WO2016098345A1 - Composition photodurcissable pour impression, procédé de fabrication de film l'utilisant, procédé de fabrication de composant optique l'utilisant, procédé de fabrication de carte de circuit imprimé l'utilisant, et procédé de fabrication de composant électronique l'utilisant - Google Patents

Composition photodurcissable pour impression, procédé de fabrication de film l'utilisant, procédé de fabrication de composant optique l'utilisant, procédé de fabrication de carte de circuit imprimé l'utilisant, et procédé de fabrication de composant électronique l'utilisant Download PDF

Info

Publication number
WO2016098345A1
WO2016098345A1 PCT/JP2015/006244 JP2015006244W WO2016098345A1 WO 2016098345 A1 WO2016098345 A1 WO 2016098345A1 JP 2015006244 W JP2015006244 W JP 2015006244W WO 2016098345 A1 WO2016098345 A1 WO 2016098345A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
photocurable composition
producing
imprint
meth
Prior art date
Application number
PCT/JP2015/006244
Other languages
English (en)
Inventor
Shiori YONEZAWA
Toshiki Ito
Tomonori OTANI
Kazumi Sakamoto
Takeshi Honma
Original Assignee
Canon Kabushiki Kaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2015099486A external-priority patent/JP6624808B2/ja
Priority claimed from JP2015232535A external-priority patent/JP6324363B2/ja
Application filed by Canon Kabushiki Kaisha filed Critical Canon Kabushiki Kaisha
Priority to KR1020177019229A priority Critical patent/KR101988782B1/ko
Priority to KR1020197016193A priority patent/KR102059314B1/ko
Priority to KR1020197037480A priority patent/KR102246568B1/ko
Priority to CN201580069521.5A priority patent/CN107112208B/zh
Priority to US15/537,320 priority patent/US11003073B2/en
Publication of WO2016098345A1 publication Critical patent/WO2016098345A1/fr
Priority to US17/220,759 priority patent/US20210223690A1/en

Links

Images

Classifications

    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
    • H01L21/0334—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
    • H01L21/0337—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment

