WO2011021573A1 - パターン形成方法 - Google Patents

パターン形成方法 Download PDF

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WO2011021573A1
WO2011021573A1 PCT/JP2010/063719 JP2010063719W WO2011021573A1 WO 2011021573 A1 WO2011021573 A1 WO 2011021573A1 JP 2010063719 W JP2010063719 W JP 2010063719W WO 2011021573 A1 WO2011021573 A1 WO 2011021573A1
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group
resin layer
formula
examples
carbon atoms
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PCT/JP2010/063719
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English (en)
French (fr)
Japanese (ja)
Inventor
郁宏 豊川
匡史 岡本
幸生 西村
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Jsr株式会社
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Priority to JP2011527656A priority Critical patent/JPWO2011021573A1/ja
Priority to KR1020127004084A priority patent/KR101680407B1/ko
Publication of WO2011021573A1 publication Critical patent/WO2011021573A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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

Definitions

  • the present invention relates to a pattern forming method. More specifically, the present invention relates to a pattern forming method using an optical imprint lithography method using a translucent stamper.
  • a finer processing technique In order to improve the integration degree and recording density of circuits such as semiconductor elements, a finer processing technique is required.
  • a photolithography technique using an exposure process can perform a fine processing of a large area at a time, but does not have a resolution below the wavelength of light.
  • photolithography technology using short wavelength light of 193 nm (ArF), 157 nm (F2), and 13.5 nm (EUV) has been developed.
  • the wavelength of light becomes shorter, the substances that can be transmitted at that wavelength are limited.
  • the resolution does not depend on the wavelength of light and a fine structure can be created, but poor throughput is a problem.
  • the resist-coated substrate is heated above the glass transition temperature to soften the resist, so that when the pressed stamper is peeled off from the resist film, the resist film is peeled off with a part of the resist film attached.
  • resist film peeling In order to solve this “resist film peeling”, improvement of a stamper has been studied.
  • Patent Document 3 below is known.
  • Patent Document 4 discloses a pattern forming method in which another material is embedded in a concave portion of a pattern after imprinting and the pattern is inverted.
  • Patent Document 3 is a stamper whose surface is fluorinated.
  • this method has a problem that the effect of the surface treatment is lost as the number of times of use of the stamper is increased, and if the number of times of use of the stamper is large, "resist film peeling" may occur frequently.
  • the resist film (which is a shape-transferring layer referred to in the present invention) has not yet been prevented from peeling off.
  • Patent Document 4 discloses a method of etching a substrate to be processed by a RIE (reactive ion etching) method using a pattern after inversion as a mask.
  • Patent Document 4 discloses a method of peeling a stamper.
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide a pattern forming method capable of suppressing “resist film peeling”.
  • a first resin layer forming step (1) for forming a first resin layer mainly composed of an organic polymer on a substrate
  • a second resin layer forming step (2) for forming a second resin layer mainly composed of an organic polymer on the surface of the first resin layer
  • a recess forming step (3) for forming a recess in the second resin layer by pressing and releasing a stamper having a protrusion on the second resin layer
  • a filling part forming step (4) for forming a filling part mainly composed of an inorganic polymer in the concave part
  • An etching step (5) for etching the first resin layer and the second resin layer using the filling portion as a mask.
  • ⁇ 2> The pattern forming method according to ⁇ 1>, wherein the inorganic polymer is polysiloxane.
  • ⁇ 3> The pattern forming method according to ⁇ 1> or ⁇ 2>, wherein the first resin layer is made of a material having an etching rate slower than that of the second resin layer.
  • a pattern can be formed while suppressing peeling of the resist film. Further, a residual film in which the resist film is left in the recess formed in the recess forming step is formed, so that an adhesive surface between the first resin layer and the second resin layer is increased, and the resist film is peeled off (first film). The delamination between the first resin film and the second resin film) can be more effectively suppressed. That is, normally, when a process such as etching is performed using a pattern as a mask, the remaining film in the concave portion which is avoided functions advantageously in this method.
  • the etching process in step (5) and the pattern obtained by this method are not affected, and precise control of the remaining film in the recesses is unnecessary. It is.
