WO2016132803A1 - Composition pour incorporation de motif organique, procédé de formation de motif et procédé de fabrication de dispositif électronique - Google Patents

Composition pour incorporation de motif organique, procédé de formation de motif et procédé de fabrication de dispositif électronique Download PDF

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Publication number
WO2016132803A1
WO2016132803A1 PCT/JP2016/051708 JP2016051708W WO2016132803A1 WO 2016132803 A1 WO2016132803 A1 WO 2016132803A1 JP 2016051708 W JP2016051708 W JP 2016051708W WO 2016132803 A1 WO2016132803 A1 WO 2016132803A1
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Prior art keywords
group
pattern
resin
organic
composition
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PCT/JP2016/051708
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English (en)
Japanese (ja)
Inventor
大輔 浅川
研由 後藤
啓太 加藤
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富士フイルム株式会社
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Priority to JP2017500557A priority Critical patent/JP6467033B2/ja
Publication of WO2016132803A1 publication Critical patent/WO2016132803A1/fr

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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
    • 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
    • G03F7/22—Exposing sequentially with the same light pattern different positions of the same surface
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

  • the present invention relates to an organic pattern embedding composition, a pattern forming method, an electronic device manufacturing method, and an electronic device. More specifically, the present invention relates to a pattern forming method suitable for a semiconductor manufacturing process such as an IC (Integrated Circuit), a circuit board such as a liquid crystal and a thermal head, and other photofabrication lithography processes, and a method for using the same.
  • the present invention relates to an organic pattern embedding composition.
  • the present invention also relates to an electronic device manufacturing method including the pattern forming method and an electronic device manufactured by the method.
  • a planarization layer may be formed as a base for forming a resist pattern (for example, Patent Document 1).
  • the present inventors have used the composition for forming a flattened film disclosed in Patent Document 1 to flatten an organic pattern such as a resist pattern as in the pattern forming method of the present invention described later.
  • the embedding property and the flatness and etching property (high etching property) of the formed flattening layer do not necessarily satisfy the required levels. Became clear.
  • the present invention provides an organic pattern embedding composition excellent in embedding property, flatness and etching property, a pattern forming method using the above composition, and an electronic device manufacturing method. For the purpose.
  • the present inventors have found that the above problems can be solved by using a resin whose Onishi parameter is larger than a specific value. That is, the present inventors have found that the above problem can be solved by the following configuration.
  • An organic pattern embedding composition containing a resin having an Onishi parameter greater than 5.0.
  • the composition for embedding an organic pattern according to the above (1) wherein the resin is at least one resin selected from the group consisting of a poly (meth) acrylic resin, a polyester resin, and a polyether resin.
  • R 2 is a lactone structure-containing group, a carbonate structure-containing group, an acetal structure-containing group, a hydroxy group-containing group, or a group represented by Formula (P) described later.
  • FIG. 1A to FIG. 1I are schematic cross-sectional views for explaining an embodiment of a planarization method and a pattern formation method used in the present invention.
  • an “alkyl group” that does not explicitly indicate substitution or unsubstituted includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). I will do it.
  • active light or “radiation” means, for example, an emission line spectrum of a mercury lamp, a deep ultraviolet ray represented by an excimer laser, an extreme ultraviolet ray (EUV light), an X-ray, an electron beam, an ion beam or other particle beam. Means.
  • light means actinic rays or radiation.
  • exposure in the present specification is not limited to exposure to far ultraviolet rays, X-rays, extreme ultraviolet rays (EUV light) and the like represented by mercury lamps and excimer lasers. It is also assumed that drawing by particle beams such as.
  • (meth) acrylate” means “at least one of acrylate and methacrylate”.
  • (Meth) acrylic acid” means “at least one of acrylic acid and methacrylic acid”.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • composition for embedding organic pattern contains a resin having an Onishi parameter of greater than 5.0. Since the composition of this invention takes such a structure, it is thought that a desired effect is acquired. The reason for this is not clear, but by increasing the Onishi parameter of the resin above a specific value, the etchability is improved, the wettability is improved by improving the polarity, and both embedding and flatness are compatible. It is speculated that it can be achieved.
  • the resin used for the organic pattern embedding composition is also referred to as “embedding resin”.
  • the composition of the present invention contains a resin having an Onishi parameter of greater than 5.0.
  • a resin having an Onishi parameter greater than 5.0 is also referred to as a “specific resin”.
  • the Onishi parameter of the specific resin is preferably 5.5 to 20.0, and more preferably 6.0 to 15.0.
  • the Onishi parameter of A-1 used in the examples described later is calculated as follows.
  • the second repeating unit from the left of A-1 has 23 total atoms, 7 carbon atoms, and 4 oxygen atoms, so the Onishi parameter is 23 / (7-4) ⁇ 7.7. It is.
  • the third repeating unit from the left of A-1 has 43 total atoms, 7 carbon atoms, and 4 oxygen atoms, so the Onishi parameter is 43 / (13-6) ⁇ 6.1. It is.
  • the mole fraction of the first repeating unit from the left of A-1 is 0.3
  • the mole fraction of the second repeating unit from the left of A-1 is 0.5
  • the third repeating unit from the left of A-1 Since the molar fraction of the unit is 0.2
  • the Onishi parameter of A-1 is 5.5 ⁇ 0.3 + 7.7 ⁇ 0.5 + 6.1 ⁇ 0 in consideration of the Onishi parameter of each repeating unit described above. .2 ⁇ 6.7.
  • the specific resin is not particularly limited as long as the Onishi parameter is greater than 5.0, but specific examples thereof include poly (meth) acrylic resin, polyester resin, polyether resin, polystyrene resin, polyvinyl alcohol resin, polysiloxane resin. Etc. Among these, at least one resin selected from the group consisting of a poly (meth) acrylic resin, a polyester resin, and a polyether resin is preferable.
  • the specific resin preferably does not contain an aromatic ring.
  • the glass transition temperature (Tg) of the specific resin is not particularly limited, but is preferably 200 ° C. or lower, and more preferably 60 ° C. or lower.
  • the lower limit of Tg is not particularly limited, but is usually ⁇ 100 ° C. or higher. For reasons of better embedding and flatness, a lower Tg is preferred. Tg is measured using a differential scanning calorimeter (DSC).
  • the weight average molecular weight of the specific resin is not particularly limited, but is preferably 500 to 100,000, more preferably 20,000 or less, and more preferably 15,000 or less. More preferably, it is as follows.
  • a weight average molecular weight is a standard polystyrene conversion value calculated
  • GPC gel permeation chromatography
  • the specific resin preferably has a repeating unit represented by the following formula (1-1).
  • the specific resin may have two or more types of repeating units represented by the following formula (1-1).
  • R 1 represents a hydrogen atom or an organic group.
  • R 2 represents a hydrocarbon group having a hetero atom. However, for the number of carbon atoms contained in R 2, the ratio of the number of the heteroatom contained in R 2 is 0.30 or more.
  • R 1 represents a hydrogen atom or an organic group.
  • the alkyl group which may have substituents, such as a fluorine atom and a hydroxyl group is mentioned, for example, A hydrogen atom, a methyl group, a trifluoromethyl group, and a hydroxymethyl group are preferable.
  • R 2 represents a hydrocarbon group having a hetero atom.
  • the hetero atom is not particularly limited, but specific examples include a nitrogen atom, an oxygen atom, a sulfur atom, and the like. Of these, an oxygen atom is preferable.
  • the hydrocarbon group having a heteroatom is not particularly limited, but an aliphatic hydrocarbon group having a heteroatom (for example, 1 to 10 carbon atoms) (straight, branched, or cyclic), an aromatic carbon having a heteroatom Examples thereof include a hydrogen group (for example, having 6 to 20 carbon atoms), an alicyclic heterocyclic group, an aromatic heterocyclic group, or a combination of these.
  • the ratio of the number of the heteroatom contained in R 2 (hereinafter, also referred to as "R2 hetero ratio”.) Is at least 0.30. Especially, it is preferable that it is 0.50 or more.
  • the upper limit of the R2 hetero ratio is not particularly limited, but is usually 1.00 or less.
  • R 2 examples include a hydrocarbon group, a lactone structure-containing group, a carbonate structure-containing group, an acetal structure-containing group, a hydroxy group-containing group, or a group represented by the formula (P) described below.
  • a lactone structure-containing group, a carbonate structure-containing group, an acetal structure-containing group, a hydroxy group-containing group, or a group represented by the formula (P) described later is preferable.
  • the hydrocarbon group is not particularly limited, but an aliphatic hydrocarbon group (for example, 1 to 10 carbon atoms) (straight, branched, or cyclic), an aromatic hydrocarbon group (for example, 6 to 20 carbon atoms), etc. Is mentioned.
  • an aliphatic hydrocarbon group is preferable.
  • a repeating unit in which R 2 of the repeating unit represented by the formula (1-1) is a lactone structure-containing group is hereinafter referred to as “the repeating unit represented by the formula (1-1) (R 2 : Lactone structure-containing group) "(the same applies when R 2 is a hydrocarbon group having a hetero atom other than the lactone structure-containing group).
  • the lactone structure-containing group is a group having a lactone structure (cyclic ester structure).
  • Specific examples of the lactone structure include a lactone structure in a “repeating unit having a lactone structure” which may be contained in the resin (A) described later.
  • the carbonate structure-containing group represents a group containing a carbonate structure (cyclic carbonate structure).
  • Specific examples of the carbonate structure include a cyclic carbonate structure in “a repeating unit having a cyclic carbonate structure” which may be contained in the resin (A) described later.
  • the acetal structure-containing group represents a group containing an acetal structure.
  • the acetal structure is represented by the following formula (Q).
  • R 1 to R 4 each independently represents a hydrocarbon group.
  • the hydrocarbon group is not particularly limited, but an aliphatic hydrocarbon group (for example, 1 to 10 carbon atoms) (straight, branched, or cyclic), an aromatic hydrocarbon group (for example, 6 to 20 carbon atoms), etc. Is mentioned. Of these, an aliphatic hydrocarbon group is preferable.
  • R 1 to R 4 may combine with each other to form a ring.
  • the hydroxy group-containing group represents a group containing a hydroxy group (—OH). Of these, a hydrocarbon group containing a hydroxy group is preferred. Specific examples and preferred embodiments of the hydrocarbon group are the same as R 1 to R 4 in the above-described formula (Q).
  • the hydroxy group-containing group is preferably a group containing two or more hydroxy groups.
  • R A represents a divalent hydrocarbon group.
  • R B represents a monovalent hydrocarbon group.
  • n represents an integer of 1 or more. When n is an integer of 2 or more, a plurality of R A may be the same or different. * Represents a binding position.
  • R A represents a divalent hydrocarbon group. Specific examples and preferred embodiments of the hydrocarbon group are the same as R 1 to R 4 in the above-described formula (Q).
  • R B represents a monovalent hydrocarbon group. Specific examples and preferred embodiments of the hydrocarbon group are the same as R 1 to R 4 in the above-described formula (Q).
  • n represents an integer of 1 or more. n is preferably an integer of 1 to 10.
