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WO2018105353A1 - Procédé de production d'un moule de nano-impression - Google Patents

Procédé de production d'un moule de nano-impression Download PDF

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Publication number
WO2018105353A1
WO2018105353A1 PCT/JP2017/041323 JP2017041323W WO2018105353A1 WO 2018105353 A1 WO2018105353 A1 WO 2018105353A1 JP 2017041323 W JP2017041323 W JP 2017041323W WO 2018105353 A1 WO2018105353 A1 WO 2018105353A1
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Prior art keywords
group
meth
acrylate
mold
pattern
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PCT/JP2017/041323
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English (en)
Japanese (ja)
Inventor
直樹 溜
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Stanley Electric Co Ltd
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Stanley Electric Co Ltd
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/38—Moulds or cores; Details thereof or accessories therefor characterised by the material or the manufacturing process
    • B29C33/40—Plastics, e.g. foam or rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing

Definitions

  • the present invention relates to a method for manufacturing a replica mold for nanoimprint lithography.
  • the imprint technique is a method in which a pattern having a pattern corresponding to a pattern to be formed on a substrate is embossed onto a coating film formed on the substrate surface to thereby apply a pattern formed on the substrate surface.
  • This is a technique for transferring to a film.
  • a nano-order fine pattern can be formed on the coating film.
  • imprint techniques a technique for forming ultrafine patterns of several hundreds to several nanometers (nm) is called a nanoimprint technique.
  • the method is roughly classified into two types according to the characteristics of the material of the coating film (hereinafter referred to as “coating material”) formed on the substrate surface.
  • coating material a material of the coating film formed on the substrate surface.
  • One of them is a method of transferring the pattern to the coating film by heating and plastically deforming the coating film material to which the pattern is transferred, pressing the mold, cooling, and curing the coating film material. is there.
  • Another one uses a mold or a substrate in which at least one of the substrates is light transmissive and forms a coating film by applying a coating material made of a liquid photocurable composition on the substrate.
  • the pattern is transferred to the coating film by pressing the mold into contact with the coating film and then irradiating light through the mold or the substrate to cure the coating material.
  • the photoimprint method of transferring a pattern by light irradiation is capable of forming a highly accurate pattern, and thus is widely used in nanoimprint technology, and is suitably used as a coating material in the method. Development of photocurable compositions is underway.
  • adhesion between a substrate surface and a pattern obtained by curing a coating material, and releasability between the pattern and a mold (hereinafter referred to as “from a mold”). "Releasability" is important.
  • the surface of the mold is treated with a fluorine treatment agent to provide mold release, and pentafluoropropane gas or the like is applied to the interface between the photocurable composition and the mold.
  • a technique for imprinting with a fluorine-based gas is generally known.
  • improvement of the adhesion to the substrate has been attempted by surface treatment of the substrate and the composition of the photocurable composition.
  • a mold used in the nanoimprint technology is usually produced by forming a target pattern by electron beam lithography or optical lithography and used as a master mold. Quartz, silicon, sapphire, etc. are used as the material, and the master mold requires time for production and the production equipment is expensive, so one piece is very expensive. There is a problem such as contamination due to or damage. Generally, a resin replica mold is produced from a master mold, and imprinting is performed using the replica mold. In particular, the larger the area, the more serious the above-mentioned problem for the master mold.
  • the replica mold is required to have a high-precision pattern forming ability and a releasability from the formed pattern.
  • durability against repeated use hereinafter simply referred to as “repetitive durability”).
  • a replica mold is often a laminate composed of a substrate layer such as a resin film and a concavo-convex pattern layer made of a coating material formed on the surface thereof, and the adhesion between the concavo-convex pattern layer and the substrate layer Furthermore, from the viewpoint of the cost of the replica mold, further improvement in the productivity of the replica mold is desired.
  • replica mold in the present invention is exactly the same as a replica mold having a pattern forming surface of a concavo-convex pattern complementary to the concavo-convex pattern formed on the pattern forming surface of the master mold, and the master mold. It includes both replica molds having a pattern forming surface of a concavo-convex pattern.
  • the adhesion between the concavo-convex pattern layer and the base material layer, and the peelability between the concavo-convex pattern layer formed from the coating material and the mold having the concavo-convex pattern for replica mold manufacture is also called “releasability from the mold”) by curing the substrate surface and the coating material in the nanoimprint technology. Similar to the relationship between the adhesiveness to the pattern to be formed and the releasability between the pattern and the mold, these are contradictory characteristics.
  • the object of the present invention is to reduce the film thickness of the coating material on which the uneven pattern on the replica mold is formed and to change the pattern while maintaining the releasability between the replica mold and the coating material of the substrate. It is an object of the present invention to provide a replica mold manufacturing method capable of suppressing the decrease of the above.