  • the inorganic polymer is polysiloxane, it is possible to obtain better selectivity in etching the first resin layer and the second resin layer and the filling portion. Furthermore, since the flatness of the coating film when applied by spin coating is good, when an unnecessary filling portion forming resin layer (a layer made of filling portion forming resin) is removed from the first resin layer. Damage to the filling portion forming resin to be left in the recess can be minimized.
  • fever to the 1st resin layer can be suppressed.
  • the first resin layer is made of a material whose etching rate is slower than that of the second resin layer, a pattern with a higher aspect ratio can be produced by processing the substrate using the filling portion as a mask.
  • throughput can be increased.
  • (meth) acryl means acryl and methacryl
  • (meth) acrylate means acrylate and methacrylate
  • the pattern forming method of the present invention includes a first resin layer forming step (1), a second resin layer forming step (2), a recess forming step (3), and a filling portion forming step (4). And an etching step (5) (see FIGS. 1 and 2).
  • the “first resin layer forming step (1)” is a step of forming the first resin layer 31 mainly composed of an organic polymer on the substrate 20.
  • the first resin layer is a resin layer containing an organic polymer as a main component.
  • the organic polymer as a main component means that the organic polymer (polymer having a carbon skeleton) is 95% by mass or more (100% by mass) when the entire first resin layer is 100% by mass. ) Means contained. That is, in other words, it means that the inorganic polymer described later is not contained, or even if it is contained, it is less than 5% by mass.
  • the first resin layer only needs to have an organic polymer as a main component, and the composition thereof is not particularly limited.
  • JP 2004-168748 A JP 2005-128509 A, and JP 2007-240630 A. It is preferable to use a resin layer used as a resist underlayer film described in the publication. Furthermore, a first resin layer formed on a substrate using the following first resin layer forming compositions (1) to (3) is preferable.
  • the first resin layer forming composition (1) includes (1A) an alkali-soluble resin having a phenolic hydroxyl group, (1B) an acid generator represented by the following formula (1), (1C) a crosslinking agent, Containing.
  • each R independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, —R 1 OH, —R 2 OR 3 or —R 4 OR 5 OR 6 , and n represents 1 or 2
  • each X independently represents a halogen atom.
  • R 1 is a methylene group or an alkylene group having 2 to 6 carbon atoms
  • R 2 is a methylene group or an alkylene group having 2 to 4 carbon atoms
  • R 3 is an alkyl group having 1 to 6 carbon atoms
  • R 4 is a methylene group or An alkylene group having 2 to 4 carbon atoms
  • R 5 represents a methylene group or an alkylene group having 2 to 6 carbon atoms
  • R 6 represents an alkyl group having 1 to 6 carbon atoms.
  • n is 1 or 2.
  • alkali-soluble resin (1A) examples include novolak resin, polyhydroxystyrene ⁇ hydroxystyrene homopolymer, styrene derivatives such as hydroxystyrene, styrene, vinylbenzoic acid, and (meth) acrylic acid derivatives.
  • a copolymer using at least hydroxystyrene ⁇ , a phenol-xylylene glycol condensation resin, and the like are preferable.
  • the novolak resin include a phenol / formaldehyde condensation type, a cresol / formaldehyde condensation type, and a phenol-naphthol / formaldehyde condensation type.
  • the alkali-soluble resin (1A) has a polystyrene equivalent weight average molecular weight of preferably 2000 or more, and more preferably 2000 to 20000. Further, the content of the alkali-soluble resin (1A) is preferably 30 to 90% by mass, more preferably 40 to 80% by mass with respect to 100% by mass of the entire composition (1) excluding the solvent.
  • the acid generator (1B) is a compound having an s-triazine skeleton, and includes 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (m -Methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [4- [2- ⁇ 4,6-bis (trichloromethyl) -1,3,5-triazine- 2-yl ⁇ vinyl] phenoxy] ethanol, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- ( 2,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine and the like.
  • the amount of the acid generator (1B) is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight, and more preferably 0.5 to 3 parts by weight with respect to 100 parts by weight of the alkali-soluble resin (1A). Part is more preferred.
