JP2017085148A - Composition for optical imprint, method for manufacturing film by using the composition for optical imprint, method for manufacturing optical component, method for manufacturing circuit board, and method for manufacturing electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for optical imprint which has high positioning accuracy and reduced pattern collapse defects, and to provide a method for manufacturing a film by using the composition for optical imprint, a method for manufacturing an optical component, a method for manufacturing a circuit board, and a method for manufacturing an electronic component.SOLUTION: A composition for optical imprint comprises at least a component (A) consisting of a polymerizable compound and a component (B) consisting of a photoinitiator. The composition satisfies the following expressions (1) and (2): 0.800≤Er/Er(1); and 2.55 GPa≤Er(2).SELECTED DRAWING: Figure 1

Description

  The present invention relates to a composition for optical imprinting, a film manufacturing method, an optical component manufacturing method, a circuit board manufacturing method, and an electronic component manufacturing method using the composition.

  The demand for miniaturization of semiconductor devices and MEMS has advanced, and in addition to conventional photolithography technology, a resist (photoimprint composition) on a substrate (wafer) is molded with a mold, and the resist pattern is formed on the substrate. The microfabrication technology (also called optical nanoimprint technology) formed on top is attracting attention.

  In the optical nanoimprint technique described in Patent Document 1, first, a resist is 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 (a mold contact step). And after irradiating light and hardening a resist (light irradiation process), it peels away (mold release process), and the pattern (photocured material) of resin is formed on a board | substrate. Further, by repeating all the above steps at other positions on the substrate, a fine structure is formed on the entire substrate.

  In particular, in the manufacture of semiconductor devices, MEMS, and the like, there are cases in which fine processing is further performed on a substrate that has already been processed using an optical nanoimprint technique. In such a case, it is necessary to accurately align the mold position with respect to the pattern already formed on the substrate. This process is called an alignment process and is performed between the mold contact process and the light irradiation process. In many cases, the optical nanoimprint technique performs a series of steps (shots) from an arrangement step to a release step on the same substrate a plurality of times.

JP 2010-073811 A

  However, in the light irradiation step, heat (exposure heat) is generated when the irradiated light is absorbed by the substrate, and the thermal distortion of the substrate caused by the exposure heat reaches the adjacent portion of the light irradiation portion and is adjacent. There is a problem that the alignment accuracy is low in the area shot.

  Moreover, in order to reduce the exposure heat and improve the alignment accuracy, if the exposure dose to be irradiated is reduced, the composition for photoimprint becomes defective in curing, resulting in a defect that the pattern collapses in the release process. Arise.

Therefore, the first embodiment of the composition for photoimprinting according to the present invention has at least a component (A) that is a polymerizable compound and a component (B) that is a photopolymerization initiator, and has the following formula ( 1) and the following formula (2) are satisfied.
0.800 ≦ Er ₁₀ / Er ₂₀₀ (1)
2.55 GPa ≦ Er ₁₀ (2)
(In Formula (1) and Formula (2), Er10 represents the composite elastic modulus (GPa) of the photocured film obtained when the composition for photoimprinting is exposed at an exposure amount of 10 mJ / cm ² , Er200 is (The composite elastic modulus (GPa) of the photocured film obtained when the composition for photoimprinting is exposed at an exposure amount of 200 mJ / cm ² is shown.)

Moreover, the 2nd aspect of the composition for photoimprints which concerns on this invention has (A) component which is a polymeric compound, and (B) component which is a photoinitiator, and has following formula ( 5) and the following formula (6) are satisfied.
0.880 ≦ E ₁₀ / E ₂₀₀ (5)
4.00 GPa ≦ E ₁₀ (6)
(In the formulas (5) and (6), E ₁₀ represents the Young's modulus (GPa) of the photocured film obtained when the composition for photoimprinting was exposed at an exposure amount of 10 mJ / cm ² , and E ₂₀₀ Indicates the Young's modulus (GPa) of the cured film obtained when the composition for photoimprinting is exposed at an exposure amount of 200 mJ / cm ^2. )

  According to the present invention, in the optical nanoimprint method, a film, an optical component, a circuit board, a method for manufacturing an electronic component, and a composition for optical imprint for forming the same, which achieve both high alignment accuracy and a small pattern collapse defect Things can be provided.

It is a schematic cross section which shows the example of the manufacturing method of the film | membrane of this embodiment.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings as appropriate. However, the present invention is not limited to the embodiments described below. Further, in the present invention, the scope of the present invention also includes those in which the embodiments described below are appropriately modified and improved based on the ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. include.

[Composition for optical imprint]
The composition for photoimprinting of the present embodiment has the following two aspects.

The first aspect of the composition for photoimprint has at least a component (A) that is a polymerizable compound and a component (B) that is a photopolymerization initiator,
The following formula (1) and the following formula (2) are satisfied.
0.800 ≦ Er ₁₀ / Er ₂₀₀ (1)
2.55 GPa ≦ Er ₁₀ (2)
(In Formula (1) and Formula (2), Er ₁₀ represents the composite elastic modulus (GPa) of the photocured film obtained when the composition for photoimprinting was exposed at an exposure amount of 10 mJ / cm ² , Er ₂₀₀ represents the composite elastic modulus (GPa) of the photocured film obtained when the composition for photoimprinting is exposed at an exposure amount of 200 mJ / cm ^2. )

Moreover, a 2nd aspect has (A) component which is a polymeric compound, and (B) component which is a photoinitiator, and satisfy | fills following formula (5) and following formula (6). It is characterized by.
0.880 ≦ E ₁₀ / E ₂₀₀ (5)
4.00 GPa ≦ E ₁₀ (6)
(In the formulas (5) and (6), E ₁₀ represents the Young's modulus (GPa) of the photocured film obtained when the composition for photoimprinting was exposed at an exposure amount of 10 mJ / cm ² , and E ₂₀₀ Indicates the Young's modulus (GPa) of the cured film obtained when the composition for photoimprinting is exposed at an exposure amount of 200 mJ / cm ^2. )
By satisfying at least one of the above two aspects, it is possible to provide a composition for optical imprinting that achieves both high alignment accuracy and few pattern collapse defects.

  In addition, in this embodiment and this invention, the composition for optical imprint shows the composition for imprint which superpose | polymerizes and hardens | cures by irradiating light.

  First, each component will be described in detail.

<Component (A) Polymerizable Compound>
Component (A) is a polymerizable compound. Here, in the present embodiment and the present invention, the polymerizable compound is a polymer compound that reacts with a polymerization factor (radical or the like) generated from the photopolymerization initiator (component (B)) and undergoes a chain reaction (polymerization reaction). It is a compound which forms the film | membrane which consists of.

  Examples of such a polymerizable compound include a radical polymerizable compound. The polymerizable compound as the component (A) may be composed of one kind of polymerizable compound or may be composed of a plurality of kinds of polymerizable compounds.

  In the present embodiment and the present invention, “A is composed of B” means that A is B (that is, A is composed only of B).

  The radical polymerizable compound is preferably a compound having at least one acryloyl group or methacryloyl group, that is, a (meth) acrylic compound.

  Therefore, the polymerizable compound preferably contains a (meth) acrylic compound, the main component of the polymerizable compound is more preferably a (meth) acrylic compound, and most preferably a (meth) acrylic compound. In addition, the main component of the polymerizable compound described here being a (meth) acrylic compound indicates that 90% by weight or more of the polymerizable compound is a (meth) acrylic compound.

  When the radically polymerizable compound is composed of a plurality of types of compounds having one or more acryloyl groups or methacryloyl groups, it is preferable to include a monofunctional acrylic monomer and a polyfunctional acrylic monomer. This is because a cured film having high strength can be obtained by combining a monofunctional acrylic monomer and a polyfunctional acrylic monomer.

  Examples of monofunctional (meth) acrylic compounds having one acryloyl group or methacryloyl group include phenoxyethyl (meth) acrylate, phenoxy-2-methylethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, and 3-phenoxy. 2-hydroxypropyl (meth) acrylate, 2-phenylphenoxyethyl (meth) acrylate, 4-phenylphenoxyethyl (meth) acrylate, 3- (2-phenylphenyl) -2-hydroxypropyl (meth) acrylate, EO-modified p-cumylphenol (meth) acrylate, 2-bromophenoxyethyl (meth) acrylate, 2,4-dibromophenoxyethyl (meth) acrylate, 2,4,6-tribromophenoxyethyl (meth) acrylate EO-modified phenoxy (meth) acrylate, PO-modified phenoxy (meth) acrylate, polyoxyethylene nonylphenyl ether (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-methyl-2- Adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Cyclohexyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2 Hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t -Butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (medium) Acrylate), stearyl (meth) acrylate, isostearyl (meth) acrylate, benzyl (meth) acrylate, 1-naphthylmethyl (meth) acrylate, 2-naphthylmethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxy Ethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) Acrylate, methoxypolypropylene glycol (meth) acrylate, diacetone (meth) acrylamide, isobutoxymethyl (Meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) Examples thereof include, but are not limited to, acrylate, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide and the like.

  Commercially available products of the above monofunctional (meth) acrylic compounds include Aronix M101, M102, M110, M111, M113, M117, M5700, TO-1317, M120, M150, M156 (above, manufactured by Toagosei Co., Ltd.), MEDOL10, MIBDOL10, CHDOL10, MMDOL30, MEDOL30, MIBDOL30, CHDOL30, LA, IBXA, 2-MTA, HPA, Biscote # 150, # 155, # 158, # 190, # 192, # 193, # 220, # 2000, # 2100, # 2150 (Osaka Organic Chemical 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, Epoxy S M-600A (above, manufactured by Kyoeisha Chemical Co., Ltd.), KAYARAD TC110S, R-564, R-128H (above, manufactured by Nippon Kayaku), NK ester AMP-10G, AMP-20G (above, manufactured by Shin-Nakamura Chemical Co., Ltd.) FA-511A, 512A, 513A (manufactured by Hitachi Chemical), PHE, CEA, PHE-2, PHE-4, BR-31, BR-31M, BR-32 (manufactured by Daiichi Kogyo Seiyaku), VP ( BASF), ACMO, DMAA, DMAPAA (above, manufactured by Kojin) and the like, but are not limited thereto.

  Examples of the polyfunctional (meth) acrylic compound having two or more acryloyl groups or methacryloyl groups include trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and EO-modified trimethylolpropane tri (meth) acrylate. , PO-modified trimethylolpropane tri (meth) acrylate, EO, PO-modified trimethylolpropane tri (meth) acrylate, dimethyloltricyclodecane di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, phenylethylene glycol di (meth) acrylate, polyethylene glycol Di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,3-adamantanedimethanol di (meth) acrylate, o-xylylene di (meth) acrylate, m-xylylene di (meth) acrylate , P-xylylene di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (acryloyloxy) isocyanurate, bis (hydroxymethyl) tricyclodecanedi (meth) acrylate, dipe Taerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, EO-modified 2,2-bis (4-((meth) acryloxy) phenyl) propane, PO-modified 2,2-bis (4-((meta ) Acryloxy) phenyl) propane, EO, PO-modified 2,2-bis (4-((meth) acryloxy) phenyl) propane and the like, but are not limited thereto.

  Commercially available products of the above polyfunctional (meth) acrylic compounds include Iupimer UV SA1002, SA2007 (above, manufactured by Mitsubishi Chemical), Biscoat # 195, # 230, # 215, # 260, # 335HP, # 295, # 300, # 360, # 700, GPT, 3PA (manufactured by Osaka Organic Chemical Industry), light acrylate 4EG-A, 9EG-A, NP-A, DCP-A, BP-4EA, BP-4PA, TMP-A, PE- 3A, PE-4A, DPE-6A (manufactured by Kyoeisha Chemical), KAYARAD PET-30, TMPTA, R-604, DPHA, DPCA-20, -30, -60, -120, HX-620, D-310 , D-330 (above, Nippon Kayaku), Aronix M208, M210, M215, M220, M240, M305, M309 , M310, M315, M325, M400 (above, manufactured by Toagosei Co., Ltd.), Lipoxy VR-77, VR-60, VR-90 (above, manufactured by Showa Denko) and the like, but are not limited thereto.

  In the above compound group, (meth) acrylate means acrylate and methacrylate having an alcohol residue equivalent thereto. The (meth) acryloyl group means an acryloyl group and a methacryloyl group having an alcohol residue equivalent thereto. EO represents ethylene oxide, and EO-modified compound A refers to a compound in which the (meth) acrylic acid residue and alcohol residue of compound A are bonded via a block structure of an ethylene oxide group. PO represents propylene oxide, and PO-modified compound B refers to a compound in which the (meth) acrylic acid residue and alcohol residue of compound B are bonded via a block structure of a propylene oxide group.