  • the ratio of the repeating unit (R 2 : lactone structure-containing group) represented by the above formula (1-1) in the specific resin is preferably 10 to 80 mol%. More preferably, it is ⁇ 60 mol%. In the first preferred embodiment, the ratio of the repeating unit (R 2 : carbonate structure-containing group) represented by the above formula (1-1) in the specific resin is preferably 10 to 80 mol%. More preferably, it is ⁇ 50 mol%. In the first preferred embodiment, the ratio of the repeating unit (R 2 : acetal structure-containing group) represented by the above formula (1-1) in the specific resin is preferably 10 to 80 mol%. More preferably, it is ⁇ 30 mol%. In the first preferred embodiment, the ratio of the repeating unit represented by the above formula (1-1) (R 2 : group represented by the formula (P)) in the specific resin is 10 to 80 mol%. It is preferably 10 to 30 mol%.
  • the ratio of the repeating unit represented by the above formula (1-1) in the specific resin is not particularly limited, but is preferably 10 to 100 mol%, more preferably 80 to 100 mol%.
  • the specific resin preferably has a repeating unit represented by the above formula (1-1) (R 2 : a group represented by the formula (P)).
  • the ratio of the repeating unit represented by formula (1-1) (R 2 : group represented by formula (P)) is more preferably 15 mol% or more, and among them, the above formula (1-1)
  • the specific resin may have a repeating unit other than the repeating unit represented by the formula (1-1) described above.
  • a repeating unit having an R2 hetero ratio of less than 0.30 in the above formula (1-1) can be used.
  • the resin preferably has a repeating unit represented by the following formula (1-2).
  • the specific resin may have two or more types of repeating units represented by the following formula (1-2).
  • L represents a divalent hydrocarbon group.
  • X represents —O—, —S—, or —CO—O—.
  • L represents a divalent hydrocarbon group.
  • Specific examples and preferred embodiments of the hydrocarbon group are the same as R 1 to R 4 in the above-described formula (Q).
  • the ratio of the repeating unit represented by the above formula (1-2) in the specific resin (X: —O—) is preferably 20 to 100 mol%, It is more preferably from ⁇ 100 mol%, more preferably from 80 to 100 mol%.
  • the ratio of the repeating unit represented by the above formula (1-2) in the specific resin (when two or more repeating units represented by the above formula (1-2) are contained)
  • the total ratio is not particularly limited, but is preferably 10 to 100 mol%, more preferably 80 to 100 mol%.
  • the content of the specific resin is not particularly limited, but is preferably 10 to 100% by mass, and more preferably 80 to 100% by mass based on the total solid content.
  • composition of the present invention may contain components other than the specific resin.
  • components include resins other than specific resins, solvents, surfactants, and the like.
  • Specific examples of the solvent and the surfactant are the same as those of the resist composition described later.
  • the composition of this invention contains a solvent.
  • the composition of the present invention is excellent in embedding property, flatness, and etching property. It can be suitably used for coating and embedding in a gap or the like of a pattern (for example, a resist pattern).
  • the shape and size of the gap are not particularly limited, and may be a hole-like gap or a groove-like gap.
  • the planarization method used in the present invention is: (A) a step of forming a first resist film on the substrate using the first resist composition; (B) exposing the first resist film; (C) developing the exposed first resist film to form a first pattern; (D) A step of forming a planarization layer on the substrate provided with the first pattern using the composition of the present invention described above, In this order.
  • the pattern forming method of the present invention after the steps (A) to (D), (E) a second resist film is formed on the planarizing layer using the second resist composition.
  • the “planarization method used in the present invention” and the “pattern formation method of the present invention” are collectively referred to as “the method of the present invention”.
  • the first pattern and / or the second pattern is preferably a pattern formed by developing using a developer containing an organic solvent.
  • each of the steps (A) to (G) can be performed by a generally known method.
  • a first resist film 52 is formed on a substrate 51 using a first resist composition (process).
  • the first resist composition preferably contains a resin whose polarity is increased by the action of an acid and the solubility in a developer containing an organic solvent (organic developer) is reduced.
  • the first pattern obtained through the steps (B) and (C) described later contains a resin whose solubility in an organic developer is lowered by exposure.
  • the above-described composition of the present invention can be insoluble and is not easily affected by the solvent in the above-described composition of the present invention used in step (D), and a desired pattern is easily formed. Because. Details of the first resist composition and the resin that it preferably contains will increase in polarity by the action of an acid and have reduced solubility in a developer containing an organic solvent will be described later.
  • the method of forming the first resist film using the first resist composition on the substrate can be typically performed by applying the first resist composition on the substrate.
  • the coating method a conventionally known spin coating method, spray method, roller coating method, dipping method or the like can be used, and the first resist composition is preferably coated by a spin coating method.
  • the film thickness of the first resist film is preferably 20 to 160 nm, more preferably 25 to 140 nm, and still more preferably 30 to 120 nm.
  • the substrate 51 on which the first resist film is formed is not particularly limited, and is an inorganic substrate such as silicon, SiN, SiO 2 or SiN, a coated inorganic substrate such as SOG (Spin on Glass), or the like, such as an IC (Integrated Circuit). ) And the like, semiconductor substrate manufacturing processes such as liquid crystal and thermal heads, and other photolithographic lithography processes can be used. Furthermore, a lower layer film such as an antireflection film may be formed between the first resist film and the substrate as necessary. As the lower layer film, an organic antireflection film, an inorganic antireflection film, and the like can be appropriately selected.
  • the underlayer film material is available from Brewer Science, Nissan Chemical Industries, Ltd. As a lower layer film suitable for the process of developing using a developer containing an organic solvent, for example, a lower layer film described in WO2012 / 039337A can be mentioned.
  • the method of the present invention preferably includes a post-exposure heating step (PEB; Post Exposure Bake) between the step (B) and the step (C).
  • the heating temperature is preferably 70 to 130 ° C., more preferably 80 to 120 ° C. for both PB and PEB.
  • the heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds. Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like. The reaction of the exposed part is promoted by baking, and the sensitivity and pattern profile are improved.
  • At least one of the preheating step and the post-exposure heating step may include a plurality of heating steps.
  • the resist film 52 is irradiated with actinic rays or radiation 71 through a mask 61 (that is, exposed), thereby being exposed.
  • a mask 61 that is, exposed
  • One resist film 53 is obtained (step (B)).
  • the mask pattern in the mask 61 is not particularly limited.
  • the mask 61 is a mask having a line-and-space pattern having a line portion as a light shielding portion and a space portion as a light transmission portion, A mask having a space portion width ratio of 1: 3 can be mentioned.
  • the wavelength of the light source used in the exposure apparatus is not limited, but examples include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams.
  • KrF excimer laser, ArF excimer laser, EUV or electron beam are preferable, and ArF excimer laser is more preferable.
  • Step (B) may include a plurality of exposure steps.
  • an immersion exposure method can be applied in the step (B). Furthermore, it can be combined with super-resolution techniques such as the phase shift method and the modified illumination method that are currently being studied.
  • the immersion liquid is preferably a liquid that is transparent to the exposure wavelength and has a refractive index temperature coefficient as small as possible so as to minimize distortion of the optical image projected onto the first resist film.
  • the exposure light source is an ArF excimer laser (wavelength: 193 nm)
  • a hydrophobic resin (D) described later can be further added as necessary.
  • the receding contact angle of the first resist film is preferably 60 ° to 90 °, more preferably 70 ° or more.
  • the immersion head needs to move on the wafer following the movement of the exposure head scanning the wafer at high speed to form the exposure pattern, so that the dynamic state is reached. In this case, the contact angle of the immersion liquid with respect to the first resist film becomes important, and the resist is required to follow the high-speed scanning of the exposure head without remaining droplets.
  • an immersion liquid hardly soluble film (hereinafter referred to as “top”).
  • top an immersion liquid hardly soluble film
  • functions necessary for the top coat or the composition for forming a top coat include suitability for application to the resist upper layer, transparency to radiation, particularly radiation having a wavelength of 193 nm, and poor immersion liquid solubility. It is preferable that the composition for forming the top coat is not mixed with the resist and can be uniformly applied to the resist upper layer.
  • step (C) is typically a step of developing the exposed first resist film with a developer containing an organic solvent to form a first pattern
  • the first pattern 54 is Typically, a negative pattern.
  • the first resist film is developed using a developer containing an organic solvent to form the first pattern, and the developer (hereinafter also referred to as “organic developer”) in the step of forming the first pattern.
  • a polar solvent such as a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, an ether solvent, and a hydrocarbon solvent can be used.
  • ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.
  • ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, cyclohexyl acetate, isobutyl isobutyrate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol Monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, Examples thereof include butyl lactate, propyl lactate, isoamyl acetate, butyl butanoate, methyl 2-hydroxyisobutyrate,
  • the alcohol solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, alcohols such as n-octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, Diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethyl butano It can be mentioned glycol ether solvents such as Le.
  • ether solvent examples include dioxane, tetrahydrofuran, phenetole, dibutyl ether and the like in addition to the glycol ether solvent.
  • amide solvents include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone and the like.
  • hydrocarbon solvent examples include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane and decane.
  • the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of moisture. That is, the amount of the organic solvent used relative to the organic developer is preferably 90% by mass or more and 100% by mass or less, and more preferably 95% by mass or more and 100% by mass or less with respect to the total amount of the developer. .
  • the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents.
  • the vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C.
  • the vapor pressure of the organic developer is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less at 20 ° C.
  • the surfactant is not particularly limited, and for example, ionic or nonionic fluorine-based and / or silicon-based surfactants can be used.
  • fluorine and / or silicon surfactants include, for example, JP-A No. 62-36663, JP-A No. 61-226746, JP-A No. 61-226745, JP-A No. 62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, The surfactants described in US Pat. Nos.
  • the surfactant is a nonionic surfactant.
  • it does not specifically limit as a nonionic surfactant, It is still more preferable to use a fluorochemical surfactant or a silicon-type surfactant.
  • the amount of the surfactant used is usually from 0.001 to 5% by mass, preferably from 0.005 to 2% by mass, more preferably from 0.01 to 0.5% by mass, based on the total amount of the developer.
  • the organic developer may contain a basic compound as necessary.
  • basic compounds include nitrogen-containing basic compounds, such as nitrogen-containing compounds described in JP-A-2013-11833, particularly ⁇ 0021> to ⁇ 0063>.
  • a resin whose polarity is increased by the action of an acid and its solubility in a developer containing an organic solvent is reduced can also be a resin whose polarity is increased by the action of an acid and its solubility in an alkaline developer is increased. Therefore, the method of the present invention is performed between step (B) and step (C), or between step (C) and step (D) (when performing step (C ′) described later, Between the step (C) and the step (C ′), a step of developing using an alkaline developer may be further included.
  • a step of developing using an alkaline developer may be further included.
  • examples of the alkali developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia.
  • Inorganic alkalis primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine and triethanolamine
  • Alkaline aqueous solutions such as alcohol amines such as quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and cyclic amines such as pyrrole and piperidine can be used.
  • an appropriate amount of alcohol or surfactant may be added to the alkaline aqueous solution.