  • the present inventor has intensively studied to solve the above problems.
  • mold release process a process to improve the mold release property of the replica mold
  • the pattern surface on the replica mold transferred from the master mold is in the presence of H 2 O.
  • the silane coupling agent and release the mold react with the silane coupling agent and release the mold, thereby suppressing the decrease in film thickness and pattern change of the coating material on which the uneven pattern on the replica mold is formed
  • the present inventors have found that the releasability between the replica mold and the coating material of the base material can be obtained satisfactorily, and have completed the present invention.
  • the present invention comprises a laminate comprising a base material layer and a pattern layer, using a photocurable composition containing a polymerizable monomer, a silicon compound and a photopolymerization initiator as a coating material.
  • a method of manufacturing a replica mold for nanoimprinting wherein a laminate having a photocured film surface of a coating material formed by transferring a pattern with a mold is formed directly or indirectly on the base material layer.
  • a method for producing a replica mold for nanoimprinting characterized in that after being subjected to a plasma atmosphere in the presence of 2 O, a release treatment is performed by reacting with a silane coupling agent.
  • the atmospheric pressure in the plasma atmosphere is preferably 0.1 Pa to 100 Pa, and the partial pressure ratio of H 2 O in the plasma atmosphere is 0.001. It is preferable that it is above 0.03.
  • the pattern of the nanoimprint replica mold preferably has a diameter of 10 nm to 5 ⁇ m and a height of 10 nm to 5 ⁇ m.
  • the replica mold and the coating material on the substrate to be imprinted are suppressed while suppressing the decrease in the film thickness of the coating material on which the uneven pattern on the replica mold is formed and the change in the uneven pattern. It is possible to manufacture a nanoimprint replica mold having a high mold releasability.
  • the manufacturing method of the present invention has not yet been clarified in detail about the factors that can suppress the decrease in the film thickness of the coating material on which the uneven pattern on the replica mold is formed and the change in the uneven pattern. Guesses as follows. That is, in order to improve the mold releasability between the replica mold and the coating material on the imprint substrate, the mold release treatment is necessary, but it is used to form an uneven pattern on the replica mold.
  • the coating material is a photo-curable composition, and since ozone gas is generated by ⁇ ⁇ ⁇ V ozone treatment or vacuum ultraviolet light irradiation used in the mold release treatment, the coating material is etched by this ozone gas, As a result, it is presumed that the film thickness of the coating material has decreased and the uneven pattern has changed.
  • the manufacturing method of the present invention since it is used in a plasma atmosphere in the presence of H 2 O, it is presumed that water molecules become OH ⁇ ions in the plasma atmosphere and the surface of the concavo-convex pattern is made hydrophilic. For this reason, since the ozone gas which etches a coating-film material is not generated, it is estimated that the reduction
  • the present invention relates to a nanoimprint comprising a laminate comprising a base material layer and a pattern layer, using a photocurable composition containing a polymerizable monomer, a silicon compound and a photopolymerization initiator as a coating material.
  • a method for producing a replica mold for nanoimprinting characterized in that after being subjected to a plasma atmosphere in the presence of O, a release treatment is performed by reacting with a silane coupling agent.
  • the nanoimprint replica mold pattern manufactured by the method of the present invention has a diameter of 10 nm to 5 ⁇ m and a height of 10 nm to 5 ⁇ m from the viewpoint of being used for forming a semiconductor integrated circuit. Preferably there is.
  • the production method of the present invention can also be applied to the production of a replica mold for nanoimprint having a pattern larger than that.
  • the photocurable composition comprises a polymerizable monomer, a silicon compound, and a photopolymerization initiator.
  • any known polymerizable monomer can be used without any limitation.
  • the substrate layer and pattern such as high-precision pattern forming ability, mold releasability, repeated durability, resin film, etc. It is important to have excellent adhesion to the layer, and further to productivity. From the viewpoint of adhesion to the substrate layer such as a resin film and productivity, the photocurable monomer is preferable.
  • polymerizable monomer having a (meth) acrylic group meaning a methacrylic group or an acrylic group
  • polymerizable monomer having a (meth) acrylic group is a (meth) acrylic group-containing alkoxysilane represented by the general formula (3) which is a silicon compound described later and its hydrolysis. It shall not contain anything.
  • the polymerizable monomer having a (meth) acryl group (hereinafter also simply referred to as “polymerizable monomer”) is not particularly limited, and is a known polymerizable used for photopolymerization.
  • Monomers can be used.
  • the polymerizable monomer include polymerizable monomers having a (meth) acryl group and containing no silicon atom in the molecule.