  Among these, component (A) is isobornyl acrylate, benzyl acrylate, 2-naphthylmethyl acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, dimethylol tricyclodecane diacrylate, phenylethylene glycol. It is preferable to contain at least one of diacrylate or m-xylylene diacrylate, and it is more preferable to contain at least two. Furthermore, it consists of isobornyl acrylate, benzyl acrylate, and neopentyl glycol diacrylate, or it consists of isobornyl acrylate and 1,6-hexanediol diacrylate, or benzyl acrylate, Dimethylol tricyclodecane diacrylate, or benzyl acrylate and phenylethylene glycol diacrylate, or benzyl acrylate and m-xylylene diacrylate, or benzyl acrylate, It preferably consists of 2-naphthylmethyl acrylate and m-xylylene diacrylate.

<Component (B) Photopolymerization initiator>
Component (B) is a photopolymerization initiator.

  In the present embodiment and the present invention, the photopolymerization initiator is a compound that generates the polymerization factor (radical) by sensing light of a predetermined wavelength. Specifically, the photopolymerization initiator is a polymerization initiator (radical generator) that generates radicals by light (infrared rays, visible rays, ultraviolet rays, far ultraviolet rays, charged particle beams such as X-rays, electron beams, etc., radiation). It is.

  Component (B) may be composed of one type of photopolymerization initiator, or may be composed of a plurality of types of photopolymerization initiators.

  Examples of the radical generator include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- It may have a substituent such as (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o- or p-methoxyphenyl) -4,5-diphenylimidazole dimer 2, 4,5-triarylimidazole dimer; benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy -4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diamino Benzophenone derivatives such as nzophenone; 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane- Α-amino aromatic ketone derivatives such as 1-one; 2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, etc. Quinones; benzoin methyl ester Benzoin ether derivatives such as ether, benzoin ethyl ether and benzoin phenyl ether; benzoin derivatives such as benzoin, methyl benzoin, ethyl benzoin and propyl benzoin; benzyl derivatives such as benzyl dimethyl ketal; 9-phenylacridine, 1,7-bis (9 , 9'-acridinyl) heptane derivatives; N-phenylglycine derivatives such as N-phenylglycine; acetophenone, 3-methylacetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2- Acetophenone derivatives such as phenylacetophenone; thioxanthones such as thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone Xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1 -Phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2, 4,4-trimethylpentylphosphine oxide, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl]- 1-(O-acetyl oxime) and the like, but not limited to.

  Commercially available products of the above photoradical generator include Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI-1700, -1750, -1850, CG24-61, Darocur 1116, 1173, Lucirin TPO, LR8883, LR8970 (above, manufactured by BASF), Ubekrill P36 (manufactured by UCB), and the like are exemplified, but not limited thereto.

  Among these, the component (B) is preferably an alkylphenone polymerization initiator, an oxime ester polymerization initiator, or an acyl phosphine oxide polymerization initiator.

  In the above examples, the alkylphenone polymerization initiators are benzoin ether derivatives such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin derivatives such as benzoin, methyl benzoin, ethyl benzoin and propyl benzoin; benzyldimethyl Benzyl derivatives such as ketals; acetophenone derivatives such as acetophenone, 3-methylacetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone; 2-benzyl-2-dimethylamino-1- Α-amino aromatics such as (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one Is a ton derivatives.

  Moreover, among the above examples, the oxime ester polymerization initiator is 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9- An oxime ester compound such as ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime).

  Furthermore, among the above examples, the acyl phosphine oxide-based polymerization initiator includes 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and other acylphosphine oxide compounds.

  Among these, component (B) is 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 represented by the following formula (a), 1 represented by the following formula (b) , 2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide represented by the following formula (e), Or 2,4,6-trimethylbenzoyldiphenylphosphine oxide represented by the following formula (c) is particularly preferable.

  The blending ratio in the composition for photoimprinting of the component (B) that is a polymerization initiator is 0.01% by weight or more and 10% by weight or less, preferably with respect to the total amount of the component (A) that is a polymerizable compound. Is 0.1 wt% or more and 7 wt% or less.

  When the blending ratio of the component (B) is 0.01% by weight or more with respect to the total amount of the polymerizable compound, the curing rate of the composition can be increased and the reaction efficiency can be improved. Moreover, the hardened | cured material obtained turns into a hardened | cured material with a certain amount of mechanical strength because the mixture ratio of a component (B) shall be 10 weight% or less with respect to the whole quantity of a polymeric compound.

<Component (C) Other additive components>
In addition to the component (A) and component (B) described above, the composition for optical imprinting according to the present embodiment is a further additive component (C) as long as the effects of the present invention are not impaired depending on various purposes. ) May be contained. Examples of such additive component (C) include a surfactant, a sensitizer, a hydrogen donor, an antioxidant, a solvent, and a polymer component.

  A sensitizer is a compound added as appropriate for the purpose of promoting the polymerization reaction or improving the reaction conversion rate. Examples of the sensitizer include sensitizing dyes.

  The sensitizing dye is a compound that is excited by absorbing light of a specific wavelength and interacts with the polymerization initiator that is component (B). In addition, the interaction described here is an energy transfer, an electron transfer, etc. from the sensitizing dye in an excited state to the polymerization initiator which is the component (B).

  Specific examples of the sensitizing dye include anthracene derivatives, anthraquinone derivatives, pyrene derivatives, perylene derivatives, carbazole derivatives, benzophenone derivatives, thioxanthone derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, phenothiazine derivatives, camphorquinone derivatives, acridine dyes, Examples include thiopyrylium salt dyes, merocyanine dyes, quinoline dyes, styrylquinoline dyes, ketocoumarin dyes, thioxanthene dyes, xanthene dyes, oxonol dyes, cyanine dyes, rhodamine dyes, and pyrylium salt dyes. However, it is not limited to these.

  A sensitizer may be used individually by 1 type and may be used in mixture of 2 or more types.

  Among these, the sensitizer is preferably a benzophenone sensitizer or a thioxanthone sensitizer.

  In the above examples, the benzophenone sensitizer is a benzophenone compound such as 4,4'-bis (dialkylamino) benzophenone.

  Of the above examples, the thioxanthone sensitizer is a thioxanthone compound such as 2-isopropylthioxanthone.

  Among these, the sensitizer is particularly preferably 4,4′-bis (diethylamino) benzophenone represented by the following formula (f) or 2-isopropylthioxanthone represented by the following formula (i).

  The hydrogen donor is a compound that reacts with an initiation radical generated from the polymerization initiator as the component (B) or a radical at the polymerization growth terminal to generate a radical having higher reactivity. It is preferable to add when the polymerization initiator which is the component (B) is a photo radical generator.

  Specific examples of such hydrogen donors include N-butylamine, di-n-butylamine, tri-n-butylphosphine, allylthiourea, s-benzylisothiuronium-p-toluenesulfinate, triethylamine, diethylaminoethyl. Methacrylate, triethylenetetramine, 4,4′-bis (dialkylamino) benzophenone, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethanol Examples include amine compounds such as amines and N-phenylglycine, mercapto compounds such as 2-mercapto-N-phenylbenzimidazole and mercaptopropionic acid esters, but are not limited thereto.

  One hydrogen donor may be used alone, or two or more hydrogen donors may be mixed and used.

  The hydrogen donor may have a function as a sensitizer. Examples of the hydrogen donor having a function as a sensitizer include the aforementioned 4,4'-bis (dialkylamino) benzophenone.

  Examples of 4,4'-bis (dialkylamino) benzophenone include 4,4'-bis (diethylamino) benzophenone and derivatives thereof. Of these, 4,4′-bis (diethylamino) benzophenone represented by the following formula (f) is particularly preferable.

  When the composition for photoimprinting of this embodiment contains a sensitizer or a hydrogen donor as an additive component, it is preferably 0.1% by weight with respect to the total amount of the component (A) that is a polymerizable compound. It is 20 wt% or less, more preferably 0.1 wt% or more and 5.0 wt% or less, and still more preferably 0.2 wt% or more and 2.0 wt% or less. If the sensitizer is contained in an amount of 0.1% by weight or more based on the total amount of the component (A), the polymerization promoting effect can be expressed more effectively. Further, when the content of the sensitizer or hydrogen donor is 5.0% by weight or less, the molecular weight of the polymer compound constituting the photocured product to be produced is sufficiently high, and the composition for photoimprinting It is possible to suppress poor dissolution in the resin and deterioration of the storage stability of the composition for photoimprinting.

  For the purpose of reducing the interfacial bonding force between the mold and the resist, a surfactant can be added to the photoimprinting composition.

  As the surfactant, a silicone-based surfactant and a fluorine-based surfactant can be used. Among these, a fluorosurfactant is preferable from the viewpoint of excellent release force reduction effect. In the present invention, the surfactant has no polymerizability.

  Fluorosurfactants include polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.) adducts of alcohols having a perfluoroalkyl group, polyalkylene oxide (polyethylene oxide, polypropylene oxide, etc.) adducts of perfluoropolyether, etc. included. In addition, the fluorine-based surfactant may have a hydroxyl group, an alkyl group, an amino group, a thiol group, or the like in a part of the molecular structure (for example, a terminal group). A commercially available surfactant may be used.

  Commercially available fluorosurfactants include, for example, MegaFace F-444, TF-2066, TF-2067, TF-2068 (above, manufactured by DIC), Florard FC-430, FC-431 (above, Sumitomo 3M). ), Surflon S-382 (manufactured by AGC), EFTOP EF-122A, 122B, 122C, EF-121, EF-126, EF-127, MF-100 (above, manufactured by Tochem Products), PF-636, PF -6320, PF-656, PF-6520 (manufactured by OMNOVA Solutions), Unidyne DS-401, DS-403, DS-451 (manufactured by Daikin Industries), Footage 250, 251, 222F, 208G (and above) Neos) and the like.

  Further, the surfactant may be a hydrocarbon surfactant.

  Examples of the hydrocarbon-based surfactant include an alkyl alcohol polyalkylene oxide adduct obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an alkyl alcohol having 1 to 50 carbon atoms.

  Examples of the alkyl alcohol polyalkylene oxide adduct include methyl alcohol ethylene oxide adduct, decyl alcohol ethylene oxide adduct, lauryl alcohol ethylene oxide adduct, cetyl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide adduct, stearyl alcohol ethylene oxide adduct / Examples thereof include propylene oxide adducts. The terminal group of the alkyl alcohol polyalkylene oxide adduct is not limited to a hydroxyl group that can be produced by simply adding a polyalkylene oxide to an alkyl alcohol. This hydroxyl group may be converted to other substituents, for example, a polar functional group such as a carboxyl group, an amino group, a pyridyl group, a thiol group, or a silanol group, or a hydrophobic functional group such as an alkyl group.

  A commercial item may be used for the alkyl alcohol polyalkylene oxide adduct. Examples of commercially available products include polyoxyethylene methyl ether (methyl alcohol ethylene oxide adduct) (BLAUNON MP-400, BLAUNONMP-550, BLAUNON MP-1000) manufactured by Aoki Yushi Kogyo, and polyoxyethylene decyl manufactured by Aoki Yushi Kogyo. Ether (decyl alcohol ethylene oxide adduct) (FINESURFD-1303, FINESURF D-1305, FINESURF D-1307, FINESURF D-1310), polyoxyethylene lauryl ether (lauryl alcohol ethylene oxide adduct) (BLAUUNON) manufactured by Aoki Oil & Fat Co., Ltd. EL-1505), polyoxyethylene cetyl ether (cetyl alcohol ethylene oxide adduct) (BLAUNO, manufactured by Aoki Yushi Kogyo Co., Ltd.) CH-305, BLAUNON CH-310), polyoxyethylene stearyl ether (stearyl alcohol ethylene oxide adduct) manufactured by Aoki Yushi Kogyo (BLAUNON SR-705, BLAUNON SR-707, BLAUNON SR-715, BLAUNON SR-720, BLAUNON SR-730, BLAUNON SR-750), random polymerized polyoxyethylene polyoxypropylene stearyl ether (BLAUNON SA-50 / 50 1000R, SA-30 / 70 2000R) manufactured by Aoki Yushi Kogyo, polyoxyethylene methyl manufactured by BASF Ether (Pluriol A760E), Kao polyoxyethylene alkyl ether (Emulgen series), and the like can be mentioned.

  Among these hydrocarbon surfactants, the internally added mold release agent is preferably an alkyl alcohol polyalkylene oxide adduct, and more preferably a long-chain alkyl alcohol polyalkylene oxide adduct.

  In particular, it is preferable to use a compound represented by the following formula (O) as a hydrocarbon surfactant.