Definitions

  • the present invention relates to a photocurable composition for imprint, a method for producing a film using the same, a method for producing an optical component using the same, a method for producing a circuit board using the same, and a method for producing an electronic component using the same.
  • a micromachining technique utilizing a pattern of a resist (photocurable composition for nanoimprint) which is formed on a substrate (wafer) and has a predetermined shape as a mold has recently drawn attention in addition to a former photolithographic technique.
  • This technique is also referred to as an optical imprint (optical nanoimprint) and can form a fine structure of the order of several nanometers on a substrate (PTL 1).
  • a resist is first applied to a pattern formation region on a substrate (Arrangement step). Next, this resist is molded using a mold on which a pattern is formed (Mold contact step).
  • the pattern of the resist cured substance (photocured film) having a predetermined shape is formed on the substrate. Furthermore, by repeating all the steps described above at other positions on the substrate, a fine structure can be formed on the entire substrate.
  • the photocured film having the pattern formed on the substrate by the optical imprint technique is sometimes utilized as a mask in processing a base substrate using a dry etching technique.
  • the photocured film in order to process the base substrate with a good yield, the photocured film is required to have high dry etching resistance.
  • it is required to form a circuit pattern with an accuracy of about ⁇ 10 to 12% of a desired line width.
  • the resist cured substance thermally expands due to the reaction heat generated in etching. Therefore, when the coefficient of thermal expansion of the resist cured substance is large, expansion and distortion of the pattern line width are caused, which has posed a problem that a circuit pattern with a demanded accuracy is not obtained.
  • the present invention provides a photocurable composition for imprint having small thermal expansion in dry etching and having excellent filling properties in an optical imprint method.
  • the present invention also provides a film production method using a photocurable composition for imprint, a method for producing an optical component using the same, a method for producing a circuit board using the same, and a method for producing an electronic component using the same.
  • the present invention is a photocurable composition for imprint at least having a polymerizable compound (A) and a photopolymerization initiator (B), in which the polymerizable compound (A) contains 20% by weight or more of a multifunctional (meth)acrylic monomer and the glass transition temperature of a photocured substance of the photocurable composition is 90°C or more.
  • FIG. 1A is a schematic cross sectional view illustrating an example of a method for producing a film of this embodiment.
  • FIG. 1B includes FIGs. 1B(b-1) and 1B(b-2) illustrating schematic cross sectional views illustrating the example of a method for producing a film of this embodiment.
  • FIG. 1C is a schematic cross sectional view illustrating the example of a method for producing a film of this embodiment.
  • FIG. 1D includes FIGs. 1D(d-1) and 1D(d-2) illustrating schematic cross sectional views illustrating the example of a method for producing a film of this embodiment.
  • FIG. 1E is a schematic cross sectional view illustrating the example of a method for producing a film of this embodiment.
  • FIG. 1F is a schematic cross sectional view illustrating the example of a method for producing a film of this embodiment.
  • FIG. 1G is a schematic cross sectional view illustrating the example of a method for producing a film of this embodiment.
  • a photocurable composition for imprint is a curable composition at least containing a component (A) and a component (B) described below: Component (A): polymerizable compound; and Component (B): Photopolymerization initiator.
  • the photocurable composition for imprint is suitable for the use of forming a nano-order (1 nm to several hundreds nm) pattern of a photocured film on a base material, such as a semiconductor substrate, which is referred to as nanoimprint.
  • the photocurable composition for imprint is also suitable for the use of dry etching a photocured film formed by the nanoimprint to process the base material.
  • the photocured film means a film obtained by polymerizing the photocurable composition on a substrate, and then curing the same. Furthermore, the photocured film may have a pattern shape.
  • the component (A) is a polymerizable compound.
  • the polymerizable compound is a compound which reacts with a polymerization factor (radical and the like) generated from the photopolymerization initiator (component (B)) to form a film containing a high molecular weight compound by a chain reaction (polymerization reaction).
  • the polymerizable compound which is the component (A) may contain one kind of a polymerizable compound or may contain two or more kinds of polymerizable compounds.
  • the radical polymerizable compound is suitably a compound having one or more acryloyl groups or methacryloyl groups, i.e., a (meth)acrylic compound.
  • the component (A) (polymerizable compound) of the photocurable composition for nanoimprint suitably contains a (meth)acrylic compound.
  • the main component of the component (A) is more suitably a (meth)acrylic compound. It is the most suitable for the component (A) to contain only a (meth)acrylic compound.
  • the fact that the main component of the component (A) is a (meth)acrylic compound means that the component (A) contains 90% by weight or more of a (meth)acrylic compound.
  • the radical polymerizable compound contains two or more kinds of compounds having one or more acryloyl groups or methacryloyl groups
  • the radical polymerizable compound suitably contains a monofunctional (meth)acrylic monomer and a multifunctional (meth)acrylic monomer. This is because, by combining a monofunctional (meth)acrylic monomer and a multifunctional (meth)acrylic monomer, a photocured film having strong mechanical strength is obtained.
  • the multifunctional (meth)acrylic monomer is suitably contained in a proportion of 25% by weight or more. Thus, it is considered that the crosslink density of the photocured film increases and the thermal expansion in dry etching can be made small.
  • Examples of monofunctional(meth)acrylic compounds having one acryloyl group or methacryloyl group include, for example, phenoxyethyl(meth)acrylate, phenoxy-2-methylethyl(meth)acrylate, phenoxyethoxyethyl(meth)acrylate, 3-phenoxy-2-hydroxypropyl(meth)acrylate, 2-phenylphenoxyethyl(meth)acrylate, 4-phenylphenoxyethyl(meth)acrylate, 3-(2-phenylphenyl)-2-hydroxypropyl(meth)acrylate, (meth)acrylate of EO-modified p-cumylphenol, 2-bromophenoxyethyl(meth)acrylate, 2,4-dibromophenoxyethyl(meth)acrylate, 2,4,6-tribromophenoxyethyl(meth)acrylate, EO-modified phenoxy(meth)acrylate, PO-modified phenoxy
  • Examples of commercially-available items of the monofunctional(meth)acrylic compound include Aronix M101, M102, M110, M111, M113, M117, M5700, TO-1317, M120, M150, and M156 (all manufactured by Toagosei Co., Ltd.), MEDOL10, MIBDOL10, CHDOL10, MMDOL30, MEDOL30, MIBDOL30, CHDOL30, LA, IBXA, 2-MTA, HPA, Viscoat #150, #155, #158, #190, #192, #193, #220, #2000, #2100, and #2150 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Light acrylate BO-A, EC-A, DMP-A, THF-A, HOP-A, HOA-MPE, HOA-MPL, PO-A, P-200A, NP-4EA, NP-8EA, and Epoxyester M-600A (all manufactured by Kyoeisha Chemical Co., Ltd
  • multifunctional (meth)acrylic compounds having two or more acryloyl groups or methacryloyl groups include, for example, trimethylol propane di(meth)acrylate, trimethylol propane tri(meth)acrylate, EO-modified trimethylol propane tri(meth)acrylate, PO-modified trimethylol propane tri(meth)acrylate, EO,PO-modified trimethylol propane tri(meth)acrylate, dimethylol tricyclodecane di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, phenyl ethylene glycol di(meth)acrylate, 2-phenyl-1,3-propanediol diacrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)
  • Examples of commercially-available items of the multifunctional (meth)acrylic compound include Yupimer UV SA1002 and SA2007 (all manufactured by Mitsubishi Chemical Corporation), Viscoat #195, #230, #215, #260, #335HP, # 295, #300, #360, #700, GPT, and 3PA (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Light acrylate 4EG-A, 9EG-A, NP-A, DCP-A, BP-4EA, BP-4PA, TMP-A, PE-3A, PE-4A, and DPE-6A (all manufactured by a Kyoeisha Chemical Co., Ltd.), KAYARAD PET-30, TMPTA, R-604, DPHA, DPCA-20, -30, -60, -120, HX-620, D-310, and D-330 (all manufactured by Nippon Kayaku Co., Ltd.), Aronix M208, M210, M215, M220, M240, M305, M309, M310, M