  • the surfactant include those described above.
  • the alkali concentration of the alkali developer is usually from 0.1 to 20% by mass.
  • the pH of the alkali developer is usually from 10.0 to 15.0.
  • an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide is desirable.
  • a developing method for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time (paddle) Method), a method of spraying the developer on the substrate surface (spray method), a method of continuously discharging the developer while scanning the developer discharge nozzle on the substrate rotating at a constant speed (dynamic dispensing method) Etc.
  • dip method a method in which a substrate is immersed in a tank filled with a developer for a certain period of time
  • paddle a method in which the developer is raised on the surface of the substrate by surface tension and is left stationary for a certain time
  • spray method a method of spraying the developer on the substrate surface
  • step (C) and step (D) between step (C) and step (C ′) when step (C ′) described later
  • a step of washing with a rinse containing an organic solvent may be included.
  • the rinsing solution used in the rinsing step after the step of developing with a developer containing an organic solvent is not particularly limited as long as the resist pattern is not dissolved, and a solution containing a general organic solvent can be used.
  • a rinsing liquid a rinsing liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents is used. Is preferred. Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent are the same as those described in the developer containing an organic solvent.
  • a step of washing with a rinsing liquid containing an organic solvent is carried out, more preferably a step of washing with a rinsing liquid containing a hydrocarbon solvent, an alcohol solvent or an ester solvent, and particularly preferably carbonization.
  • a cleaning step is performed using a rinsing liquid containing a hydrogen solvent and a monohydric alcohol, and most preferably, a cleaning step is performed using a rinsing liquid containing a monohydric alcohol having 5 or more carbon atoms.
  • examples of the monohydric alcohol used in the rinsing step include linear, branched, and cyclic monohydric alcohols. Specific examples include 1-butanol, 2-butanol, and 3-methyl-1-butanol. Tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2 -Octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and the like can be used, and particularly preferable monohydric alcohols having 5 or more carbon atoms are 1-hexanol, 2-hexanol, 4-methyl- Use 2-pentanol, 1-pentanol, 3-methyl-1-butanol, etc.
  • the rinse liquid containing a hydrocarbon solvent is preferably a hydrocarbon compound having 6 to 30 carbon atoms, more preferably a hydrocarbon compound having 8 to 30 carbon atoms, and particularly preferably a hydrocarbon compound having 10 to 30 carbon atoms. Especially, pattern collapse is suppressed by using the rinse liquid containing a decane and / or undecane.
  • a glycol ether solvent may be used in addition to the ester solvent (one or more). Specific examples in this case include using an ester solvent (preferably butyl acetate) as a main component and a glycol ether solvent (preferably propylene glycol monomethyl ether (PGME)) as a subcomponent. Thereby, a residue defect is suppressed more.
  • a plurality of the above-described components may be mixed, or may be used by mixing with an organic solvent other than the above.
  • the method of the present invention may include a step of developing with an alkaline developer, or a step of rinsing with a rinse solution (rinsing step).
  • a rinsing liquid in this case, pure water is used, and an appropriate amount of a surfactant can be added and used.
  • the cleaning method in the rinsing step is not particularly limited.
  • a method of continuously discharging a rinsing liquid onto a substrate rotating at a constant speed (rotary coating method), a substrate in a bath filled with the rinsing liquid Can be applied for a certain period of time (dip method), a method of spraying a rinsing liquid on the substrate surface (spray method), etc.
  • a cleaning process is performed by a spin coating method, and the substrate is washed at 2000 rpm or more after cleaning. It is preferable to rotate at a rotational speed of 4000 rpm to remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step.
  • the developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed by baking.
  • the heating step after the rinsing step is usually performed at 40 to 160 ° C., preferably 70 to 95 ° C., usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.
  • the temperature in this heating step (C ′) is preferably 130 ° C. or higher, more preferably 150 ° C. or higher, and even more preferably 170 ° C. or higher.
  • the said temperature is normally made into 240 degrees C or less.
  • the heating time in this heating step (C ′) is about 30 to 120 seconds.
  • the heating step (C ′) is also preferably performed under reduced pressure from the viewpoint that the heating temperature can be reduced and the heating time can be shortened by promoting the volatilization of the decomposition residue of the organic matter.
  • the first pattern 54 is not necessary because it has sufficient solvent resistance, but the present invention excludes application of a known freezing material to the first pattern 54. It is not a thing.
  • a planarization layer 81 is formed on the substrate 51 on which the first pattern 54 has been formed using the above-described composition of the present invention (process). (D)).
  • the method of forming the planarization layer using the composition of the present invention described above is the same as the method of forming the first resist film using the first resist composition in the step (A). It is the same.
  • the film thickness of the planarization layer with the surface of the first pattern as the reference plane is preferably 0 to 50 nm, more preferably 2 to 40 nm, and even more preferably 5 to 30 nm.
  • the film thickness of the planarization layer using the surface of the first pattern as a reference plane may be 0 nm. In other words, the surface of the first pattern and the surface of the planarization layer may be flush.
  • the first pattern is flattened by the steps (A) to (D) described above.
  • the pattern forming method of the present invention further includes the following steps (E) to (G) after the steps (A) to (D).
  • the second resist composition preferably contains a resin whose polarity increases by the action of an acid and whose solubility in an organic developer decreases.
  • the second pattern obtained through the steps (F) and (G) described later can be a negative pattern formed using an organic developer, as described above, This is because an ultrafine space pattern (for example, a space width of 40 nm or less) can be reliably formed as compared with the mold pattern.
  • the details of the second resist composition and the resin that it contains preferably will increase in polarity by the action of an acid and have reduced solubility in a developer containing an organic solvent will be described later.
  • the method of forming the second resist film using the second resist composition is the same as the method of forming the first resist film using the first resist composition in the step (A). It is the same.
  • the preferable range of the thickness of the second resist film is the same as that described as the preferable range of the first resist film.
  • the pattern forming method of the present invention preferably includes a preheating step (PB; Prebake) between the step (E) and the step (F). Moreover, it is also preferable that the pattern formation method of this invention includes a post-exposure heating process (PEB; Post Exposure Bake) between a process (F) and a process (G).
  • the heating temperature is preferably 70 to 130 ° C., more preferably 80 to 120 ° C. for both PB and PEB.
  • the heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds. Heating can be performed by means provided in a normal exposure / developing machine, and may be performed using a hot plate or the like. The reaction of the exposed part is promoted by baking, and the sensitivity and pattern profile are improved.
  • At least one of the preheating step and the post-exposure heating step may include a plurality of heating steps.
  • the resist film 56 is irradiated with actinic rays or radiation 71 through a mask 61 (that is, exposed), thereby being exposed.
  • a second resist film 57 is obtained (step (F)).
  • the mask pattern in the mask 61 is not particularly limited, but is the same as the mask used in the step (B) (for example, a line and space having a line portion as a light shielding portion and a space portion as a light transmission portion). And a mask having a pattern in which the ratio of the width of the line portion to the width of the space portion is 1: 3.
  • the mask 61 is arranged so that the position of the light shielding portion is shifted by a half pitch with respect to the position in the step (B) (that is, finally, the line direction of the first pattern and the line of the second pattern). More specifically, when viewed from a direction perpendicular to the substrate, the center line of the space portion of the second pattern is changed to the center line of the line portion of the first pattern so that the direction is parallel to the direction.
  • the ultra fine 1: 1 line and space pattern can be formed by carrying out the steps (G), (H) and (I) described later. Can be formed.
  • the same method as described in the exposure in the step (B) can be employed.
  • the exposed second resist film 57 is developed to form a second pattern 58 (step (G)).
  • the developer that can be used in the step of developing the second resist film to form the second pattern may be an organic developer or an alkali developer, What was demonstrated about the organic type developing solution in a process (C), and the alkali in the said "process developed using an alkali developing solution" which may be implemented between a process (C) and a process (D), for example. What was demonstrated about the developing solution can be used similarly.
  • a step of forming a negative pattern using a developer containing an organic solvent and as a second pattern, a step of forming a positive pattern using an alkaline developer. Can be preferably mentioned.
  • the second pattern 58 may be a negative pattern or a positive pattern.
  • an ultrafine (for example, a space width of 40 nm or less) space pattern is surely formed.
  • a negative pattern is preferred, and step (G) is more preferably a step of forming a negative pattern using a developer containing an organic solvent as the second pattern.
  • the step (G) may include any one of a step of developing using an organic developer and a step of developing using an alkaline developer, but using an organic developer. You may have both the process to develop, and the process to develop using an alkaline developing solution, and the order of each development process in this case is not specifically limited.
  • step (G) The development method in the step (G) is the same as that described for the step (C), and may be performed between the step (C) and the step (D). What was described for the “process” can be used similarly.
  • the pattern forming method of the present invention may include a step of washing with a rinsing liquid (rinsing step) after the step (G).
  • a rinsing solution in the rinsing step after the step of developing with the organic developer the step of rinsing with a rinsing solution containing an organic solvent (rinsing step) that may be included after the step (C) has been described.
  • the rinse liquid in the rinse step after the step of developing with an alkaline developer for example, the above “alkali” may be carried out between the step (C) and the step (D). What has been described in the rinsing step that can be included after the “developing step using a developer” can be used in the same manner.
  • the second pattern is formed on the flattened layer obtained by flattening the first pattern by the steps (A) to (G) described above.
  • An ultrafine 1: 1 line and space pattern can be formed by further performing the step (H) and the step (I) on the substrate on which the second pattern is formed.
  • the etching gas 75 or the like is used for the planarization layer 81 and the first pattern 54 using the second pattern 58 as a mask. Etching is performed to convert the first pattern 54 into a fine pattern 55.
  • the method for the etching treatment is not particularly limited, and any known method can be used, and various conditions and the like are appropriately determined according to the type of the layer subjected to the etching treatment.
  • Proc. Of SPIE Vol. Etching can be performed in accordance with 6924, 692420 (2008), Japanese Patent Application Laid-Open No. 2009-267112, and the like.
  • the form in which at least any one of a 1st pattern and a 2nd pattern contains a silicon atom can be mentioned suitably.
  • at least one of the first resist composition and the second resist composition contains a silicon atom (for example, a resin having a silicon atom), or the first pattern and the second pattern At least one of them is preferably in a form containing a silicon atom (for example, a resin having a silicon atom).
  • the first etching condition can be obtained by employing an etching condition in which an etching reaction easily occurs with respect to a film containing silicon atoms, or an etching condition in which an etching reaction easily occurs with respect to a film not containing silicon atoms.
  • step (I) the planarization layer 81 and the second pattern 58 are removed.
  • the step (I) is not particularly limited as long as the planarization layer and the second pattern can be removed. It can be suitably carried out by applying one or more treatments selected from “exposure with an aqueous solution (for example, an acidic aqueous solution or a basic aqueous solution)”. That is, the same kind of processing may be performed on the planarization layer and the second pattern, or different kinds of processing may be performed.
  • the planarization layer 81 and the second pattern 58 are removed without damaging the miniaturized pattern 55, in other words, the planarization layer 81 and the second pattern 58. It is preferable to selectively remove the planarizing layer 81 and the second pattern 58 even in the above-described processing.