(O)
In the above formula (O), Rc is a monovalent hydrocarbon group having 5 to 50 carbon atoms, Ra represents an alkylene group, and m is an integer of 1 to 10. X is any one of an alkoxy group, a hydroxyl group, a carboxyl group, a pyridyl group, a silanol group, and a sulfo group.

  As the surfactant, one kind may be used alone, or two or more kinds may be mixed and used.

  When the composition for photoimprinting of this embodiment contains a surfactant as an additive component, the content of this surfactant is, for example, relative to the total weight of the component (A) that is a polymerizable compound, 0.001 wt% or more and 10 wt% or less. Preferably, they are 0.01 weight% or more and 7 weight% or less, More preferably, they are 0.05 weight% or more and 5 weight% or less. By setting it in the range of at least 0.001 wt% or more and 10 wt% or less, the composition for photoimprinting has an effect of reducing the releasing force and also has an effect that the filling property is excellent.

  It is preferable that the composition for optical imprinting of this embodiment is a composition for optical nanoimprinting.

  In addition, by analyzing the photocured product obtained by exposing the composition for photoimprinting of the present embodiment by infrared spectroscopy, ultraviolet-visible spectroscopy, pyrolysis gas chromatography mass spectrometry, etc., component (A) The ratio of component (B) can be determined, and as a result, the ratio of component (A) and component (B) in the composition for photoimprinting can be determined.

<Temperature when compounding composition for optical imprint>
When preparing the composition for photoimprinting of this embodiment, at least the component (A) and the component (B) are mixed and dissolved under a predetermined temperature condition. Specifically, it is performed in the range of 0 ° C. or higher and 100 ° C. or lower.

<Viscosity of composition for photoimprint>
The viscosity at 23 ° C. of the mixture of components excluding the solvent of the composition for photoimprinting of the present embodiment is preferably 1 cP or more and 100 cP or less, more preferably 5 cP or more and 50 cP or less, and still more preferably, It is 6 cP or more and 20 cP or less.

  When the viscosity of the composition for photoimprint is 100 cP or less, when the composition for photoimprint is brought into contact with the mold, it takes a long time for the composition to fill the recesses in the fine pattern on the mold. You do n’t have time. Also, pattern defects due to poor filling are less likely to occur.

  In addition, when the viscosity is 1 cP or more, uneven coating is less likely to occur when the photoimprinting composition is applied onto the substrate, and the end of the mold when the photoimprinting composition is brought into contact with the mold. Therefore, the composition for photoimprinting hardly flows out.

<Surface tension of composition for photoimprint>
The surface tension of the composition for photoimprinting of the present embodiment is such that the surface tension at 23 ° C. of the mixture of components excluding the solvent is preferably 5 mN / m or more and 70 mN / m or less, more preferably 7 mN / m. m to 35 mN / m, more preferably 10 mN / m to 32 mN / m. Here, when the surface tension is 5 mN / m or more, when the composition for photoimprinting is brought into contact with the mold, it takes a long time to fill the recess with the composition in the fine pattern on the mold. I'm sorry.

  Moreover, when the surface tension is 70 mN / m or less, a cured product obtained by exposing the composition for photoimprinting becomes a cured product having surface smoothness.

<Impurities mixed in the composition for photoimprint>
It is preferable that the composition for photoimprinting of the present embodiment contains as little impurities as possible. The impurity described here means a component other than the component (A), the component (B) and the additive component described above.

  Therefore, the photoimprinting composition is preferably obtained through a purification process. As such a purification step, filtration using a filter or the like is preferable.

  When performing filtration using a filter, specifically, after mixing the above-described component (A), component (B) and additional components added as necessary, for example, a pore size of 0.001 μm or more and 5. It is preferable to filter with a filter of 0 μm or less. When performing filtration using a filter, it is more preferable to carry out in multiple stages or repeat many times. Moreover, you may filter the filtered liquid again. Filtration may be performed using a plurality of filters having different pore diameters. As a filter used for filtration, filters made of polyethylene resin, polypropylene resin, fluororesin, nylon resin, etc. can be used, but are not particularly limited.

  Through such a purification step, impurities such as particles mixed in the photoimprinting composition can be removed. Thereby, it is possible to prevent the occurrence of pattern defects due to inadvertent irregularities in the photocured product obtained after exposure of the composition for photoimprinting due to impurities such as particles.

  When the composition for photoimprinting of the present embodiment is used for manufacturing a semiconductor integrated circuit, the composition for photoimprinting contains a metal atom so as not to hinder the operation of the product. It is preferable to avoid mixing impurities (metal impurities) as much as possible. In such a case, the concentration of the metal impurity contained in the photoimprinting composition is preferably 10 ppm or less, and more preferably 100 ppb or less.

<Preferred combination of components>
The imprinting composition of the present invention can be prepared by combining the components (A), (B), and (C) described above.

  In particular, a monofunctional compound composed of isobornyl acrylate or isobornyl acrylate and benzyl acrylate, and a polyfunctional compound composed of neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, or dimethylol tricyclodecane diacrylate. A component (A) containing a functional compound, and a component (B) containing at least one of the compounds represented by the following formulas (a), (b), (c), and (e): The weight ratio of the monofunctional compound to the polyfunctional compound is preferably 1: 1 to 3: 1.

_(C)

_(E)

  Moreover, it is preferable to further have a compound represented by the following formula (f) as a sensitizer.

(F)

  Moreover, it is preferable to further have the compound as described in a following formula (g) as a mold release agent.

_(G)

  In particular, the component (A) is preferably contained as a main component, and 90% or more of the composition for photoimprinting is preferably the component (A).

[Curing film]
A cured film is obtained by exposing the coating film of the above-mentioned photoimprinting composition. A specific example of the method for forming the coating film of the composition for photoimprinting is described in the arranging step [1] in the method for producing a film having a pattern shape described later. Moreover, the specific example of the method of hardening a coating film is described in the method of the light irradiation process [4] which irradiates light to the composition for photoimprint in the manufacturing method of the film | membrane which has the pattern shape mentioned later.

<Measurement of Young's modulus and composite elastic modulus of cured film>
The obtained cured film can be measured for Young's modulus and composite elastic modulus by a method such as nanoindentation. Nanoindentation is a method in which the indenter is pushed into a desired location on the measurement sample and the load and displacement are measured simultaneously. From the load-displacement curve at this time, the hardness and Young's modulus (elastic modulus) of the measurement sample are determined. Can be sought.

  Specific examples of the measuring apparatus include Nano Indenter G200 (manufactured by Agilent Technologies), ENT series (manufactured by Elionix), and TI series (manufactured by Hystron).

The composition for optical imprinting of this embodiment has, as a first aspect, the composite elastic modulus (GPa) of a cured film obtained when the film of the composition for optical imprinting is exposed at 10 mJ / cm ² , Er _10. When the composite elastic modulus (GPa) of the cured film of the composition for photoimprint obtained when exposed at 200 mJ / cm ² is Er ₂₀₀ , the optical imprint satisfying the following formulas (1) and (2) It is a composition for printing.
0.800 ≦ Er ₁₀ / Er ₂₀₀ (1)
2.55 GPa ≦ Er ₁₀ (2)

The composite elastic modulus can be obtained as a composite elastic modulus at an indentation depth of 200 nm when measured by the Oliver-Pharr method using TI-950 TriboIndenter (manufactured by Hystron). The film thickness of the composition for photoimprint when exposed at 10 mJ / cm ² and the thickness of the film of the composition for photoimprint when exposed at 200 mJ / cm ² are both 3.2 μm. Moreover, the composite elastic modulus measurement of a cured film can be performed, for example, 24 hours after the exposure of the film of the composition for photoimprinting.

When the composition for optical imprint satisfies the formula (1), it is preferable that the following formula (3) is also satisfied.
0.855 ≦ Er ₁₀ / Er ₂₀₀ ≦ 0.993 (3)

Incidentally, _{Er 10} and _{Er 200} in the formula (3) is the same as _{Er 10} and _{Er 200} in Formula (1), respectively, obtained when exposed to light for imprints composition in 10 mJ / cm ² curing The composite elastic modulus (GPa) of the film and the composite elastic modulus (GPa) of the cured film obtained when the composition for photoimprinting is exposed at 200 mJ / cm ² .

Moreover, the composition for optical imprint which satisfy | fills Formula (2) is good to satisfy | fill the following formula | equation (4).
2.81 GPa ≦ Er ₁₀ ≦ 3.27 GPa (4)

Incidentally, _{Er 10} in the formula (4) is the same as _{Er 10} in the formula (1), a composite modulus of elasticity of the resulting cured film upon exposure to light imprint composition at 10 mJ / cm ^2.

A second aspect of photoimprints composition of the present embodiment, the Young's modulus of the cured film obtained a film of photoimprints composition upon exposure at 10 mJ / cm ² a (GPa) and E _10, Young's modulus of the cured film of the photo-printing composition obtained upon exposure with 200 mJ / cm ² a (GPa) when an _{E 200,} the following equation (5) and the composition for optical imprint satisfying (6) It is a thing.
0.880 ≦ E ₁₀ / E ₂₀₀ (5)
4.00 GPa ≦ E ₁₀ (6)

Incidentally, _{E 10} in the formula (6) is the same as _{E 10} in the formula (5), Young's modulus of the cured film obtained upon exposure to light imprint composition at 10 mJ / cm ² (GPa) is there.

Even if the composition for optical imprint which satisfy | fills Formula (5) is a case where the composition for optical imprint is exposed with the low exposure amount of 10 mJ / cm < ² >, it is a photo imprint with the high exposure amount of 200 mJ / cm < ² >. It is the composition for optical imprint from which the hardened | cured material which shows the same degree of hardening as the case where the composition for light exposure is exposed.

  Here, the composition for photoimprinting of the present embodiment may satisfy both the formula (1) and the formula (5). Furthermore, both of formula (2) and formula (6) may be satisfied.

In addition, when 0.880 is expressed by two digits after the decimal point, it is 0.88, and when it is described by two digits after the decimal point, the expression (5) may be written as 0.88 ≦ E ₁₀ / E ₂₀₀ it can.

The Young's modulus can be determined as an average value of Young's modulus at an indentation depth of 100 to 150 nm when measured by a continuous stiffness measurement (CSM) method using Nano Indenter G200 (manufactured by Agilent Technologies). The film thickness of the composition for photoimprint when exposed at 10 mJ / cm ² and the thickness of the film of the composition for photoimprint when exposed at 200 mJ / cm ² are both 3.2 μm. In addition, the Young's modulus of the cured film can be measured, for example, 24 hours after the exposure of the film of the composition for photoimprint.

Furthermore, when the composition for photoimprints satisfies Formula (5), it is preferable that the following Formula (7) is also satisfied.
0.956 ≦ E ₁₀ / E ₂₀₀ ≦ 1.05 (7)

Also, _{E 10} and _{E 200} in the formula (7) is the same as _{E 10} and _{E 200} in the formula (5), respectively, obtained when exposed to light for imprints composition in 10 mJ / cm ² curing The Young's modulus (GPa) of the film and the Young's modulus (GPa) of the cured film obtained when the composition for photoimprinting is exposed at 200 mJ / cm ² .

Moreover, it is preferable that the composition for optical imprint which satisfy | fills Formula (6) satisfy | fills the following formula | equation (8).
4.17 GPa ≦ E ₁₀ ≦ 5.94 GPa (8)

Incidentally, _{E 10} in the formula (8) is the same as _{E 10} in the formula (5), Young's modulus of the cured film obtained upon exposure to light imprint composition at 10 mJ / cm ² (GPa) is there.

[Method for producing film having pattern shape]
Next, the manufacturing method of the film | membrane which has the pattern shape of this embodiment is demonstrated.

  FIG. 1 is a schematic cross-sectional view showing an example of a method for producing a film having a pattern shape according to this embodiment.

The manufacturing method of the film having the pattern shape of the present embodiment is as follows.
[1] An arrangement step of arranging the above-described photoimprinting composition of the present embodiment on a substrate;
[2] A mold contact step in which the composition for photoimprint and a mold are brought into contact with each other
[3] An alignment process for aligning the position of the mold and the substrate to be processed;
[4] A light irradiation step of irradiating the composition for photoimprint with light;
[5] A mold release step for separating the cured product obtained from the step [4] from the mold;
Have

  The manufacturing method of the film | membrane which has the pattern shape of this embodiment is a preparation method of the film | membrane using the optical nanoimprint method.

  The film obtained by the method for producing a film having a pattern shape according to this embodiment is preferably a film having a pattern having a size of 1 nm to 10 mm, and preferably having a pattern having a size of 10 nm to 100 μm. More preferred. In general, a pattern forming technique for producing a film having a nano-size (1 nm to 100 nm) pattern (uneven structure) using light is called an optical nanoimprint method. The manufacturing method of the film | membrane which has has utilized the optical nanoimprint method.