  • These polymerizable monomers may be monofunctional polymerizable monomers having one (meth) acryl group in one molecule, or have two or more (meth) acryl groups in one molecule.
  • a polyfunctional polymerizable monomer may be used.
  • these monofunctional polymerizable monomers and polyfunctional polymerizable monomers can also be used in combination.
  • a polymerizable monomer which has one (meth) acryl group in 1 molecule, methyl (meth) acrylate, ethyl (meth), for example Acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, isoamyl (meth) acrylate, Isomyristyl (meth) acrylate, n-lauryl (meth) acrylate, n-stearyl (meth) acrylate, isostearyl (meth) acrylate, long chain alkyl (meth) acrylate, n-butoxyethyl (meth) acrylate, butoxydi
  • polyfunctional polymerizable monomer having two (meth) acryl groups in one molecule
  • polymerizable monomer having three or more (meth) acrylate groups in one molecule, ethoxylated glycerin tri (meth) acrylate, trimethylolpropane tri (meta) ) Acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, Examples include ethoxylated pentaerythritol tetra (meth) acrylate and dipentaerythritol polyacrylate.
  • polymerizable monomers may be used alone or in combination of a plurality of types.
  • the photocurable composition used in the present invention contains a silicon compound in addition to the polymerizable monomer described above.
  • silicon compounds it is more preferable to contain a silicon compound having a siloxane bond.
  • the silicon compound having such a siloxane bond any known compound can be used, but alkoxysilanes or hydrolysates of alkoxysilanes can be used, and alkoxysilanes or alkoxysilanes can be used.
  • the hydrolyzate of silanes for example, the following compounds can be used.
  • alkoxysilanes or hydrolysates of alkoxysilanes As alkoxysilanes, in addition to a general alkoxysilane in which one or more alkoxy groups are bonded to a silicon atom, an aromatic ring such as a phenyl group, a naphthyl group, or a biphenyl group can be used as a group other than the alkoxy group.
  • an alkoxysilane having a functional group such as an alkoxysilane, (meth) acryl group, epoxy group, thiol group, hydroxyl group, carboxyl group, phosphonium group or sulfonyl group, or an alkoxysilane having a halogen element such as fluorine or chlorine. It may be composed of a mixture thereof.
  • the hydrolyzate of alkoxysilanes is a product of hydrolysis of a part or all of the alkoxy groups of the above alkoxysilanes, a polycondensate of alkoxysilane, and a hydrolysis of part or all of the alkoxy groups of the polycondensate. Meaning products and various mixtures thereof.
  • the hydrolyzate of alkoxysilanes is preferable because the pattern transfer is easier as the dispersibility with the polymerizable monomer is better.
  • the hydrolyzate of alkoxysilanes It is preferable to use a hydrolyzate of an alkoxysilane having a (meth) acryl group, and when the polymerizable monomer has an epoxy group, a hydrolyzate of an alkoxysilane containing an epoxy group is preferable. .
  • alkoxysilanes that are alkoxysilanes, (meth) acryl group-containing alkoxysilanes, and alkoxysilanes having a halogen element will be described.
  • general alkoxysilane or its hydrolyzate Among the alkoxysilanes, general alkoxysilanes include those represented by the general formula (1)
  • An alkoxysilane represented by the formula (wherein R 1 is the same or different alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 10) can be preferably used.
  • the resulting photocurable composition is advantageous for pattern transfer at a relatively lower pressure.
  • R 1 which is an alkyl group having 1 to 4 carbon atoms includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, and a ter-butyl group. Of these, a methyl group and an ethyl group are preferable.
  • alkoxysilanes include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and polycondensates thereof.
  • tetramethoxysilane, tetraethoxysilane, and polycondensates thereof are preferred because they are alcohols that can be easily removed after the formation of the coating film, and because of reactivity, in particular, the value of n or n Preferred is tetramethoxysilane having a mean value of 3 to 7 or a polycondensate of tetraethoxysilane.
  • R 2 is a hydrogen atom or a methyl group
  • R 3 is an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, or a polymethylene group having 3 to 10 carbon atoms
  • R 4 is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms
  • R 5 is an alkyl group having 1 to 4 carbon atoms or 3 carbon atoms
  • Alkoxysilane can be preferably used
  • the hydrolyzate of the above (meth) acrylic group-containing alkoxysilane By using the hydrolyzate of the above (meth) acrylic group-containing alkoxysilane, a photocurable composition with good dispersibility can be obtained, purification by filtration is easy, and productivity is good, which is preferable.
  • the photocurable composition contains a hydrolyzate of this (meth) acrylic group-containing alkoxysilane, the inorganic component and the organic component are relatively homogeneous in the fine structure of the photocured film obtained by photocuring. It is dispersed in a state (the dispersion state is not such that inorganic components are extremely aggregated). As a result, it is estimated that a uniform transfer pattern and a uniform residual film can be formed.
