WO2014069313A1 - Composition durcissable pour impression, procédé de formation de motif et motif - Google Patents

Composition durcissable pour impression, procédé de formation de motif et motif Download PDF

Info

Publication number
WO2014069313A1
WO2014069313A1 PCT/JP2013/078761 JP2013078761W WO2014069313A1 WO 2014069313 A1 WO2014069313 A1 WO 2014069313A1 JP 2013078761 W JP2013078761 W JP 2013078761W WO 2014069313 A1 WO2014069313 A1 WO 2014069313A1
Authority
WO
WIPO (PCT)
Prior art keywords
curable composition
group
mold
pattern
present
Prior art date
Application number
PCT/JP2013/078761
Other languages
English (en)
Japanese (ja)
Inventor
雄一郎 後藤
大松　禎
雄一郎 榎本
北川　浩隆
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Publication of WO2014069313A1 publication Critical patent/WO2014069313A1/fr

Links

Images

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0752—Silicon-containing compounds in non photosensitive layers or as additives, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer

Definitions

  • the present invention relates to a curable composition for imprints capable of forming a fine pattern and a method for producing the same.
  • the nanoimprint method is a technique for transferring a fine pattern onto a material by pressing a mold (generally called a mold or a stamper) on which a pattern is formed.
  • a mold generally called a mold or a stamper
  • application in various fields is expected because a precise fine pattern can be easily produced by using the nanoimprint method.
  • a thermal imprint method As the nanoimprint method, methods called a thermal imprint method and an optical imprint method have been proposed based on the transfer method.
  • a thermal nanoimprint method a mold is pressed on a thermoplastic resin heated to a glass transition point or higher, and the mold is released after cooling to form a fine pattern.
  • This method can select various materials, but also has problems that high pressure is required at the time of pressing, and that it is difficult to form a fine pattern due to heat shrinkage or the like.
  • the photoimprint method the mold is released after photocuring in a state where the mold is pressed against the photocurable composition.
  • the optical imprint method since imprinting is performed on an uncured product, there is no need for high-pressure and high-temperature heating, and a fine pattern can be easily produced.
  • a specific example of the optical imprint method is proposed by Willson et al.
  • a photocurable composition is applied on a substrate (adhesion treatment is performed if necessary) by a method such as spin coating or ink jet, and then a mold made of a light transmissive material such as quartz is pressed against the substrate.
  • the composition is cured by light irradiation while the mold is pressed, and then the mold is released to produce a cured product to which the target pattern is transferred.
  • Non-Patent Document 1 As a method for improving releasability, it is known to use a polymerizable compound such that a cured product has a low elastic modulus (see, for example, Non-Patent Document 1). Specifically, it is described that a monofunctional polymerizable compound, a polymerizable compound not containing an aromatic ring, or the like is used.
  • Patent Document 1 discloses a method of adding a surfactant to the composition. This is an attempt to improve the releasability by controlling the affinity of the interface between the mold and the cured product by adding a surfactant having uneven distribution to the mold. Are listed.
  • Patent Document 2 discloses a method of adding a lubricant to the curable composition for imprints. Examples of the lubricant include phosphoric acid tris (2-ethylhexyl) ester.
  • Patent Document 3 in a roll-to-roll process, a cleaning resin containing an internal release agent is sandwiched between a mold and a substrate during the manufacturing process of an article having a fine concavo-convex structure on the surface and cured.
  • the internal release agent is supplied from the cleaning resin to the mold surface, it is possible to suppress the deterioration of the release performance due to repeated imprinting.
  • an oxyalkylene alkyl phosphate compound is described.
  • Patent Document 2 describes that the addition amount of the internal mold release agent is intended to cover the mold surface, so that a very small amount of about 0.1 parts by mass is preferable with respect to 100 parts by mass of the polymerizable compound. .
  • Non-Patent Document 1 when a polymerizable compound having a low elastic modulus is used, it becomes hard from the root to the tip of the pattern due to the low elastic modulus. The frequency of pattern collapse increased, and a good structure could not be obtained. This phenomenon is remarkable when a fine pattern of several tens of nanometers is transferred, and is considered to be caused by a decrease in pattern strength due to a reduction in elastic modulus. Moreover, in the technique described in Patent Document 1, for example, as shown in FIGS. 1A and 1B, a surfactant 2 is added to the curable composition 1, and the surfactant 2 is curable.
  • an object of the present invention is to solve the above-described problems, and an object of the present invention is to provide a curable composition for imprints that can reduce a releasing force while maintaining pattern transfer performance.
  • a curable composition for imprints having a structure selected from the following (2).
  • the additive (C) is an unsubstituted linear or branched alkylene group having 15 or more carbon atoms, or — (CH 2 ) n1 — (n1 represents an integer of 1 or more) and —O. — And / or — (Si (R 1 ) (R 2 ) —O) n2 — (R 1 and R 2 each independently represents a hydrogen atom or a monovalent organic group, and n2 represents an integer of 1 or more.
  • ⁇ 4> The curable composition for imprints according to any one of ⁇ 1> to ⁇ 3>, containing 0.1 part by mass or more of the additive (C) with respect to 100 parts by mass of the polymerizable compound (A).
  • ⁇ 5> The curable composition for imprints according to any one of ⁇ 1> to ⁇ 4>, further comprising a surfactant.
  • ⁇ 6> The curable composition for imprints according to any one of ⁇ 1> to ⁇ 5>, wherein the additive (C) does not have an aromatic group.
  • ⁇ 7> The curable composition for imprints according to any one of ⁇ 1> to ⁇ 6>, which contains two or more types of (B) photopolymerization initiators.
  • a laminate comprising a substrate, a lower layer film obtained by curing the imprint lower layer film composition, and a cured product of the curable composition for imprints according to any one of ⁇ 1> to ⁇ 7> ⁇ 9>
  • the curable composition for imprints according to any one of ⁇ 1> to ⁇ 7> is applied on a substrate or a mold, and the photocurable composition is sandwiched between the mold and the substrate.
  • the pattern forming method according to ⁇ 9>, wherein the method of applying the curable composition for imprints on a substrate or a mold is an inkjet method.
  • ⁇ 11> The method for imprinting according to any one of ⁇ 1> to ⁇ 7>, further comprising a step of forming a lower layer film by applying the lower layer film composition for imprinting on the substrate.
  • ⁇ 9> or ⁇ 10> wherein a curable composition is applied and light irradiation is performed with the curable composition for imprints and the lower layer film sandwiched between the substrate and the mold.
  • ⁇ 12> A pattern obtained by the method according to any one of ⁇ 9> to ⁇ 11>.
  • ⁇ 13> 60% by mass or more of the total amount of the additive (C) is present in the range of 10 to 50% in the thickness direction from the surface on the side in contact with the mold of the pattern, ⁇ 12> Pattern described in
  • (A) is sectional drawing which shows an example of the relationship when the mold and the conventional curable composition for imprints contact during exposure
  • (B) is the conventional curable composition hardened
  • (B) is sectional drawing which shows an example when only the structure of (2) in the additive used for this invention exists