  • the (meth)acrylate refers to acrylate or methacrylate having an alcohol residue equivalent thereto.
  • the (meth)acryloyl group refers to an acryloyl group or a methacryloyl group having an alcohol residue equivalent thereto.
  • the EO refers to ethylene oxide.
  • the EO-modified compound A refers to a compound in which a (meth)acrylic acid residue and an alcohol residue of the compound A are bonded to each other through the block structure of an ethylene oxide group.
  • the PO refers to propylene oxide.
  • the PO-modified compound B refers to a compound in which a (meth)acrylic acid residue and an alcohol residue of the compound B are bonded to each other through the block structure of a propylene oxide group.
  • N/(N C -N O ) is commonly referred to as a "Ohnishi parameter".
  • PTL 1 describes a technique of obtaining a photocurable composition having high dry etching resistance by the use of a polymerizable compound component having a small Ohnishi parameter.
  • the Ohnishi parameter is calculated using the following expression (2) as the mole fraction weighted average value.
  • OP n 1 OP 1 + n 2 OP 2 + ... + n n OP n (2)
  • the Ohnishi parameter of the component (A) is suitably 3.2 or less.
  • the component (A) is configured by a polymerizable compound in which the Ohnishi parameter is smaller than 3.2, good dry etching resistance is obtained.
  • the component (A) is configured by a polymerizable compound in which the Ohnishi parameter is larger than 3.2, the dry etching resistance is low, and therefore, a desired substrate processing accuracy cannot be obtained in some cases, which may lead to a reduction in yield.
  • the component (B) is a photopolymerization initiator.
  • the photopolymerization initiator is a compound which detects light of a predetermined wavelength to cause generation of the polymerization factor (radical).
  • the photopolymerization initiator is a polymerization initiator (radical generating agent) which generates a radical by light (radiation rays, such as infrared rays, visible rays, ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams, such as electron beams).
  • the component (B) may be configured from one kind of photopolymerization initiator or may be configured from two or more kinds of photopolymerization initiators.
  • radical generating agents include, for example, 2,4,5-triaryl imidazole dimers which may have substituents, such as a 2-(o-chlorophenyl)-4,5-diphenyl imidazole dimer, a 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, a 2-(o-fluorophenyl)-4,5-diphenyl imidazole dimer, and a 2-(o- or p- methoxyphenyl)-4,5-diphenyl imidazole dimer;
  • Benzophenone derivatives such as benzophenone, N,N'- tetramethyl-4,4'-diaminobenzophenone (Michler's Ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,
  • the component (B) of the photocurable composition for nanoimprint is suitably an acylphosphine oxide polymerization initiator.
  • the acyl phosphine oxide polymerization initiator is an acyl phosphine oxide compound, such as 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, bis(2,4,6-trimethyl benzoyl)phenyl phosphine oxide, or bis(2,6-dimethoxy benzoyl)-2,4,4-trimethyl pentyl phosphine oxide.
  • the compounding ratio of the component (B) which is a photopolymerization initiator in the photocurable composition for nanoimprint is suitably 0.01% by weight or more and 10% by weight or less and more suitably 0.1% by weight or more and 7% by weight or less based on the total amount of the component (A) which is a polymerizable compound.
  • the photocured film to be obtained is a photocured film having a certain degree of mechanical strength.
  • the photocurable composition for nanoimprint of this embodiment may contain further additive components (C) in addition to the component (A) and the component (B) described above according to various purposes insofar as the effects of the present invention are not impaired.
  • additive components (C) include a sensitizer, a hydrogen donor, an internal mold release agent, a surfactant, an antioxidant, a solvent, a polymer component, and a polymerization initiator which is not the component (B), and the like.
  • the sensitizer is a compound to be added as appropriate for the purpose of promoting the polymerization reaction and improving the reaction conversion rate.
  • a sensitizing dye and the like are mentioned, for example.
  • the sensitizing dye is a compound which is excited by absorbing light of a specific wavelength and interacts with the photopolymerization initiator which is the component (B).
  • the interaction described herein is energy transfer, electron transfer, and the like from the sensitizing dye in the excited state to the photopolymerization initiator which is the component (B).
  • the sensitizing dye examples include an anthracene derivative, an anthraquinone derivative, a pyrene derivative, a perylene derivative, a carbazole derivative, a benzophenone derivative, a thioxanthone derivative, a xanthone derivative, a coumarin derivative, a phenothiazine derivative, a camphorquinone derivative, an acridine dye, a thiopyrylium salt dye, a merocyanine dye, a quinoline dye, a styryl quinoline dye, a ketocoumarin dye, a thioxanthene dye, a xanthene dye, an oxonol dye, a cyanine dye, a rhodamine dye, a pyrylium salt dye, and the like but the sensitizing dye is not limited thereto.
  • the sensitizers may be used alone or as a mixture of two or more kinds thereof.
  • the hydrogen donor is a compound which reacts with an initiation radical generated from the photopolymerization initiator which is the component (B) or a radical at the polymerization growth terminal to generate a radical having higher reactivity. It is suitable to add the hydrogen donor when the photopolymerization initiator which is the component (B) is a photoradical generating agent.
  • a hydrogen donor examples include amine compounds, such as n-butyl amine, di-n-butyl amine, tri-n-butyl phosphine, allylthio urea, s-benzyl isothiuronium-p-toluene sulfinate, triethyl amine, diethyl amino ethyl methacrylate, triethylene tetramine, 4,4'-bis(dialkyl amino)benzophenone, N,N-dimethylamino benzoic acid ethyl ester, N,N-dimethylamino benzoic acid isoamyl ester, pentyl-4-dimethylamino benzoate, triethanol amine, and N-phenylglycine, mercapto compounds, such as 2-mercapto-N-phenyl benzimidazole and mercaptopropionic acid ester, and the like but the hydrogen donor is not limited thereto.
  • the hydrogen donors may be used alone or as a mixture of two or more kinds thereof.
  • the hydrogen donor may have a function as a sensitizer.
  • the photocurable composition for nanoimprint of this embodiment contains the sensitizer or the hydrogen donor as the additive component (C)
  • the content of each of the sensitizer and the hydrogen donor is suitably 0.1% by weight or more and 20% by weight or less, more suitably 0.1% by weight or more and 5.0% by weight or less, and still more suitably 0.2% by weight or more and 2.0% by weight or less based on the total amount of the component (A) which is the polymerizable compound.
  • the sensitizer is contained in a proportion of 0.1% by weight or more based on the total amount of the component (A), the polymerization promotion effect can be more effectively demonstrated.
  • the molecular weight of a high molecular weight compound configuring a photocured film to be produced becomes sufficiently high and also poor dissolution in the photocurable composition for nanoimprint or degradation of the storage stability of the photocurable composition for nanoimprint can be suppressed.
  • an internal mold release agent can be added to the photocurable composition for nanoimprint.
  • the internal type means that the mold release agent is added to a curable composition in advance before an arrangement step of the photocurable composition for nanoimprint.
  • the internal mold release agent As the internal mold release agent, surfactants, such as a silicone based surfactant, a fluorine based surfactant, and a hydrocarbon based surfactant, and the like can be used. In this embodiment, the internal mold release agent does not have polymerizability.
  • the fluorine based surfactant includes polyalkylene oxide (polyethylene oxide, polypropylene oxide, and the like) adducts of alcohols having a perfluoro alkyl group), polyalkylene oxides (polyethylene oxide, polypropylene oxide, and the like) adducts of perfluoro polyether, and the like.
  • the fluorine based surfactant may have a hydroxyl group, an alkoxy group, an alkyl group, an amino group, a thiol group, and the like in a part of the molecular structure (for example, terminal group).
  • fluorine based surfactant commercially-available items may be used.
