 except that a predetermined amount of each component shown in Table 2 was blended.
<レジストパターンの形成>
ウエハー表面に有機反射防止膜形成剤(日産化学社、ARC66)をスピンコーター(CLEAN TRACK Lithius Pro i、東京エレクトロン社)を使用して塗布した後、205℃で60秒間加熱することにより膜厚105nmの有機反射防止膜を形成した。この基板の表面に、クリーントラック(東京エレクトロン社、ACT12)を用いて各感放射線性樹脂組成物をスピンコートにより塗布し、ホットプレート上にて、100℃で60秒間ソフトベークを行い、膜厚0.10μmのレジスト膜を形成した。次いで、ArF液浸露光装置(NSR-S610C、ニコン精機カンパニー社)を使用し、NA=1.3、クアドロポールの光学条件にて、ベストフォーカスの条件で露光した。露光は1/4倍投影のスキャナー(NSR-S610C、ニコン精機カンパニー社)を使用し、レチクル上のサイズは0.220umクロム/0.440umピッチで、マスクバイアスは0nmであった。その後、ホットプレートにて表3に記載の温度で、60秒間ポストエクスポージャーベークを行った後、酢酸ブチルにより23℃で30秒間現像し、4-メチル-2-ペンタノール溶媒で10秒間リンス処理を行った後、乾燥してネガ型のレジストパターンを形成した。 <Formation of resist pattern>
An organic antireflection film forming agent (Nissan Chemical Co., ARC66) was applied to the wafer surface using a spin coater (CLEAN TRACK Lithius Pro i, Tokyo Electron), and then heated at 205 ° C. for 60 seconds to give a film thickness of 105 nm. An organic antireflection film was formed. On the surface of this substrate, each radiation sensitive resin composition was applied by spin coating using a clean track (Tokyo Electron Co., Ltd., ACT12), and soft-baked on a hot plate at 100 ° C. for 60 seconds to obtain a film thickness. A 0.10 μm resist film was formed. Next, using an ArF immersion exposure apparatus (NSR-S610C, Nikon Seiki Company), exposure was performed under the best focus condition with NA = 1.3 and quadropole optical conditions. For exposure, a 1 / 4-times projection scanner (NSR-S610C, Nikon Seiki Company) was used, the size on the reticle was 0.220 um chrome / 0.440 um pitch, and the mask bias was 0 nm. Thereafter, post-exposure baking was performed on the hot plate at the temperature shown in Table 3 for 60 seconds, followed by development with butyl acetate at 23 ° C. for 30 seconds and rinsing with 4-methyl-2-pentanol solvent for 10 seconds. After performing, it dried and formed the negative resist pattern.
ウエハー表面に有機反射防止膜形成剤(日産化学社、ARC66)をスピンコーター(CLEAN TRACK Lithius Pro i、東京エレクトロン社)を使用して塗布した後、205℃で60秒間加熱することにより膜厚105nmの有機反射防止膜を形成した。この基板の表面に、クリーントラック(東京エレクトロン社、ACT12)を用いて各感放射線性樹脂組成物をスピンコートにより塗布し、ホットプレート上にて、100℃で60秒間ソフトベークを行い、膜厚0.10μmのレジスト膜を形成した。次いで、ArF液浸露光装置(NSR-S610C、ニコン精機カンパニー社)を使用し、NA=1.3、クアドロポールの光学条件にて、ベストフォーカスの条件で露光した。露光は1/4倍投影のスキャナー(NSR-S610C、ニコン精機カンパニー社)を使用し、レチクル上のサイズは0.220umクロム/0.440umピッチで、マスクバイアスは0nmであった。その後、ホットプレートにて表3に記載の温度で、60秒間ポストエクスポージャーベークを行った後、酢酸ブチルにより23℃で30秒間現像し、4-メチル-2-ペンタノール溶媒で10秒間リンス処理を行った後、乾燥してネガ型のレジストパターンを形成した。 <Formation of resist pattern>
An organic antireflection film forming agent (Nissan Chemical Co., ARC66) was applied to the wafer surface using a spin coater (CLEAN TRACK Lithius Pro i, Tokyo Electron), and then heated at 205 ° C. for 60 seconds to give a film thickness of 105 nm. An organic antireflection film was formed. On the surface of this substrate, each radiation sensitive resin composition was applied by spin coating using a clean track (Tokyo Electron Co., Ltd., ACT12), and soft-baked on a hot plate at 100 ° C. for 60 seconds to obtain a film thickness. A 0.10 μm resist film was formed. Next, using an ArF immersion exposure apparatus (NSR-S610C, Nikon Seiki Company), exposure was performed under the best focus condition with NA = 1.3 and quadropole optical conditions. For exposure, a 1 / 4-times projection scanner (NSR-S610C, Nikon Seiki Company) was used, the size on the reticle was 0.220 um chrome / 0.440 um pitch, and the mask bias was 0 nm. Thereafter, post-exposure baking was performed on the hot plate at the temperature shown in Table 3 for 60 seconds, followed by development with butyl acetate at 23 ° C. for 30 seconds and rinsing with 4-methyl-2-pentanol solvent for 10 seconds. After performing, it dried and formed the negative resist pattern.