  • (C) It is sectional drawing which shows an example in case the structure of (1) and the structure of (2) in the additive used for this invention exist.
  • (A) is sectional drawing which shows an example of the relationship when a mold and the curable composition of this invention contact during exposure
  • (B) is hardening which the curable composition of this invention hardened
  • (meth) acrylate represents acrylate and methacrylate
  • (meth) acryl represents acryl and methacryl
  • (meth) acryloyl represents acryloyl and methacryloyl.
  • monomer and “monomer” are synonymous.
  • the monomer in the present invention is distinguished from an oligomer and a polymer and refers to a compound having a weight average molecular weight of 2,000 or less.
  • the “imprint” in the present invention preferably refers to pattern transfer with a size of 1 nm to 10 mm, and more preferably refers to pattern transfer with a size (nanoimprint) of approximately 10 nm to 100 ⁇ m.
  • the description which has not described substitution and no substitution includes what has a substituent with what does not have a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • the curable composition for imprints of the present invention includes (A) a polymerizable compound, and (B). It contains a photopolymerization initiator and (C) an additive.
  • the polymerizable compound used in the curable composition of the present invention contains at least a polyfunctional polymerizable compound.
  • a polyfunctional polymerizable compound since the three-dimensional cross-linked structure is taken, the strength of the cured product is increased, and a good transfer pattern without pattern collapse can be obtained.
  • the ratio of the polyfunctional polymerizable compound in the polymerizable compound is preferably 30 to 90% by mass of the total polymerizable compound, more preferably 50 to 85% by mass, and further preferably 70 to 80% by mass. is there.
  • the number of functional groups in the polyfunctional polymerizable compound in the polymerizable compound is preferably 2 to 6, more preferably 2 to 4, and still more preferably 2 or 3.
  • the type of the polymerizable compound is not particularly limited.
  • Specific examples of the polymerizable compound include those described in paragraph Nos. 0020 to 0098 of JP2011-231308A, the contents of which are incorporated herein.
  • the polymerizable compound used in the curable composition of the present invention is preferably a (meth) acrylate compound, and in particular, from the viewpoint of etching resistance, a (meth) acrylate compound having an alicyclic hydrocarbon group and / or an aromatic group. Are more preferable, and (meth) acrylate compounds having an aromatic group are more preferable. Moreover, you may contain the polymeric compound which has a silicon atom and / or a fluorine atom. Examples thereof include those described in JP 2010-239121 A, the contents of which are incorporated herein.
  • the molecular weight of the polymerizable compound is preferably 50 to 999, and more preferably 100 to 300.
  • the total of the polymerizable compounds having an alicyclic hydrocarbon group and / or an aromatic group is 30 to 100% by mass of the total polymerizable compound. It is preferably 50 to 100% by mass, more preferably 70 to 100% by mass.
  • the (meth) acrylate polymerizable compound containing an aromatic group as the polymerizable compound is preferably 30 to 100% by mass of the total polymerizable component, more preferably 50 to 100% by mass, and 70 to 100%. It is particularly preferable that the content is% by mass.
  • the following polymerizable compound (A1) is 20 to 100% by mass, preferably 50 to 100% of the total polymerizable component
  • the following polymerizable compound (A2) is the total polymerizable component.
  • the case is 0 to 80% by mass, preferably 0 to 50% by mass.
  • a polymerizable compound having one aromatic group (preferably phenyl group, naphthyl group, more preferably naphthyl group) and one (meth) acrylate group (A2) aromatic group (preferably phenyl group, naphthyl group, A polymerizable compound containing a (preferably phenyl group) and having two (meth) acrylate groups
  • the curable composition of the present invention contains a photopolymerization initiator.
  • Any photopolymerization initiator may be used as long as it is a compound that generates an active species that polymerizes the above-described polymerizable compound by light irradiation.
  • a radical polymerization initiator and a cationic polymerization initiator are preferable, and a radical polymerization initiator is more preferable.
  • a plurality of photopolymerization initiators may be used in combination.
  • radical photopolymerization initiator used in the present invention a commercially available initiator can be used.
  • those described in paragraph No. 0091 of JP-A-2008-105414 can be preferably used.
  • acetophenone compounds, acylphosphine oxide compounds, and oxime ester compounds are preferred from the viewpoints of curing sensitivity and absorption characteristics.
  • Irgacure (registered trademark) 379 Irgacure (registered trademark) 369, Irgacure (registered trademark) 754, Irgacure (registered trademark) OXE01, Irgacure (registered trademark) OXE02, Irgacure (registered trademark) available from BASF 1800, Irgacure (registered trademark) 651, Irgacure (registered trademark) 907, Lucyrin TPO, Darocur 1173, and the like can be used.
  • a preferred ratio (mass ratio) when a photopolymerization initiator is used in combination is preferably 9: 1 to 1: 9, preferably 8: 2 to 2: 8, and 7: 3 to 3: 7. Is more preferable.
  • “light” includes not only light having a wavelength in the ultraviolet, near-ultraviolet, far-ultraviolet, visible, infrared, and the like, electromagnetic waves, but also radiation.
  • the radiation include microwaves, electron beams, EUV, and X-rays.
  • Laser light such as a 248 nm excimer laser, a 193 nm excimer laser, and a 172 nm excimer laser can also be used.
  • the light may be monochromatic light (single wavelength light) that has passed through an optical filter, or may be light having a plurality of different wavelengths (composite light).
  • the content of the photopolymerization initiator used in the present invention is, for example, 0.01 to 15% by mass, preferably 0.1 to 10% by mass, and more preferably 0% in the entire composition excluding the solvent. .5-7% by mass.
  • the total amount becomes the said range.
  • the content of the photopolymerization initiator is 0.01% by mass or more, sensitivity (fast curing), resolution, line edge roughness, and coating film strength tend to be improved, which is preferable.
  • content of a photoinitiator is 15 mass% or less, it exists in the tendency for a light transmittance, coloring property, a handleability, etc. to improve, and it is preferable.
  • the additive (C) of the present invention has a structure selected from the following (1) and a structure selected from the following (2).
  • (1) Polyalkylene oxide structure, polyalkylene glycol ether structure, polyalkylene glycol ester structure, amine structure, phosphate ester group, sulfonyl group, and sulfate ester group (hereinafter also referred to as the structure of (1))
  • (2) Alkyl structure having 15 or more carbon atoms, alicyclic structure, urethane structure and silicone structure (hereinafter also referred to as (2) structure)
  • the structure 6A of (1) contained in the additive 6 used in the present invention is usually a part that forms an adsorption structure to the mold 3, and the mold 6 When 3 and the curable composition 5 of this invention contact, it arrange
  • the structure (2) plays a role in uneven distribution near the interface between the mold and the curable composition.
  • the vicinity of the interface between the mold and the curable composition is, for example, more than 0% in the thickness direction from the surface in contact with the mold of the pattern obtained by curing the curable composition of the present invention to 50%. It means the range within.
  • the structure of (1) for example, a structure that is stable in terms of energy when present on the quartz mold side is preferable.