  • the etching rate of the planarizing layer 81 is larger than the etching rate of the miniaturized pattern 55 with respect to the planarizing layer 81. It is preferable to include a step of performing an etching process under conditions. In the case where the planarizing layer 81 is removed by the etching process, the step (I) is performed under the condition that the etching rate of the planarizing layer 81 is higher than the etching rate of the second pattern 58 with respect to the planarizing layer 81. It is also preferable to include the process of implementing a process.
  • the above conditions can be achieved by appropriately adjusting the content of each composition of the first resist composition, the second resist composition, and the composition of the present invention described above, the type of etching gas, and the like. is there.
  • the composition of the present invention described above is excellent in etching properties, the above conditions are easily achieved.
  • the present invention typically has the first pattern pattern as viewed from the direction perpendicular to the substrate as in the above embodiment.
  • the first pattern and the second pattern are formed so that the pattern of the second pattern viewed from the direction perpendicular to the substrate does not completely overlap.
  • the first pattern and the second pattern are both line-and-space patterns in which the line width is larger than the space width.
  • the line direction of the first pattern is parallel to the line direction of the second pattern.
  • Such an embodiment is suitable as being capable of easily forming an ultrafine pattern (for example, a line-and-space pattern having both a line width and a space width of 40 nm or less).
  • the first pattern and the second pattern are both line and space patterns, but the present invention is limited to this form.
  • one of the first pattern and the second pattern is a line and space pattern
  • the other is a hole pattern
  • both the first pattern and the second pattern Examples include a hole pattern.
  • the type and size of each pattern of the first pattern and the second pattern can be appropriately selected according to the pattern of the fine pattern to be finally formed, and limited to specific contents. Is not to be done.
  • step (G) another planarization layer is further formed on the planarization layer provided with the second pattern using the above-described composition of the present invention. Then, a third resist film is formed on the other planarizing layer using the third resist composition, and then the third resist film is exposed and developed to form a third pattern. It may be formed. According to such a form, by performing an etching process on the second pattern using the third pattern as a mask, the second pattern to which the pattern of the third pattern is transferred is formed. Etching is performed on the first pattern using the second pattern to which the pattern of the third pattern is transferred as a mask, so that the pattern of the second pattern and the pattern of the third pattern are the first pattern.
  • a miniaturized pattern transferred to the pattern can be formed.
  • the pattern forming method of the present invention is described as follows: “Further planarization layer formation, further resist film formation, and further pattern formation by exposure and development of this resist film. May be included at least once.
  • First resist composition A known composition can be used as the first resist composition (actinic ray-sensitive or radiation-sensitive resin composition).
  • the first resist composition is typically a chemically amplified resist composition.
  • the first resist composition has an increased polarity due to the action of an acid. It is preferable to contain a resin whose solubility in the developer is reduced.
  • a resin for example, a main chain or side chain of the resin, or both a main chain and a side chain are decomposed by the action of an acid to generate a polar group (hereinafter, referred to as “acid-decomposable group”). (Hereinafter also referred to as “acid-decomposable resin” or “resin (A)”).
  • the acid-decomposable group preferably has a structure protected by a group capable of decomposing and leaving a polar group by the action of an acid.
  • the polar group is not particularly limited as long as it is a group that is hardly soluble or insoluble in a developer containing an organic solvent.
  • Methylan Group dissociates in onium hydroxide aqueous solution), or alcoholic hydroxyl group.
  • the alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group and means a hydroxyl group other than a hydroxyl group directly bonded on an aromatic ring (phenolic hydroxyl group).
  • An aliphatic alcohol substituted with a functional group for example, a fluorinated alcohol group (such as a hexafluoroisopropanol group)) is excluded.
  • the alcoholic hydroxyl group is preferably a hydroxyl group having a pKa of 12 or more and 20 or less.
  • Preferred polar groups include carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), and sulfonic acid groups.
  • a preferable group as the acid-decomposable group is a group in which the hydrogen atom of these groups is substituted with a group capable of leaving with an acid.
  • Examples of the group leaving with an acid include —C (R 36 ) (R 37 ) (R 38 ), —C (R 36 ) (R 37 ) (OR 39 ), —C (R 01 ) (R 02 ). ) (OR 39 ) and the like.
  • R 36 to R 39 each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
  • R 36 and R 37 may be bonded to each other to form a ring.
  • R 01 and R 02 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
  • the alkyl group of R 36 to R 39 , R 01 and R 02 is preferably an alkyl group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl Group, octyl group and the like.
  • the cycloalkyl group of R 36 to R 39 , R 01 and R 02 may be monocyclic or polycyclic.
  • the monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • the polycyclic type is preferably a cycloalkyl group having 6 to 20 carbon atoms. For example, an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, ⁇ -pinel group, tricyclodecanyl group, tetracyclododecyl group. Group, androstanyl group and the like.
  • the aryl group of R 36 to R 39 , R 01 and R 02 is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
  • the aralkyl group of R 36 to R 39 , R 01 and R 02 is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group and a naphthylmethyl group.
  • the alkenyl group of R 36 to R 39 , R 01 and R 02 is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.
  • the ring formed by combining R 36 and R 37 is preferably a cycloalkyl group (monocyclic or polycyclic).
  • the cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group.
  • a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable, and a monocyclic cycloalkyl group having 5 carbon atoms is particularly preferable.
  • the acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like. More preferably, it is a tertiary alkyl ester group.
  • Resin (A) preferably has a repeating unit having an acid-decomposable group.
  • the resin (A) preferably has a repeating unit represented by the following general formula (AI) as a repeating unit having an acid-decomposable group.
  • the repeating unit represented by the general formula (AI) generates a carboxyl group as a polar group by the action of an acid, and in a plurality of carboxyl groups, shows a high interaction due to hydrogen bonding.
  • the pattern can be more reliably insolubilized or hardly soluble in the solvent in the composition of the present invention described above.
  • Xa 1 represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom.
  • T represents a single bond or a divalent linking group.
  • Rx 1 to Rx 3 each independently represents an alkyl group or a cycloalkyl group. Two of Rx 1 to Rx 3 may combine to form a ring structure.
  • Examples of the divalent linking group for T include an alkylene group, —COO—Rt— group, —O—Rt— group, phenylene group and the like.
  • Rt represents an alkylene group or a cycloalkylene group.
  • T is preferably a single bond or a —COO—Rt— group.
  • Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a —CH 2 — group, — (CH 2 ) 2 — group, or — (CH 2 ) 3 — group. More preferably, T is a single bond.
  • the alkyl group of Xa1 may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).
  • the alkyl group for X a1 preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group, and a methyl group is preferable.
  • X a1 is preferably a hydrogen atom or a methyl group.
  • the alkyl group of Rx 1 , Rx 2 and Rx 3 may be linear or branched, and is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl. Group, t-butyl group and the like are preferable.
  • the number of carbon atoms of the alkyl group is preferably 1 to 10, and more preferably 1 to 5.
  • Examples of the cycloalkyl group of Rx 1 , Rx 2 and Rx 3 include polycyclic rings such as a monocyclic cycloalkyl group such as cyclopentyl group and cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group. Are preferred.
  • the ring structure formed by combining two of Rx 1 , Rx 2 and Rx 3 includes a monocyclic cycloalkane ring such as cyclopentyl ring and cyclohexyl ring, norbornane ring, tetracyclodecane ring, tetracyclododecane ring, adamantane ring
  • a polycyclic cycloalkyl group such as is preferable.
  • a monocyclic cycloalkane ring having 5 or 6 carbon atoms is particularly preferable.
  • Rx 1 , Rx 2 and Rx 3 are preferably each independently an alkyl group, more preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
  • Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (1 to 4 carbon atoms), a cycloalkyl group (3 to 8 carbon atoms), a halogen atom, an alkoxy group (carbon 1 to 4), a carboxyl group, an alkoxycarbonyl group (2 to 6 carbon atoms), and the like, and 8 or less carbon atoms are preferable.
  • a substituent having no hetero atom such as an oxygen atom, a nitrogen atom, or a sulfur atom is more preferable (for example, More preferably, it is not an alkyl group substituted with a hydroxyl group, etc.), more preferably a group consisting of only a hydrogen atom and a carbon atom, and particularly preferably a linear or branched alkyl group or a cycloalkyl group. .
  • Rx 1 to Rx 3 are each independently an alkyl group, and it is preferable that two of Rx 1 to Rx 3 are not bonded to form a ring structure.
  • an increase in the volume of the group represented by —C (Rx 1 ) (Rx 2 ) (Rx 3 ) as a group capable of decomposing and leaving by the action of an acid can be suppressed, and after the exposure step and the exposure step In the post-exposure heating step that may be performed, the volume shrinkage of the exposed portion tends to be suppressed.
  • Rx represents a hydrogen atom, CH 3 , CF 3 , or CH 2 OH.
  • Rxa and Rxb each independently represents an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms).
  • Xa 1 represents a hydrogen atom, CH 3 , CF 3 , or CH 2 OH.
  • Z represents a substituent, and when a plurality of Zs are present, the plurality of Zs may be the same as or different from each other.
  • p represents 0 or a positive integer.
  • Specific examples and preferred examples of Z are the same as specific examples and preferred examples of the substituent that each group such as Rx 1 to Rx 3 may have.
  • the resin (A) preferably has a repeating unit described in paragraphs ⁇ 0057> to ⁇ 0071> of JP-A No. 2014-202969 as a repeating unit having an acid-decomposable group.
  • the resin (A) may have a repeating unit that generates an alcoholic hydroxyl group described in paragraphs ⁇ 0072> to ⁇ 0073> of JP-A-2014-202969 as a repeating unit having an acid-decomposable group. Good.
  • One type of repeating unit having an acid-decomposable group may be used, or two or more types may be used in combination.
  • the content of the repeating unit having an acid-decomposable group contained in the resin (A) (when there are a plurality of repeating units having an acid-decomposable group, the total) is based on the total repeating units of the resin (A), It is preferably 15 mol% or more, more preferably 20 mol% or more, further preferably 25 mol% or more, and particularly preferably 40 mol% or more.
  • the resin (A) has a repeating unit represented by the above general formula (AI), and the content of the repeating unit represented by the above general formula (AI) with respect to all the repeating units of the resin (A) is 40 mol. % Or more is preferable.
  • the content of the repeating unit having an acid-decomposable group is preferably 80 mol% or less, preferably 70 mol% or less, and 65 mol% with respect to all the repeating units of the resin (A). The following is more preferable.
  • Resin (A) may contain a repeating unit having a lactone structure or a sultone structure.
  • Any lactone structure or sultone structure can be used as long as it has a lactone structure or sultone structure, but a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure is preferable.
  • Other ring structures are condensed in a form that forms a bicyclo structure or spiro structure in a membered lactone structure, or other rings that form a bicyclo structure or a spiro structure in a 5- to 7-membered ring sultone structure Those having a condensed ring structure are more preferable.
  • Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), (LC1-17), especially A preferred lactone structure is (LC1-4).