  Hereinafter, each step will be described.

<Arrangement process [1]>
In this step (arrangement step), as shown in FIG. 1A, the optical imprinting composition 101 of the present embodiment described above is arranged (applied) on the substrate 102 to form a coating film.

  The substrate 102 on which the optical imprint composition 101 is to be placed is a substrate to be processed, and a silicon wafer is usually used.

  However, the substrate 102 is not limited to a silicon wafer, and is known as a substrate for semiconductor devices such as aluminum, titanium-tungsten alloy, aluminum-silicon alloy, aluminum-copper-silicon alloy, silicon oxide, and silicon nitride. You may choose arbitrarily from things and use. The substrate 102 (substrate to be processed) used is a substrate having improved adhesion to the photoimprinting composition by surface treatment such as silane coupling treatment, silazane treatment, and organic thin film formation. It may be used.

  Examples of the method for disposing the optical imprint composition of the present embodiment on a substrate to be processed include, for example, an inkjet method, a dip coating method, an air knife coating method, a curtain coating method, a wire barcode method, a gravure coating method, an extensible method. A rouge coating method, a spin coating method, a slit scanning method, or the like can be used. In addition, although the film thickness of a to-be-shaped transfer layer (coating film) changes with uses to be used, they are 0.01 micrometer or more and 100.0 micrometers or less, for example. In the optical nanoimprint method, an inkjet method is particularly preferable.

<Die contact process of optical imprinting composition and mold [2]>
Next, as shown in FIG. 1B, a mold 104 having an original pattern for transferring the pattern shape to the coating film made of the photoimprinting composition 101 formed in the previous step (placement step) is contacted. Let In this step, the mold 104 is brought into contact with the optical imprinting composition 101 (shape transfer layer) (FIG. 1 (b-1)), whereby the concave portion of the fine pattern on the surface of the mold 104 is used for optical imprinting A coating film (part) of the composition 101 is filled to form a coating film 106 filled in a fine pattern of the mold (FIG. 1B-2).

  The mold 104 needs to be made of a light transmissive material in consideration of the next process (light irradiation process). Specifically, the constituent material of the mold 104 is preferably a light transparent resin such as glass, quartz, PMMA, or polycarbonate resin, a transparent metal vapor-deposited film, a flexible film such as polydimethylsiloxane, a photocured film, or a metal film. . However, in the case where a light-transparent resin is used as the constituent material of the mold 104, it is necessary to select a resin that does not dissolve in the solvent contained in the photo-imprinting composition 101. Quartz is particularly preferable because it has a small thermal expansion coefficient and a small pattern distortion.

  In order to improve the releasability between the photoimprinting composition 101 and the surface of the mold 104, the mold 104 is subjected to a surface treatment before this step, which is a mold contact process between the photoimprinting composition and the mold. You can go. Examples of the surface treatment method include a method of forming a release agent layer by applying a release agent to the surface of the mold. Here, as a mold release agent applied to the mold surface, a silicon mold release agent, a fluorine mold release agent, a polyethylene mold release agent, a polypropylene mold release agent, a paraffin mold release agent, a montan mold release agent And carnauba release agents. For example, a commercially available coating mold release agent such as OPTOOL DSX manufactured by Daikin Industries, Ltd. can also be suitably used. In addition, a mold release agent may be used individually by 1 type, and may be used in combination of 2 or more types. Among these, a fluorine-based mold release agent is particularly preferable.

  In this step (mold contact step), as shown in FIG. 1 (b-1), when the mold 104 and the optical imprinting composition 101 are brought into contact with each other, the pressure applied to the optical imprinting composition 101 is particularly Although not limited, it is usually 0 MPa or more and 100 MPa or less. Among them, it is preferably 0 MPa or more and 50 MPa or less, more preferably 0 MPa or more and 30 MPa or less, and further preferably 0 MPa or more and 20 MPa or less.

  In addition, the time during which the mold 104 is brought into contact with the photoimprinting composition 101 in this step is not particularly limited, but is usually 0.1 seconds to 600 seconds and 0.1 seconds to 300 seconds. Is more preferably 0.1 seconds or more and 180 seconds or less, and particularly preferably 0.1 seconds or more and 120 seconds or less.

  Although this step can be performed under any conditions of air atmosphere, reduced pressure atmosphere, and inert gas atmosphere, since it can prevent the influence of oxygen and moisture on the photocuring reaction, the reduced pressure atmosphere and An active gas atmosphere is preferable. Specific examples of the inert gas that can be used when this step is performed in an inert gas atmosphere include nitrogen, carbon dioxide, helium, argon, various chlorofluorocarbons, and a mixed gas thereof. When this step is performed in an atmosphere of a specific gas including an air atmosphere, a preferable pressure is 0.0001 atm or more and 10 atm or less.

  This step may be performed in an atmosphere containing a condensable gas (hereinafter referred to as a condensable gas atmosphere). In the present invention and the present specification, the condensable gas means an atmosphere before the composition for photoimprint 101 (shape transfer layer) and the mold 104 are in contact with each other in the mold contact step (FIG. 1 (b-1)). It exists as a gas inside, and is applied to the concave portion of the fine pattern formed on the mold 104 and the gap between the mold and the substrate when the photoimprinting composition 101 (shaped transfer layer) and the mold 104 come into contact with each other. When the gas in the atmosphere is filled together with (a part of) the membrane 106, it is defined as a gas that condenses and liquefies at the capillary pressure generated by the pressure at the time of filling.

  When the mold contact step is performed in a condensable gas atmosphere, the gas filled in the concave portions of the fine pattern is liquefied, and bubbles disappear, so that the filling property is excellent. The condensable gas may be dissolved in the curable composition.

  The boiling point of the condensable gas is not limited as long as it is not higher than the atmospheric temperature in the mold contact step, but is preferably −10 ° C. to 23 ° C., more preferably 10 ° C. to 23 ° C. If it is this range, a filling property will be further excellent.

  The vapor pressure of the condensable gas at the atmospheric temperature in the mold contact process is not limited as long as it is equal to or lower than the mold pressure when imprinting in the mold contact process, but is preferably 0.1 to 0.4 MPa. If it is this range, a filling property will be further excellent. When the vapor pressure at the atmospheric temperature is larger than 0.4 MPa, there is a tendency that the effect of eliminating the bubbles cannot be obtained sufficiently. On the other hand, if the vapor pressure at the ambient temperature is less than 0.1 MPa, pressure reduction is required and the apparatus tends to be complicated.

  The atmosphere temperature in the mold contact step is not particularly limited, but is preferably 20 ° C to 25 ° C.

Specific examples of the condensable gas include chlorofluorocarbon (CFC) such as trichlorofluoromethane, fluorocarbon (FC), hydrochlorofluorocarbon (HCFC), 1,1,1,3,3-pentafluoropropane (CHF ₂ CH ₂ Fluorocarbons such as hydrofluorocarbons (HFC) such as CF ₃ , HFC-245fa, PFP) and hydrofluoroethers such as pentafluoroethyl methyl ether (CF ₃ CF ₂ OCH ₃ , HFE-245mc). .

  Among these, 1,1,1,3,3-pentafluoropropane (vapor pressure at 23 ° C., 0.14 MPa, from the viewpoint that the filling property at 20 ° C. to 25 ° C. is excellent in the atmosphere temperature in the mold contact process. From the viewpoint of having a higher boiling point of 15 ° C.), trichlorofluoromethane (vapor pressure of 0.1056 MPa at 23 ° C., boiling point of 24 ° C.), and pentafluoroethyl methyl ether, and 1,1,1,3, 3-pentafluoropropane is particularly preferred.

  One type of condensable gas may be used alone, or two or more types may be mixed and used. These condensable gases may be mixed with non-condensable gases such as air, nitrogen, carbon dioxide, helium, and argon and used as a mixed gas. The non-condensable gas mixed with the condensable gas is preferably helium from the viewpoint of filling properties. In the case of helium, when the concave portion of the fine pattern formed on the mold 104 in the mold contact process is filled with the gas (condensable gas and helium) in the atmosphere together with the coating film (a part) 106, the helium is condensed. Since the property gas is liquefied and helium can permeate the mold, the filling property is excellent.

<Mold and process substrate alignment process [3]>
Next, as shown in FIG. 1C, the position of the substrate to be processed is adjusted so that the mold side positioning mark 105 and the positioning mark 103 of the substrate to be processed coincide with each other.

<Light irradiation process [4] which irradiates light to the composition for photoimprints>
Next, as shown in FIG. 1 (d), in the state of alignment in the step [3], in more detail, in the contact portion with the mold of the composition for photoimprinting, more specifically, the fineness of the mold. The coating film 106 filled in the pattern is irradiated with light through the mold 104 (FIG. 1 (d-1)). Thereby, the coating film 106 filled in the fine pattern of the mold 104 is cured by the irradiated light to become a cured film 108 (FIG. 1 (d-2)).

  Here, the light applied to the photoimprinting composition 101 constituting the coating film 106 filled in the fine pattern of the mold is selected according to the sensitivity wavelength of the photoimprinting composition 101. For this, ultraviolet light having a wavelength of 150 nm or more and 400 nm or less, an X-ray, an electron beam or the like is preferably selected and used.

Among these, the light (irradiation light 107) with which the composition 101 for photoimprinting is irradiated is particularly preferably ultraviolet light. This is because many commercially available curing aids (photopolymerization initiators) are sensitive to ultraviolet light. Examples of light sources that emit ultraviolet light include high pressure mercury lamps, ultrahigh pressure mercury lamps, low pressure mercury lamps, deep-UV lamps, carbon arc lamps, chemical lamps, metal halide lamps, xenon lamps, KrF excimer lasers, ArF excimer lasers, and F _2. Although an excimer laser etc. are mentioned, an ultrahigh pressure mercury lamp is especially preferable. Further, the number of light sources used may be one or plural. Further, the light irradiation may be performed on the entire surface of the coating film 106 filled in the fine pattern of the mold, or may be performed only on a partial region.

  Further, the light irradiation can be intermittently performed a plurality of times on the substrate. For example, a partial region A is irradiated in the first irradiation process, and a region B different from the region A is irradiated in the second irradiation process. can do.

  In this case, the composition can be cured with a small amount of irradiation by using the above-described composition for photoimprinting of the present embodiment.

That is, even when the photoimprinting composition is irradiated under a low exposure condition of 10 mJ / cm ² , it is cured to the same extent as when it is irradiated under a high exposure condition of 200 mJ / cm ² .

Therefore, the low exposure condition is such that the thermal distortion due to the expansion of the substrate due to the heat (exposure heat) generated by the light being absorbed by the substrate does not easily reach the portion adjacent to the region A that is the region irradiated with the light. (10 mJ / cm ² or more 75 mJ / cm ² or less, more preferably 10 mJ / cm ² or more 30 mJ / cm ² or less), the can be cured with light imprint composition. Therefore, it is difficult to cause a defect that the pattern collapses in the next mold release step, and the accuracy of the alignment that is the step [3] when the steps [1] to [5] are repeated in adjacent portions. It becomes difficult to decrease.

  Note that the thermal expansion amount of the substrate due to exposure can be calculated as follows.

For example, when the processing substrate is a silicon substrate (linear thermal expansion coefficient 2.6 ppm / K), the exposure area is a rectangular shape of 26 × 33 mm, and the exposure amount of ultraviolet light is 90 mJ / cm ² , the thermal expansion amount is calculated. This means that a thermal strain of 2.9 nm at the maximum occurs at the end portion.

<Releasing step for separating the cured product and the mold [5]>
Next, the cured film 108 and the mold 104 are separated to form a cured film 109 having a predetermined pattern shape on the substrate 102.

  In this step (release step), as shown in FIG. 1E, the cured film 108 and the mold 104 are separated from each other, and in the step [4] (light irradiation step), the fine pattern formed on the mold 104 is removed. A reverse pattern is obtained as a pattern of the cured film 109 having a pattern shape.

  In addition, when the mold contact process is performed in a condensable gas atmosphere, the pressure at the interface between the cured film 108 and the mold 104 decreases when the cured film 108 and the mold 104 are separated in the mold release process. Along with this, the condensable gas is vaporized, so that there is a tendency to exert a releasing force reduction effect.

  The method for separating the cured film 108 and the mold 104 is not particularly limited as long as a portion of the cured film 108 is not physically damaged when being separated, and various conditions are not particularly limited. For example, the substrate 102 (substrate to be processed) may be fixed and the mold 104 may be moved away from the substrate 102 to be peeled off, or the mold 104 may be fixed and moved away from the mold 102 to be peeled off. Alternatively, both of them may be peeled by pulling in the opposite direction.