  • the crosslinking agent (1C) acts as a crosslinking component (curing component) that reacts with the alkali-soluble resin (1A).
  • the cross-linking agent (1C) include compounds having at least two alkyl etherified amino groups in the molecule such as hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethylglycoluril, etc.
  • a crosslinking agent having an —OR x group (where R x is an n-butyl group or an iso-butyl group) is more preferable.
  • the cross-linking agent containing an —OR x group can control the sublimation property of the cross-linking agent (in particular, suppress the sublimation property of the cross-linking agent).
  • a gas (under standard conditions) (1-butene, 2-butene, iso-butene) derived from the —OR x group can be generated at the time of thermal decomposition, and this is preferable because contamination at various places can be suppressed.
  • crosslinking agent having —OR x group examples include —OR x group-modified glycoluril compound, —OR x group-modified polynuclear phenol, —OR x group-modified amino resin, and the like.
  • examples of the —OR x group-modified glycoluril compound include the hexabutoxymethyl melamine and the tetrabutoxymethyl glycoluril.
  • the above-mentioned polynuclear phenol is —OR x
  • the above-mentioned polynuclear phenol is —OR x
  • the —OR x group-modified amino resin include co-condensates of urea, thiourea, ethylene urea, melamine benzoguanamine and the like with formaldehyde, their n-butyl alcohol, and iso-butyl. Alcohol or methyl alcohol processed material etc. are mentioned.
  • the amount of the crosslinking agent (1C) is preferably 1 to 100 parts by mass and more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the alkali-soluble resin (1A). Further, when the total of the alkyl etherified compound having an amino group and the oxirane ring-containing compound is 100% by mass, the content of the oxirane ring-containing compound is preferably 50% by mass or less, more preferably 5 to 40% by mass. preferable. In addition, it can contain at least one of adhesion assistants (1D), surfactants (1E), solvents (1F), etc., which will be described later.
  • the first resin layer forming composition (2) comprises (2A) a polymer containing one of the structural unit represented by the following formula (2) and the structural unit represented by the following formula (3); 2B) An acid generator and (2C) a crosslinking agent.
  • R 1 represents a monovalent organic group
  • R 2 and R 3 each independently represent a hydrogen atom or a C 1-6 substitutable alkyl group.
  • R 1 represents a monovalent organic group
  • R 2 represents a hydrogen atom or a substitutable alkyl group having 1 to 6 carbon atoms
  • n is 0 or 1.
  • the monovalent organic group as R 1 in the formula (2) includes a substitutable alkyl group having 1 to 6 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, a carbonyl group, and 1 to 6 carbon atoms. And an alkoxymethylol group having 1 to 6 carbon atoms.
  • Examples of the substitutable alkyl group having 1 to 6 carbon atoms as R 1 in the formula (2) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a 1-methylpropyl group. 2-methylpropyl group, t-butyl group, n-pentyl group, n-hexyl group and the like.
  • examples of the substituent include alkyl groups having 1 to 4 carbon atoms, aryl groups having 6 to 20 carbon atoms, and polar groups other than hydrocarbon groups. Only 1 type may be used for a substituent and it may use 2 or more types together.
  • each substituent may be the same and may differ.
  • examples of polar groups include alkoxy groups (methoxy groups, ethoxy groups, propoxy groups, butoxy groups, etc.), hydroxy groups, carboxyl groups, oxo groups ( ⁇ O), alkyloxycarbonyl groups, acetoxy groups (—OCOCH 3 ), etc. Is mentioned.
  • the alkoxy group having 1 to 6 carbon atoms as R 1 in the formula (2) includes methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 1-methylpropoxy group, 2- Examples include a methylpropoxy group, a t-butoxy group, an n-pentyloxy group, and an n-hexyloxy group.
  • the alkoxycarbonyl group having 1 to 6 carbon atoms as R 1 in the formula (2) includes a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, 1- Examples include methylpropoxycarbonyl group, 2-methylpropoxycarbonyl group, t-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group and the like.