  • R 2 is a hydrogen atom or a methyl group.
  • a hydrogen atom is preferable because the photocuring speed when curing the photocurable composition is high.
  • R 3 is an alkylene group having 1 to 10 carbon atoms or a cycloalkylene group having 3 to 10 carbon atoms.
  • the alkylene group having 1 to 10 carbon atoms includes methylene group, ethylene group, propylene group, isopropylene group, cyclopropylene group, butylene group, isobutylene group, sec-butylene group, tert-butylene group, cyclohexane Butylene group, cyclopropylmethylene group, 2,2-dimethylpropylene group, 2-methylbutylene group, 2-methyl-2-butylene group, 3-methylbutylene group, 3-methyl-2-butylene group, pentylene group, 2 -Pentylene group, 3-pentylene group, 2,3-dimethyl-2-butylene group, 3,3-dimethylbutylene group, 3,3-dimethyl-2-butylene group, 2-ethylbutylene group, hexylene group, 2- Hexylene group
  • the alkylene group having 1 to 10 carbon atoms is preferably a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, a trimethylene group, or a tetramethylene group.
  • the cycloalkylene group having 3 to 10 carbon atoms include a cyclopentylene group, a cyclohexylene group, and a cyclooctylene group.
  • R 4 is an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
  • the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group;
  • Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, and a cyclopropylmethyl group;
  • examples of the aryl group having 6 to 12 carbon atoms include benzene derivatives such as a phenyl group and a benzyl group, a 1-naphthyl group, a 2-naphthyl group, and o- Naphthalene derivatives such as
  • R 5 is an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 4 carbon atoms.
  • the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group;
  • Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, and a cyclopropylmethyl group.
  • R 5 is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group.
  • L is an integer from 0 to 2
  • m is an integer from 0 to 2
  • k is an integer from 1 to 3
  • l + m + k is 4.
  • (meth) acrylic group-containing alkoxysilanes include trimethoxysilylmethylene (meth) acrylate, trimethoxysilyldimethylene (meth) acrylate, trimethoxysilyltrimethylene (meth) acrylate, triethoxy Silylmethylene (meth) acrylate, triethoxysilyldimethylene (meth) acrylate, triethoxysilyltrimethylene (meth) acrylate, tripropoxysilylmethylene (meth) acrylate, tripropoxysilylethylene (meth) acrylate, tripropoxysilyl trimethylene (Meth) acrylate, tributoxysilylmethylene (meth) acrylate, tributoxysilyldimethylene (meth) acrylate, tributoxysilyltrimethylene (meth) acryl , Triisopropoxysilylmethylene (meth) acrylate, triisopropoxysilyldimethylene
  • alkoxysilane with halogen element As the alkoxysilane having a halogen element, the general formula (3)
  • R 6 and R 8 are each an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms;
  • R 7 is a fluorine-containing alkyl group, a fluorine-containing cycloalkyl group or a group containing A fluorine alkoxy ether group;
  • a is an integer of 1 to 3
  • the plurality of R 6 , R 7 and R 8 may be the same or different groups).
  • R 6 and R 8 are an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms, preferably a methyl group, an ethyl group, a propyl group, an isopropyl group. Butyl group, sec-butyl group, isobutyl group, and ter-butyl group. Specifically, R 6 is more preferably a methyl group, an ethyl group, or a propyl group.
  • R 7 is a fluorine-containing alkyl group, a fluorine-containing cycloalkyl group or a fluorine-containing alkoxy ether group.
  • the fluorine-containing alkyl group means one obtained by substituting one or more hydrogen atoms of an alkyl group with a fluorine atom, and other fluorine-containing cycloalkyl groups or fluorine-containing alkoxy ether groups are also cycloalkyl groups.
  • the fluorine-containing alkyl group and fluorine-containing alkoxy group preferably have 1 to 10 carbon atoms, and the fluorine-containing cycloalkyl group preferably has 3 to 10 carbon atoms. Further, the fluorine-containing alkoxy ether group in the present invention has the general formula (4)
  • x is preferably 1 to 6
  • y is preferably 5 to 50.