  A cured film having a desired concavo-convex pattern shape (a pattern shape due to the concavo-convex shape of the mold 104) at a desired position can be obtained by the manufacturing process of the above steps [1] to [5]. The obtained cured film can also be used as an optical member (including a case where it is used as one member of an optical member) such as a Fresnel lens or a diffraction grating. In such a case, an optical member having at least the substrate 102 and the cured film 109 having a pattern shape disposed on the substrate 102 can be obtained.

  In the method for manufacturing a film having a pattern shape according to the present embodiment, the repeating unit (shot) including the steps [1] to [5] can be repeated a plurality of times on the same substrate. By repeating the repeating unit (shot) consisting of the steps [1] to [5] a plurality of times, a plurality of desired concavo-convex pattern shapes (pattern shapes due to the concavo-convex shape of the mold 104) are formed at desired positions on the substrate to be processed. The cured film which has can be obtained.

  In particular, when the steps [1] to [5] are one shot, the time from the end of the first shot step [4] to the end of the second shot step [3] is 1.2. A film having a pattern shape can be manufactured with high throughput.

<Residual film removing step [6] for removing a part of the cured film>
Although the cured film obtained by the mold release step [5] has a specific pattern shape, a part of the film may remain in a region other than the region where the pattern shape is formed (hereinafter described) In this case, a part of such a film may be called a residual film). In such a case, as shown in FIG. 1 (f), the cured film (residual film) in the region to be removed is removed from the cured film having the obtained pattern shape to obtain a desired uneven pattern shape ( A cured product pattern 110 having a pattern shape due to the uneven shape of the mold 104 can be obtained.

  Here, as a method for removing the residual film, for example, a film (residual film) that is a concave portion of the cured film 109 is removed by a method such as etching, and the surface of the substrate 102 is exposed in the concave portion of the pattern of the cured film 109. A method is mentioned.

When the film in the concave portion of the cured film 109 is removed by etching, the specific method is not particularly limited, and a conventionally known method such as dry etching can be used. A conventionally known dry etching apparatus can be used for the dry etching. The source gas at the time of dry etching is appropriately selected depending on the elemental composition of the cured film that is the film to be etched, but CF ₄ , C ₂ F ₆ , C ₃ F ₈ , CCl ₂ F ₂ , CCl ₄ , CBrF ₃ , BCl ₃ , PCl ₃ , SF ₆ , Cl _{2 and} other halogen gases, O ₂ , CO, CO _{2 and} other oxygen atoms, He, N ₂ , Ar and other inert gases, H ₂ , NH ₃ The gas etc. can be used. These gases can be used in combination.

  The cured product pattern 110 having a desired concavo-convex pattern shape (pattern shape due to the concavo-convex shape of the mold 104) at a desired position can be obtained and cured by the manufacturing process of the above steps [1] to [6]. An article having an object pattern can be obtained. Furthermore, when processing the board | substrate 102 using the obtained hardened | cured material pattern 110, the board | substrate processing process (process [7]) mentioned later is performed.

  On the other hand, the obtained cured product pattern 110 can be used as an optical member (including a case where it is used as one member of an optical member) such as a diffraction grating or a polarizing plate, thereby obtaining an optical component. In such a case, an optical component having at least the substrate 102 and the cured product pattern 110 disposed on the substrate 102 can be obtained.

<Substrate processing step [7]>
The cured product pattern 110 having a concavo-convex pattern shape obtained by the method for producing a film having a pattern shape according to this embodiment is represented by a semiconductor element such as an LSI, a system LSI, a DRAM, an SDRAM, an RDRAM, or a D-RDRAM. It can also be used as a film for an interlayer insulating film included in an electronic component, and can also be used as a resist film at the time of manufacturing a semiconductor element.

  When the cured product pattern 110 is used as a resist film, etching, ion implantation, or the like is performed on a portion of the substrate (region 111 in FIG. 1F) whose surface is exposed in the etching process which is the process [6]. I do. At this time, the cured product pattern 110 functions as an etching mask. Thereby, the circuit structure 112 (FIG. 1G) based on the pattern shape of the cured product pattern 110 can be formed on the substrate 102. Thereby, the circuit board utilized by a semiconductor element etc. can be manufactured. In addition, electronic parts such as a display, a camera, and a medical device can be formed by providing an electronic member such as a circuit control mechanism on the circuit board.

  Similarly, an optical component can be obtained by performing etching or ion implantation using the cured product pattern 110 as a resist film.

  When a circuit board or an electronic component is manufactured, the cured product pattern 110 may be finally removed from the processed substrate, but may be left as a member constituting the element.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the technical scope of this invention is not limited to the Example described below.

Example 1
(1) Preparation of composition for optical imprint (a-1) First, the following components (A) and (B) are blended, and this is filtered through a 0.2 μm ultrahigh molecular weight polyethylene filter. The composition for photoimprinting (a-1) of Example 1 was prepared.

(1-1) Component (A): 94 parts by weight in total <A-1> Isobornyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: IB-XA): 9 parts by weight <A-2> Benzyl acrylate (Osaka Organic Chemistry) Industrial product, trade name: V # 160): 38 parts by weight <A-3> Neopentyl glycol diacrylate (manufactured by Kyoeisha Chemicals, trade name: NP-A): 47 parts by weight

(1-2) Component (B): 3 parts by weight in total <B-1> Irgacure 369 (manufactured by BASF): 3 parts by weight

(2) Production of cured film of photoimprinting composition 2 μL of photoimprinting composition (a-1) prepared on a silicon wafer on which an adhesion promoting layer having a thickness of 60 nm was formed as an adhesion layer was dropped. A quartz glass with a thickness of 1 mm was covered from above, and an area of 25 mm × 25 mm was filled with the composition for photoimprint (a-1).

Next, light emitted from a UV light source equipped with an ultrahigh pressure mercury lamp from quartz glass was applied to the coating film for 10 seconds through the quartz glass after passing through an interference filter described later. The interference filter used at the time of light irradiation is VPF-25C-10-15-31300 (manufactured by Sigma Kogyo Co., Ltd.). 1 mW / cm ² .

When the quartz glass is peeled off after light irradiation, a cured film (a-1-10) having an average film thickness of 3.2 μm is obtained by exposing the composition for photoimprint (a-1) on the silicon wafer at an exposure amount of 10 mJ / cm ^2. ) Was produced.

Similarly, light irradiation was performed for 200 seconds, and the cured film (a-1) having an average film thickness of 3.2 μm was obtained by exposing the photoimprinting composition (a-1) on the silicon wafer at an exposure amount of 200 mJ / cm ^2. -200).

(3-1) Measurement of Young's modulus of cured film The Young's modulus of the produced cured film (a-1-10) and cured film (a-1-200) was measured after the nanoindenter ( Measurement was carried out using Nano Indenter G200 (manufactured by Agilent Technologies). The Young's modulus is obtained in the range of 100 nm to 150 nm when the indenter is pushed down to the depth of 500 nm from the cured film surface at a certain point using the continuous stiffness measurement (CSM) method which is a dynamic test method. The average value of the modulus was measured, and this was repeated 15 times to calculate the average value of the measured values.

Each Young's modulus _{E 200} of the cured film (a-1-10) Young's modulus _{E 10} and cured film (a-1-200) is 5.94GPa and _{6.20GPa, E} 10 _/ E ₂₀₀ is zero. 958.

(3-2) Measurement of composite elastic modulus of cured film The composite elastic modulus of the produced cured film (a-1-10) and cured film (a-1-200) was measured after the nanoindenter after 24 hours from exposure. It measured using the apparatus (TI-950 TriboIndenter, Hystron company make). The composite elastic modulus is measured by using the Oliver-Pharr method, which is a quasi-static test method, to measure the composite elastic modulus when an indenter is pushed down to 200 nm in the depth direction from the surface of the cured film at a certain point. It calculated as an average value of the values measured by repeating the points.

The composite elastic modulus Er ₁₀ of the cured film (a-1-10) and the composite elastic modulus Er ₂₀₀ of the cured film (a-1-200) are 3.27 GPa and 3.51 GPa, respectively, and Er ₁₀ / Er ₂₀₀ is 0.932.

(4) Observation of nanoimprint pattern Next, by the method shown below, a nanoimprint pattern of the composition for photoimprint (a-1) is formed, and a 6.75 μm square region of the nanoimprint pattern is formed using an electron microscope. Observed.

(4-1) Arrangement Step A droplet of the composition for optical imprint (a-1) (one droplet) on a 300 mm silicon wafer on which an adhesion promoting layer having a thickness of 3 nm was formed as an adhesion layer by an inkjet method. 1440 drops in total was dropped. In addition, when each droplet was dropped, the droplets were dropped in an area of 26 mm length and 33 mm width so that the intervals between the droplets were almost uniform.

(4-2) Mold Contact Step, Light Irradiation Step Next, a 28 nm line and space (L / S) pattern is formed on the photoimprint composition (a-1) on the silicon wafer. Then, a quartz mold (length 26 mm, width 33 mm) that was not surface-treated was brought into contact.

Next, 30 seconds after contacting the quartz mold, UV light is applied to the composition for photoimprinting through the quartz mold using a UV light source (EXECURE 3000, manufactured by HOYA CANDEO OPTRONICS CORPORATION) equipped with a 200 W mercury xenon lamp. Irradiated. When irradiating UV light, an interference filter (VPF-50C-10-25-31300, manufactured by Sigma Kogyo Co., Ltd.) that selectively transmits a wavelength of 313 ± 5 nm is disposed between the UV light source and the quartz mold. did. The illuminance of UV light directly under the quartz mold was 40 mW / cm ² at a wavelength of 313 nm. Under the above conditions, UV light irradiation was performed for 0.75 seconds (exposure amount 30 mJ / cm ² ).

(4-3) Mold Release Step Next, the quartz mold was pulled up under the condition of 0.5 mm / s to release the mold from the photocured film.

(4-4) Observation of nanoimprint pattern using electron microscope When the nanoimprint pattern was observed using an electron microscope, a good pattern free of defects such as pattern collapse was formed.

  Pattern collapse refers to a state in which a 28 nm line and space (L / S) pattern is not linear but partially curved when observed from directly above.

Since the composition for optical imprint (a-1) can form a good pattern at an exposure amount of 30 mJ / cm ² , the thermal strain remaining in the next shot is 1 nm or less, and high alignment accuracy is obtained. There is expected.

(Example 2)
(1) Preparation of photoimprinting composition (a-2) Photoimprinting composition in the same manner as in Example 1 except that the component (B) was a compound represented by the following formula (b). (A-2) was prepared.

  <B-2> Irgacure OXE01 (manufactured by BASF): 3 parts by weight

(2) Production of cured film of composition for photoimprinting In the same manner as in Example 1, a film having a thickness of 3.2 μm of the composition for photoimprinting (a-2) on a silicon wafer was exposed to 10 mJ. Cured film (a-2-10) exposed at / cm ² and a cured film (3.2 μm thick) of the composition for photoimprint (a-2) exposed at an exposure amount of 200 mJ / cm ² ( a-2-200) was produced.

(3-1) Measurement of Young's modulus of cured film The Young's modulus of the produced cured film (a-2-10) and the cured film (a-2-200) was measured in the same manner as in Example 1. The Young's modulus E _{10 of the} film (a-2-10) and the Young's modulus E ₂₀₀ of the cured film (a-2-200) are 5.56 GPa and 6.18 GPa, respectively, and E ₁₀ / E ₂₀₀ is 0.900. Met.

(3-2) Measurement of composite elastic modulus of cured film When the composite elastic modulus of the produced cured film (a-2-10) and cured film (a-2-200) was measured in the same manner as in Example 1. each composite elastic modulus _{Er 200} of composite elastic modulus _{Er 10} and the cured film of the cured film (a-2-10) (a- 2-200) is 3.01GPa and _{3.52GPa, Er} 10 _/ Er ₂₀₀ Was 0.855.

(4) Observation of nanoimprint pattern In the same manner as in Example 1, a nanoimprint pattern of the composition for photoimprint (a-2) was formed, and the nanoimprint pattern was observed using an electron microscope. A good pattern without defects such as was formed.

Since the composition for optical imprint (a-2) can form a good pattern at an exposure amount of 30 mJ / cm ² , the thermal strain remaining in the next shot is 1 nm or less, and high alignment accuracy is obtained. There is expected.

(Comparative Example 1)
(1) Preparation of composition for optical imprinting (b-1) Light in the same manner as in Example 1 except that the component (B) was a compound represented by the following formula (c) and formula (d). An imprinting composition (b-1) was prepared.