  • the alkoxymethylol group having 1 to 6 carbon atoms as R 1 in the formula (2) includes a methoxymethylol group, an ethoxymethylol group, an n-propoxymethylol group, an i-propoxymethylol group, an n-butoxymethylol group, 1- Examples thereof include a methylpropoxymethylol group, a 2-methylpropoxymethylol group, a t-butoxymethylol group, an n-pentyloxymethylol group, and an n-hexyloxymethylol group.
  • the substitutable alkyl group having 1 to 6 carbon atoms as R 2 and R 3 in the formula (2) is the same as the substitutable alkyl group having 1 to 6 carbon atoms as R 1 in the formula (2). Applicable. However, R 2 and R 3 in the formula (2) may be the same or different, and R 2 and R 3 in the formula (2) are the same as R 1 in the formula (2). Or may be different.
  • Examples of the monomer that gives the structural unit represented by the formula (2) include hydroxymethylacenaphthylene (3-, 4-, 5-), methoxymethylacenaphthylene (3-, 4-, 5-). -), Acetoxymethylacenaphthylene (3-, 4-, 5-) and the like are preferable. These monomers may use only 1 type and may use 2 or more types together.
  • the 1st resin layer excellent in etching tolerance can be obtained.
  • the content ratio of the structural unit represented by the formula (2) in the polymer (2A) is preferably 5 to 80 mol% with respect to 100 mol% in total of all the structural units constituting the polymer (2A). 30 to 80 mol% is more preferable, and 50 to 70 mol% is still more preferable.
  • the monovalent organic group as R 1 in the formula (2) can be directly applied to the monovalent organic group as R 1 in the formula (3).
  • R 1 of each of the formulas (2) and (3) may be the same or may be different.
  • the monovalent organic group as R 2 in the formula (2) can be directly applied to the monovalent organic group as R 2 in the formula (3).
  • R 2 in Formula (2) and Formula (3) may be the same or different.
  • the 1st resin layer excellent in etching tolerance can be obtained.
  • the content ratio of the structural unit represented by the formula (3) in the polymer (2A) is preferably 5 to 80 mol% with respect to 100 mol% in total of all the structural units constituting the polymer (2A). 30 to 80 mol% is more preferable, and 50 to 70 mol% is still more preferable.
  • the polymer (2A) includes at least one of a structural unit represented by the following formula (4), a structural unit represented by the following formula (5), and a structural unit represented by the following formula (6).
  • a structural unit represented by the following formula (4), R 2 and R 3 each independently represent a hydrogen atom or a C 1-6 substitutable alkyl group.
  • R 1 represents a hydrogen atom or a C 1-6 substitutable alkyl group
  • R 2 represents a hydrogen atom or a methyl group
  • X represents a methylene group or a phenylene group.
  • R 1 represents a monovalent organic group
  • n is an integer of 0 to 3.
  • R 2 represents a hydrogen atom or a substitutable alkyl group having 1 to 6 carbon atoms.
  • the group can be applied as it is.
  • the R 2 and R 3 of the the R 2 and R 3 in the formula (2) (4) may be another same or may be different.
  • a hydrogen atom or a methyl group is preferable.
  • Examples of the monomer that gives the structural unit represented by the formula (4) include acenaphthylene, 1-methylacenaphthylene, 1,2-dimethylacenaphthylene, and the like.
  • These monomers may use only 1 type and may use 2 or more types together.
  • the structural unit represented by the formula (4) in the polymer (2A) is included, the content ratio is 5 to 95 with respect to 100 mol% in total of all the structural units constituting the polymer (2A). Mole% is preferable, 10 to 90 mol% is more preferable, and 20 to 80 mol% is still more preferable.
  • the substitutable alkyl group having 1 to 6 carbon atoms as R 2 in the formula (5) is the same as the substitutable alkyl group having 1 to 6 carbon atoms as R 2 and R 3 in the formula (2). Applicable. However, the formula (2) and R 2 and R 3 with R 2 of the formula (5) may be each other identical or different. Examples of the monomer that gives the structural unit represented by the formula (5) include N-methylolacrylamide, N-methoxymethylacrylamide, Nn-butoxymethylacrylamide, N-isobutoxymethylacrylamide, dimethylaminopropylmethacrylamide.