  • fluorinated silane compounds include (heptadecafluoro-1,1,2,2-tetrahydrodecyl) -triethoxysilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) -Trimethoxysilane, nonafluorohexyltriethoxysilane, nonafluorohexyltrimethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl) -triethoxysilane, (tridecafluoro-1,1,2 , 2-tetrahydrooctyl) -trimethoxysilane, pentafluoro-1,1,2,2-tetrahydropentyltriethoxysilane, pentafluoro-1,1,2,2-tetrahydropentyltrimethoxysilane, (3,3, 3-trifluoropropyl) dimethylethoxysilane,
  • Examples of the fluorinated silane compound having a fluorine-containing alkoxy ether group of the above general formula (4) include, for example, OPTOOL HD-1100TH manufactured by Daikin Industries, Ltd. Among these, the interaction between molecules is relatively weak and the molecular arrangement structure is disturbed, which is considered advantageous for surface releasability, and the ease of hydrolysis of the alkoxy group consisting of —OR 6 in the general formula (3). (Tridecafluoro-1,1,2,2-tetrahydrooctyl) -trimethoxysilane and (3,3,3-trifluoropropyl) trimethoxysilane are preferred.
  • the silicon compound is represented by the general formula (2).
  • Preferred is a hydrolyzed (meth) acrylic group-containing alkoxysilane, a general alkoxysilane represented by the general formula (1), and a (meth) acrylic group-containing general formula (2).
  • What hydrolyzed the fluorinated silane compound of alkoxysilane and the alkoxysilane which has a halogen element represented by the said General formula (3) is more preferable, Furthermore, the mixture containing the metal alkoxide mentioned later other than these alkoxysilanes A product obtained by hydrolyzing is preferable.
  • the preferable compounding quantity of the hydrolyzate of said alkoxysilane is, for example, when a photocurable composition contains the polymerizable monomer which has a (meth) acryl group as a polymerizable monomer.
  • the hydrolyzate of the (meth) acrylic group-containing alkoxysilane obtained by hydrolyzing 3 to 300 parts by mass with respect to 100 parts by mass of the polymerizable monomer having a (meth) acrylic group Furthermore, in addition to the (meth) acryl group-containing alkoxysilane, in the case where the general alkoxysilane is included, it is preferable to blend a hydrolyzate obtained by hydrolyzing 10 mass parts to 250 mass parts of a general alkoxysilane, When the fluorinated silane compound is contained in addition to the previous composition, 0.001 to 4 parts by mass of the fluorinated silane compound, In addition to silanes, when a metal alkoxide described later is included, it is preferable to blend a hydrolyzate obtained by hydrolyzing 1 to 100 parts by weight of the metal alkoxide.
  • the photocurable composition further includes a general formula (5) which is a metal alkoxide excluding alkoxylanes.
  • M is zirconium or titanium; and R 9 is the same or different alkyl group having 1 to 10 carbon atoms).
  • R 9 is more preferably an alkyl group having 2 to 4 carbon atoms from the viewpoint of an appropriate hydrolysis rate. Specifically, R 9 is preferably an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, or a ter-butyl group.
  • suitable metal alkoxides include tetramethyltitanium alkoxide, tetraethyltitanium alkoxide, tetraisopropyltitanium alkoxide, tetrapropyltitanium alkoxide, tetraisobutyltitanium alkoxide, tetrabutyltitanium alkoxide, tetrasec-butyltitanium alkoxide, tetrater-butyltitanium.
  • tetraethyl zirconium alkoxide tetraethyl zirconium alkoxide, tetraisopropyl zirconium alkoxide, tetrapropyl zirconium alkoxide, tetraisobutyl zirconium alkoxide, and tetrabutyl zirconium alkoxide are preferable.
  • the photocurable composition used in the present invention is a hydrolyzate of alkoxysilanes, a hydrolyzate of zirconium alkoxide or titanium alkoxide, a polycondensate of zirconium alkoxide or titanium alkoxide, and an alkoxy group of the polycondensate.
  • the photocurable composition may contain water, a hydrolysis catalyst, and the like.
  • water, a hydrolysis catalyst, and the like used when preparing the photocurable composition are vacuum-dried in any step of the preparation, It may be removed by distillation, heating or the like. At that time, in the case where the solvent is removed at the same time, a necessary amount of the solvent may be appropriately added after removing water, the hydrolysis catalyst, and the like.
  • Photopolymerization initiator Specific examples of the photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- ON, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy- 2-methylpropionyl) -benzyl] -phenyl ⁇ -2-methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-dimethylamino-2- (4 Acetophenone derivatives such as methylbenzyl) -1- (4-morph
  • photopolymerization initiators are used alone or in admixture of two or more.
  • ⁇ -diketone when used, it is preferably used in combination with a tertiary amine compound.
  • Tertiary amine compounds that can be used in combination with ⁇ -diketone include N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, N, N-dibenzylaniline.
  • acetophenone derivatives When used in nanoimprint technology, it is preferable to use acetophenone derivatives, acylphosphine oxide derivatives, o-acyloxime derivatives, and ⁇ -diketones.
  • the amount of the photopolymerization initiator used is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer.
  • a coating film is formed by applying a photocurable composition on a substrate according to a known method.