  • the commercially-available items include, for example, Megafac F-444, TF-2066, TF-2067, and TF-2068 (all manufactured by DIC), Fluorad FC-430 and FC-431 (all manufactured by Sumitomo 3M Limited), Surflon S-382 (manufactured by AGC), EFTOP EF-122A, 122B, 122C, EF-121, EF-126, EF-127, and MF-100 (all manufactured by Tokem Products Co., Ltd.), PF-636, PF-6320, PF-656, and PF-6520 (all manufactured by OMNOVA Solutions), Unidyne DS-401, DS-403, and DS-451 (all manufactured by Daikin Industries), Ftergent 250, 251, 222F, and 208G (all manufactured by NEOS Co. Ltd.), and the like.
  • the internal mold release agent may be a hydrocarbon based surfactant.
  • the hydrocarbon based surfactant includes alkylalcohol polyalkylene oxide adducts obtained by adding alkylene oxide having 2 to 4 carbon atoms to alkyl alcohols having 1 to 50 carbon atoms and the like.
  • alkylalcohol polyalkylene oxide adducts examples include a methyl alcohol ethylene oxide adduct, a decyl alcohol ethylene oxide adduct, a lauryl alcohol ethylene oxide adduct, a cetyl alcohol ethylene oxide adduct, a stearyl alcohol ethylene oxide adduct, a stearyl alcohol ethylene oxide/propylene oxide adduct, and the like.
  • the terminal group of the alkylalcohol polyalkylene oxide adduct is not limited to a hydroxyl group which can be produced by simply adding polyalkylene oxide to alkyl alcohol.
  • the hydroxyl group may be converted to other substituents, e.g., polar functional groups, such as a carboxyl group, an amino group, a pyridyl group, a thiol group, and a silanol group, and hydrophobic functional groups, such as an alkyl group and an alkoxy group.
  • polar functional groups such as a carboxyl group, an amino group, a pyridyl group, a thiol group, and a silanol group
  • hydrophobic functional groups such as an alkyl group and an alkoxy group.
  • alkylalcohol polyalkylene oxide adduct commercially-available items may be used.
  • commercially-available items include for example, polyoxy ethylene methyl ether (methyl alcohol ethylene oxide adduct) (BLAUNON MP-400, MP-550, and MP-1000) manufactured by AOKI OIL INDUSTRIAL Co., LTD., polyoxy ethylene decyl ether (decyl alcohol ethylene oxide adduct) (FINESURF D-1303, D-1305, D-1307, and D-1310) manufactured by AOKI OIL INDUSTRIAL Co., LTD., polyoxy ethylene lauryl ether (lauryl alcohol ethylene oxide adduct) (BLAUNON EL-1505) manufactured by AOKI OIL INDUSTRIAL Co., LTD., polyoxy ethylene cetyl ether (cetyl alcohol ethylene oxide adduct) (BLAUNON CH-305 and CH-310) manufactured by AOKI OIL INDUSTRIAL Co., LTD.,
  • the internal mold release agent is suitably an alkylalcohol polyalkylene oxide adduct and more suitably a long chain alkylalcohol polyalkylene oxide adduct.
  • the internal mold release agents may be used alone or as a mixture of two or more kinds thereof.
  • the content of the internal mold release agent is 0.001% by weight or more and 10% by weight or less based on the total amount of the component (A) which is the polymerizable compound.
  • the content is suitably 0.01% by weight or more and 7% by weight or less and more suitably 0.05% by weight or more and 5% by weight or less.
  • the proportions of the component (A) and the component (B) can be determined, and consequently the proportions of the component (A) and the component (B) in the photocurable composition for imprint can be determined. Also when the additive component (C) is contained, the proportions of the component (A), the component (B), and the additive component (C) in the photocurable composition for imprint can be similarly determined.
  • the glass transition temperature of a photocured substance of the photocurable composition for imprint of this embodiment is suitably 90°C or more and more suitably 120°C or more. It is considered that, by setting the glass transition temperature to 90°C or more, thermal expansion and thermal distortion in dry etching are hard to occur.
  • the glass transition temperature of the photocured substance can be measured using differential scanning calorimeter (DSC) or a dynamic viscoelasticity device.
  • DSC differential scanning calorimeter
  • the extrapolation glass transition initiating temperature (Tig) is determined from the intersection of the straight line obtained by extending the baseline (DSC curve portion in a temperature region where transition and a reaction does not occur in a test piece) on the low temperature side of the DSC curve of the photocured substance to the high temperature side and the tangent drawn in such a manner that the gradient of the curve of a step-like change portion of the glass transition reaches the maximum, and then the extrapolation glass transition start temperature (Tig) can be determined as the glass transition temperature.
  • STA-6000 manufactured by Perkin Eimer
  • the transition temperature is measured using a dynamic viscoelasticity device
  • the temperature at which the loss tangent (tan ⁇ ) of the photocured substance reaches the maximum is defined as the glass transition temperature.
  • MCR301 manufactured by Anton Paar
  • the glass transition temperature is 90°C or more by any one of the measuring methods described above.
  • a photocurable composition having a glass transition temperature of 90°C or more in the measurement of the loss tangent using a dynamic viscoelasticity device is suitable.
  • the dynamic viscoelasticity device can consistently perform the production of the photocured substance and the measurement of the glass transition temperature and further the measurement of the coefficient of thermal expansion described later.
  • the transmittance to a 0.1 ⁇ m thick photocured film decreases, so that the glass transition temperature cannot be measured with good accuracy in some cases. Specifically, the measurement becomes difficult when the transmittance is 30% or less.
  • the photocurable composition for imprint has a glass transition temperature of 90°C or more.
  • Lucirin TPO which is a photopolymerization initiator (B) having low influence on a reduction in transmittance based on 100 parts by weight of the photopolymerizable compound (A) to be used is compounded to produce a photocurable composition, and then the loss tangent tan ⁇ of a photocured film is measured while increasing the temperature. Then, due to the fact that the temperature at which the tan ⁇ reaches the maximum is 90°C or more, it can be specified that the glass transition temperature of the photocurable composition is 90°C or more.
  • the composition of the photopolymerizable compound (A) is the main factor of determining the glass transition temperature.
  • the influence of the photopolymerization initiator of a small content on the glass transition temperature of the photocurable composition (B) is low. Therefore, it can be specified by carrying out the measuring method described above that the glass transition temperature of the photocurable composition is 90°C or more.
  • the component (A) and the component (B) are mixed and dissolved under predetermined temperature conditions. Specifically, the mixing and the dissolution are carried out in the range of 0°C or more and 100°C or less. The same applies to the case where the additive component (C) is contained.
  • the viscosity at 23°C of a mixture of the components except a solvent of the photocurable composition for imprint of this embodiment is suitably 1 mPa*s or more and 100 mPa*s or less, more suitably 3 mPa*s or more and 50 mPa*s or less, and still more suitably 5 mPa*s or more and 12 mPa*s or less.
  • the viscosity of the photocurable composition for imprint is 100 mPa*s or less, when the photocurable composition for imprint is brought into contact with a mold, the time required for the composition to fill into concave portions of a fine pattern on the mold is not prolonged. More specifically, the optical imprint method can be carried out with high productivity. Moreover, pattern defects due to poor filling are hard to occur.
  • the viscosity By setting the viscosity to 1 mPa*s or more, when the photocurable composition for imprint is applied onto a substrate, application unevenness is hard to occur and, when the photocurable composition for imprint is brought into contact with a mold, the photocurable composition for imprint is difficult to flow out of end portions of the mold.
  • the surface tension at 23°C of the mixture of the components except a solvent is suitably 5 mN/m or more and 70 mN/m or less, more suitably 7 mN/m or more and 35 mN/m or less, and still more suitably 10 mN/m or more and 32 mN/m or less.
  • the surface tension at 23°C of the mixture of the components except a solvent is suitably 5 mN/m or more and 70 mN/m or less, more suitably 7 mN/m or more and 35 mN/m or less, and still more suitably 10 mN/m or more and 32 mN/m or less.
  • a photocured film obtained by curing the photocurable composition for imprint is a photocured film having surface smoothness.
  • the photocurable composition for imprint of this embodiment not to contain impurities as much as possible.