<評価>
形成した各レジストパターンについて下記の各評価をした。結果を表3に示す。 <Evaluation>
Each of the formed resist patterns was evaluated as follows. The results are shown in Table 3.
形成した各レジストパターンについて下記の各評価をした。結果を表3に示す。 <Evaluation>
Each of the formed resist patterns was evaluated as follows. The results are shown in Table 3.
[感度(mJ/cm2)]
縮小投影露光後のホールパターンの直径が0.055μmとなるように、ドットパターンを有するマスクを、液浸水を介して露光し、形成されるホールパターンが直径0.055μmのホールサイズとなるような露光量を最適露光量とし、この最適露光量を感度(mJ/cm2)とした。なお、測長には走査型電子顕微鏡(日立ハイテクノロジーズ社、CG4000)を用いた。このとき、感度が16(mJ/cm2)以下の場合を感度が良好と判断した。 [Sensitivity (mJ / cm 2 )]
A mask having a dot pattern is exposed through immersion water so that the diameter of the hole pattern after reduced projection exposure is 0.055 μm, and the hole pattern formed has a hole size of 0.055 μm in diameter. The exposure amount was the optimum exposure amount, and this optimum exposure amount was the sensitivity (mJ / cm 2 ). Note that a scanning electron microscope (Hitachi High-Technologies Corporation, CG4000) was used for length measurement. At this time, the sensitivity was judged to be good when the sensitivity was 16 (mJ / cm 2 ) or less.
縮小投影露光後のホールパターンの直径が0.055μmとなるように、ドットパターンを有するマスクを、液浸水を介して露光し、形成されるホールパターンが直径0.055μmのホールサイズとなるような露光量を最適露光量とし、この最適露光量を感度(mJ/cm2)とした。なお、測長には走査型電子顕微鏡(日立ハイテクノロジーズ社、CG4000)を用いた。このとき、感度が16(mJ/cm2)以下の場合を感度が良好と判断した。 [Sensitivity (mJ / cm 2 )]
A mask having a dot pattern is exposed through immersion water so that the diameter of the hole pattern after reduced projection exposure is 0.055 μm, and the hole pattern formed has a hole size of 0.055 μm in diameter. The exposure amount was the optimum exposure amount, and this optimum exposure amount was the sensitivity (mJ / cm 2 ). Note that a scanning electron microscope (Hitachi High-Technologies Corporation, CG4000) was used for length measurement. At this time, the sensitivity was judged to be good when the sensitivity was 16 (mJ / cm 2 ) or less.
[断面形状]
上記感度の評価における0.055μmホールパターンの断面形状を日立ハイテクノロジーズ社、S-4800を用いて観察した。レジストパターンの中間における線幅Lbと、膜の上部における線幅Laを測り、0.9≦(La/Lb)≦1.1の範囲内である場合を「A」(良好と判断)、範囲外である場合を「B」(不良と判断)とした。 [Cross-sectional shape]
The cross-sectional shape of the 0.055 μm hole pattern in the sensitivity evaluation was observed using Hitachi High-Technologies Corporation, S-4800. The line width Lb in the middle of the resist pattern and the line width La in the upper part of the film are measured, and when the range is 0.9 ≦ (La / Lb) ≦ 1.1, “A” (determined as good), range The case of being outside was designated as “B” (determined as defective).
上記感度の評価における0.055μmホールパターンの断面形状を日立ハイテクノロジーズ社、S-4800を用いて観察した。レジストパターンの中間における線幅Lbと、膜の上部における線幅Laを測り、0.9≦(La/Lb)≦1.1の範囲内である場合を「A」(良好と判断)、範囲外である場合を「B」(不良と判断)とした。 [Cross-sectional shape]
The cross-sectional shape of the 0.055 μm hole pattern in the sensitivity evaluation was observed using Hitachi High-Technologies Corporation, S-4800. The line width Lb in the middle of the resist pattern and the line width La in the upper part of the film are measured, and when the range is 0.9 ≦ (La / Lb) ≦ 1.1, “A” (determined as good), range The case of being outside was designated as “B” (determined as defective).