  • the substrate is not particularly limited, and a plate, sheet, or film can be used.
  • Specific examples include silicon wafers, quartz, glass, sapphire, various metal materials, ceramics such as alumina, aluminum nitride, silicon carbide, and silicon nitride, polyethylene terephthalate, polypropylene, polycarbonate, triacetyl cellulose, polystyrene, and cycloolefin resin.
  • a sheet or film made of any known thermoplastic resin can be used.
  • the photocured film which consists of a coating-film material used by this invention more on the base-material surface it can also surface-treat.
  • the surface treatment include known methods such as flame treatment, corona discharge treatment in the atmosphere or nitrogen gas, atmospheric pressure plasma treatment, blast treatment, honing treatment, soot V ozone treatment, and the like.
  • the coating material used in the present invention used in the present invention on the substrate
  • there are known methods such as a spin coating method, a dipping method, a dispensing method, and an ink jet method.
  • the thickness of the coating film is not particularly limited, and is usually 0.1 to 10 ⁇ m, and a coating film having a thickness of 0.01 to 0.1 ⁇ m can be suitably formed.
  • a pattern can also be formed by incorporating processes appropriately.
  • the pattern forming surface of the mold is brought into contact with the coating film.
  • the coating material is applied to the pattern forming surface of the mold by the above-described coating method to form a coating film, and the coating film is brought into contact with the base material of the replica mold.
  • the coating film formed on the pattern forming surface of the mold and having the pattern transferred may be integrated with the substrate.
  • a mold having a pattern forming surface can be cured with a transparent material such as quartz or sapphire or thermoplastic so that the coated film material to which the pattern is transferred can be cured by light irradiation and a cured coating film can be formed. It is preferably formed of a resin. If the mold with the pattern forming surface is a material with poor transparency such as a silicon wafer, the replica mold material must be light transmissive, such as quartz, sapphire, or thermoplastic that has light transmissive properties. A resin is preferred.
  • the photocurable composition used in the present invention can transfer a pattern at a relatively low pressure when pressing a mold.
  • the pressure at this time is not particularly limited, but is in the range of 0.01 MPa to 3 MPa.
  • the pattern can be transferred even at a pressure higher than the upper limit of the pressure.
  • the coating film on which the pattern has been transferred is photocured.
  • the pattern forming surface of the mold is kept in contact with the substrate layer including the coating film surface to which the pattern is transferred, or the mold
  • a pattern is formed by applying a coating material on the pattern surface
  • light is applied with the substrate in contact with the coating film on which the pattern on the pattern formation surface of the mold is transferred. Irradiate to cure the coating and to integrate the coating with the substrate.
  • the light to be irradiated has a wavelength of 500 nm or less, and the light irradiation time is selected from the range of 0.1 to 300 seconds. Although it depends on the thickness of the coating film, it is usually 1 to 60 seconds.
  • the atmosphere during photopolymerization can be polymerized even in the air, but in order to accelerate the photopolymerization reaction, photopolymerization in an atmosphere with little oxygen inhibition is preferred.
  • a nitrogen gas atmosphere, an inert gas atmosphere, a fluorine gas atmosphere, a vacuum atmosphere, or the like is preferable.
  • the surface of the laminate obtained by the above method is subjected to a mold release treatment.
  • a mold release treatment agent such as a silane coupling agent containing fluorine.
  • a pattern formation surface of a laminate that is a replica mold produced using a photocurable composition is subjected to a plasma atmosphere in the presence of H 2 O and then reacted with a silane coupling agent.
  • a plasma atmosphere in the presence of H 2 O and then reacted with a silane coupling agent.
  • OH ⁇ ions are generated from H 2 O in a plasma atmosphere to make the pattern formation surface hydrophilic.
  • ozone gas for etching the coating material is not generated, it is presumed that a decrease in the thickness of the coating material and a change in the uneven pattern can be suppressed.
  • H 2 O content is adjustable enclosed space.
  • Plasma maintains the inert gas and reactive gas pressure in the chamber at a constant reduced pressure, and uses the impact ionization of electrons and gas molecules accelerated by the electric field generated by the DC voltage or high-frequency voltage applied between the electrodes. Generated.
  • the plasma is composed of cations, electrons, and neutral atoms, and the plasma density increases as the voltage or pressure applied between the electrodes increases.
  • the electron density of a film forming apparatus or an etching apparatus using plasma is about 10 16 to 10 20 m ⁇ 3 .
  • the higher the plasma density the greater the damage to the coating material on the replica mold. From the viewpoint of the hydrophilic effect and the damage to the coating material, the applied voltage and pressure may be optimized.
  • the atmospheric pressure in the plasma atmosphere is preferably performed under a pressure of 0.1 Pa to 100 Pa from the viewpoint of ease of plasma discharge.