  • the lactone structure portion or the sultone structure portion may or may not have a substituent (Rb 2 ).
  • Preferred substituents (Rb 2 ) include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 2 to 8 carbon atoms, and carboxyl groups. , Halogen atom, hydroxyl group, cyano group, acid-decomposable group and the like. More preferred are an alkyl group having 1 to 4 carbon atoms, a cyano group, and an acid-decomposable group.
  • n 2 represents an integer of 0 to 4. When n 2 is 2 or more, the plurality of substituents (Rb 2 ) may be the same or different. A plurality of substituents (Rb 2 ) may be bonded to form a ring.
  • the repeating unit having a lactone structure or a sultone structure usually has an optical isomer, but any optical isomer may be used.
  • One optical isomer may be used alone, or a plurality of optical isomers may be mixed and used.
  • the optical purity (ee) thereof is preferably 90% or more, more preferably 95% or more.
  • the content of the repeating unit having a lactone structure or a sultone structure is 5 to 60 mol% with respect to all the repeating units in the resin (A). It is preferably 5 to 55 mol%, more preferably 10 to 50 mol%.
  • the resin (A) may have a repeating unit having a cyclic carbonate structure.
  • the repeating unit having a cyclic carbonate structure is preferably a repeating unit represented by the following general formula (A-1).
  • R A 1 represents a hydrogen atom or an alkyl group.
  • R A 2 each independently represents a substituent when n is 2 or more.
  • A represents a single bond or a divalent linking group.
  • Z represents an atomic group that forms a monocyclic or polycyclic structure together with a group represented by —O—C ( ⁇ O) —O— in the formula.
  • n represents an integer of 0 or more.
  • one type of repeating units represented by the general formula (A-1) may be contained alone, or two or more types may be contained.
  • the content of the repeating unit having a cyclic carbonate structure (preferably, the repeating unit represented by the general formula (A-1)) is based on the total repeating units constituting the resin (A). It is preferably 3 to 80 mol%, more preferably 3 to 60 mol%, particularly preferably 3 to 30 mol%, and most preferably 10 to 15 mol%.
  • Resin (A) may have a repeating unit having a hydroxyl group or a cyano group.
  • Examples of such repeating units include the repeating units described in paragraphs ⁇ 0081> to ⁇ 0084> of JP-A No. 2014-089921.
  • the resin (A) may have a repeating unit having an alkali-soluble group.
  • the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol (for example, a hexafluoroisopropanol group) in which the ⁇ -position is substituted with an electron withdrawing group.
  • the repeating unit having an alkali-soluble group include the repeating units described in paragraphs ⁇ 0085> to ⁇ 0086> of JP-A No. 2014-098921.
  • the resin (A) can further have a repeating unit that has an alicyclic hydrocarbon structure having no polar group (for example, an alkali-soluble group, a hydroxyl group, a cyano group, etc.) and does not exhibit acid decomposability.
  • a repeating unit that has an alicyclic hydrocarbon structure having no polar group (for example, an alkali-soluble group, a hydroxyl group, a cyano group, etc.) and does not exhibit acid decomposability.
  • a repeating unit include the repeating units described in paragraphs ⁇ 0114> to ⁇ 0123> of JP 2014-106299 A.
  • the resin (A) may contain, for example, repeating units described in paragraphs ⁇ 0045> to ⁇ 0065> of JP-A-2009-258586.
  • Resin (A) adjusts dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc., which are general required characteristics of resist, in addition to the above repeating structural units.
  • various repeating structural units can be included. Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers.
  • the performance required for the resin (A) in particular, (1) solubility in coating solvents, (2) film-forming properties (glass transition point), (3) alkali developability, (4) film slipping (familiarity) Fine adjustments such as (selection of aqueous and alkali-soluble groups), (5) adhesion of unexposed portions to the substrate, and (6) dry etching resistance are possible.
  • a monomer for example, a compound having one addition polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. Etc.
  • any addition-polymerizable unsaturated compound that can be copolymerized with monomers corresponding to the above various repeating structural units may be copolymerized.
  • the molar ratio of each repeating structural unit is the resist dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and the general required performance of the resist, resolving power, heat resistance, sensitivity. It is set appropriately in order to adjust etc.
  • the resin (A) When the first resist composition is for ArF exposure, the resin (A) preferably has substantially no aromatic group from the viewpoint of transparency to ArF light. More specifically, the repeating unit having an aromatic group in all the repeating units of the resin (A) is preferably 5 mol% or less, more preferably 3 mol% or less, ideally Is more preferably 0 mol%, that is, having no repeating unit having an aromatic group.
  • the resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
  • resin (A) does not contain a fluorine atom and a silicon atom from a compatible viewpoint with hydrophobic resin (D) mentioned later.
  • Resin (A) is preferably a resin in which all repeating units are composed of (meth) acrylate repeating units.
  • all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are methacrylate repeating units and acrylate repeating units.
  • the acrylate-based repeating unit is preferably 50 mol% or less of the total repeating units.
  • the blending ratio of the resin (A) in the entire composition is preferably 30 to 99% by mass, more preferably 60 to 95% by mass based on the total solid content.
  • the resin (A) may be used alone or in combination.
  • the first resist composition contains a compound that generates acid upon irradiation with actinic rays or radiation (hereinafter also referred to as “acid generator”). .
  • an acid generator it does not specifically limit as an acid generator, It is preferable that it is a compound which generate
  • the acid generator photo-initiator of photocation polymerization, photo-initiator of photo-radical polymerization, photo-decoloring agent of dyes, photo-discoloring agent, irradiation of actinic ray or radiation used for micro resist, etc.
  • Known compounds that generate an acid and mixtures thereof can be appropriately selected and used.
  • compounds described in paragraphs ⁇ 0039> to ⁇ 0103> of JP-A-2010-61043 examples thereof include compounds described in paragraphs ⁇ 0284> to ⁇ 0389> of Kaikai 2013-4820, but the present invention is not limited thereto.
  • Examples include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, and o-nitrobenzyl sulfonates.
  • produces an acid by irradiation of the actinic ray or radiation represented by following General formula (3) suitably is mentioned suitably, for example. Can do.
  • Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
  • R 4 and R 5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom, and when there are a plurality of R 4 and R 5 , R 4 and R 5 are the same But it can be different.
  • L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
  • W represents an organic group containing a cyclic structure. o represents an integer of 1 to 3.
  • p represents an integer of 0 to 10.
  • q represents an integer of 0 to 10.
  • Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
  • the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms.
  • the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
  • Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.
  • Xf is more preferably a fluorine atom or CF 3 . In particular, it is preferable that both Xf are fluorine atoms.
  • R 4 and R 5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom, and when there are a plurality of R 4 and R 5 , R 4 and R 5 are the same But it can be different.
  • the alkyl group as R 4 and R 5 may have a substituent, and preferably has 1 to 4 carbon atoms.
  • R 4 and R 5 are preferably a hydrogen atom.
  • Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in formula (3).
  • L represents a divalent linking group, and when there are a plurality of L, L may be the same or different.
  • the divalent linking group include —COO — (— C ( ⁇ O) —O—), —OCO—, —CONH—, —NHCO—, —CO—, —O—, —S—, — SO—, —SO 2 —, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 10 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), or a combination thereof And divalent linking groups.
  • —COO—, —OCO—, —CONH—, —NHCO—, —CO—, —O—, —SO 2 —, —COO-alkylene group—, —OCO-alkylene group—, —CONH— alkylene group - or -NHCO- alkylene group - are preferred, -COO -, - OCO -, - CONH -, - SO 2 -, - COO- alkylene group - or -OCO- alkylene group - is more preferable.
  • W represents an organic group containing a cyclic structure.
  • a cyclic organic group is preferable.
  • the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.
  • the alicyclic group may be monocyclic or polycyclic.
  • the monocyclic alicyclic group include monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • polycyclic alicyclic group examples include polycyclic cycloalkyl groups such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.
  • an alicyclic group having a bulky structure having 7 or more carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, is a PEB (heating after exposure) step. From the viewpoints of suppressing diffusibility in the film and improving MEEF (Mask Error Enhancement Factor).
  • the aryl group may be monocyclic or polycyclic.
  • Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. Among these, a naphthyl group having a relatively low light absorbance at 193 nm is preferable.
  • the heterocyclic group may be monocyclic or polycyclic, but the polycyclic group can suppress acid diffusion more. Moreover, the heterocyclic group may have aromaticity or may not have aromaticity.
  • heterocyclic ring having aromaticity examples include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring.
  • heterocyclic ring that does not have aromaticity examples include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring.
  • heterocyclic ring in the heterocyclic group a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable.
  • lactone ring and sultone ring include the lactone structure and sultone structure exemplified in the aforementioned resin.
  • the cyclic organic group may have a substituent.
  • substituents include an alkyl group (which may be linear or branched, preferably 1 to 12 carbon atoms), and a cycloalkyl group (monocyclic, polycyclic or spirocyclic).
  • alkyl group which may be linear or branched, preferably 1 to 12 carbon atoms
  • a cycloalkyl group monocyclic, polycyclic or spirocyclic.
  • Well preferably having 3 to 20 carbon atoms
  • aryl group preferably having 6 to 14 carbon atoms
  • hydroxyl group alkoxy group
  • ester group amide group, urethane group, ureido group, thioether group, sulfonamide group, and sulfonic acid
  • An ester group is mentioned.
  • the carbon constituting the cyclic organic group may be a carbonyl carbon.
  • o represents an integer of 1 to 3.
  • p represents an integer of 0 to 10.
  • q represents an integer of 0 to 10.
  • Xf is preferably a fluorine atom
  • R 4 and R 5 are preferably both hydrogen atoms
  • W is preferably a polycyclic hydrocarbon group.
  • o is more preferably 1 or 2, and still more preferably 1.
  • p is preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1.
  • W is more preferably a polycyclic cycloalkyl group, and further preferably an adamantyl group or a diamantyl group.
  • X + represents a cation.
  • X + is not particularly limited as long as it is a cation, and preferred embodiments include, for example, cations (parts other than Z ⁇ ) in the general formula (ZI), (ZII) or (ZIII) described later.
  • R 201 , R 202 and R 203 each independently represents an organic group.
  • the organic group as R 201 , R 202 and R 203 generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
  • Two of R 201 to R 203 may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group.
  • Examples of the group formed by combining two members out of R 201 to R 203 include an alkylene group (eg, butylene group, pentylene group).
  • Z ⁇ represents an anion in the general formula (3), and specifically represents the following anion.
  • Examples of the organic group represented by R 201 , R 202 and R 203 include the corresponding groups in the compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described later. Can be mentioned.
  • the compound which has two or more structures represented by general formula (ZI) may be sufficient.
  • at least one of R 201 to R 203 of the compound represented by the general formula (ZI) is a single bond or at least one of R 201 to R 203 of the other compound represented by the general formula (ZI). It may be a compound having a structure bonded through a linking group.
  • R 204 to R 207 each independently represents an aryl group, an alkyl group, or a cycloalkyl group.
  • the aryl group of R 204 to R 207 is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
  • the aryl group of R 204 to R 207 may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like.
  • Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
  • the alkyl group and cycloalkyl group in R 204 to R 207 are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Examples thereof include cycloalkyl groups having a number of 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group).
  • the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may have a substituent.
  • substituents that the aryl group, alkyl group, and cycloalkyl group of R 204 to R 207 may have include an alkyl group (eg, having 1 to 15 carbon atoms) and a cycloalkyl group (eg, having 3 to 15 carbon atoms). ), Aryl groups (for example, having 6 to 15 carbon atoms), alkoxy groups (for example, having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups, and the like.
  • Z ⁇ represents an anion in the general formula (3), specifically as described above.
  • the acid generator (including a specific acid generator; the same shall apply hereinafter) may be in the form of a low molecular compound or may be incorporated in a part of the polymer. Moreover, you may use together the form incorporated in a part of polymer and the form of a low molecular compound.
  • the molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.
  • the acid generator is incorporated in a part of the polymer, it may be incorporated in a part of the resin described above or in a resin different from the resin.
  • the acid generator can be synthesized by a known method, for example, according to the method described in JP-A No.
  • An acid generator can be used individually by 1 type or in combination of 2 or more types.
  • the content of the acid generator in the composition is preferably 0.1 to 30% by mass, more preferably 0.5 to 25%, based on the total solid content of the composition. % By mass, more preferably 3 to 20% by mass, particularly preferably 3 to 15% by mass.
  • the content of the acid generator contained in the composition (when there are plural kinds, the total thereof) Is preferably 5 to 35% by mass, more preferably 8 to 30% by mass, still more preferably 9 to 30% by mass, and particularly preferably 9 to 25% by mass based on the total solid content of the composition.
  • the first resist composition may contain a hydrophobic resin (hereinafter also referred to as “hydrophobic resin (D)” or simply “resin (D)”).
  • the hydrophobic resin (D) is preferably different from the resin (A).
  • the hydrophobic resin (D) is preferably designed to be unevenly distributed at the interface, but unlike the surfactant, it does not necessarily have a hydrophilic group in the molecule, and polar and nonpolar substances are mixed uniformly. You don't have to contribute to Examples of the effect of adding the hydrophobic resin include control of static and dynamic contact angles on the resist film surface with respect to water, improvement of immersion liquid followability, suppression of outgas, and the like.
  • the hydrophobic resin (D) is selected from any one of “fluorine atom”, “silicon atom”, and “CH 3 partial structure contained in the side chain portion of the resin” from the viewpoint of uneven distribution in the film surface layer. It is preferable to have the above, and it is more preferable to have two or more.
  • the hydrophobic resin (D) contains a fluorine atom and / or a silicon atom
  • the fluorine atom and / or silicon atom in the hydrophobic resin (D) may be contained in the main chain of the resin. , May be contained in the side chain.
  • the hydrophobic resin (D) contains a fluorine atom
  • it is a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom as a partial structure having a fluorine atom.
  • the alkyl group having a fluorine atom preferably having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms
  • a cycloalkyl group having a fluorine atom and an aryl group having a fluorine atom are a cycloalkyl group in which one hydrogen atom is substituted with a fluorine atom and an aryl group having a fluorine atom, respectively, and further a substituent other than a fluorine atom is substituted. You may have.
  • alkyl group having a fluorine atom examples include the groups described in paragraphs ⁇ 0287> to ⁇ 0290> of JP-A No. 2014-202969.
  • the present invention is not limited to this.
  • the hydrophobic resin (D) may contain a silicon atom.
  • the partial structure having a silicon atom is preferably a resin having an alkylsilyl structure (preferably a trialkylsilyl group) or a cyclic siloxane structure.
  • Examples of the repeating unit having a fluorine atom or a silicon atom include those exemplified in US2012 / 0251948A1 [0519].
  • the hydrophobic resin (D) it is also preferred to include CH 3 partial structure side chain moiety.
  • the CH 3 partial structure of the side chain portion in the hydrophobic resin (D) includes the CH 3 portion of an ethyl group, a propyl group, or the like. Includes structure.
  • a methyl group directly bonded to the main chain of the hydrophobic resin (D) is caused by the influence of the main chain on the surface of the hydrophobic resin (D). Since the contribution to uneven distribution is small, it is not included in the CH 3 partial structure in the present invention.
  • the hydrophobic resin (D) is a repeating unit derived from a monomer having a polymerizable moiety having a carbon-carbon double bond, such as a repeating unit represented by the following general formula (M).
  • R 11 to R 14 are CH 3 “as is”, the CH 3 is not included in the CH 3 partial structure of the side chain moiety in the present invention.
  • CH 3 partial structure exists through some atoms from C-C backbone, and those falling under CH 3 partial structures in the present invention.
  • R 11 is an ethyl group (CH 2 CH 3 )
  • R 11 to R 14 each independently represents a side chain portion.
  • R 11 to R 14 in the side chain portion include a hydrogen atom and a monovalent organic group.
  • the monovalent organic group for R 11 to R 14 include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylaminocarbonyl.
  • Group, an arylaminocarbonyl group, and the like, and these groups may further have a substituent.
  • the hydrophobic resin (D) is preferably a resin having a repeating unit having a CH 3 partial structure in the side chain portion, and as such a repeating unit, paragraphs ⁇ 0298> to ⁇ It is more preferable to have the repeating unit (x) described in 0321>.
  • the hydrophobic resin (D) includes the following (x) to (z) regardless of whether (i) a fluorine atom and / or a silicon atom is included or (ii) a CH 3 partial structure is included in the side chain portion. ) May have at least one group selected from the group of (X) an acid group, (Y) a group having a lactone structure, an acid anhydride group, or an acid imide group, (Z) a group decomposable by the action of an acid
  • Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, and an (alkylsulfonyl) (alkyl Carbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) A methylene group etc. are mentioned.
  • Preferred acid groups include fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, and
  • the repeating unit having an acid group (x) includes a repeating unit in which an acid group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid or methacrylic acid, or a resin having a linking group. Examples include a repeating unit in which an acid group is bonded to the main chain, and a polymerization initiator or chain transfer agent having an acid group can be introduced at the end of the polymer chain at the time of polymerization. preferable.
  • the repeating unit having an acid group (x) may have at least one of a fluorine atom and a silicon atom.
  • the content of the repeating unit having an acid group (x) is preferably from 1 to 50 mol%, more preferably from 3 to 35 mol%, still more preferably from 5 to 5%, based on all repeating units in the hydrophobic resin (D). 20 mol%.
  • Specific examples of the repeating unit having an acid group (x) include the repeating units described in paragraphs ⁇ 0447> to ⁇ 0448> of JP2014-235179A, but the present invention is not limited thereto. It is not a thing.
  • the group having a lactone structure As the group having a lactone structure, the acid anhydride group, or the acid imide group (y), a group having a lactone structure is particularly preferable.
  • the repeating unit containing these groups is a repeating unit in which this group is directly bonded to the main chain of the resin, such as a repeating unit of acrylic acid ester and methacrylic acid ester.
  • this repeating unit may be a repeating unit in which this group is bonded to the main chain of the resin via a linking group.
  • this repeating unit may be introduce
  • Examples of the repeating unit having a group having a lactone structure include those similar to the repeating unit having a lactone structure described above in the section of the resin (A).
  • the content of the repeating unit having a group having a lactone structure, an acid anhydride group, or an acid imide group is preferably 1 to 100 mol% based on all repeating units in the hydrophobic resin (D), The content is more preferably 3 to 98 mol%, further preferably 5 to 95 mol%.
  • examples of the repeating unit having a group (z) capable of decomposing by the action of an acid are the same as the repeating unit having an acid-decomposable group exemplified in the resin (A).
  • the repeating unit having a group (z) that decomposes by the action of an acid may have at least one of a fluorine atom and a silicon atom.
  • the content of the repeating unit having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol% with respect to all the repeating units in the resin (D). The amount is preferably 10 to 80 mol%, more preferably 20 to 60 mol%.
  • the hydrophobic resin (D) may further have a repeating unit different from the above-described repeating unit.
  • the repeating unit containing a fluorine atom is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, based on all repeating units contained in the hydrophobic resin (D). Further, the repeating unit containing a silicon atom is preferably 10 to 100 mol%, more preferably 20 to 100 mol% in all repeating units contained in the hydrophobic resin (D).
  • hydrophobic resin (D) contains a CH 3 partial structure in the side chain portion
  • a mode in which the hydrophobic resin (D) does not substantially contain a fluorine atom and a silicon atom is also preferable.
  • hydrophobic resin (D) is substantially comprised only by the repeating unit comprised only by the atom chosen from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom, and a sulfur atom.
  • the standard polystyrene equivalent weight average molecular weight of the hydrophobic resin (D) is preferably 1,000 to 100,000, more preferably 1,000 to 50,000.
  • the hydrophobic resin (D) may be used alone or in combination.
  • the content of the hydrophobic resin (D) in the composition is preferably 0.01 to 10% by mass and more preferably 0.05 to 8% by mass with respect to the total solid content in the first resist composition.
  • the residual monomer and oligomer components are preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass.
  • the molecular weight distribution (also referred to as “Mw / Mn” or “dispersity”) is preferably in the range of 1 to 5, more preferably in the range of 1 to 3.
  • hydrophobic resin (D) various commercially available products can be used, and the hydrophobic resin (D) can be synthesized according to a conventional method (for example, radical polymerization).
  • the first resist composition preferably contains an acid diffusion control agent.
  • the acid diffusion controller acts as a quencher that traps the acid generated from the acid generator or the like during exposure and suppresses the reaction of the acid-decomposable resin in the unexposed area due to excess generated acid.
  • Examples of the acid diffusion controller include a basic compound, a low molecular compound having a nitrogen atom and a group capable of leaving by the action of an acid, a basic compound whose basicity is reduced or disappeared by irradiation with actinic rays or radiation, or An onium salt that is a weak acid relative to the acid generator can be used.
  • Preferred examples of the basic compound include compounds having structures represented by the following formulas (A) to (E).
  • R 200 , R 201 and R 202 may be the same or different and are a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl group (having a carbon number). 6-20), wherein R 201 and R 202 may combine with each other to form a ring.
  • R 203 , R 204 , R 205 and R 206 may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.
  • the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.
  • the alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.
  • Preferred compounds include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like, and more preferred compounds include imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate Examples thereof include a compound having a structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, and an aniline derivative having a hydroxyl group and / or an ether bond. Specific examples of preferred compounds include those exemplified in US2012 / 0219913A1 ⁇ 0379>.
  • Preferred examples of the basic compound further include an amine compound having a phenoxy group, an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group.
  • These basic compounds may be used individually by 1 type, and may be used in combination of 2 or more types.
  • the first resist composition may or may not contain a basic compound.
  • the content of the basic compound is usually 0.001 to 10 based on the solid content of the composition. % By mass, preferably 0.01 to 5% by mass.
  • a low molecular weight compound having a nitrogen atom and having a group capable of leaving by the action of an acid is an amine derivative having a group on the nitrogen atom that is leaving by the action of an acid. It is preferable that As the group capable of leaving by the action of an acid, an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, and a hemiaminal ether group are preferable, and a carbamate group and a hemiaminal ether group are particularly preferable. .