  • energetically stable means that the affinity for the mold surface is higher than that of the imprint composition, the substrate or the lower layer film.
  • the structure 6B of (2) contained in the additive 6 used in the present invention is usually a part that forms a plastic structure, while maintaining the pattern transfer performance, This contributes to reducing the mold release force.
  • the mold 3 and the curable composition 5 of the present invention are in contact with each other.
  • the structure 6A of the above (1) is disposed at the interface 7 between the mold 3 and the curable composition 5 of the present invention, and the mold release force is maintained while sufficiently maintaining the pattern transfer performance which is the effect of the present invention. It is difficult to achieve a sufficient reduction.
  • the peeling force is reduced by plasticization by the structure 6B of (2). Although it is possible, the strength of the pattern obtained by curing the curable composition of the present invention is reduced, and pattern collapse tends to occur.
  • the additive 6 used in the present invention has the structure 6A of (1) and the structure 6B of (2).
  • the structure 6B of the above (2) is located near the interface between the mold 3 and the curable composition 5 of the present invention due to the uneven distribution performance of the structure 6A of the above (1). Can be unevenly distributed.
  • the additive 6 used in the present invention is a cured product 5A obtained by curing the curable composition 5 of the present invention (hereinafter, the cured product of the present invention).
  • the structure 6B of the above (2) is located near the interface 7A between the mold 3 and the cured product 5A of the present invention due to the uneven distribution performance of the structure 6A of the above (1). Stays unevenly distributed.
  • the structure 6B of (2) reduces the elastic modulus in the vicinity of the interface 7A and releases the mold 3 from the cured product 5A of the present invention. It contributes to reducing. Further, according to the additive 6 used in the present invention, as shown in FIGS.
  • FIG. 5 is a diagram showing an example of the relationship between the concentration of the additive in the curable composition of the present invention and the depth from the interface.
  • the horizontal axis represents the depth from the interface between the mold and the curable composition
  • the left side of the horizontal axis represents the interface side between the mold and the curable composition
  • the right side of the horizontal axis represents the substrate side.
  • the vertical axis represents the additive concentration.
  • the broken line in FIG. 5 shows the position about 50% of the film thickness of the curable composition of this invention.
  • the additive of the present invention has the surface elasticity of the cured product of the present invention even when the structure (2) is unevenly distributed from the surface of the cured product of the present invention.
  • the additive 6 used in the present invention is not unevenly distributed on the surface of the cured product after nanoimprinting, so that the surface of the mold is not easily covered with the additive used in the present invention.
  • the mold can be appropriately filled with the curable composition of the present invention (the mold filling property is improved), and film unevenness and defects can be more effectively suppressed.
  • the additive used for the curable composition of the present invention has the structure (1) and the structure (2), the mold release force can be reduced while maintaining the pattern transfer performance. Can be made possible.
  • the structure (1) and the structure (2) will be described in more detail.
  • polyalkylene oxide structure Polyalkylene glycol ether structure, polyalkylene glycol ester structure
  • the repeating unit of the alkylene oxide chain, alkylene glycol ether chain or alkylene glycol ester chain is preferably 2 to 500, and preferably 15 to 60 More preferably.
  • the polyalkylene oxide structure, the polyalkylene glycol ether structure, and the polyalkylene glycol ester structure preferably have 2 to 30 alkylene oxide units having 1 to 6 carbon atoms, and 2 to 20 ethylene oxide or propylene oxide units.
  • polyalkylene oxide structure More preferred is a structure comprising 4 to 15 ethylene oxide or propylene oxide units.
  • the polyalkylene oxide structure, polyalkylene glycol ether structure, and polyalkylene glycol ester structure may form a cyclic structure. These alkylene chains may have a substituent, but are preferably unsubstituted.
  • the amine structure may be any of primary amine, secondary amine or tertiary amine, and secondary amine or tertiary amine is preferred.
  • the amine structure may form a monomer or an oligomer.
  • the formula weight of the amine structure is preferably 15 to 150.
  • the amine structure may constitute either the main chain or the side chain of the additive used in the curable composition of the present invention.
  • the phosphoric acid ester group may form a phosphoric acid monoester, a phosphoric acid diester or a phosphoric acid triester, but preferably forms a phosphoric acid triester.
  • sulfate group examples include those represented by the general formula (—O—SO 2 —O—), which may form a monoester or a diester.
  • the alkyl structure having 15 or more carbon atoms means a structure in which one or more linear or branched alkyl structures having 15 or more carbon atoms exist.
  • the alkyl structure having 15 or more carbon atoms may be substituted or unsubstituted, but is preferably unsubstituted.
  • the alkyl structure having 15 or more carbon atoms has 15 or more carbon atoms, and more preferably 17 or more carbon atoms. It is preferable that two or more alkyl structures having 15 or more carbon atoms exist in one molecule of the additive (C).
  • the structure having 15 or more carbon atoms when one or more branched alkyl structures having 15 or more carbon atoms are present, the structure becomes bulky, so that the plastic hardening can be further improved and the peeling force is further reduced. Can be made. Moreover, since there are few entanglements of a molecular chain, the viscosity of the curable composition of this invention can be made smaller. In the alkyl structure having 15 or more carbon atoms, when one or more linear alkyl structures having 15 or more carbon atoms are present, the molecular chain is easily deformed, so that transferability to an ultrafine pattern can be improved. it can.
  • alicyclic structure examples include a cyclic structure having a carbon atom as a skeleton, and a part of the carbon atoms forming the ring is replaced with an oxygen atom or a sulfur atom.
  • the alicyclic structure may form one ring or two or more rings, but preferably forms one ring.
  • the alicyclic ring is preferably a 5- to 30-membered ring. Specifically, crown ether, thiacrown ether, azacrown ether and the like are exemplified.
  • the urethane structure examples include a structure having one or more urethane groups (—O—C ( ⁇ O) —NH—), which may have a substituent or may be unsubstituted.
  • the (C) additive used in the present invention may be a compound containing one urethane group, or an oligomer or polymer having a plurality of repeating units containing a urethane group.
  • the urethane structure may constitute either the main chain or the side chain of the additive used in the curable composition of the present invention.
  • silicone structure examples include a (poly) siloxane structure represented by “— (Si (R 1 ) (R 2 ) —O) n —”.
  • R 1 and R 2 each independently represents a hydrogen atom or a monovalent organic group.
  • R 1 and R 2 may be the same or different, and the plurality of R 1 and R 2 may be the same or different from each other.
  • n represents an integer of 1 or more.
  • the monovalent organic group represented by R 1 and R 2 is a group that can be covalently bonded to the Si atom, and may be unsubstituted or substituted.