  • the impurities described herein mean substances other than the component (A), the component (B), and the additive component (C) described above.
  • the photocurable composition for imprint is suitably one obtained passing through a purification step.
  • a purification step filtration using a filter or the like are suitable.
  • the component (A), the component (B), and the additive component to be added as necessary described above are mixed, and then the mixture is filtered with a filter having a pore size of 0.001 ⁇ m or more and 5.0 ⁇ m or less.
  • a filter having a pore size of 0.001 ⁇ m or more and 5.0 ⁇ m or less.
  • the filtered liquid may be filtered again.
  • a plurality of filters having different pore sizes may be used.
  • filters formed of polyethylene resin, polypropylene resin, fluororesin, nylon resin, and the like can be used but the filter is not particularly limited thereto.
  • impurities such as particles
  • the photocurable composition for imprint By passing through such a purification step, impurities, such as particles, mixed in the photocurable composition for imprint, can be removed.
  • pattern defects caused by irregularities accidentally formed in a photocured film, which is obtained after curing the photocurable composition for imprint, due to the impurities, such as particles, can be prevented.
  • the photocurable composition for imprint of this embodiment is used for manufacturing a semiconductor integrated circuit, it is suitable to avoid the mixing of impurities (metal impurities) containing metal atoms into the photocurable composition for imprint as much as possible in order not to inhibit an operation of a product.
  • the concentration of the metal impurities contained in the photocurable composition for imprint is adjusted to suitably 10 ppm or less and more suitably 100 ppb or less.
  • the present invention can take various aspects but suitably takes an aspect containing at least either the following item (A) or (B):
  • the multifunctional acrylic monomer contained in the polymerizable compound (A) is any one of m-xylylene diacrylate, phenyl ethylene glycol diacrylate, and 2-phenyl-1,3-propanediol diacrylate.
  • FIGs. 1A to 1G are schematic cross sectional views illustrating an example of the method for producing a film having a pattern shape of this embodiment.
  • the method for producing a film having a pattern shape of this embodiment has: [1] an arrangement step of arranging the photocurable composition for imprint of the embodiment described above on a substrate; [2] a mold contact step of bringing the photocurable composition for imprint into contact with a mold; [3] an alignment step of aligning the positions of the mold and a substrate to be processed; [4] a light irradiation step of irradiating the photocurable composition for imprint with light; and [5] a releasing step of releasing the photocured film obtained by the step [4] and the mold from each other.
  • the method for producing a photocured film having a pattern shape of this embodiment is a method for producing a film utilizing the optical imprint method.
  • the photocured film obtained by the method for producing a photocured film having a pattern shape of this embodiment is suitably a film having a pattern of a size 1 nm or more and 10 mm or less and more suitably a film having a pattern of a size of 10 nm or more and 100 ⁇ m or less.
  • a pattern formation technique of producing a film having a pattern (irregular structure) of a nano size (1 nm or more 100 nm or less) utilizing light is referred to as an optical nanoimprint method.
  • the method for producing a photocured film having a pattern shape of this embodiment employs the optical nanoimprint method.
  • a photocurable composition for imprint 101 of this embodiment described above is arranged (applied) on a substrate 102 to form a coating film as illustrated in FIG. 1A.
  • the substrate 102 which is a target on which the photocurable composition for imprint 101 is to be arranged is a substrate to be processed and a silicon wafer is usually used.
  • the substrate 102 is not limited to the silicon wafer and may be arbitrarily selected from those known as substrates for semiconductor devices, such as aluminum, a titanium-tungsten alloy, an aluminum-silicon alloy, an aluminum-copper-silicon alloy, silicon oxide, silicon nitride, and the like for use.
  • substrates for semiconductor devices such as aluminum, a titanium-tungsten alloy, an aluminum-silicon alloy, an aluminum-copper-silicon alloy, silicon oxide, silicon nitride, and the like for use.
  • a substrate whose adhesiveness with the photocurable composition for imprint is improved by surface treatment, such as silane coupling treatment, silazane treatment, and film formation of an organic thin film.
  • an ink jet method for example, an ink jet method, a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spin coating method, a slit scan method, and the like can be used.
  • the ink jet method is particularly suitable.
  • the film thickness of a layer to which a shape is to be transferred (coating film) varies depending on the intended use and is 0.01 ⁇ m or more and 100.0 ⁇ m or less, for example.
  • a mold 104 having an original pattern for transferring a pattern shape is brought into contact with the coating film containing the photocurable composition for imprint 101 formed in the previous step (arrangement step).
  • the coating film (partially) containing the photocurable composition for imprint 101 is filled into concave portions of a fine pattern on the surface of the mold 104, so that a coating film 106 filled into the fine pattern of the mold is obtained (FIG. 1B(b-2)).
  • the mold 104 is required to contain a light-transmitting material in consideration of the following step (light irradiation step).
  • the constituent material of the mold 104 is specifically suitably a light transparent resin, such as glass, quartz, PMMA, or polycarbonate resin, a flexible film, such as a transparent metal vapor deposition film or polydimethyl siloxane, a photocured film, a metal film, or the like.
  • a light transparent resin such as glass, quartz, PMMA, or polycarbonate resin
  • a flexible film such as a transparent metal vapor deposition film or polydimethyl siloxane
  • a photocured film a metal film, or the like.
  • Quartz is particularly suitable because the thermal expansion coefficient is low and pattern distortion is small.
  • the fine pattern on the surface of the mold 104 suitably has a pattern height of 4 nm or more and 200 nm or less and an aspect ratio of 1 or more and 10 or less.
  • the mold 104 may be surface treated before this step which is the mold contact step of the photocurable composition for imprint and the mold.
  • the surface treatment method a method including applying a mold release agent to the surface of the mold to form a mold release agent layer is mentioned.
  • the mold release agent to be applied to the surface of the mold include a silicone mold release agent, a fluorine mold release agent, a hydrocarbon mold release agent, a polyethylene mold release agent, a polypropylene mold release agent, a paraffin mold release agent, a montan mold release agent, a carnauba mold release agent, and the like.
  • a commercially-available coating type mold release agent such as Optool DSX manufactured by Daikin Industries, LTD.
  • the mold release agents may be used alone or in combination of two or more kinds thereof.
  • the fluorine mold release agent and the hydrocarbon mold release agent are particularly suitable.
  • the pressure to be applied to the photocurable composition for imprint 101 is not particularly limited and is usually 0 MPa or more and 100 MPa or less.
  • the pressure is suitably 0 MPa or more and 50 MPa or less, more suitably 0 MPa or more and 30 MPa or less, and still more suitably 0 MPa or more and 20 MPa or less.
  • the period of time while the mold 104 is brought into contact with the photocurable composition for imprint 101 in this step is not particularly limited and is usually 0.1 second or more and 600 seconds or less, suitably 0.1 second or more and 300 seconds or less, still more suitably 0.1 second or more and 180 seconds or less, and particularly suitably 0.1 second or more and 120 seconds or less.
  • This step can also be performed under any condition of under an air atmosphere, under reduced pressure atmosphere, and under an inactive gas atmosphere and the reduced pressure atmosphere or the inactive gas atmosphere is suitable because influence of oxygen or moisture on the curing reaction can be prevented.
  • Specific examples of the inactive gas usable when performing this step under the inactive gas atmosphere include nitrogen, carbon dioxide, helium, argon, various kinds of fluorocarbon gas, and the like or a mixed gas thereof.
  • a suitable pressure is 0.0001 atm or more and 10 atm or less.