  • the molecular weight of the compound (C) is preferably 100 to 1000, more preferably 100 to 700, and particularly preferably 100 to 500.
  • Compound (C) may have a carbamate group having a protecting group on the nitrogen atom.
  • the protecting group constituting the carbamate group can be represented by the following general formula (d-1).
  • R b each independently represents a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably 3 to 30 carbon atoms), an aralkyl group. (Preferably having 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably having 1 to 10 carbon atoms).
  • R b may be connected to each other to form a ring.
  • the alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by R b are substituted with a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, and an oxo group, an alkoxy group, and a halogen atom. May be. The same applies to the alkoxyalkyl group represented by Rb .
  • R b is preferably a linear or branched alkyl group, cycloalkyl group, or aryl group. More preferably, it is a linear or branched alkyl group or cycloalkyl group.
  • Examples of the ring formed by connecting two R b to each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group, or a derivative thereof.
  • Specific examples of the group represented by the general formula (d-1) include structures disclosed in US2012 / 0135348 A1 ⁇ 0466>, but are not limited thereto.
  • the compound (C) has a structure represented by the following general formula (6).
  • R a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group.
  • l represents 2 R a may be the same or different, and two R a may be connected to each other to form a heterocyclic ring together with the nitrogen atom in the formula.
  • the heterocyclic ring may contain a hetero atom other than the nitrogen atom in the formula.
  • R b has the same meaning as R b in formula (d-1), and preferred examples are also the same.
  • l represents an integer of 0 to 2
  • the alkyl group, cycloalkyl group, aryl group and aralkyl group as R a are the groups in which the alkyl group, cycloalkyl group, aryl group and aralkyl group as R b may be substituted. It may be substituted with a group similar to the group described above.
  • alkyl group, cycloalkyl group, aryl group, and aralkyl group of R a (these alkyl group, cycloalkyl group, aryl group, and aralkyl group may be substituted with the above group) And the same groups as the specific examples of R b in formula (d-1).
  • Specific examples of the particularly preferable compound (C) in the present invention include compounds disclosed in US2012 / 0135348 A1 ⁇ 0475>, but are not limited thereto.
  • the compound represented by the general formula (6) can be synthesized based on JP2007-298869A, JP2009-199021A, and the like.
  • the low molecular compound (C) having a nitrogen atom and having a group capable of leaving by the action of an acid can be used singly or in combination of two or more.
  • the content of the compound (C) in the first resist composition is preferably 0.001 to 20% by mass, more preferably 0.001 to 10% by mass, based on the total solid content of the composition. More preferably, the content is 0.01 to 5% by mass.
  • an onium salt that becomes a weak acid relative to the acid generator can be used as an acid diffusion control agent.
  • an acid generator and an onium salt that generates an acid that is a relatively weak acid with respect to the acid generated from the acid generator are mixed and used, the acid generated from the acid generator by irradiation with actinic rays or radiation When it collides with an onium salt having an unreacted weak acid anion, a weak acid is released by salt exchange to produce an onium salt having a strong acid anion.
  • the strong acid is exchanged with a weak acid having a lower catalytic ability, so that the acid is apparently deactivated and the acid diffusion can be controlled.
  • the onium salt that is a weak acid relative to the acid generator is preferably a compound represented by the following general formulas (d1-1) to (d1-3).
  • R 51 represents a hydrocarbon group which may have a substituent
  • Z 2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (however, a carbon adjacent to S).
  • R 52 is an organic group
  • Y 3 is a linear, branched or cyclic alkylene group or an arylene group
  • Rf is a fluorine atom.
  • Each of the M + is independently a sulfonium or iodonium cation.
  • sulfonium cation or iodonium cation represented by M + include a sulfonium cation exemplified by the general formula (ZI) and an iodonium cation exemplified by the general formula (ZII).
  • Preferable examples of the anion moiety of the compound represented by the general formula (d1-1) include the structures exemplified in paragraph [0198] of JP2012-242799A.
  • Preferable examples of the anion moiety of the compound represented by the general formula (d1-2) include the structures exemplified in paragraph [0201] of JP2012-242799A.
  • Preferable examples of the anion moiety of the compound represented by the general formula (d1-3) include the structures exemplified in paragraphs [0209] and [0210] of JP2012-242799A.
  • the onium salt that is a weak acid relative to the acid generator is a compound (C) having a cation moiety and an anion moiety in the same molecule, and the cation moiety and the anion moiety being linked by a covalent bond (Hereinafter also referred to as “compound (CA)”).
  • the compound (CA) is preferably a compound represented by any one of the following general formulas (C-1) to (C-3).
  • R 1 , R 2 and R 3 represent a substituent having 1 or more carbon atoms.
  • L 1 represents a divalent linking group or a single bond linking the cation moiety and the anion moiety.
  • -X - it is, -COO -, -SO 3 - represents an anion portion selected from -R 4 -, -SO 2 -, -N.
  • R 4 is a group having a carbonyl group: —C ( ⁇ O) —, a sulfonyl group: —S ( ⁇ O) 2 —, and a sulfinyl group: —S ( ⁇ O) — at the site of connection with the adjacent N atom.
  • R 1 , R 2 , R 3 , R 4 and L 1 may be bonded to each other to form a ring structure.
  • R 1 to R 3 may be combined to form a double bond with the N atom.
  • Examples of the substituent having 1 or more carbon atoms in R 1 to R 3 include alkyl group, cycloalkyl group, aryl group, alkyloxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, alkylaminocarbonyl group, cycloalkylamino A carbonyl group, an arylaminocarbonyl group, etc. are mentioned. Preferably, they are an alkyl group, a cycloalkyl group, and an aryl group.
  • L 1 as the divalent linking group is a linear or branched alkylene group, cycloalkylene group, arylene group, carbonyl group, ether bond, ester bond, amide bond, urethane bond, urea bond, and two types thereof. Examples include groups formed by combining the above. L 1 is more preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.
  • Preferable examples of the compound represented by the general formula (C-1) include paragraphs [0037] to [0039] of JP2013-6827A and paragraphs [0027] to [0029] of JP2013-8020A. ] Can be mentioned.
  • Preferable examples of the compound represented by the general formula (C-2) include compounds exemplified in paragraphs [0012] to [0013] of JP2012-189977A.
  • Preferable examples of the compound represented by the general formula (C-3) include the compounds exemplified in paragraphs [0029] to [0031] of JP 2012-252124 A.
  • the content of the onium salt that is a weak acid relative to the acid generator is preferably 0.5 to 10.0% by mass, and preferably 0.5 to 8.0% by mass based on the solid content of the composition. % Is more preferable, and 1.0 to 8.0% by mass is even more preferable.
  • the first resist composition usually contains a solvent.
  • Solvents that can be used in preparing the composition include, for example, alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactate esters, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 4 carbon atoms). 10), an organic solvent such as a monoketone compound (preferably having 4 to 10 carbon atoms) which may have a ring, alkylene carbonate, alkyl alkoxyacetate, alkyl pyruvate and the like. Specific examples of these solvents include those described in US Patent Application Publication No. 2008/0187860 ⁇ 0441> to ⁇ 0455>.
  • the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group the above-mentioned exemplary compounds can be selected as appropriate.
  • the solvent containing a hydroxyl group alkylene glycol monoalkyl ether, alkyl lactate and the like are preferable, and propylene glycol monomethyl ether ( PGME, also known as 1-methoxy-2-propanol), ethyl lactate, and methyl 2-hydroxyisobutyrate are more preferred.
  • alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, monoketone compound which may contain a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene glycol monomethyl ether Acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone, ⁇ -butyrolactone, cyclohexanone, butyl acetate are particularly preferred, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2 -Heptanone is most preferred.
  • PGMEA propylene glycol monomethyl ether Acetate
  • ethyl ethoxypropionate 2-heptanone
  • ⁇ -butyrolactone cyclohexanone
  • the mixing ratio (mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. .
  • a mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is particularly preferred from the viewpoint of coating uniformity.
  • the solvent preferably contains propylene glycol monomethyl ether acetate, and is preferably a propylene glycol monomethyl ether acetate single solvent or a mixed solvent of two or more containing propylene glycol monomethyl ether acetate.
  • the first resist composition may or may not further contain a surfactant. When it is contained, it contains a fluorine-based and / or silicon-based surfactant (fluorine-based surfactant, silicon It is more preferable to contain any one of a surfactant or a surfactant having both a fluorine atom and a silicon atom, or two or more thereof.
  • the first resist composition contains a surfactant
  • a surfactant When the first resist composition contains a surfactant, it is possible to provide a resist pattern with less adhesion and development defects with good sensitivity and resolution when using an exposure light source of 250 nm or less, particularly 220 nm or less. It becomes.
  • the fluorine-based and / or silicon-based surfactant include surfactants described in paragraph ⁇ 0276> of US Patent Application Publication No. 2008/0248425.
  • surfactants other than the fluorine-based and / or silicon-based surfactants described in paragraph ⁇ 0280> of US Patent Application Publication No. 2008/0248425 can also be used.
  • the amount of the surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.0005 to the total solid content of the composition. 1% by mass.
  • the addition amount of the surfactant 10 ppm or less with respect to the total amount of the composition (excluding the solvent) the surface unevenness of the hydrophobic resin is increased, thereby making the resist film surface more hydrophobic. It is possible to improve water followability at the time of immersion exposure.
  • the first resist composition may or may not contain a carboxylic acid onium salt.
  • carboxylic acid onium salts include those described in US Patent Application Publication No. 2008/0187860 ⁇ 0605> to ⁇ 0606>. These carboxylic acid onium salts can be synthesized by reacting sulfonium hydroxide, iodonium hydroxide, ammonium hydroxide and carboxylic acid with silver oxide in a suitable solvent.
  • the content thereof is generally 0.1 to 20% by mass, preferably 0.5 to 10% by mass, based on the total solid content of the composition. %, More preferably 1 to 7% by mass.
  • the first resist composition further includes an acid multiplier, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, and a compound that promotes solubility in a developer.
  • an acid multiplier a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, and a compound that promotes solubility in a developer.
  • a phenol compound having a molecular weight of 1000 or less, an alicyclic compound having a carboxyl group, or an aliphatic compound can be contained.
  • Such a phenol compound having a molecular weight of 1000 or less can be obtained by referring to, for example, the methods described in JP-A-4-1222938, JP-A-2-28531, US Pat. No. 4,916,210, European Patent 219294, etc. It can be easily synthesized by those skilled in the art.
  • alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure such as cholic acid, deoxycholic acid, lithocholic acid, adamantane carboxylic acid derivatives, adamantane dicarboxylic acid, cyclohexane carboxylic acid, cyclohexane Examples thereof include, but are not limited to, dicarboxylic acids.
  • the solid content concentration of the first resist composition is usually 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, more preferably 2.0 to 5.3% by mass. .
  • the resist solution can be uniformly applied on the substrate, and further, a resist pattern having excellent line width roughness can be formed.