<B-3> Lucirin TPO (made by BASF): 4 parts by weight <B-4> Darocur 1173 (made by BASF): 4 parts by weight

(2) Production of cured film of composition for photoimprinting In the same manner as in Example 1, a film having a thickness of 3.2 μm of the composition for photoimprinting (b-1) on a silicon wafer was exposed to 10 mJ. Cured film (b-1-10) exposed at / cm ² and a cured film (3.2 μm thick film of photoimprinting composition (b-1)) exposed at an exposure amount of 200 mJ / cm ² ( b-1-200).

(3-1) Measurement of Young's modulus of cured film The Young's modulus of the produced cured film (b-1-10) and cured film (b-1-200) was measured in the same manner as in Example 1, and the cured film was cured. film (b-1-10) each Young's modulus _{E 200} Young's modulus _{E 10} and the cured film (b-1-200) is of a 4.87GPa and _{5.73GPa, E} 10 _/ E ₂₀₀ is 0.850 Met.

(3-2) Measurement of composite elastic modulus of cured film In the same manner as in Example 1, the composite elastic modulus of the produced cured film (b-1-10) and cured film (b-1-200) was measured. The composite elastic modulus Er ₁₀ of the cured film (b-1-10) and the composite elastic modulus Er ₂₀₀ of the cured film (b-1-200) are 2.50 GPa and 3.18 GPa, respectively, and Er ₁₀ / Er ₂₀₀ Was 0.786.

(4) Observation of nanoimprint pattern When the nanoimprint pattern of the composition for optical imprint (b-1) was formed by the same method as Example 1, and the said nanoimprint pattern was observed using the electron microscope, it was about 50%. The pattern had a defect such as falling down.

When the minimum exposure amount necessary for the composition for optical imprint (b-1) to form a good pattern free of defects such as pattern collapse is examined, an exposure amount of 75 mJ / cm ² or more is required. I understood it. At the exposure amount, the thermal strain remaining in the next shot is expected to be 2.9 nm or more, and the alignment accuracy is expected to be lower than those in Examples 1-12.

(Example 3)
(1) Preparation of photoimprinting composition (a-3) Photoimprinting composition in the same manner as in Example 1 except that component (B) was a compound represented by the following formula (e). (A-3) was prepared.

  <B-5> Irgacure 819 (manufactured by BASF): 3 parts by weight

(2) Production of cured film of composition for photoimprinting In the same manner as in Example 1, a film having a thickness of 3.2 μm of the composition for photoimprinting (a-3) on a silicon wafer was exposed to 10 mJ. Cured film (a-3-10) exposed at / cm ² and a cured film (3.2 μm thick film of photoimprinting composition (a-3)) exposed at an exposure dose of 200 mJ / cm ² ( a-3-200).

(3-1) Measurement of Young's modulus of cured film Not performed.

(3-2) Measurement of composite elastic modulus of cured film In the same manner as in Example 1, the composite elastic modulus of the produced cured film (a-3-10) and cured film (a-3-200) was measured. The composite elastic modulus Er ₁₀ of the cured film (a-3-10) and the composite elastic modulus Er ₂₀₀ of the cured film (a-3-200) are 3.14 GPa and 3.49 GPa, respectively, and Er ₁₀ / Er ₂₀₀ Was 0.900.

(4) Observation of nanoimprint pattern From the result of the composite elastic modulus, when the nanoimprint pattern of the composition for photoimprint (a-3) is formed by the same method as in Example 1, there is no defect such as pattern collapse. It is estimated that a pattern is formed.

It is considered that the composition for optical imprint (a-3) can form a good pattern at an exposure amount of 30 mJ / cm ² , and the thermal strain remaining in the next shot is 1 nm or less, and high alignment accuracy is obtained. Expected to be.

Example 4
(1) Preparation of composition for photoimprint (a-4) Composition for photoimprint, except that component (B) was a compound represented by the following formula (c) (A-4) was prepared.

  <B-3> Lucirin TPO (manufactured by BASF): 3 parts by weight

(2) Production of cured film of composition for photoimprinting In the same manner as in Example 1, a film having a thickness of 3.2 μm of the composition for photoimprinting (a-4) on a silicon wafer was exposed to 10 mJ. Cured film (a-4-10) exposed at / cm ² and a cured film (3.2 μm thick film of photoimprinting composition (a-4)) exposed at an exposure amount of 200 mJ / cm ² ( a-4-200).

(3-1) Measurement of Young's modulus of cured film Not performed.

(3-2) Measurement of composite elastic modulus of cured film When the composite elastic modulus of the produced cured film (a-4-10) and cured film (a-4-200) was measured in the same manner as in Example 1. The composite elastic modulus Er ₁₀ of the cured film (a-4-10) and the composite elastic modulus Er ₂₀₀ of the cured film (a-4-200) are 3.22 GPa and 3.64 GPa, respectively, and Er ₁₀ / Er ₂₀₀ Was 0.885.

(4) Observation of nanoimprint pattern From the result of the composite elastic modulus, when the nanoimprint pattern of the composition for photoimprint (a-4) is formed by the same method as in Example 1, there is no defect such as pattern collapse. It is estimated that a pattern is formed.

The composition for optical imprint (a-4) is considered to be able to form a good pattern at an exposure amount of 30 mJ / cm ² , and the thermal distortion remaining in the next shot is 1 nm or less, and high alignment accuracy is obtained. Expected to be.

(Example 5)
(1) Preparation of composition for photoimprint (a-5) The component (B) is a compound represented by the following formula (c), and the components other than the component (A) and the component (B) As (C), a composition for photoimprinting (a-5) was prepared in the same manner as in Example 1 except that the compound represented by the following formula (f) was used.

<B-3> Lucirin TPO (manufactured by BASF): 3 parts by weight <C-1> 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry): 0.5 part by weight

(2) Production of cured film of composition for photoimprinting In the same manner as in Example 1, a film having a thickness of 3.2 μm of the composition for photoimprinting (a-5) on a silicon wafer was exposed to 10 mJ. Cured film (a-5-10) exposed at / cm ² and a cured film (3.2 m thick) of the photoimprinting composition (a-5) exposed at an exposure dose of 200 mJ / cm ² ( a-5-200).

(3-1) Measurement of Young's modulus of cured film The Young's modulus of the produced cured film (a-5-10) and cured film (a-5-200) was measured in the same manner as in Example 1, and the cured film was cured. film (a-5-10), respectively the Young's modulus _{E 200} Young's modulus _{E 10} and the cured film (a-5-200) is of a 4.83GPa and _{5.05GPa, E} 10 _/ E ₂₀₀ is 0.956 Met.

(3-2) Measurement of composite elastic modulus of cured film In the same manner as in Example 1, the composite elastic modulus of the produced cured film (a-5-10) and cured film (a-5-200) was measured. The composite elastic modulus Er _{10 of} the cured film (a-5-10) and the composite elastic modulus Er ₂₀₀ of the cured film (a-5-200) are 3.13 GPa and 3.48 GPa, respectively, and Er ₁₀ / Er ₂₀₀ Was 0.899.

(4) Observation of nanoimprint pattern In the same manner as in Example 1, a nanoimprint pattern of the composition for photoimprint (a-5) was formed, and the nanoimprint pattern was observed using an electron microscope. A good pattern without defects such as was formed.

Since the composition for optical imprint (a-5) can form a good pattern at an exposure amount of 30 mJ / cm ² , the thermal strain remaining in the next shot is 1 nm or less, and high alignment accuracy is obtained. There is expected.

(Example 6)
(1) Preparation of composition for photoimprint (a-6) The following component (A), component (B), and additive component (C) were blended, and this was made of ultra high molecular weight polyethylene of 0.2 μm. It filtered with the filter and the composition for optical imprint (a-6) of Example 6 was prepared.

(1-1) Component (A): 100 parts by weight in total <A-1> Isobornyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: IB-XA): 75 parts by weight <A-4> 1,6-hexanediol Diacrylate (Kyoeisha Chemical Co., Ltd., trade name: 1.6HX-A): 25 parts by weight

(1-2) Component (B): 3 parts by weight in total <B-3> Lucirin TPO (manufactured by BASF): 3 parts by weight

(1-3) Additive component (C) other than component (A) and component (B): 0.5 parts by weight in total <C-1> 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry): 0 .5 parts by weight

(2) Production of cured film of composition for photoimprinting In the same manner as in Example 1, a film having a thickness of 3.2 μm of the composition for photoimprinting (a-6) on a silicon wafer was exposed to 10 mJ. Cured film (a-6-10) exposed at / cm ² and a cured film (3.2 μm thick film of photoimprinting composition (a-6)) exposed at an exposure dose of 200 mJ / cm ² ( a-6-200).

(3-1) Measurement of Young's modulus of cured film The Young's modulus of the produced cured film (a-6-10) and cured film (a-6-200) was measured in the same manner as in Example 1, and the cured film was cured. film (a-6-10), respectively the Young's modulus _{E 200} Young's modulus _{E 10} and the cured film (a-6-200) is of a 4.33GPa and _{4.13GPa, E} 10 _/ E ₂₀₀ 1.05 Met.

(3-2) Measurement of composite elastic modulus of cured film When the composite elastic modulus of the produced cured film (a-6-10) and cured film (a-6-200) was measured in the same manner as in Example 1. The composite elastic modulus Er _{10 of} the cured film (a-6-10) and the composite elastic modulus Er ₂₀₀ of the cured film (a-6-200) are 2.94 GPa and 2.96 GPa, respectively, Er ₁₀ / Er ₂₀₀ Was 0.993.

(4) Observation of nanoimprint pattern In the same manner as in Example 1, a nanoimprint pattern of the composition for photoimprint (a-6) was formed, and the nanoimprint pattern was observed using an electron microscope. A good pattern without defects such as was formed.

Since the composition for optical imprint (a-6) can form a good pattern at an exposure amount of 30 mJ / cm ² , the thermal strain remaining in the next shot is 1 nm or less, and high alignment accuracy is obtained. There is expected.

(Example 7)
(1) Preparation of composition for photoimprint (a-7) As an additive component (C) other than component (A) and component (B), compounds represented by the following formula (f) and formula (g) are used. A photoimprinting composition (a-7) was prepared in the same manner as in Example 6 except that it was used.

<C-1> 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry): 0.5 part by weight <C-2> 0.5 part by weight of polyoxyethylene stearyl ether SR-705 (manufactured by Aoki Yushi)

(2) Production of cured film of composition for photoimprinting In the same manner as in Example 1, a film having a thickness of 3.2 μm of the composition for photoimprinting (a-7) on a silicon wafer was exposed to 10 mJ. Cured film (a-7-10) exposed at / cm ² and a cured film (3.2 μm thick film of photoimprinting composition (a-7)) exposed at an exposure dose of 200 mJ / cm ² ( a-7-200).

(3-1) Measurement of Young's modulus of cured film The Young's modulus of the produced cured film (a-7-10) and the cured film (a-7-200) was measured in the same manner as in Example 1. film (a-7-10), respectively the Young's modulus _{E 200} Young's modulus _{E 10} and the cured film (a-7-200) is of a 4.17GPa and _{4.27GPa, E} 10 _/ E ₂₀₀ is 0.977 Met.

(3-2) Measurement of composite elastic modulus of cured film When the composite elastic modulus of the produced cured film (a-7-10) and cured film (a-7-200) was measured in the same manner as in Example 1. The composite elastic modulus Er ₁₀ of the cured film (a-7-10) and the composite elastic modulus Er ₂₀₀ of the cured film (a-7-200) are 2.81 GPa and 3.11 GPa, respectively, Er ₁₀ / Er ₂₀₀ Was 0.904.

(4) Observation of nanoimprint pattern In the same manner as in Example 1, a nanoimprint pattern of the composition for photoimprint (a-7) was formed, and the nanoimprint pattern was observed using an electron microscope. A good pattern without defects such as was formed.

Since the composition for optical imprint (a-7) can form a good pattern at an exposure amount of 30 mJ / cm ² , the thermal strain remaining in the next shot is 1 nm or less, and high alignment accuracy is obtained. There is expected.

(Comparative Example 2)
(1) Preparation of composition for photoimprint (b-2) Composition for photoimprint, except that component (B) was a compound represented by the following formula (h) (B-2) was prepared.

  <B-6> Irgacure 651 (manufactured by BASF): 3 parts by weight

(2) Production of cured film of composition for photoimprinting In the same manner as in Example 1, a film having a thickness of 3.2 μm of the composition for photoimprinting (b-2) on a silicon wafer was exposed to 200 mJ. A cured film (b-2-200) exposed at / cm ² was produced. The film having a thickness of 3.2 μm of the composition for photoimprint (b-2) was not a cured film at an exposure amount of 10 mJ / cm ² , but became a film with insufficient curing (b-2-10). .