  • an alkyl group An aryl group, an aralkyl group, an alkoxy group, and the like. Particularly, a hydrogen atom and an unsubstituted or substituted alkyl group having 1 to 4 carbon atoms are preferable.
  • n is preferably 1 to 5000, and more preferably 1 to 1000.
  • the additive used for the curable composition of the present invention may have the structure (1) described above also serves as the structure (2).
  • examples of such additives include crown ethers having a cyclic polyalkylene oxide structure.
  • the additive used in the curable composition of the present invention preferably has no aromatic group. By not having an aromatic group, it is possible to further reduce the release force when the mold is released from the curable composition of the present invention while maintaining the strength of the entire cured product obtained by curing the curable composition. As a result, better pattern transfer characteristics can be obtained.
  • the additive used in the curable composition of the present invention has the above-described polyalkylene glycol ether structure, phosphate group, sulfonyl group or polyalkylene oxide structure as the structure of (1), and (2)
  • the structure having an alkyl structure having 15 or more carbon atoms, a silicone structure or an alicyclic structure as described above is preferable.
  • additives used in the curable composition of the present invention include those having a phosphate group and an alkyl structure having 15 or more carbon atoms, those having a phosphate group and a silicone structure, sulfonyl groups and 15 or more carbon atoms.
  • those having a polyalkylene oxide structure and an alicyclic structure are preferred.
  • the first preferred embodiment of the additive is represented by the following general formula (I).
  • Formula (I) (In the general formula (I), A represents a structure represented by the following general formula (II) or —SO 2 —.
  • R 1 represents a substituent, at least one of which is substituted or substituted with 15 or more carbon atoms. (It has an unsubstituted linear or branched alkyl group or a silicone structure. M represents 2 or 3.)
  • Formula (II) In the general formula (I), R 1 represents a substituent, and at least one has an unsubstituted linear or branched alkylene group having 15 or more carbon atoms or a silicone structure.
  • R 1 is an unsubstituted linear or branched alkylene group having 15 or more carbon atoms, or — (CH 2 ) n1 — (n1 represents an integer of 1 or more), —O— and / or —.
  • m represents 2 or 3, and in the general formula (I), when A represents the structure of the above general formula (II), it represents 3, and in the general formula (I), A represents When -SO 2 -is represented, 2 is represented.
  • a second preferred embodiment of the additive used in the curable composition of the present invention is a compound having an alicyclic structure composed of a combination of an alkylene group, —O—, —S—, —NR— and the like.
  • crown ether, thiacrown ether, azacrown ether and the like are preferable, crown ether having 10 or more carbon atoms and 4 or more oxygen atoms is more preferable, (—CH 2 —
  • a crown ether in which CH 2 —O—) n (n is an integer of 4 to 20) is cyclic is particularly preferred.
  • additives used in the curable composition of the present invention include the following compounds C-1 to C-15, but the additives used in the present invention are not limited to these compounds. Absent. (C-1, 2) (C-3) n represents 3 to 15. (C-4, 5) (C-6, 7) (C-9) (C-10) (C-11) n represents 3 to 15. (C-12) n represents 3 to 15. (C-13) (C-14) (C-15)
  • the molecular weight of the additive used in the curable composition of the present invention is preferably about 100 to 10,000, more preferably 400 to 5,000.
  • the plastic effect can be further improved, and a more effective release effect can be obtained.
  • the pattern transfer performance tends to be improved particularly in a fine pattern of 100 nm or less.
  • the addition amount of the additive used in the curable composition of the present invention is not particularly limited, and is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the polymerizable compound, for example, and 1 to 10 parts by mass. More preferably, it is a part.
  • the addition amount 0.1 mass part or more the plasticizing effect can be further improved, and a sufficient release effect can be obtained.
  • the addition amount 10 parts by mass or less it is possible to prevent the elastic modulus of the entire film from being lowered and to prevent the transfer pattern from falling.
  • the additive used in the present invention has an alkyl structure having 15 or more carbon atoms as the structure of (2), a small amount of about 1 part by mass with respect to 100 parts by mass of the polymerizable compound. By adding, the effect of the present invention can be sufficiently achieved.
  • a low mold release force can be achieved by mix
  • “Substantially free” means, for example, that it is 1% by mass or less of the amount of the additive (C).
  • the curable composition of the present invention maintains the pattern transfer performance by containing the above-described (A) polymerizable compound, (B) photopolymerization initiator, and (C) additive. Meanwhile, the release force can be reduced. Moreover, according to the curable composition of this invention, applicability
  • the curable composition of the present invention preferably contains a polymerization inhibitor.
  • the content of the polymerization inhibitor is 0.001 to 1% by mass, more preferably 0.005 to 0.5% by mass, and still more preferably 0.008 to 0.
  • the polymerization inhibitor may be added during the production of the polymerizable monomer, or may be added later to the curable composition of the present invention. Specific examples of the polymerization inhibitor include those described in paragraph No. 0121 of JP2012-169462A, the contents of which are incorporated herein.
  • the curable composition of the present invention may contain a surfactant. By including the surfactant, it is possible to further reduce the release force while maintaining the pattern transfer performance.
  • the surfactant used in the present invention is preferably a nonionic surfactant, and preferably contains at least one of a fluorine-based surfactant, a Si-based surfactant, and a fluorine / Si-based surfactant. Nonionic surfactants are most preferred.
  • the “fluorine / Si-based surfactant” refers to one having both the requirements of both a fluorine-based surfactant and a Si-based surfactant.
  • fluorine-based nonionic surfactant examples include the trade names Florard (Sumitomo 3M), Megafuc (DIC), Surflon (AGC Seimi Chemical), Unidyne (Daikin Industries), Footagen (Neos), Examples include F-top (Mitsubishi Materials Electronic Chemical), Polyflow (Kyoeisha Chemical), KP (Shin-Etsu Chemical), Troisol (Troy Chemical), PolyFox (OMNOVA), Capstone (DuPont), and the like.
  • the content of the surfactant used in the present invention is, for example, 0.001 to 5% by mass, preferably 0.002 to 4% by mass, and more preferably 0.005 to 4% by mass in the entire composition. 3% by mass.
  • the total amount becomes the said range.
  • the surfactant is in the range of 0.001 to 5% by mass in the curable composition of the present invention, the effect of coating uniformity is good, and mold transfer characteristics are hardly deteriorated due to excessive surfactant. .
  • a low mold release force can be achieved by mix
  • the curable composition of the present invention includes a photosensitizer, an antioxidant, an ultraviolet absorber, a light stabilizer, an anti-aging agent, a plasticizer, and an adhesive as necessary.
  • Accelerator, thermal polymerization initiator, photobase generator, colorant, inorganic particles, elastomer particles, basic compound, photoacid generator, photoacid multiplier, chain transfer agent, antistatic agent, flow regulator, antifoaming An agent, a dispersant and the like may be added.
  • Specific examples of such components include those described in JP-A-2008-105414, paragraph numbers 0092 to 0093 and paragraph numbers 0113 to 0137, the contents of which are incorporated herein.