  • the reason for this is not clear, but perhaps the solid content concentration is 10% by mass or less, preferably 5.7% by mass or less, which suppresses aggregation of the material in the resist solution, particularly the photoacid generator. As a result, it is considered that a uniform resist film was formed.
  • the solid content concentration is a mass percentage of the mass of other resist components excluding the solvent with respect to the total mass of the composition.
  • the method for preparing the first resist composition is not particularly limited, but it is preferable to dissolve the above-described components in a predetermined organic solvent, preferably the above mixed solvent, and filter the solution.
  • the pore size of the filter used for filter filtration is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and still more preferably 0.03 ⁇ m or less made of polytetrafluoroethylene, polyethylene, or nylon.
  • filter filtration for example, as in JP-A-2002-62667, circulation filtration may be performed, or filtration may be performed by connecting a plurality of types of filters in series or in parallel.
  • the composition may be filtered multiple times. Furthermore, you may perform a deaeration process etc. with respect to a composition before and behind filter filtration.
  • the first resist composition relates to an actinic ray-sensitive or radiation-sensitive resin composition whose properties change upon irradiation with actinic rays or radiation. More specifically, the present invention relates to semiconductor manufacturing processes such as ICs, circuit boards such as liquid crystals and thermal heads, production of imprint mold structures, and other photofabrication processes, lithographic printing plates, acid-curing properties. The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition used in the composition.
  • the second resist composition may be a negative resist composition or a positive resist composition, and a known resist composition can be used for each. However, for the reasons described above, a negative resist composition can be used. It is preferably a resist composition (more specifically, a negative resist composition for developing an organic solvent).
  • the second resist composition is typically a chemically amplified resist composition.
  • the second resist composition preferably contains a resin whose polarity increases by the action of an acid and whose solubility in a developer containing an organic solvent decreases.
  • a resin include the same resins as those described in the first resist composition that increase in polarity by the action of an acid and decrease in solubility in a developer containing an organic solvent.
  • the preferable range of the content of the resin with respect to the total amount of the resist composition is the same as that described in the first resist composition.
  • the second resist composition can similarly contain the above-described components that the first resist composition can contain, and the preferred range of the content of each component with respect to the total amount of the second resist composition. Is the same as that described in the first resist composition.
  • the organic pattern embedding composition of the present invention and various materials used in the pattern forming method of the present invention preferably do not contain impurities such as metals.
  • the content of impurities contained in these materials is preferably 1 ppm or less, more preferably 100 ppt or less, still more preferably 10 ppt or less, and particularly preferably (not more than the detection limit of the measuring device). Examples of a method for removing impurities such as metals from the various materials include filtration using a filter.
  • the pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less.
  • the filter material is preferably a polytetrafluoroethylene, polyethylene, or nylon filter.
  • a filter that has been washed in advance with an organic solvent may be used.
  • a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters and / or materials may be used in combination. Moreover, various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulating filtration step.
  • a raw material having a low metal content is selected as a raw material constituting the various materials, and filter filtration is performed on the raw materials constituting the various materials.
  • the inside of the apparatus may be lined with Teflon (registered trademark), and distillation may be performed under a condition in which contamination is suppressed as much as possible.
  • the preferable conditions for filter filtration performed on the raw materials constituting the various materials are the same as those described above.
  • impurities may be removed with an adsorbent, or a combination of filter filtration and adsorbent may be used.
  • the adsorbent known adsorbents can be used.
  • inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
  • the present invention also relates to an electronic device manufacturing method including the above-described planarization method used in the present invention and the pattern forming method of the present invention, and an electronic device manufactured by this manufacturing method.
  • the electronic device of the present invention is suitably mounted on electrical and electronic equipment (home appliances, OA (Office Automation) / media related equipment, optical equipment, communication equipment, etc.).
  • ⁇ Preparation of resist composition The components shown in Table 1 below were dissolved in PGMEA (propylene glycol monomethyl ether acetate) and PGME (propylene glycol monomethyl ether) (70 wt% / 30 wt%) at a solid content concentration of 6.0 wt%, and the resulting solution was dissolved. The mixture was filtered through a polyethylene filter having a pore size of 0.03 ⁇ m to obtain a resist composition (composition for embedding an organic pattern) having a solid content concentration of 6.0 wt%.
  • the numerical values described in the structure column of the resin (A) represent the composition ratio (molar ratio) of each repeating unit.
  • An organic antireflection film-forming composition ARC29A (manufactured by Brewer Science) was applied onto a silicon wafer to form an organic antireflection film having a thickness of 86 nm.
  • the resist composition prepared on the organic antireflection film was applied and baked at 100 ° C. for 60 seconds (Pre Bake; PB) to form a resist film having a thickness of 200 nm.
  • the obtained resist film was subjected to pattern exposure using an ArF excimer laser scanner (NA (numerical aperture) 0.75) through a 6% halftone mask having a pitch of 150 nm and a light shielding part width of 75 nm.
  • NA ArF excimer laser scanner
  • the resist film after pattern exposure is baked at a temperature of 115 ° C. for 60 seconds (Post Exposure Bake; PEB), and then developed by paddle with a butyl acetate developer for 30 seconds. Line and 90 nm line portions and 60 nm space portions are developed. Got a space pattern.
  • PEB Post Exposure Bake
  • the obtained pattern was baked at a temperature of 200 ° C. for 60 seconds, and the prepared organic pattern embedding composition was applied thereon to form a planarization film (planarization layer).
  • the cross section of the formed planarization film was confirmed by SEM (scanning electron microscope), and embeddability was evaluated based on the following evaluation criteria. ⁇ Evaluation criteria> A (excellent): No voids are observed.
  • An organic antireflection film was formed on the silicon wafer and a resist film was formed on the organic antireflection film by a method similar to the evaluation of the embedding property described above.
  • the obtained resist film was subjected to pattern exposure using an ArF excimer laser scanner (NA 0.75) through a 6% halftone mask having a pitch of 600 nm and a light shielding part of 300 nm.
  • the resist film after pattern exposure was baked at a temperature of 150 ° C. for 60 seconds, and then developed by paddle with a butyl acetate developer for 30 seconds to obtain a line-and-space pattern having a line portion of 300 nm and a space portion of 300 nm.
  • planarization layer Observe the film thickness difference between the line part and the space part after forming the flattening film with an atomic force microscope, and calculate the difference between the maximum film thickness and the minimum film thickness (that is, the film thickness difference between the line part and the space part).
  • the flatness was evaluated based on the following evaluation criteria. ⁇ Evaluation criteria> A (very good): The film thickness difference between the line part and the space part is less than 5 nm. B (excellent): The film thickness difference between the line part and the space part is 5 nm or more and less than 10 nm.
  • the prepared organic pattern embedding composition was applied onto a silicon wafer and baked at 150 ° C. for 60 seconds to form a flattened film (flattened layer).
  • the obtained film was etched for 5 seconds using oxygen gas, and the etching rate was calculated from the change in film thickness before and after the treatment.
  • the results are shown in Table 2. The higher the etching rate, the better the etching property. Practically, the etching rate is preferably 100 ⁇ (angstrom) / sec (second) or more.
  • a line and space pattern (first pattern) was formed by the same method as the evaluation of embedding described above, and a planarizing film was formed thereon. Further, using the same resist composition (second resist composition) as the resist composition (first resist composition) used for forming the first pattern on the planarizing film, the first pattern A resist film (second resist film) was formed by the same method as the formation, and then exposure and development were performed to form a line and space pattern (second pattern).
  • Table 2 the structure of the resin used is as follows.
  • the numerical values listed in the chemical formulas of A-1 to A-10, A-13, and B-1 to B-5 represent the composition ratio (molar ratio) of each repeating unit.
  • N in A-12 and A-14 to A-17 represents the number of repeating units.
  • Table 3 below shows the number of carbon atoms and oxygen atoms in R 2 of each repeating unit and the R2 hetero ratio for A-1 to A-10.
  • the Onishi parameter in Table 2 represents the Onishi parameter of each resin (A-1 to A-21, B-1 to B-6).
  • the onishi parameter calculation method is as described above.
  • Tg in Table 2 represents the glass transition temperature Tg of each resin (A-1 to A-21, B-1 to B-6). The measuring method of Tg is as described above.
  • each of Examples 1 to 21 containing a resin (specific resin) having an Onishi parameter greater than 5.0 exhibited excellent embedding properties, flatness, and etching properties.
  • the repeating unit represented by the above formula (1-1) R 2 : Formula (P)
  • Examples 1 to 2 and 4 to 7 having a group represented by the following formulas showed better embedding property and flatness.
  • Examples 1 to 2, 4 and 6 to 7 in which the ratio of the repeating unit represented by the above formula (1-1) (R 2 : group represented by the formula (P)) is 15 mol% or more are It showed better etching properties.
  • the repeating unit represented by the formula (1-1) apart from the repeating unit in which R 2 is a group represented by the formula (P), the repeating unit represented by the formula (1-1) In Examples 1 and 2 in which R 2 has a repeating unit that is a group containing two or more hydroxy groups, further excellent etching properties were exhibited. From the comparison of Examples 14 to 17 in which the specific resin has only the repeating unit (X: —O—) represented by the above formula (1-2), the specific resin has a weight average molecular weight of 8000 or less. No. 17 showed more excellent etching properties. Among them, Examples 16 to 17 in which the weight average molecular weight of the specific resin is 5,000 or less showed further excellent etching properties. Among them, Example 17 in which the weight average molecular weight of the specific resin is 2,000 or less showed more excellent embedding property, flatness, and etching property.
  • Comparative Examples 1 to 6 which did not contain a resin having an Onishi parameter greater than 5.0 had insufficient embeddability, flatness and etchability.

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  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Polyethers (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

L'invention concerne une composition d'incorporation de motif organique qui contient une résine présentant un paramètre d'Ohnishi supérieur à 5,0. Ce procédé de formation de motif et ce procédé de fabrication d'un dispositif électronique comprennent, dans cet ordre, les étapes suivantes : une étape consistant à former un premier film de réserve ; une étape consistant à exposer le premier film de réserve à la lumière ; une étape consistant à former un premier motif ; une étape consistant à former une couche de planarisation ; une étape consistant à former un second film de réserve ; une étape consistant à exposer le second film de réserve à la lumière ; et une étape consistant à former un second motif.
PCT/JP2016/051708 2015-02-20 2016-01-21 Composition pour incorporation de motif organique, procédé de formation de motif et procédé de fabrication de dispositif électronique WO2016132803A1 (fr)

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WO2015016191A1 (fr) * 2013-07-31 2015-02-05 富士フイルム株式会社 Procédé de formation de motif, motif et procédé de gravure, procédé de fabrication de dispositif électronique et dispositif électronique l'utilisant
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JP2010039035A (ja) * 2008-08-01 2010-02-18 Fujifilm Corp レジストパターン形成用表面処理剤、レジスト組成物、それらを用いたレジストパターンの表面処理方法及びレジストパターンの形成方法
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WO2015016191A1 (fr) * 2013-07-31 2015-02-05 富士フイルム株式会社 Procédé de formation de motif, motif et procédé de gravure, procédé de fabrication de dispositif électronique et dispositif électronique l'utilisant
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