(3-1) Measurement of Young's modulus of cured film The Young's modulus of the produced cured film (b-2-200) was measured in the same manner as in Example 1, and the Young of the cured film (b-2-200) was measured. The rate E ₂₀₀ was 4.60 GPa. The Young's modulus _{E 10} of the cured insufficient film (b-2-10) is almost _zero, E 10 _{/ E 200} was judged to be substantially zero.

(3-2) Measurement of composite elastic modulus of cured film When the composite elastic modulus of the produced cured film (b-2-200) was measured in the same manner as in Example 1, the cured film (b-2-200) was measured. The composite elastic modulus Er ₂₀₀ was 3.11 GPa. The composite elastic modulus _{Er 10} of cured insufficient film (b-2-10) is almost _zero, Er 10 _{/ Er 200} was judged to be substantially zero.

(4) Observation of nanoimprint pattern A nanoimprint pattern of the composition for photoimprint (b-2) was formed in the same manner as in Example 1, and the nanoimprint pattern was observed using an electron microscope. The pattern had a defect such as falling down.

When the minimum exposure amount necessary for the composition for optical imprint (b-2) to form a good pattern free of defects such as pattern collapse is examined, an exposure amount of 75 mJ / cm ² or more is necessary. I understood it. At the exposure amount, the thermal strain remaining in the next shot is expected to be 2.9 nm or more, and the alignment accuracy is expected to be lower than those in Examples 1-12.

(Comparative Example 3)
(1) Preparation of composition for optical imprint (b-3) The composition for optical imprint (b-3) was prepared in the same manner as in Comparative Example 2 except that the component (A) was a compound shown below. Prepared.

<A-1> Isobornyl acrylate (Kyoeisha Chemical Co., Ltd., trade name: IB-XA): 75 parts by weight <A-4> 1,6-hexanediol diacrylate (Kyoeisha Chemical Co., Ltd., trade name: 1.6HX-) A): 25 parts by weight

(2) Production of cured film of composition for photoimprinting In the same manner as in Example 1, a film having a thickness of 3.2 μm of the composition for photoimprinting (b-3) on a silicon wafer was exposed to 200 mJ. A cured film (b-3-200) exposed at / cm ² was produced. The film having a thickness of 3.2 μm of the composition for photoimprint (b-3) did not become a cured film at an exposure amount of 10 mJ / cm ² , but became a film with insufficient curing (b-3-10). .

(3-1) Measurement of Young's modulus of cured film Not performed.

(3-2) Measurement of composite elastic modulus of cured film When the composite elastic modulus of the produced cured film (b-3-200) was measured in the same manner as in Example 1, the cured film (b-3-200) was measured. The composite elastic modulus Er ₂₀₀ was 3.11 GPa. The composite elastic modulus _{Er 10} of cured insufficient film (b-3-10) is almost _zero, Er 10 _{/ Er 200} was judged to be substantially zero.

(4) Observation of nanoimprint pattern When the nanoimprint pattern of the composition for photoimprint (b-3) is formed by the same method as in Example 1, it is presumed that the pattern has many defects such as collapse.

  In addition, it is considered that the minimum exposure amount required for the photoimprinting composition (b-3) to form a good pattern free of defects such as pattern collapse is increased, and there is a thermal strain remaining in the next shot. It is expected to be 2.9 nm or more, and it is expected that the alignment accuracy is lower than in Examples 1-12.

(Example 8)
(1) Preparation of composition for photoimprint (a-8) The following component (A), component (B), and additive component (C) were blended, and this was made of ultra high molecular weight polyethylene of 0.2 μm. It filtered with the filter and the composition for optical imprint (a-8) of Example 8 was prepared.

(1-1) Component (A): 100 parts by weight in total <A-2> Benzyl acrylate (manufactured by Osaka Organic Chemical Industry, trade name: V # 160): 50 parts by weight <A-5> dimethylol tricyclodecandi Acrylate (Kyoeisha Chemical Co., Ltd., trade name: DCP-A): 50 parts by weight

(1-2) Component (B): 3 parts by weight in total <B-3> Lucirin TPO (manufactured by BASF): 3 parts by weight

(1-3) Additive component (C) other than component (A) and component (B): 2.1 parts by weight in total <C-1> 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry): 0 .5 parts by weight <C-3> polyoxyethylene stearyl ether SR-730 (Aoki Yushi): 1.6 parts by weight

(2) Production of cured film of composition for photoimprinting In the same manner as in Example 1, a film having a thickness of 3.2 μm of the composition for photoimprinting (a-8) on a silicon wafer was exposed to 10 mJ. Cured film (a-8-10) exposed at / cm ² and a cured film (3.2 μm thick film of photoimprinting composition (a-8)) exposed at an exposure dose of 200 mJ / cm ² ( a-8-200).

(3-1) Measurement of Young's modulus of cured film Not performed.

(3-2) Measurement of composite elastic modulus of cured film When the composite elastic modulus of the produced cured film (a-8-10) and cured film (a-8-200) was measured in the same manner as in Example 1. each composite elastic modulus _{Er 200} of composite elastic modulus _{Er 10} and the cured film of the cured film (a-8-10) (a- 8-200) is 3.51GPa and _{3.99GPa, Er} 10 _/ Er ₂₀₀ Was 0.880.

(4) Observation of nanoimprint pattern From the result of the composite elastic modulus, when the nanoimprint pattern of the composition for photoimprint (a-8) is formed by the same method as in Example 1, there is no defect such as pattern collapse. It is estimated that a pattern is formed.

Moreover, it is thought that the composition for optical imprint (a-8) can form a favorable pattern with the exposure amount of 30 mJ / cm ² , the thermal strain remaining in the next shot is 1 nm or less, and high alignment accuracy is obtained. Expected to be obtained.

Example 9
(1) Preparation of composition for photoimprint (a-9) Composition for photoimprint (a-9) was carried out in the same manner as in Example 8, except that component (A) was used in the ratio of the compounds shown below. ) Was prepared.

(1-1) Component (A): 100 parts by weight in total <A-2> Benzyl acrylate (manufactured by Osaka Organic Chemical Industry, trade name: V # 160): 60 parts by weight <A-5> dimethylol tricyclodecandi Acrylate (Kyoeisha Chemical Co., Ltd., trade name: DCP-A): 40 parts by weight

(2) Production of cured film of composition for photoimprinting In the same manner as in Example 1, a film having a thickness of 3.2 μm of the composition for photoimprinting (a-9) on a silicon wafer was exposed to 10 mJ. Cured film (a-9-10) exposed at / cm ² and a cured film (3.2 μm thick film of photoimprinting composition (a-9)) exposed at an exposure dose of 200 mJ / cm ² ( a-9-200).

(3-1) Measurement of Young's modulus of cured film Not performed.

(3-2) Measurement of composite elastic modulus of cured film When the composite elastic modulus of the produced cured film (a-9-10) and cured film (a-9-200) was measured in the same manner as in Example 1. The composite elastic modulus Er ₁₀ of the cured film (a-9-10) and the composite elastic modulus Er ₂₀₀ of the cured film (a-9-200) are 3.49 GPa and 3.82 GPa, respectively, Er ₁₀ / Er ₂₀₀ Was 0.914.

(4) Observation of nanoimprint pattern From the result of the composite elastic modulus, when the nanoimprint pattern of the composition for photoimprint (a-9) is formed by the same method as in Example 1, there is no defect such as pattern collapse. It is estimated that a pattern is formed.

Moreover, it is thought that the composition for optical imprint (a-9) can form a favorable pattern with the exposure amount of 30 mJ / cm ² , the thermal strain remaining in the next shot is 1 nm or less, and high alignment accuracy is obtained. Expected to be obtained.

(Example 10)
(1) Preparation of composition for optical imprint (a-10) The following component (A), component (B), and additive component (C) are blended, and this is made of ultra high molecular weight polyethylene of 0.2 μm. It filtered with the filter and the composition for optical imprint (a-10) of Example 10 was prepared.

(1-1) Component (A): 100 parts by weight in total <A-2> Benzyl acrylate (manufactured by Osaka Organic Chemical Industry, trade name: V # 160): 50 parts by weight <A-6> Phenylethylene glycol diacrylate: 50 parts by weight

(1-2) Component (B): 3 parts by weight in total <B-3> Lucirin TPO (manufactured by BASF): 3 parts by weight

(1-3) Additive component (C) other than component (A) and component (B): 1.3 parts by weight in total <C-1> 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry): 0 .5 parts by weight <C-3> polyoxyethylene stearyl ether Emulgen 320P (manufactured by Kao): 0.8 parts by weight

(2) Production of cured film of composition for photoimprinting In the same manner as in Example 1, a film having a thickness of 3.2 μm of the composition for photoimprinting (a-10) on a silicon wafer was exposed to 10 mJ. Cured film (a-10-10) exposed at / cm ² and a cured film (3.2 μm thick film of photoimprinting composition (a-10)) exposed at an exposure dose of 200 mJ / cm ² ( a-10-200).

(3-1) Measurement of Young's modulus of cured film Not performed.

(3-2) Measurement of composite elastic modulus of cured film In the same manner as in Example 1, the composite elastic modulus of the produced cured film (a-10-10) and cured film (a-10-200) was measured. The composite elastic modulus Er _{10 of} the cured film (a-10-10) and the composite elastic modulus Er ₂₀₀ of the cured film (a-10-200) are 3.25 GPa and 3.76 GPa, respectively, Er ₁₀ / Er ₂₀₀ Was 0.864.

(4) Observation of nanoimprint pattern From the result of the composite elastic modulus, when the nanoimprint pattern of the composition for photoimprint (a-10) is formed by the same method as in Example 1, there is no defect such as pattern collapse. It is estimated that a pattern is formed.

Moreover, it is thought that the composition for optical imprint (a-10) can form a favorable pattern with the exposure amount of 30 mJ / cm ² , the thermal strain remaining in the next shot is 1 nm or less, and has high alignment accuracy. Expected to be obtained.

(Example 11)
(1) Preparation of composition for photoimprint (a-11) Composition for photoimprint (a-11) was prepared in the same manner as in Example 10 except that component (A) was a compound shown below. Prepared.

<A-2> benzyl acrylate (trade name: V # 160, manufactured by Osaka Organic Chemical Industry): 50 parts by weight <A-7> m-xylylene diacrylate: 50 parts by weight

(2) Production of cured film of composition for photoimprinting In the same manner as in Example 1, a film having a thickness of 3.2 μm of the composition for photoimprinting (a-11) on a silicon wafer was exposed to 10 mJ. Cured film (a-11-10) exposed at / cm ² and a cured film (3.2 μm thick film of photoimprinting composition (a-11)) exposed at an exposure dose of 200 mJ / cm ² ( a-11-200).

(3-1) Measurement of Young's modulus of cured film Not performed.

(3-2) Measurement of composite elastic modulus of cured film When the composite elastic modulus of the produced cured film (a-11-10) and cured film (a-11-200) was measured in the same manner as in Example 1. The composite elastic modulus Er ₁₀ of the cured film (a-11-10) and the composite elastic modulus Er ₂₀₀ of the cured film (a-11-200) are 3.73 GPa and 4.04 GPa, respectively, Er ₁₀ / Er ₂₀₀ Was 0.923.

(4) Observation of nanoimprint pattern From the result of the composite elastic modulus, when the nanoimprint pattern of the composition for photoimprint (a-11) is formed by the same method as in Example 1, there is no defect such as pattern collapse. It is estimated that a pattern is formed.

Moreover, it is thought that the composition for optical imprint (a-11) can form a favorable pattern with the exposure amount of 30 mJ / cm ² , the thermal strain remaining in the next shot is 1 nm or less, and has high alignment accuracy. Expected to be obtained.

(Example 12)
(1) Preparation of composition for photoimprint (a-12) Composition for photoimprint (a-12) was prepared in the same manner as in Example 10 except that component (A) was a compound shown below. Prepared.

<A-2> benzyl acrylate (manufactured by Osaka Organic Chemical Industry, trade name: V # 160): 45 parts by weight <A-7> m-xylylene acrylate: 50 parts by weight

  <A-8> 2-naphthylmethyl acrylate: 5 parts by weight

(2) Preparation of cured film of composition for photoimprinting In the same manner as in Example 1, a film having a thickness of 3.2 μm of the composition for photoimprinting (a-12) on a silicon wafer was exposed to 10 mJ. Cured film (a-12-10) exposed at / cm ² and a cured film (3.2 m thick) of the photoimprinting composition (a-12) exposed at an exposure dose of 200 mJ / cm ² ( a-12-200).

(3-1) Measurement of Young's modulus of cured film Not performed.