  • a solvent can also be used for the curable composition of this invention, it is preferable that it is 5 mass% or less, it is more preferable that it is 3 mass% or less, and does not contain a solvent substantially. Is particularly preferred.
  • substrate by the inkjet method when there are few compounding quantities of a solvent, the viscosity change of the composition by volatilization of a solvent can be suppressed.
  • the curable composition of this invention does not necessarily contain a solvent, you may add arbitrarily, when adjusting the viscosity of a composition finely.
  • Solvents that can be preferably used in the curable composition of the present invention include those commonly used in curable compositions for photoimprints and photoresists, and dissolve and uniformly disperse the compounds used in the present invention. It is not particularly limited as long as it can be used and it does not react with these components. Examples of the solvent that can be used in the present invention include those described in paragraph No. 0088 of JP-A-2008-105414, the contents of which are incorporated herein.
  • the curable composition of the present invention can be prepared by mixing the above-described components.
  • the mixing / dissolution of the curable composition of the present invention is usually carried out in the range of 0 ° C to 100 ° C.
  • the components are mixed and then filtered, for example, through a filter having a pore diameter of 0.003 ⁇ m to 5.0 ⁇ m. Filtration may be performed in multiple stages or repeated many times.
  • the filtered liquid can be refiltered.
  • the material of the filter used for filtration may be polyethylene resin, polypropylene resin, fluorine resin, nylon resin or the like, but is not particularly limited.
  • the laminate of the present invention comprises a substrate, a lower layer film obtained by curing the lower layer film composition for imprinting, and a cured product of the curable composition of the present invention.
  • Substrate The substrate (substrate or support) that can be used in the present invention can be selected depending on various applications. For example, quartz, glass, optical film, ceramic material, deposited film, magnetic film, reflective film, Ni , Cu, Cr, Fe and other metal substrates, paper, SOG (Spin On Glass), polyester films, polycarbonate films, polyimide films and other polymer substrates, TFT array substrates, PDP electrode plates, glass and transparent plastic substrates There are no particular restrictions on materials, conductive substrates such as ITO and metals, insulating substrates, semiconductor fabrication substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon. However, when using it for an etching use, a semiconductor preparation base material is preferable as it mentions later.
  • the underlayer film composition used in the present invention preferably contains a polymerizable compound (D) and a solvent (E).
  • the polymerizable compound (D) may be thermosetting or photocurable, and is preferably thermosetting.
  • the polymerizable compound (D) is preferably, for example, a (meth) acrylic resin having an ethylenically unsaturated group (P) and a hydrophilic group (Q).
  • the ethylenically unsaturated group (P) include a (meth) acryloyloxy group, a (meth) acryloylamino group, a maleimide group, an allyl group, and a vinyl group.
  • hydrophilic group (Q) examples include alcoholic hydroxyl group, carboxyl group, phenolic hydroxyl group, ether group (preferably polyoxyalkylene group), amino group, amide group, imide group, ureido group, urethane group, cyano group, sulfone. Examples thereof include an amide group, a lactone group, and a cyclocarbonate group.
  • the hydrophilic group is a urethane group
  • the group adjacent to the urethane group is preferably present in the resin as an oxygen atom, for example, —O—C ( ⁇ O) —NH—.
  • the acrylic resin preferably contains 20 to 100 mol% of repeating units containing an ethylenically unsaturated group (P).
  • the acrylic resin preferably contains 20 to 100 mol% of repeating units containing a hydrophilic group (Q).
  • the ethylenically unsaturated group (P) and the hydrophilic group (Q) may be contained in the same repeating unit or may be contained in separate repeating units.
  • the acrylic resin may contain other repeating units that do not contain both the ethylenically unsaturated group (P) and the hydrophilic group (Q).
  • the ratio of other repeating units in the acrylic resin is preferably 50 mol% or less.
  • the acrylic resin preferably contains a repeating unit represented by the following general formula.
  • R 1 and R 2 each represent a hydrogen atom, a methyl group, or a hydroxymethyl group
  • L 1 represents a trivalent linking group
  • L 2a represents a single bond or a divalent group.
  • L 2b represents a single bond, a divalent linking group, or a trivalent linking group
  • P represents an ethylenically unsaturated group
  • Q represents a hydrophilic group
  • n represents 1 or 2
  • R 1 and R 2 each independently represents a hydrogen atom, a methyl group or a hydroxymethyl group, preferably a hydrogen atom or a methyl group, more preferably a methyl group.
  • L 1 represents a trivalent linking group, and is an aliphatic group, an alicyclic group, an aromatic group, or a trivalent group obtained by combining these, and includes an ester bond, an ether bond, a sulfide bond, and a nitrogen atom. It may be included.
  • the trivalent linking group preferably has 1 to 9 carbon atoms.
  • L 2a represents a single bond or a divalent linking group.
  • the divalent linking group is an alkylene group, a cycloalkylene group, an arylene group, or a divalent group obtained by combining these, and may include an ester bond, an ether bond, and a sulfide bond.
  • the divalent linking group preferably has 1 to 8 carbon atoms.
  • L 2b represents a single bond, a divalent linking group, or a trivalent linking group.
  • the divalent linking group represented by L 2b has the same meaning as the divalent linking group represented by L 2a , and the preferred range is also the same.
  • the trivalent linking group represented by L 2b has the same meaning as the trivalent linking group represented by L 1 , and the preferred range is also the same.
  • P represents an ethylenically unsaturated group and is synonymous with the ethylenically unsaturated group exemplified above, and the same applies to preferred ethylenically unsaturated groups.
  • Q represents a hydrophilic group, and is synonymous with the above-exemplified hydrophilic groups, and the preferred hydrophilic groups are also the same.
  • n is 1 or 2, and 1 is preferable.
  • L 1 , L 2a and L 2b do not contain an ethylenically unsaturated group or a hydrophilic group.
  • the acrylic resin may further have a repeating unit represented by the following general formula.
  • R 3 and R 4 each represent a hydrogen atom, a methyl group, or a hydroxymethyl group
  • L 3 and L 4 each represent a single bond or a divalent linking group
  • Q is Represents a hydrophilic group
  • R 5 represents an aliphatic group having 1 to 12 carbon atoms, an alicyclic group having 3 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms.
  • R 3 and R 4 each represent a hydrogen atom, a methyl group, or a hydroxymethyl group, preferably a hydrogen atom or a methyl group, and more preferably a methyl group.
  • L 3 and L 4 each represent a single bond or a divalent linking group. Examples of the divalent linking group has the same meaning as the divalent linking group represented by L 2a described above, and preferred ranges are also the same.
  • Q represents a hydrophilic group and is synonymous with the above-exemplified hydrophilic groups, and the preferred hydrophilic groups are also the same.
  • R 5 represents an aliphatic group having 1 to 12 carbon atoms, an alicyclic group, or an aromatic group.
  • the aliphatic group having 1 to 12 carbon atoms include an alkyl group having 1 to 12 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group).