[円形性]
上記最適露光量において、基板上のレジスト塗膜に形成された0.055μmのホールパターンを、測長SEM(日立ハイテクノロジーズ社、CG4000)を用いてパターン上部から観察した。直径を任意のポイントで測定し、その測定ばらつきを3σで評価し、0.009μm以下である場合を「良好」と判断し、0.009μmを超える場合を「不良」と判断した。 [Circularity]
At the optimum exposure amount, a 0.055 μm hole pattern formed on the resist coating film on the substrate was observed from above the pattern using a length measurement SEM (Hitachi High-Technologies Corporation, CG4000). The diameter was measured at an arbitrary point, and the measurement variation was evaluated by 3σ. When the diameter was 0.009 μm or less, it was judged as “good”, and when it exceeded 0.009 μm, it was judged as “bad”.
上記最適露光量において、基板上のレジスト塗膜に形成された0.055μmのホールパターンを、測長SEM(日立ハイテクノロジーズ社、CG4000)を用いてパターン上部から観察した。直径を任意のポイントで測定し、その測定ばらつきを3σで評価し、0.009μm以下である場合を「良好」と判断し、0.009μmを超える場合を「不良」と判断した。 [Circularity]
At the optimum exposure amount, a 0.055 μm hole pattern formed on the resist coating film on the substrate was observed from above the pattern using a length measurement SEM (Hitachi High-Technologies Corporation, CG4000). The diameter was measured at an arbitrary point, and the measurement variation was evaluated by 3σ. When the diameter was 0.009 μm or less, it was judged as “good”, and when it exceeded 0.009 μm, it was judged as “bad”.
[解像性]
ドットパターンを有するマスクを用いて液浸水を介して露光し、露光量を大きくしていった際に得られるホールの最小寸法を測定した。ホールの最小寸法が、0.050μm未満の場合「良好」と判断し、0.050μm以上の場合、「不良」と判断した。 [Resolution]
Exposure was performed through immersion water using a mask having a dot pattern, and the minimum size of holes obtained when the exposure amount was increased was measured. When the minimum dimension of the hole was less than 0.050 μm, it was judged as “good”, and when it was 0.050 μm or more, it was judged as “bad”.
ドットパターンを有するマスクを用いて液浸水を介して露光し、露光量を大きくしていった際に得られるホールの最小寸法を測定した。ホールの最小寸法が、0.050μm未満の場合「良好」と判断し、0.050μm以上の場合、「不良」と判断した。 [Resolution]
Exposure was performed through immersion water using a mask having a dot pattern, and the minimum size of holes obtained when the exposure amount was increased was measured. When the minimum dimension of the hole was less than 0.050 μm, it was judged as “good”, and when it was 0.050 μm or more, it was judged as “bad”.
表3から明らかなように、本発明のパターン形成方法に用いられる組成物は感度に優れ、また形成されたレジストパターンは、断面形状、円形性及び解像性に優れることがわかった。
As is clear from Table 3, it was found that the composition used in the pattern forming method of the present invention was excellent in sensitivity, and the formed resist pattern was excellent in cross-sectional shape, circularity and resolution.
本発明は、液浸露光用として好適で、かつ感度、断面形状、円形性、解像性等のリソグラフィー特性に優れるトレンチパターン又はホールパターンの形成方法、及び感放射線性樹脂組成物を提供することができる。
The present invention provides a method for forming a trench pattern or a hole pattern that is suitable for immersion exposure and has excellent lithography properties such as sensitivity, cross-sectional shape, circularity, and resolution, and a radiation-sensitive resin composition. Can do.
Claims (6)
- (1)基板上に感放射線性樹脂組成物を塗布するレジスト膜形成工程、
(2)上記レジスト膜にフォトマスクを介して放射線を照射する露光工程、及び
(3)上記露光されたレジスト膜を現像する現像工程
を含むトレンチパターン又はホールパターンの形成方法であって、
上記感放射線性樹脂組成物が、
[A]酸解離性基を有する構造単位の含有割合が10モル%以下である重合体、
[B]酸解離性基を有する構造単位の含有割合が10モル%を超える重合体、及び
[C]感放射線性酸発生体
を含有し、
上記(3)現像工程における現像液が、有機溶媒を80質量%以上含むこと
を特徴とするトレンチパターン又はホールパターンの形成方法。 (1) a resist film forming step of applying a radiation sensitive resin composition on a substrate;
(2) An exposure step of irradiating the resist film with radiation through a photomask, and (3) a trench pattern or hole pattern forming method including a development step of developing the exposed resist film,
The radiation sensitive resin composition is
[A] a polymer in which the content of the structural unit having an acid dissociable group is 10 mol% or less,
[B] a polymer in which the content ratio of the structural unit having an acid dissociable group exceeds 10 mol%, and [C] a radiation-sensitive acid generator,
(3) The method for forming a trench pattern or a hole pattern, wherein the developer in the developing step contains 80% by mass or more of an organic solvent. - [A]重合体のフッ素含有率が、[B]重合体よりも高い請求項1に記載のパターン形成方法。 The pattern formation method according to claim 1, wherein the fluorine content of the [A] polymer is higher than that of the [B] polymer.