  • the structural unit represented by the formula (5) in the polymer (2A) the content ratio is 5 to 80 with respect to 100 mol% in total of all the structural units constituting the polymer (2A). Mol% is preferable, 5 to 60 mol% is more preferable, and 5 to 60 mol% is still more preferable.
  • the monovalent organic group as R 1 in the formula (2) can be applied as it is.
  • the formula (2) is R 1 and the R 1 in the formula (4) may be another same or may be different.
  • the substitutable alkyl group having 1 to 6 carbon atoms as R 2 in the formula (6) the substitutable alkyl group having 1 to 6 carbon atoms as R 2 in the formula (3) is applied as it is. it can.
  • the formula (3) is R 2 and the R 2 in the formula (6) may be another same or may be different.
  • Examples of the monomer that provides the structural unit represented by the formula (6) include styrene, hydroxystyrene, styrene, ⁇ -methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, and 4-methoxystyrene.
  • the content ratio is 0.1% with respect to 100 mol% in total of all the structural units constituting the polymer (2A). -50 mol% is preferable, 1-30 mol% is more preferable, and 3-10 mol% is still more preferable.
  • the polystyrene equivalent weight average molecular weight (Mw) of the polymer (2A) measured by gel permeation chromatography is preferably 500 to 10,000, more preferably 2000 to 5,000.
  • onium salt compounds including thiophenium salt compounds
  • halogen-containing compounds diazoketone compounds, sulfone compounds, sulfonic acid compounds, diazomethane compounds, and the like
  • this acid generator (2B) only 1 type may be used and 2 or more types may be used together.
  • onium salt compounds examples include 4,7-di-n-butoxynaphthyltetrahydrothiophenium salt compounds, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium salt compounds, 1- (6- thiophenium salt compounds such as n-butoxynaphthalen-2-yl) tetrahydrothiophenium salt compound and 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium salt compound; bis (4-t-butylphenyl) ) Iodonium salt compounds such as iodonium salt compounds and diphenyliodonium salt compounds; triphenylsulfonium salt compounds, 4-t-butylphenyldiphenylsulfonium salt compounds, 4-cyclohexylphenyldiphenylsulfonium salt compounds, 4-methanesulfonylphenyldiphenyl Sulfonium salt compounds such as
  • halogen-containing compound examples include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Specific examples include (trichloromethyl) -s-triazine derivatives.
  • diazoketone compound examples include a 1,3-diketo-2-diazo compound, a diazobenzoquinone compound, a diazonaphthoquinone compound, and the like.
  • sulfonated product include ⁇ -ketosulfone, ⁇ -sulfonylsulfone, and ⁇ -diazo compounds of these compounds.
  • Examples of the sulfonic acid compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates.
  • Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl- Examples include 1,1-dimethylethylsulfonyldiazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, and the like.
  • the blending amount of the acid generator (2B) is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and 0.5 to 3 parts by mass with respect to 100 parts by mass of the polymer (2A). Is more preferable.
  • the (1C) crosslinking agent can be applied as it is.
  • the amount of the crosslinking agent (2C) is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the polymer (2A).
  • it is the same as the composition (1) that it can contain at least one of an adhesion assistant (1D), a surfactant (1E), a solvent (1F) and the like which will be described later.
  • the first resin layer forming composition (3) is (3A) a structural unit represented by the following formula (7), a structural unit represented by the following formula (8), and a structure represented by the following formula (10).
  • a polymer containing a unit, (3B) an acid generator, and (3C) a crosslinking agent are contained.
  • R 1 to R 4 each independently represents a hydrogen atom, a hydroxyl group, a substitutable alkyl group having 1 to 20 carbon atoms, a substitutable alkoxy group having 1 to 20 carbon atoms, a carbon number Represents an alkoxycarbonyl group having 1 to 20 carbon atoms, an acetoxy group, an aryl group having 6 to 10 carbon atoms, an isocyanate group or a glycidyl ether group;
  • R 5 to R 8 each independently represents a hydrogen atom, a hydroxyl group, a substitutable alkyl group having 1 to 20 carbon atoms, a substitutable alkoxy group having 1 to 20 carbon atoms, a carbon number Represents an alkoxycarbonyl group having 1 to 20 carbon atoms, an acetoxy group, an aryl group having 6 to 10 carbon atoms, an isocyanate group, a glycidyl ether group, or
  • R 9 represents an alkylene group having 1 to 4 carbon atoms
  • R 10 represents a group having a cyclic structure having 4 to 20 carbon atoms.