  • the mold contact step may be performed under an atmosphere containing condensable gas (hereinafter referred to as a condensable gas atmosphere).
  • a condensable gas atmosphere refers to gas which is condensed and liquefied by the capillary pressure generated when the gas in the atmosphere is filled into the concave portions of the fine pattern formed on the mold 104 and a gap between the mold and the substrate together with the coating film (partially) 106.
  • the condensable gas is present in the form of gas in the atmosphere before the photocurable composition 101 (layer to which a shape is to be transferred) and the mold 104 are brought into contact with each other in the mold contact step (FIG. 1B(b-1)).
  • the condensable gas may dissolve in the photocurable composition 101.
  • the boiling point of the condensable gas is not particularly limited insofar as the boiling point is equal to or less than the atmospheric temperature of the mold contact step and is suitably -10°C to 23°C and more suitably 10°C to 23°C. When the boiling point is in this range, the filling properties are more excellent.
  • the vapor pressure of the condensable gas at the atmospheric temperature in the mold contact step is not particularly limited insofar as the vapor pressure is equal to or less than the mold pressure when impressed in the mold contact step and is suitably 0.1 to 0.4 MPa.
  • the vapor pressure is in this range, the filling properties are more excellent.
  • the vapor pressure at the atmospheric temperature is larger than 0.4 MPa, there is a tendency that the effect that air bubbles disappear cannot be sufficiently obtained.
  • the vapor pressure at the atmospheric temperature is smaller than 0.1 MPa, the pressure needs to be reduced, so that there is a tendency for a device to be complicated.
  • the atmospheric temperature of the mold contact step is not particularly limited and is suitably 20°C to 25°C.
  • chlorofluocarbon such as: chlorofluorocarbon (CFC), such as trichlorofluoro methane, hydrofluorocarbon (HFC), such as fluorocarbon (FC), hydrochlorofluorocarbon (HCFC), and 1,1,1,3,3-pentafluoro propane (CHF 2 CH 2 CF 3 ,HFC-245fa, PFP), and hydrofluoro ether (HFE), such as pentafluoroethyl methyl ether (CF 3 CF 2 OCH 3 , HFE-245mc).
  • CFC chlorofluorocarbon
  • HFC hydrofluorocarbon
  • HFC hydrofluorocarbon
  • FC fluorocarbon
  • HCFC hydrochlorofluorocarbon
  • HPFC-245fa 1,1,1,3,3-pentafluoro propane
  • HFE hydrofluoro ether
  • pentafluoroethyl methyl ether CF 3 CF 2 OCH 3 , HFE-245mc
  • 1,1,1,3,3-pentafluoro propane (Vapor pressure at 23°C of 0.14 MPa, Boiling point of 15°C), trichlorofluoro methane (Vapor pressure at 23°C of 0.1056 MPa, Boiling point of 24°C), and pentafluoroethyl methyl ether are suitable.
  • 1,1,1,3,3-pentafluoro propane is particularly suitable.
  • the condensable gas may be used alone or as a mixture of two or more kinds thereof.
  • the condensable gas may be mixed with non-condensable gas, such as air, nitrogen, carbon dioxide, helium, and argon for use.
  • the non-condensable gas to be mixed with the condensable gas is suitably helium from the viewpoint of the filling properties. Helium can permeate the mold 104. Therefore, when the gas (condensable gas and helium) in the atmosphere is filled into the concave portions of the fine pattern formed on the mold 104 together with the coating film (partially) 106 in the mold contact step, the condensable gas is liquefied and also helium permeates the mold. [Alignment step [3]]
  • the positions of the mold and/or the substrate to be processed are adjusted in such a manner that a mold side aligning mark 105 and an aligning mark 103 of the substrate to be processed are in agreement with each other.
  • a contact portion with the mold of the photocurable composition for imprint in detail the coating film 106 filled into the fine pattern of the mold, is irradiated with light through the mold 104 in the state where the positions are aligned in the step [3] as illustrated in FIG. 1D (FIG. 1D(d-1)).
  • the coating film 106 filled into the fine pattern of the mold 104 is cured by the emitted light to be a photocured film 108 (FIG. 1D(d-2)).
  • the light irradiating the photocurable composition for imprint 101 configuring the coating film 106 filled into the fine pattern of the mold is selected according to the sensitivity wavelength of the photocurable composition for imprint 101. Specifically, it is suitable to select ultraviolet light of a wavelength of 150 nm or more and 400 nm or less, X-rays, electron beams, or the like as appropriate for use.
  • the light (irradiation light 107) irradiating the photocurable composition for imprint 101 is particularly suitably ultraviolet light.
  • a light source emitting ultraviolet light include, for example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a Deep-UV lamp, a carbon arc light, a chemical lamp, a metal halide lamp, a xenon lamp, a KrF excimer laser, an ArF excimer laser, an F 2 excimer laser, and the like and the ultrahigh pressure mercury lamp is particularly suitable.
  • the number of the light sources to be used may be one or two or more. When performing the light irradiation, the light irradiation may be performed to the entire surface of the coating film 106 or only to a partial region thereof.
  • the light irradiation may be intermittently performed to the entire region on the substrate two or more times or may be continuously performed to the entire region. Or, a partial region A may be irradiated with light in a first irradiation step, and then a region B different from the region A may be irradiated with light in a second irradiation step. [Mold release step [5]]
  • the photocured film 108 and the mold 104 are released from each other.
  • a photocured film 109 having a predetermined pattern shape is formed on the substrate 102.
  • step [4] light irradiation step
  • the photocured film having a desired irregular pattern shape (pattern shape following the irregular shape of the mold 104) at a desired position can be obtained.
  • the obtained photocured film can also be utilized as optical members (including the case where the photocured film is used as one member of an optical member), such as a Fresnel lens and a diffraction grating, for example.
  • the photocured film can be used as an optical member at least having the substrate 102 and the photocured film 109 having a pattern shape arranged on the substrate 102.
  • a repetition unit (shot) including the step [1] to the step [5] can be repeatedly performed two or more times on the same substrate to be processed.
  • a photocured film having a plurality of desired irregular pattern shapes pattern shape following the irregular shape of the mold 104 at desired positions of the substrate to be processed can be obtained.
  • the photocured film obtained by the mold release process which is the process [5] has a specific pattern shape but the photocured films may partially remain also in regions other than the region where the pattern shape is formed (in the following description, such a part of the photocured film is sometimes referred to as a remaining film).
  • the obtained photocured film (remaining film) in the region to be removed of the photocured film having the pattern shape is removed, whereby a photocured film pattern 110 having a desired irregular pattern shape (pattern shape following the irregular shape of the mold 104) can be obtained as illustrated in FIG. 1F.
  • a method for removing the remaining film a method removing the photocured film (remaining film) serving as the concave portions of the photocured film 109 by a method, such as etching, for example, to expose the surface of the substrate 102 in the concave portions of the pattern of the photocured film 109 is mentioned.
  • etching When the photocured film in the concave portions of the photocured film 109 is removed by etching, a specific method therefor is not particularly limited and known methods, e.g., dry etching, can be used.
  • dry etching a known dry etching device can be used.
  • a sauce gas in the dry etching is selected as appropriate according to the element composition of the photocured film which is to be etched and halogen gas, such as CF 4 , C 2 F 6 , C 3 F 8 , CCl 2 F 2 , CCl 4 , CBrF 3 , BCl 3 , PCl 3 , SF 6 , and Cl 2 , gas containing oxygen atoms, such as O 2 , CO, and CO 2 , inactive gas, such as He, N 2 , and Ar, and gas, such as H 2 and NH 3 , and the like can be used.
  • halogen gas such as CF 4 , C 2 F 6 , C 3 F 8 , CCl 2 F 2 , CCl 4 , CBrF 3 , BCl 3 , PCl 3 , SF 6 , and Cl 2
  • gas containing oxygen atoms such as O 2 , CO, and CO 2
  • inactive gas such as He, N 2 , and Ar
  • gas such
  • the photocured film pattern 110 having a desired irregular pattern shape (pattern shape following the irregular shape of the mold 104) at desired positions can be obtained and articles having the photocured film pattern can be obtained.