  • the atmosphere in which the plasma treatment is performed is preferably such that the partial pressure ratio of H 2 O is 0.01 or more in consideration of the abundance of hydroxyl groups, and the upper limit is 0.03 or less from the viewpoint of saturated water vapor pressure. Is preferred.
  • liquid H 2 O can be added.
  • Example 1 (Preparation of photocurable composition) 3.0 g of trimethoxysilyl trimethylene acrylate (KBS-5103, manufactured by Shin-Etsu Chemical Co., Ltd.) as the (meth) acrylic group-containing alkoxysilane, and ethyl silicate 40 (tetraethoxysilane, manufactured by Colcoat Co., Ltd.) as a general alkoxysilane. While stirring, a mixture of 6.8 g of ethanol and 13.6 g of ethanol was gradually added with 3.6 g of ethanol / 1.6 g of water / 2 N-HCl 0.1 g of a 2N-HCl / ethanol mixed aqueous solution.
  • KBS-5103 manufactured by Shin-Etsu Chemical Co., Ltd.
  • ethyl silicate 40 tetraethoxysilane, manufactured by Colcoat Co., Ltd.
  • the mixture is stirred at room temperature for 1 hour to obtain a mixture of a hydrolyzate of (meth) acryl group-containing alkoxysilane and a hydrolyzate of general alkoxysilane or a mixture of reaction products of a silicon compound. It was.
  • polyethylene glycol diacrylate manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-200
  • ethoxylated bisphenol A diacrylate manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A
  • BPE-10 ethoxypolyethylene glycol acrylate
  • NK ester AMP-10G ethoxypolyethylene glycol acrylate
  • NK ester A-LEN-10 5.0 g
  • tricyclodecane dimethanol diacrylate manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-DCP
  • polymerization inhibitor 0.0375 g of hydroquinone monomethyl ether and 0.005 g of butylhydroxytoluene were used.
  • the above polymerizable monomer, photopolymerization initiator and polymerization inhibitor were mixed uniformly, and 2.0 g of the mixture was taken. 7.0 g of the silicon compound obtained above was added to 2.0 g of the mixture, and the mixture was stirred at room temperature for 15 minutes to obtain a photocurable composition.
  • a 75 mm Ni mold having a pillar pattern with a height of 300 nm and a pitch of 300 nm and a PET film coated with the above-mentioned coating film are set in a nanoimprint apparatus (manufactured by SCIVAX, FLAN200), and vacuumed to 45 Pa.
  • a Ni mold and a substrate made of a PET film coated with the above-mentioned coating film were brought into contact with each other, a pressure of 3.0 MPa was applied, and light was emitted from an LED 365 nm light source for 60 seconds to perform ⁇ V nanoimprinting. . Thereafter, the PET film was peeled from the Ni mold to produce a replica mold.
  • the replica mold obtained above was set in a 108 A ⁇ toSp ⁇ terCoater made by Crestington, and in order to increase the H 2 O partial pressure ratio in the chamber, 0.1 ml of ultrapure water was dropped into the chamber in a chamber volume of 4000 ml. Thereafter, the chamber was sealed, the pressure was reduced to 10 Pa with a vacuum pump, and plasma treatment was performed for 120 seconds under the conditions of a discharge current value of 10 mA, a vacuum degree of 10 Pa, and a temperature of 25 ° C.
  • a photocurable resist (SVX-01 manufactured by SCIVAX Co., Ltd.) was applied with a spin coater so as to have a thickness of 120 nm, and the sapphire substrate was manufactured by a nanoimprint apparatus (manufactured by SCIVAX Co., Ltd.). , FLAN200), the resist surface is set upward, vacuumed to 45 Pa, the contact between the replica mold and the sapphire substrate, a pressure of 3.0 MPa is applied, and light is emitted from an LED 365 nm light source for 60 seconds to perform V nanoimprint. It was.
  • the PET film was peeled from the sapphire substrate, and pattern transfer was performed on the resist on the sapphire substrate.
  • Evaluation of releasability when peeling the PET film from the sapphire substrate and measurement of the pattern height were performed.
  • “ ⁇ ” indicates that the resist on the sapphire substrate is not peeled off
  • “ ⁇ ” indicates that the resist is peeled in an area of 10% to 50% of the wafer area
  • “ ⁇ ” indicates that the resist is peeled in an area of 50% or more.
  • the above three-level evaluation was adopted.
  • the pattern height was measured from the pattern cross section using a scanning electron microscope. In Table 1, when the pattern height was determined as “x”, the resist on the sapphire substrate was peeled off to the extent that the length could not be measured.