  • Examples of the alicyclic group having 3 to 12 carbon atoms include a cycloalkyl group having 3 to 12 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an isobornyl group, an adamantyl group, and a tricyclodecanyl group).
  • Examples of the aromatic group having 6 to 12 carbon atoms include a phenyl group, a naphthyl group, and a biphenyl group. Of these, a phenyl group and a naphthyl group are preferable.
  • the aliphatic group, alicyclic group and aromatic group may have a substituent.
  • x represents 0 to 50 mol%
  • y represents 0 to 50 mol%
  • z represents 20 to 100 mol%.
  • the main chain can also use what contains an aromatic ring.
  • the polymerizable compound (D) include those in which the main chain is composed of an aromatic ring and an alkylene group, and the main chain is a structure in which a benzene ring and a methylene group are alternately bonded.
  • the polymerizable compound (D) used in the present invention preferably has a reactive group in the side chain, more preferably has a (meth) acryloyl group in the side chain, and has an acryloyl group in the side chain. More preferred.
  • the polymerizable compound (D) used in the present invention a polymer whose main component is a structural unit represented by the following general formula can be used, and the structural unit represented by the following general formula contains 90 mol% or more. More preferably, it is an occupied polymer.
  • R is an alkyl group
  • L 1 and L 2 are each a divalent linking group
  • P is a polymerizable group
  • n is an integer of 0 to 3.
  • R is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group.
  • L 1 is preferably an alkylene group, more preferably an alkylene group having 1 to 3 carbon atoms, and more preferably —CH 2 —.
  • L 2 is preferably a divalent linking group consisting of —CH 2 —, —O—, —CHR (R is a substituent) —, and combinations of two or more thereof.
  • R is preferably an OH group.
  • P is preferably a (meth) acryloyl group, more preferably an acryloyl group.
  • n is preferably an integer of 0 to 2, and more preferably 0 or 1.
  • polymerizable compound (D) used in the present invention include an epoxy (meth) acrylate polymer.
  • polymerizable compound (D) examples include those described in paragraph Nos. 0040 to 0056 of JP-T-2009-503139, the contents of which are incorporated herein.
  • the molecular weight of the polymerizable compound (D) is usually 1000 or more and may be a low molecular compound or a polymer, but a polymer is preferred. More preferably, the molecular weight of the polymerizable compound (D) is 3000 or more, and more preferably 7500 or more.
  • the upper limit of the molecular weight of the polymerizable compound (D) is preferably 200000 or less, more preferably 100000 or less, and still more preferably 50000 or less. By setting it as such molecular weight, volatilization of a polymeric compound (D) can be suppressed.
  • the content of the polymerizable compound (D) in the lower layer film composition used in the present invention is preferably 30% by mass or more, more preferably 50% by mass or more, and more preferably 70% by mass or more in all components of the lower layer film composition excluding the solvent. Is more preferable.
  • the underlayer film composition of the present invention preferably contains a solvent. Any solvent can be used as long as it can dissolve the above-described polymerizable compound (D).
  • the solvent has one or more of an ester structure, a ketone structure, a hydroxyl group, and an ether structure. It is a solvent.
  • preferred solvents are propylene glycol monomethyl ether acetate, cyclohexanone, 2-heptanone, gamma butyrolactone, propylene glycol monomethyl ether, ethyl lactate alone or mixed solvents, particularly preferably propylene glycol monomethyl ether acetate. is there.
  • a preferable solvent is a solvent having a boiling point of 80 to 200 ° C. at normal pressure, and more preferably a solvent having a boiling point of 50 to 180 ° C. at normal pressure.
  • the content of the solvent in the lower layer film composition is optimally adjusted according to the viscosity of the component excluding the solvent, the coating property, and the target film thickness, but from the viewpoint of improving the coating property, it is 70% by mass or more in the total composition. In the range, preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 99% by mass or more.
  • the upper limit of content of the solvent in a lower layer film composition is not specifically limited, It is 100 mass% or less.
  • the underlayer film composition used in the present invention may contain at least one of a crosslinking agent, a catalyst, a surfactant, a thermal polymerization initiator, and a polymerization inhibitor as other components.
  • a compounding quantity of these other components 50 mass% or less is preferable with respect to all the components except a solvent.
  • the lower layer film composition used in the present invention substantially consists of the polymerizable compound (D) and the solvent.
  • substantially only the polymerizable compound (D) and the solvent are levels that affect the effects of the present invention, and that other components other than the polymerizable compound (D) and the solvent are not included.
  • the other component is 2% by mass or less of the total component, the other component is more preferably 1% by mass or less of the total component, and further preferably 0% by mass of the total component. .
  • Lower layer film The film thickness of the lower layer film comprising the curable composition of the present invention varies depending on the intended use, but is about 0.1 to 100 nm, preferably 0.5 to 20 nm, more preferably 1 to 10 nm. It is. Moreover, you may apply
  • the curable composition of the present invention is applied onto a substrate or a mold, and the curable composition of the present invention is sandwiched between the mold and the substrate. Irradiate with light.
  • substrate substrate or support
  • those described above can be used as the substrate (substrate or support) that can be used in the present invention.
  • a mold having a pattern to be transferred is used as the mold that can be used in the present invention.
  • the pattern on the mold can be formed according to the desired processing accuracy by, for example, photolithography, electron beam drawing, or the like, but the mold pattern forming method is not particularly limited in the present invention.
  • the light-transmitting mold material used in the present invention is not particularly limited as long as it has a predetermined strength and durability, and specifically, a light-transparent resin such as glass, quartz, PMMA, and polycarbonate resin. Examples thereof include a transparent metal vapor-deposited film, a flexible film such as polydimethylsiloxane, a photocured film, and a metal film, and quartz is particularly preferable.
  • a method of applying the curable composition of the present invention on a substrate generally well-known coating methods such as dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, By using an extrusion coating method, a spin coating method, a slit scanning method, an ink jet method, or the like, a coating film or droplets can be disposed on the substrate.
  • the exposure illuminance is preferably in the range of 1 to 200 mW / cm 2 .
  • the exposure time can be shortened so that productivity is improved.
  • the exposure time 200 mW / cm 2 or less deterioration of the properties of the cured film due to side reactions can be suppressed. It tends to be preferable.
  • the exposure amount is desirably in the range of 51000 mJ / cm 2 . If it is less than 5 mJ / cm 2 , the exposure margin becomes narrow, photocuring becomes insufficient, and problems such as adhesion of unreacted substances to the mold tend to occur.
  • the cured film may be deteriorated due to decomposition of the composition.
  • an inert gas such as nitrogen, helium, or argon may be flowed to control the oxygen concentration to less than 100 mg / L.