  • a substrate processing step (Step [7]) described later is performed.
  • the obtained photocured film pattern 110 can be utilized as optical members (including the case where the photocured film pattern 110 is used as one member of an optical member), such as a diffraction grating and a polarizing plate, and then an optical component can also be obtained.
  • an optical component at least having the substrate 102 and the photocured film pattern 110 arranged on the substrate 102 can be obtained.
  • the photocured film pattern 110 having an irregular pattern shape which is obtained by the method for producing a photocured film having a pattern shape of this embodiment can also be used as, for example, a film for interlayer insulation film contained in electronic components typified by semiconductor devices, such as LSI, System LSI, DRAM, SDRAM, RDRAM, and D-RDRAM, and can also be used as a resist film in manufacturing semiconductor devices.
  • semiconductor devices such as LSI, System LSI, DRAM, SDRAM, RDRAM, and D-RDRAM
  • the photocured film pattern 110 When the photocured film pattern 110 is utilized as a resist film, etching or ion implantation is performed to a part of the substrate exposed in the etching step which is Step [6] (region denoted by the reference numeral 111 in FIG. 1F). In this case, the photocured film pattern 110 functions as an etching mask.
  • a circuit structure 112 (FIG. 1G) based on the pattern shape of the photocured film pattern 110 can be formed on the substrate 102.
  • a circuit board to be utilized in semiconductor devices and the like can be manufactured.
  • electronic devices such as displays, cameras, and medical devices, can also be configured.
  • optical components can also be obtained by performing etching or ion implantation utilizing the photocured film pattern 110 as a resist film.
  • the photocured film pattern 110 may be finally removed from the processed substrate but a configuration in which the photocured film pattern 110 may be left as a member configuring an element may be acceptable.
  • the photocured film formed by the method is suitable for the use in which the photocured film is processed by a dry etching step. More specifically, the photocured film is useful as a photocured film for dry etching to be used for a dry etching process which is obtained by curing the photocurable composition for imprint on a substrate.
  • a semiconductor substrate pretreated by dry etching having a semiconductor substrate and the photocured film for dry etching patterned on the semiconductor substrate can be provided.
  • Part(s) used in the following description is a unit based on weight (part by weight) unless otherwise particularly specified.
  • Reagents used in any one of Examples and Comparative Examples and contained in photocurable compositions for imprint are mentioned below.
  • compositions of photocurable compositions for imprint produced using the materials mentioned above are shown in Table 1 shown below. After the preparation, filtration with a 0.2 ⁇ m filter containing ultrahigh molecular weight polyethylene was performed.
  • the viscosity of the photocurable compositions for imprint at 23°C was measured using a cone-plate type rotation viscometer RE-85L (manufactured by Toki Sangyo Co., Ltd.). (2. Production of photocured film for measurement of glass transition temperature of photocurable composition for imprint)
  • 70 ⁇ l of a resist was added dropwise and filled into a 100 ⁇ m gap between a rotating rod having a bottom surface with a diameter ⁇ of 8.0 mm and a quartz stage using a rheometer MCR301 with a UV irradiation option manufactured by Anton Paar.
  • the normal reaction of the rotating rod was set to zero N in such a manner that the gap followed curing and shrinkage of the photocurable composition.
  • the rotational vibration cycle of the rotating rod was set to 5 Hz, and 10 seconds after starting the rotation vibration, UV light irradiation was started from the quartz stage side.
  • the exposure time was set to 600 seconds, the exposure wavelength was fixed to 365 nm, the illuminance was fixed to 1.0 mW/cm 2 , and the temperature was fixed to 23°C. (3. Measurement of glass transition temperature and coefficient of thermal expansion of photocurable composition for imprint)
  • the photocured film produced in (2) was measured for the loss tangent tan ⁇ while increasing the temperature from 23°C to 200°C.
  • the temperature increase rate was set to 4°C/min.
  • the temperature at which the tan ⁇ reached the maximum was defined as the glass transition temperature.
  • the coefficient of thermal expansion of the photocured film was calculated by the following expression (3).
  • Film thickness ( ⁇ m) of photocured film at 120°C/Film thickness ( ⁇ m) of photocured film at 23°C Coefficient of thermal expansion (%) (3)
  • the film thickness of the photocured film is a gap between the rotating rod and the quartz stage.
  • the Ohnishi parameter of the (A) component of the photocurable compositions shown in the composition table shown in Table 1 was calculated using the following expression (2).
  • OP n 1 OP 1 + n 2 OP 2 + ... + n n OP n (2)
  • 5 Production of photocured film for dry etching of photocurable composition for imprint
  • the interference filter used in the light irradiation was VPF-25C-10-15-31300 (manufactured by SIGMAKOKI Co., LTD.).
  • the wavelength of the ultraviolet light which was the irradiation light was a single wavelength light of 313 ⁇ 5 nm and the illuminance was set to 1 mW/cm 2 .
  • the measurement results above are shown in Table 2 shown below.
  • the dry etching rate ratio (DE rate ratio) was obtained by calculating the relative value, when the composition of Comparative Example 1 was set to 1, in terms of percentage.
  • Examples 1 to 8 are compositions in which the thermal expansion of the resist in the dry etching was small. Furthermore, considering the fact that the DE rate ratio is equal to or higher than that of Comparative Example 1, Examples 1 to 8 are compositions having excellent dry etching resistance. Since the viscosity is also 50 mPa*s or less, the filling properties are also excellent. Considering the fact that Examples 9 and 10 have a DE rate ratio smaller than that of Comparative Example 1 and having a viscosity of 50 mPa*s or less, it is considered that Examples 9 and 10 are compositions having a small thermal expansion similarly to Examples 1 to 8.
  • Comparative Examples 1 to 3 the glass transition temperature is 90°C or more but the coefficient of thermal expansion is 10% or more. This is considered to be because the proportion of the multifunctional monomer is less than 20% by weight, i.e., only the monofunctional acrylic monomer is contained, and therefore the crosslink density of Comparative Examples 1 to 3 is lower than that of the compositions containing 20% by weight or more of the multifunctional acrylic monomer as in Examples 1 to 8. More specifically, it is considered that thermal distortion and thermal expansion are likely to occur in dry etching.
  • Comparative Examples 5 to 8 are compositions containing 20% by weight or more of the multifunctional monomer but the coefficient of thermal expansion is 10% or more. This is considered to be because the glass transition temperature is low, and therefore thermal distortion and thermal expansion are likely to occur in dry etching similarly to Comparative Examples 1 to 4.
  • the composition of Examples 1 to 8 are photocurable compositions for imprint having small thermal expansion, excellent dry etching resistance, and also excellent filling properties.
  • the present invention can provide a photocurable composition for imprint having small thermal expansion in dry etching and excellent filling properties in an optical imprint method. Moreover, the present invention can also provide a method for producing the photocurable composition for imprint, a method for producing a film, a method for producing an optical component, a method for producing a circuit board, and a method for producing an electronic component.
  • the present invention can provide a photocurable composition for imprint having small thermal expansion in dry etching and excellent filling properties in an optical imprint method. Moreover, the present invention can also provide a method for producing a film using the photocurable composition for imprint, a method for producing an optical component using the photocurable composition for imprint, a method for producing a circuit board using the photocurable composition for imprint, and a method for producing an electronic component using the photocurable composition for imprint.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Polymerisation Methods In General (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)