  • Example 2 A replica mold was prepared in the same manner as in Example 1 except for the mold release process conditions (discharge current value, plasma processing time, presence of ultrapure water dripping in the chamber), and evaluation of mold release and pattern height were performed. Measurements were made. The results are shown in Table 1.
  • Example 1 In the mold release treatment process of the replica mold, the plasma process was not performed and the film was immersed in the same silane coupling agent as in Example 1. The subsequent process was performed in the same manner as in Example 1 to produce a replica mold. Using the replica mold thus produced, pattern transfer was performed on the photocurable resist on the sapphire substrate. Table 1 shows the releasability and pattern height.
  • the photocurable film side is irradiated with ultraviolet light at a distance of 3 mm from the lamp in a chamber equipped with a low-pressure mercury lamp without performing plasma processing. It was set and irradiated with ultraviolet light for 1 minute (Comparative Example 2), 2 minutes (Comparative Example 3), and 5 minutes (Comparative Example 4) in an atmospheric environment. Then, it was immediately immersed in the silane coupling agent similar to Example 1, and the subsequent process was performed similarly to Example 1, and the replica metal mold
  • Example 2 shows the releasability and pattern height. Evaluation of releasability and pattern height were performed in the same manner as in Example 1.

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  • Mechanical Engineering (AREA)
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Abstract

Procédé de production d'un moule à empreinte pour nano-impression, qui utilise, en tant que matériau de film de revêtement, une composition photodurcissable qui contient un monomère polymérisable, un composé de silicium et un initiateur de photopolymérisation, ledit moule à empreinte étant composé d'un stratifié qui comprend une couche de matériau de base et une couche de motif. Ce procédé de production d'un moule à empreinte pour nano-impression est caractérisé en ce qu'un stratifié ayant une surface de film photodurci du matériau de film de revêtement, qui est formé directement ou indirectement sur la couche de matériau de base et a un motif transféré au moyen d'un moule, est soumis à une atmosphère de plasma en présence de H2O, et est ensuite amené à réagir avec un agent de couplage au silane pour démoulage.
PCT/JP2017/041323 2016-12-06 2017-11-16 Procédé de production d'un moule de nano-impression Ceased WO2018105353A1 (fr)

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JP2021111668A (ja) * 2020-01-08 2021-08-02 コネクテックジャパン株式会社 基板にパターン形成する導電部の形成方法
JP2023518791A (ja) * 2020-08-25 2023-05-08 エルジー・ケム・リミテッド 大面積ホログラフィック光学素子の複製方法およびこれにより複製された大面積ホログラフィック光学素子

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JP2008207475A (ja) * 2007-02-27 2008-09-11 Institute Of Physical & Chemical Research レプリカモールドの製造方法およびレプリカモールド
WO2014168237A1 (fr) * 2013-04-12 2014-10-16 株式会社カネカ Procédé de reproduction de structure, procédé de fabrication de puce de capteur à résonance plasmonique de surface localisée comprenant ce procédé de reproduction, structure, puce de capteur de résonance plasmonique de surface localisée et capteur de résonance plasmonique de surface localisée
JP2015037169A (ja) * 2013-08-16 2015-02-23 大日本印刷株式会社 インプリントシステム及びインプリント方法
JP2015131481A (ja) * 2013-12-12 2015-07-23 株式会社トクヤマ ナノインプリント用レプリカ金型の製造方法

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JP2008207475A (ja) * 2007-02-27 2008-09-11 Institute Of Physical & Chemical Research レプリカモールドの製造方法およびレプリカモールド
WO2014168237A1 (fr) * 2013-04-12 2014-10-16 株式会社カネカ Procédé de reproduction de structure, procédé de fabrication de puce de capteur à résonance plasmonique de surface localisée comprenant ce procédé de reproduction, structure, puce de capteur de résonance plasmonique de surface localisée et capteur de résonance plasmonique de surface localisée
JP2015037169A (ja) * 2013-08-16 2015-02-23 大日本印刷株式会社 インプリントシステム及びインプリント方法
JP2015131481A (ja) * 2013-12-12 2015-07-23 株式会社トクヤマ ナノインプリント用レプリカ金型の製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021111668A (ja) * 2020-01-08 2021-08-02 コネクテックジャパン株式会社 基板にパターン形成する導電部の形成方法
JP7382835B2 (ja) 2020-01-08 2023-11-17 コネクテックジャパン株式会社 半導体装置の配線形成方法
TWI872160B (zh) * 2020-01-08 2025-02-11 日商肯耐克科技股份有限公司 半導體裝置的配線形成方法
JP2023518791A (ja) * 2020-08-25 2023-05-08 エルジー・ケム・リミテッド 大面積ホログラフィック光学素子の複製方法およびこれにより複製された大面積ホログラフィック光学素子

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