  • the pattern forming method of the present invention after the pattern forming layer (the layer comprising the curable composition of the present invention) is cured by light irradiation, heat is applied to the cured pattern as necessary to further cure. May be included.
  • the heat for heat-curing the curable composition of the present invention after light irradiation is preferably 150 to 280 ° C, more preferably 200 to 250 ° C.
  • the time for applying heat is preferably 5 to 60 minutes, more preferably 15 to 45 minutes.
  • Specific examples of the pattern forming method include those described in JP-A-2012-169462, paragraph numbers 0125 to 0136, the contents of which are incorporated herein.
  • the pattern forming method of the present invention includes a step of applying the above-described underlayer film composition on a substrate to form an underlayer film, a step of applying the above-described curable composition of the present invention to the surface of the underlayer film, It includes a step of irradiating light with the curable composition and the lower layer film sandwiched between the substrate and the mold to cure the curable composition of the present invention, and a step of peeling the mold.
  • coating a lower layer film composition on a base material after hardening a part of lower layer film composition by heat or light irradiation, you may make it apply
  • the lower layer film composition used in the present invention can be prepared by mixing the above-mentioned components.
  • the components are mixed and then filtered, for example, with a filter having a pore size of 0.003 ⁇ m to 5.0 ⁇ m. Filtration may be performed in multiple stages or repeated many times. Moreover, you may refilter the filtered liquid.
  • the material of the filter used for filtration is not particularly limited, and for example, polyethylene resin, polypropylene resin, fluorine resin, nylon resin, or the like can be used.
  • the lower layer film composition is applied on a substrate to form a lower layer film.
  • the method of coating on the substrate include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spin coating method, a slit scanning method, or an inkjet method.
  • a coating film or droplets can be disposed on the substrate. From the viewpoint of film thickness uniformity, the spin coating method is more preferable.
  • the solvent is dried.
  • a preferred drying temperature is 70 ° C to 130 ° C.
  • further curing is performed by active energy (preferably heat and / or light). Heat curing is preferably performed at a temperature of 150 ° C. to 250 ° C.
  • the pattern formed by the pattern forming method of the present invention is within the range of 10 to 50% in the thickness direction from the surface on the side in contact with the mold of the pattern, out of the total amount of the additive (C). It is preferable that 60 mass% or more exists.
  • the pattern formed by the pattern forming method of the present invention can be used as a permanent film (resist for a structural member) or an etching resist used for a liquid crystal display (LCD) or the like.
  • the pattern using the curable composition of the present invention also has good solvent resistance.
  • the curable composition of the present invention preferably has high resistance to various solvents, but the film thickness when immersed in a solvent used in a general substrate manufacturing process, for example, an N-methylpyrrolidone solvent at 25 ° C. for 10 minutes. It is particularly preferred that no fluctuation occurs.
  • the pattern formed by the pattern forming method of the present invention is also useful as an etching resist.
  • a silicon wafer or the like on which a thin film such as SiO 2 is formed is used as a base material, and nano-pattern is formed on the base material by the pattern forming method of the present invention. A fine pattern of order is formed.
  • a desired pattern can be formed on the substrate by etching using an etching gas such as hydrogen fluoride in the case of wet etching or CF 4 in the case of dry etching.
  • an etching gas such as hydrogen fluoride in the case of wet etching or CF 4 in the case of dry etching.
  • the curable composition of the present invention preferably has good etching resistance against dry etching using fluorocarbon or the like.
  • A-1) Synthesis from ⁇ , ⁇ '-dichloro-p-xylene and acrylic acid
  • A-2 2-phenoxyethyl acrylate (manufactured by Osaka Organic Chemical Industry, Biscoat # 192)
  • A-3) 1,6-hexanediol diacrylate (HDDA manufactured by Daicel Cytec Co., Ltd.)
  • A-4) Benzyl acrylate (FA-BZA manufactured by Hitachi Chemical Co., Ltd.)
  • C-0 N represents 1 to 15 (manufactured by DIC, product name: MegaFuck F-444) (C-1, 2) (C-3) n represents 3 to 15. (C-4, 5) (C-6, 7) (C-9) (Nippon Soda Co., Ltd., 15-Crown-5) (C-10) (Nippon Soda Co., Ltd., 18-Crown-6) (C-11) n represents 3 to 5.
  • C-12 n represents 3 to 5.
  • NK Oligo EA-7140 / PGMAc manufactured by Shin-Nakamura Chemical Co., Ltd.
  • NK Oligo EA-7140 / PGMAc solid content 70%
  • the mold a quartz mold having a line / space with a line width of 30 nm and a depth of 60 nm was used.
  • an ink jet apparatus an ink jet printer DMP-2831 (manufactured by Fuji Film Dimatics) was used. After imprinting the curable composition for imprinting onto the silicon wafer, the mold was contacted in a helium atmosphere. A pattern was obtained by exposing from the mold surface using a high-pressure mercury lamp under conditions of 100 mJ / cm 2 and releasing the mold after exposure.
  • the lower layer film composition was spin coated on a silicon wafer and heated on a hot plate at 100 ° C. for 1 minute to dry the solvent. Furthermore, the lower layer film composition was cured by heating on a hot plate at 220 ° C. for 5 minutes to form a lower layer film. The film thickness of the lower layer film after curing was 3 nm. On the surface of the lower layer film on the silicon wafer, a 1 pl droplet per nozzle is applied to the curable composition for photoimprinting adjusted to a temperature of 23 ° C. using an inkjet printer DMP-2831 (manufactured by Fujifilm Dimatics).
  • the liquid droplets were discharged in an amount so that the liquid droplets were applied on the lower layer film so as to form a square array at intervals of about 100 ⁇ m.
  • quartz mold was exposed from the quartz mold side using a high pressure mercury lamp under the condition of 100 mJ / cm 2 . After the exposure, the quartz mold was released, and the release force (F) at that time was measured.
  • the release force (F) was measured according to the method described in Comparative Examples described in [0102] to [0107] of JP2011-209777A.
  • mold fillability evaluation As the mold, a quartz mold having a Line / Space pattern and a dot pattern of 100 nm to 10 ⁇ m was used. After imprinting the curable composition for imprinting onto the silicon wafer, the mold was contacted in a helium atmosphere. Then, mold filling property was evaluated as follows with an optical microscope. The results are shown in the table. A: The spread time (propagation time) of a curable composition was short, and the unfilled part was not seen. B: An unfilled part was not seen. C: The unfilled part was seen in part. D: Fillability was poor and inkjet marks were observed.
  • the curable compositions for imprints obtained in Examples 1 to 10 had a small release force and good evaluation of pattern shape, surface elastic modulus and pattern filling rate.
  • Examples 10 and 11 were highly effective.
  • the curable composition for imprints contains (A) a polymerizable compound, (B) a photopolymerization initiator, and the above-described (C) additive, It was found that a curable composition for imprints excellent in pattern transferability and releasability can be provided.
  • a cured product obtained by curing the imprint composition of the present invention is a permanent structure such as a semiconductor wiring layer, a micro electro mechanical system (MEMS), a nano device, an optical device, a flat panel display material, and a thin film transistor (TFT). It can also be used for applications.
  • MEMS micro electro mechanical system
  • TFT thin film transistor