Abstract

La présente invention concerne une composition photodurcissable pour impression qui comprend au moins un composé polymérisable (A) et un initiateur de photopolymérisation (B), le composé polymérisable (A) contenant au moins 20 % en poids d'un monomère (méth)acrylique multifonctionnel et la température de transition vitreuse d'une substance photodurcie de la composition photodurcissable étant supérieure ou égale à 90 °C.
PCT/JP2015/006244 2014-12-19 2015-12-15 Composition photodurcissable pour impression, procédé de fabrication de film l'utilisant, procédé de fabrication de composant optique l'utilisant, procédé de fabrication de carte de circuit imprimé l'utilisant, et procédé de fabrication de composant électronique l'utilisant WO2016098345A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
KR1020177019229A KR101988782B1 (ko) 2014-12-19 2015-12-15 임프린트용 광경화성 조성물, 이를 사용한 막의 제조 방법, 이를 사용한 광학 부품의 제조 방법, 이를 사용한 회로 기판의 제조 방법, 및 이를 사용한 전자 부품의 제조 방법
KR1020197016193A KR102059314B1 (ko) 2014-12-19 2015-12-15 임프린트용 광경화성 조성물, 이를 사용한 막의 제조 방법, 이를 사용한 광학 부품의 제조 방법, 이를 사용한 회로 기판의 제조 방법, 및 이를 사용한 전자 부품의 제조 방법
KR1020197037480A KR102246568B1 (ko) 2014-12-19 2015-12-15 임프린트용 광경화성 조성물, 이를 사용한 막의 제조 방법, 이를 사용한 광학 부품의 제조 방법, 이를 사용한 회로 기판의 제조 방법, 및 이를 사용한 전자 부품의 제조 방법
CN201580069521.5A CN107112208B (zh) 2014-12-19 2015-12-15 光固化性组合物及其应用
US15/537,320 US11003073B2 (en) 2014-12-19 2015-12-15 Photocurable composition for imprint, method for producing film using the same, method for producing optical component using the same, method for producing circuit board using the same, and method for producing electronic component using the same
US17/220,759 US20210223690A1 (en) 2014-12-19 2021-04-01 Photocurable composition for imprint, method for producing film using the same, method for producing optical component using the same, method for producing circuit board using the same, and method for producing electronic component using the same

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2014257798 2014-12-19
JP2014-257798 2014-12-19
JP2015-099486 2015-05-14
JP2015099486A JP6624808B2 (ja) 2014-07-25 2015-05-14 光硬化性組成物、これを用いた硬化物パターンの製造方法、光学部品の製造方法、回路基板の製造方法
JP2015-232535 2015-11-28
JP2015232535A JP6324363B2 (ja) 2014-12-19 2015-11-28 インプリント用光硬化性組成物、これを用いた膜の製造方法、光学部品の製造方法、回路基板の製造方法、電子部品の製造方法

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US15/537,320 A-371-Of-International US11003073B2 (en) 2014-12-19 2015-12-15 Photocurable composition for imprint, method for producing film using the same, method for producing optical component using the same, method for producing circuit board using the same, and method for producing electronic component using the same
US17/220,759 Continuation US20210223690A1 (en) 2014-12-19 2021-04-01 Photocurable composition for imprint, method for producing film using the same, method for producing optical component using the same, method for producing circuit board using the same, and method for producing electronic component using the same

Publications (1)

Publication Number Publication Date
WO2016098345A1 true WO2016098345A1 (fr) 2016-06-23

Family

ID=56126253

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2015/006244 WO2016098345A1 (fr) 2014-12-19 2015-12-15 Composition photodurcissable pour impression, procédé de fabrication de film l'utilisant, procédé de fabrication de composant optique l'utilisant, procédé de fabrication de carte de circuit imprimé l'utilisant, et procédé de fabrication de composant électronique l'utilisant

Country Status (1)

Country Link
WO (1) WO2016098345A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020219162A1 (fr) * 2019-04-26 2020-10-29 Canon Kabushiki Kaisha Composition photodurcissable

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110182805A1 (en) * 2005-06-17 2011-07-28 Desimone Joseph M Nanoparticle fabrication methods, systems, and materials
US20110227239A1 (en) * 2008-12-01 2011-09-22 Showa Denko K.K. Method of molding
JP2012227190A (ja) * 2011-04-15 2012-11-15 Nippon Shokubai Co Ltd ナノインプリント用硬化性樹脂組成物
JP2014075577A (ja) * 2012-09-13 2014-04-24 Hitachi Chemical Co Ltd パターンを有する樹脂層を製造する方法、及びそれに用いられる樹脂組成物
WO2014181533A1 (fr) * 2013-05-09 2014-11-13 Canon Kabushiki Kaisha Composé, composition photodurcissable et procédés de production d'un film porteur d'un motif, d'un composant optique, d'un circuit imprimé, d'un composant électronique en utilisant la composition photodurcissable et produit durci

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110182805A1 (en) * 2005-06-17 2011-07-28 Desimone Joseph M Nanoparticle fabrication methods, systems, and materials
US20110227239A1 (en) * 2008-12-01 2011-09-22 Showa Denko K.K. Method of molding
JP2012227190A (ja) * 2011-04-15 2012-11-15 Nippon Shokubai Co Ltd ナノインプリント用硬化性樹脂組成物
JP2014075577A (ja) * 2012-09-13 2014-04-24 Hitachi Chemical Co Ltd パターンを有する樹脂層を製造する方法、及びそれに用いられる樹脂組成物
WO2014181533A1 (fr) * 2013-05-09 2014-11-13 Canon Kabushiki Kaisha Composé, composition photodurcissable et procédés de production d'un film porteur d'un motif, d'un composant optique, d'un circuit imprimé, d'un composant électronique en utilisant la composition photodurcissable et produit durci

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020219162A1 (fr) * 2019-04-26 2020-10-29 Canon Kabushiki Kaisha Composition photodurcissable
CN113614118A (zh) * 2019-04-26 2021-11-05 佳能株式会社 光固化性组合物

Similar Documents

Publication Publication Date Title
US10073341B2 (en) Adhesion layer composition, method for forming film by nanoimprinting, methods for manufacturing optical component, circuit board and electronic apparatus
KR102100239B1 (ko) 막의 제조 방법, 광학 부품의 제조 방법, 회로 기판의 제조 방법, 전자 부품의 제조 방법, 및 광경화성 조성물
US20210223690A1 (en) Photocurable composition for imprint, method for producing film using the same, method for producing optical component using the same, method for producing circuit board using the same, and method for producing electronic component using the same
KR102045700B1 (ko) 경화성 조성물 및 그의 경화물, 경화물의 제조 방법, 광학 부품의 제조 방법, 회로 기판의 제조 방법, 및 전자 부품의 제조 방법
US10395943B2 (en) Patterning method, method for producing processed substrate, method for producing optical component, method for producing circuit board, and method for producing electronic component
EP3172247B1 (fr) Composition photodurcissable, procédé de production d'un motif de produit durci l'utilisant, procédé de production d'un composant optique, et procédé de production d'une carte de circuit
US10593547B2 (en) Photocurable composition, and methods using the same for forming cured product pattern and for manufacturing optical component, circuit board and imprinting mold
WO2016098345A1 (fr) Composition photodurcissable pour impression, procédé de fabrication de film l'utilisant, procédé de fabrication de composant optique l'utilisant, procédé de fabrication de carte de circuit imprimé l'utilisant, et procédé de fabrication de composant électronique l'utilisant
JP2016119457A (ja) インプリント用光硬化性組成物、硬化膜の製造方法、光学部品の製造方法、回路基板の製造方法、電子部品の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15869554

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 15537320

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20177019229

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 15869554

Country of ref document: EP

Kind code of ref document: A1