(3-2) Measurement of composite elastic modulus of cured film Similar to Example 1, the composite elastic modulus of the produced cured film (a-12-10) and cured film (a-12-200) was measured. The composite elastic modulus Er ₁₀ of the cured film (a-12-10) and the composite elastic modulus Er ₂₀₀ of the cured film (a-12-200) are 3.53 GPa and 4.00 GPa, respectively, and Er ₁₀ / Er ₂₀₀ Was 0.883.

(4) Observation of nanoimprint pattern From the result of the composite elastic modulus, when the nanoimprint pattern of the composition for photoimprint (a-12) is formed by the same method as in Example 1, there is no defect such as pattern collapse. It is estimated that a pattern is formed.

Moreover, it is thought that the composition for optical imprint (a-12) can form a favorable pattern with the exposure amount of 30 mJ / cm < ² >, the thermal distortion which remains in the next shot is 1 nm or less, and has high alignment precision. Expected to be obtained.

(Comparative Example 4)
(1) Preparation of composition for photoimprint (b-4) Composition for photoimprint (b-4) was prepared in the same manner as in Example 1 except that the component (B) was a compound shown below. Prepared.

  <B-3> Lucirin TPO (manufactured by BASF): 0.5 part by weight

(2) Production of cured film of composition for photoimprinting In the same manner as in Example 1, a film having a thickness of 3.2 μm of the composition for photoimprinting (b-4) on a silicon wafer was exposed to 200 mJ. A cured film (b-4-200) exposed at / cm ² was produced. The film having a thickness of 3.2 μm of the composition for photoimprint (b-4) did not become a cured film at an exposure amount of 10 mJ / cm ² , but became a film with insufficient curing (b-4-10). .

(3-1) Measurement of Young's modulus of cured film Not performed.

(3-2) Measurement of composite elastic modulus of cured film When the composite elastic modulus of the produced cured film (b-4-200) was measured in the same manner as in Example 1, the cured film (b-4-200) was measured. The composite elastic modulus Er ₂₀₀ was 2.73 GPa. The composite elastic modulus _{Er 10} of cured insufficient film (b-4-10) is almost _zero, Er 10 _{/ Er 200} was judged to be substantially zero.

(4) Observation of nanoimprint pattern From the result of the composite elastic modulus, when the nanoimprint pattern of the composition for photoimprint (b-4) is formed by the same method as in Example 1, the pattern has many defects such as collapse. Presumed to occur.

  In addition, it is considered that the minimum exposure amount required for the photoimprinting composition (b-4) to form a good pattern free of defects such as pattern collapse increases, and the thermal distortion remaining in the next shot is increased. It is expected to be 2.9 nm or more, and it is expected that the alignment accuracy is lower than in Examples 1-12.

  The results of Examples and Comparative Examples are summarized in Table 1, Table 2, and Table 3.

(note)
* Judged to be almost zero due to insufficient curing.

Pattern ○: Good pattern without pattern collapse Pattern x: Pattern with defects such as pattern collapse Positioning accuracy ○: Thermal strain remaining in the next shot is 1 nm or less Positioning accuracy ×: Remains in the next shot Thermal strain is 2.9nm or more

(note)
* Judged to be almost zero due to insufficient curing.

Pattern ○: Good pattern without pattern collapse Pattern x: Pattern with defects such as pattern collapse Positioning accuracy ○: Thermal strain remaining in the next shot is 1 nm or less Positioning accuracy ×: Remains in the next shot Thermal strain is 2.9nm or more

(note)
* Judged to be almost zero due to insufficient curing.

DESCRIPTION OF SYMBOLS 101 Photoimprinting composition 102 Substrate 103 Substrate side alignment mark 104 Mold 105 Mold side alignment mark 106 Coating film 107 Irradiation light 108 Cured film 109 Cured film having a pattern shape 110 Cured product pattern 111 Surface exposed substrate Part 112 Circuit structure

Claims (38)

It has at least a component (A) that is a polymerizable compound and a component (B) that is a photopolymerization initiator, and satisfies the following formula (1) and the following formula (2). Composition.
0.800 ≦ Er ₁₀ / Er ₂₀₀ (1)
2.55 GPa ≦ Er ₁₀ (2)
(In Formula (1) and Formula (2), Er ₁₀ represents the composite elastic modulus (GPa) of the photocured film obtained when the composition for photoimprinting was exposed at an exposure amount of 10 mJ / cm ² , Er ₂₀₀ represents the composite elastic modulus (GPa) of the photocured film obtained when the composition for photoimprinting is exposed at an exposure amount of 200 mJ / cm ^2. ) The composition for photoimprinting according to claim 1, further satisfying the following formula (3):
0.855 ≦ Er ₁₀ / Er ₂₀₀ ≦ 0.993 (3)
(In Formula (3), Er ₁₀ represents the composite elastic modulus (GPa) of the photocured film obtained when the composition for photoimprinting was exposed at an exposure amount of 10 mJ / cm ² , and Er ₂₀₀ represents an exposure amount of 200 mJ. (The composite elastic modulus (GPa) of the photocured film obtained when the composition for photoimprinting is exposed at / cm ² is shown.) The composition for photoimprinting according to claim 1 or 2, further satisfying the following formula (4):
2.81 GPa ≦ Er ₁₀ ≦ 3.73 GPa (4)
(In Formula (4), Er ₁₀ represents the composite elastic modulus (GPa) of the photocured film obtained when the composition for photoimprinting is exposed at an exposure amount of 10 mJ / cm ^2. ) It has at least a component (A) that is a polymerizable compound and a component (B) that is a photopolymerization initiator, and satisfies the following formula (5) and the following formula (6). Composition.
0.880 ≦ E10 / E ₂₀₀ (5)
4.00 GPa ≦ E ₁₀ (6)
(In the formulas (5) and (6), E ₁₀ represents the Young's modulus (GPa) of the photocured film obtained when the composition for photoimprinting was exposed at an exposure amount of 10 mJ / cm ² , and E ₂₀₀ Indicates the Young's modulus (GPa) of the cured film obtained when the composition for photoimprinting is exposed at an exposure amount of 200 mJ / cm ^2. ) The composition for photoimprinting according to claim 4, further satisfying the following formula (7).
0.956 ≦ E ₁₀ / E ₂₀₀ ≦ 1.05 (7)
In (Equation _{(7), E 10} represents a Young's modulus of the cured film obtained upon exposing the light imprint composition at an exposure dose of 10 mJ / cm ² a _{(GPa), E 200} exposure dose 200 mJ / cm ² shows the Young's modulus (GPa) of the cured film obtained when the composition for photoimprinting is exposed to ² ). The composition for photoimprinting according to claim 4 or 5, further satisfying the following formula (8).
4.17 GPa ≦ E ₁₀ ≦ 5.94 GPa (8)
(In the formula _{(8), E 10} represents a Young's modulus of the cured film obtained upon exposing the light imprint composition at an exposure dose of 10 mJ / cm ² a (GPa).)   The said (A) component is 90% or more of the said composition for optical imprints, The composition for optical imprints as described in any one of Claims 1-6 characterized by the above-mentioned.   The said component (A) has a (meth) acryl compound as a main component, The composition for optical imprints as described in any one of Claims 1-7 characterized by the above-mentioned.   The said component (A) has a monofunctional (meth) acryl compound and a polyfunctional (meth) acryl compound, The composition for optical imprint of Claim 5 characterized by the above-mentioned.   The component (A) is isobornyl acrylate, benzyl acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, dimethylol tricyclodecane diacrylate, phenylethylene glycol diacrylate, m-xylylene diacrylate, The composition for photoimprints according to any one of claims 1 to 9, comprising at least one of 2-naphthylmethyl acrylate.   The component (A) is composed of isobornyl acrylate, benzyl acrylate, and neopentyl glycol diacrylate, or composed of isobornyl acrylate and 1,6-hexanediol diacrylate. The composition for photoimprints as described in any one of Claims 1-10 characterized by the above-mentioned.   The composition for photoimprinting according to claim 7, wherein the component (A) is composed of isobornyl acrylate, benzyl acrylate, and neopentyl glycol diacrylate.   The component (B) contains at least one of an alkylphenone-based polymerization initiator, an oxime ester-based polymerization initiator, and an acylphosphine oxide-based polymerization initiator. The composition for optical imprints described in 1. The said component (B) contains the compound in any one of following formula (a), (b), (c), and (e), The composition for optical imprint of Claim 13 characterized by the above-mentioned. .



  The composition for photoimprints as described in any one of Claims 1-14 characterized by including a sensitizer. 16. The photoimprinting composition according to claim 15, wherein the sensitizer is a compound represented by the following formula (f) or the following formula (i).

  It has a mold release agent, The composition for optical imprints as described in any one of Claims 1-16 characterized by the above-mentioned. The said mold release agent is shown by following formula (O), The composition for optical imprint of Claim 17 characterized by the above-mentioned.
(In the formula (O), Rc is a monovalent hydrocarbon group having 5 to 50 carbon atoms, Ra represents an alkylene group, m is an integer of 1 to 10, X is an alkoxy group, A hydroxyl group, a carboxyl group, a pyridyl group, a silanol group, or a sulfo group) The composition for photoimprinting according to claim 18, wherein the release agent contains at least one of compounds represented by the following formulas (g), (j), and (l).

Monofunctional compound composed of isobornyl acrylate or isobornyl acrylate and benzyl acrylate, and polyfunctional compound composed of neopentyl glycol diacrylate, 1,6-hexanediol diacrylate or dimethylol tricyclodecane diacrylate And (B) component containing at least one of the compounds represented by the following formulas (a), (b), (c), and (e). A composition for photoimprinting, wherein the weight ratio of the functional compound to the polyfunctional compound is 1: 1 to 3: 1.


21. The composition for optical imprinting according to claim 20, further comprising a compound represented by the following formula (f).
The composition for photoimprinting according to claim 20 or 21, further comprising at least one of compounds represented by the following formulas (g), (j), and (l).

  The optical imprinting composition according to any one of claims 20 to 22, wherein 90% or more of the optical imprinting composition is the component (A).   24. The photoimprint composition according to any one of claims 1 to 23, wherein a thickness of a photocured film obtained when the photoimprint composition is exposed is 100 nm or less.   Hardened | cured material which hardened the said composition for optical imprints as described in any one of Claims 1-24. A step [1] of disposing the composition for photoimprinting according to any one of claims 1 to 25 on a substrate;
Contacting the composition for photoimprinting with a mold having an original pattern for transferring a pattern shape [2];
A step [3] of aligning the substrate and the mold;
Irradiating light to the photo-imprinting composition to form a cured film [4];
A step [5] of separating the cured film and the mold;
A method for producing a film having a pattern shape, characterized by comprising: 27. The method for producing a film having a pattern shape according to claim 26, wherein an exposure amount in the step of irradiating the composition for photoimprinting with light to form a cured film is 75 mJ / cm ² or less. 27. The method for producing a film having a pattern shape according to claim 26, wherein an exposure dose in the step of irradiating the composition for photoimprinting with light to form a cured film is 30 mJ / cm ² or less.   The method of manufacturing a film having a pattern shape according to any one of claims 26 to 28, wherein the steps [1] to [5] are performed a plurality of times in different regions on the substrate.   When the steps [1] to [5] are one shot, the time from the end of the step [4] of the first shot to the end of the step [3] of the second shot is 1.2. 30. The method for producing a film having a pattern shape according to claim 29, which is performed within seconds.   The method for producing a film having a pattern shape according to any one of claims 26 to 30, wherein the surface of the original pattern of the mold is quartz.   The method for producing a film having a pattern shape according to any one of claims 26 to 31, wherein the mold contact step is performed in an atmosphere containing a condensable gas.   The method for producing a film having a pattern shape according to claim 32, wherein the atmosphere containing the condensable gas is a mixed gas of helium and condensable gas.   The method for producing a film having a pattern shape according to claim 32 or 33, wherein the condensable gas is 1,1,1,3,3-pentafluoropropane.   35. A method for manufacturing an optical component, comprising a step of obtaining a film having a pattern shape by the method for manufacturing a film according to any one of claims 26 to 34.   A step of obtaining a film having a pattern shape by the method for producing a film according to any one of claims 26 to 34, and a step of performing etching or ion implantation on the substrate using the pattern shape of the obtained film as a mask. A method of manufacturing an optical component, comprising:   A step of obtaining a film having a pattern shape by the method for producing a film according to any one of claims 26 to 34, and a step of performing etching or ion implantation on the substrate using the pattern shape of the obtained film as a mask. A method of manufacturing a circuit board, comprising:   38. A method for manufacturing an electronic component, comprising: a step of obtaining a circuit board by the method for manufacturing a circuit board according to claim 37; and a step of forming an electronic member on the circuit board.