Landscapes

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

Abstract

L'invention concerne une composition durcissable pour impression, qui peut présenter une force de démoulage réduite, tout en maintenant une performance de transfert de motifs. L'invention concerne une composition durcissable pour impression, qui contient (A) un composé polymérisable polyfonctionnel, (B) un initiateur de photopolymérisation et (C) un additif qui possède une structure choisie parmi des structures (1) décrites ci-dessous et une structure choisie parmi des structures (2) décrites ci-dessous. (1) Une structure de polyalkylène oxyde, une structure d'éther glycol de polyalkylène, une structure d'ester glycol de polyalkylène, une structure d'amine, un groupement d'ester d'acide phosphorique, un groupement sulfonyle et un groupement d'ester d'acide sulfurique. (2) Une structure d'alkyle ayant 15 atomes de carbone ou plus, une structure alicyclique, une structure d'uréthane et une structure de silicone.
PCT/JP2013/078761 2012-10-31 2013-10-24 Composition durcissable pour impression, procédé de formation de motif et motif WO2014069313A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012-240442 2012-10-31
JP2012240442A JP6009907B2 (ja) 2012-10-31 2012-10-31 インプリント用硬化性組成物、パターン形成方法およびパターン

Publications (1)

Publication Number Publication Date
WO2014069313A1 true WO2014069313A1 (fr) 2014-05-08

Family

ID=50627222

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/078761 WO2014069313A1 (fr) 2012-10-31 2013-10-24 Composition durcissable pour impression, procédé de formation de motif et motif

Country Status (3)

Country Link
JP (1) JP6009907B2 (fr)
TW (1) TW201430073A (fr)
WO (1) WO2014069313A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6114221B2 (ja) * 2014-03-26 2017-04-12 富士フイルム株式会社 光インプリント用硬化性組成物、パターン形成方法およびパターン
TWI656162B (zh) * 2014-06-20 2019-04-11 日商富士軟片股份有限公司 下層膜形成用樹脂組成物、積層體、圖案形成方法及元件的製造方法
TWI783115B (zh) 2018-02-14 2022-11-11 日商富士軟片股份有限公司 試劑盒、壓印用下層膜形成組成物、圖案形成方法、半導體器件的製造方法
TWI799550B (zh) * 2018-03-27 2023-04-21 日商富士軟片股份有限公司 壓印用硬化性組成物、脫模劑、硬化物、圖案形成方法和微影方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010212392A (ja) * 2009-03-10 2010-09-24 Fujifilm Corp 光ナノインプリント用硬化性組成物
JP2011066370A (ja) * 2009-03-25 2011-03-31 Fujifilm Corp 光インプリント用硬化性組成物およびそれを用いた硬化物の製造方法
JP2012041521A (ja) * 2010-05-12 2012-03-01 Fujifilm Corp 光硬化性組成物およびそれを用いた硬化物の製造方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009073078A (ja) * 2007-09-21 2009-04-09 Fujifilm Corp 光ナノインプリント用硬化性組成物およびそれを用いた液晶表示装置用部材
JP5052534B2 (ja) * 2009-01-08 2012-10-17 株式会社ブリヂストン 光硬化性転写シート、及びこれを用いた凹凸パターンの形成方法
JP5463170B2 (ja) * 2010-03-10 2014-04-09 富士フイルム株式会社 微細パターン製造方法、微細パターン付き基板、微細パターン付き基板を含む光源装置および画像表示装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010212392A (ja) * 2009-03-10 2010-09-24 Fujifilm Corp 光ナノインプリント用硬化性組成物
JP2011066370A (ja) * 2009-03-25 2011-03-31 Fujifilm Corp 光インプリント用硬化性組成物およびそれを用いた硬化物の製造方法
JP2012041521A (ja) * 2010-05-12 2012-03-01 Fujifilm Corp 光硬化性組成物およびそれを用いた硬化物の製造方法

Also Published As

Publication number Publication date
JP2014090133A (ja) 2014-05-15
TW201430073A (zh) 2014-08-01
JP6009907B2 (ja) 2016-10-19

Similar Documents

Publication Publication Date Title
JP5857014B2 (ja) 光インプリント用硬化性組成物、パターン形成方法およびパターン
JP5827180B2 (ja) インプリント用硬化性組成物と基板の密着用組成物およびこれを用いた半導体デバイス
JP5671302B2 (ja) インプリント用硬化性組成物、パターン形成方法およびパターン
JP6029558B2 (ja) 光インプリント用硬化性組成物、パターン形成方法、微細パターン、および半導体デバイスの製造方法
TWI585178B (zh) 壓印用密合膜之製造方法及圖案形成方法
JP2010186979A (ja) インプリント用硬化性組成物、パターン形成方法およびパターン
KR20120102008A (ko) 임프린트용 경화성 조성물, 패턴 형성 방법 및 패턴
WO2017002833A1 (fr) Composition photodurcissable, procédé de formation de motif et procédé de fabrication de dispositif
JP5968933B2 (ja) インプリント用硬化性組成物、パターン形成方法およびパターン
JP6009907B2 (ja) インプリント用硬化性組成物、パターン形成方法およびパターン
JP6340088B2 (ja) インプリント用光硬化性組成物、パターン形成方法およびデバイスの製造方法
JP2012216700A (ja) パターン形成方法およびパターン
JP6379220B2 (ja) インプリント用光硬化性組成物、パターン形成方法およびデバイスの製造方法
WO2021112132A1 (fr) Film fonctionnel, composition durcissable de type film, procédé de production de film fonctionnel et procédé de transport d'article
TWI643893B (zh) 光壓印用硬化性組成物、圖案形成方法及圖案
TWI662087B (zh) 光壓印用硬化性組成物、圖案形成方法及圖案
JP2021091855A (ja) 機能性フィルム、フィルム状硬化性組成物及び機能性フィルムの製造方法

Legal Events

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

Ref document number: 13851096

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13851096

Country of ref document: EP

Kind code of ref document: A1