- 上記有機溶媒が、エーテル系溶媒、ケトン系溶媒及びエステル系溶媒からなる群より選択される少なくとも1種の有機溶媒である請求項1に記載のパターン形成方法。 The pattern forming method according to claim 1, wherein the organic solvent is at least one organic solvent selected from the group consisting of ether solvents, ketone solvents and ester solvents.
- [A]重合体が、下記式(1)で表される構造単位(I)及び下記式(2)で表される構造単位(II)からなる群より選択される少なくとも1種の構造単位を有する請求項1に記載のパターン形成方法。
- [B]重合体の酸解離性基が、鎖状の炭化水素基、又は単環若しくは多環の脂環式炭化水素基を有する請求項1に記載のパターン形成方法。 [B] The pattern forming method according to claim 1, wherein the acid dissociable group of the polymer has a chain hydrocarbon group or a monocyclic or polycyclic alicyclic hydrocarbon group.
- (1)基板上に感放射線性樹脂組成物を塗布するレジスト膜形成工程、
(2)上記レジスト膜にフォトマスクを介して放射線を照射する露光工程、及び
(3)上記露光されたレジスト膜を現像する現像工程
を含むトレンチパターン又はホールパターンの形成方法であって、
上記工程(3)における現像液が、有機溶媒を80質量%以上含み、
上記感放射線性樹脂組成物が、
[A]酸解離性基を有する構造単位の含有割合が10モル%以下である重合体、
[B]酸解離性基を有する構造単位の含有割合が10モル%を超える重合体、及び
[C]感放射線性酸発生体
を含有することを特徴とする感放射線性樹脂組成物。 (1) a resist film forming step of applying a radiation sensitive resin composition on a substrate;
(2) An exposure step of irradiating the resist film with radiation through a photomask, and (3) a trench pattern or hole pattern forming method including a development step of developing the exposed resist film,
The developer in the step (3) contains 80% by mass or more of an organic solvent,
The radiation sensitive resin composition is
[A] a polymer in which the content of the structural unit having an acid dissociable group is 10 mol% or less,
[B] A polymer in which the content of the structural unit having an acid-dissociable group exceeds 10 mol%, and [C] a radiation-sensitive resin composition, comprising a radiation-sensitive acid generator.
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US20140363770A1 (en) * | 2013-06-10 | 2014-12-11 | Tokyo Ohka Kogyo Co., Ltd. | Negative tone resist composition for solvent developing and method of forming resist pattern |
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JP2008310314A (en) * | 2007-05-15 | 2008-12-25 | Fujifilm Corp | Method for pattern formation |
JP2009025708A (en) * | 2007-07-23 | 2009-02-05 | Fujifilm Corp | Pattern forming method |
JP2010164958A (en) * | 2008-12-15 | 2010-07-29 | Fujifilm Corp | Resist composition for negative development, pattering method using the same, resist film, and pattern |
JP2011137888A (en) * | 2009-12-25 | 2011-07-14 | Fujifilm Corp | Pattern forming method, pattern, chemically amplified resist composition, and resist film |
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2011
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JP2008310314A (en) * | 2007-05-15 | 2008-12-25 | Fujifilm Corp | Method for pattern formation |
JP2009025708A (en) * | 2007-07-23 | 2009-02-05 | Fujifilm Corp | Pattern forming method |
JP2010164958A (en) * | 2008-12-15 | 2010-07-29 | Fujifilm Corp | Resist composition for negative development, pattering method using the same, resist film, and pattern |
JP2011137888A (en) * | 2009-12-25 | 2011-07-14 | Fujifilm Corp | Pattern forming method, pattern, chemically amplified resist composition, and resist film |
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US20140363770A1 (en) * | 2013-06-10 | 2014-12-11 | Tokyo Ohka Kogyo Co., Ltd. | Negative tone resist composition for solvent developing and method of forming resist pattern |
US9459528B2 (en) * | 2013-06-10 | 2016-10-04 | Tokyo Ohka Kogyo Co., Ltd. | Negative tone resist composition for solvent developing and method of forming resist pattern |
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