  • R 11 represents an alicyclic hydrocarbon group having 4 to 20 carbon atoms.
  • the substitutable alkyl group having 1 to 20 carbon atoms as R 1 to R 4 in the formula (7) includes a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, 1- Examples thereof include a methylpropyl group, a 2-methylpropyl group, a t-butyl group, an n-pentyl group, and an n-hexyl group.
  • examples of the substituent include alkyl groups having 1 to 4 carbon atoms, aryl groups having 6 to 20 carbon atoms, and polar groups other than hydrocarbon groups. Only 1 type may be used for a substituent and it may use 2 or more types together.
  • each substituent may be the same and may differ.
  • examples of polar groups include alkoxy groups (methoxy groups, ethoxy groups, propoxy groups, butoxy groups, etc.), hydroxy groups, carboxyl groups, oxo groups ( ⁇ O), alkyloxycarbonyl groups, acetoxy groups (—OCOCH 3 ), etc. Is mentioned.
  • Examples of the substitutable alkoxy group having 1 to 20 carbon atoms as R 1 to R 4 in the formula (7) include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 1- Examples thereof include a methylpropoxy group, a 2-methylpropoxy group, a t-butoxy group, an n-pentyloxy group, and an n-hexyloxy group. Further, as the substituent, the substituent in the substitutable alkyl group having 1 to 20 carbon atoms can be applied as it is.
  • the alkoxycarbonyl group having 1 to 20 carbon atoms as R 1 to R 4 in the formula (7) includes a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, and an n-butoxycarbonyl group.
  • the aryl group having 6 to 10 carbon atoms as R 1 to R 4 in the formula (7) includes a phenyl group, a tolyl group (o-, m-, p-), a naphthyl group (1-, 2-), A phenanthryl group, an anthranyl group, etc. are mentioned.
  • Monomers that give the structural unit represented by the formula (7) include phenol, cresol (o-, m-, p-), dimethylphenol (2,3-, 2,5-, 3,4- 3,5-, 2,4-, 2,6-), trimethylphenol (2,3,5-, 3,4,5-), butylphenol (2-t-, 3-t-, 4-t) -), Resorcinol, methylresorcinol (2-, 4-, 5-), catechol, 4-t-butylcatechol, methoxyphenol (2-, 3-), propylphenol (2-, 3-, 4-), Examples thereof include isopropylphenol (2-, 3-, 4-), 2-methoxy-5-methylphenol, 2-tert-butyl-5-methylphenol, pyrogallol, thymol, and isothymol.
  • the content ratio of the structural unit represented by the formula (7) in the polymer (3A) is preferably 1 to 30 mol% with respect to 100 mol% in total of all the structural units constituting the polymer (3A). 3 to 25 mol% is more preferable, and 5 to 20 mol% is still more preferable.
  • R 1 to R 4 in the above formula (8) as a C 1-20 substitutable alkyl group, a C 1-20 substitutable alkoxy group, a C 1-20 alkoxycarbonyl group, a carbon number 6
  • Each group in formula (7) can be applied as it is to the aryl groups of ⁇ 10.
  • R 1 to R 4 in the formula (7) and R 5 to R 8 in the formula (8) may be the same as or different from each other.
  • Examples of the alkylene group having 1 to 4 carbon atoms as R 9 in the formula (9) include a methylene group, an ethylene group, a propylene group, and an isopropylene group.
  • the group having a cyclic structure having 4 to 20 carbon atoms as R 10 in the formula (9) is sufficient if it has a cyclic structure, a monovalent alicyclic hydrocarbon group, a monovalent aromatic group, a monovalent group.
  • Groups having a heterocyclic structure of Examples of monovalent alicyclic hydrocarbon groups include alicyclic rings derived from norbornane, tricyclodecane, tetracyclododecane, adamantane, cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane. And a monovalent group having.
  • alicyclic hydrocarbon groups may or may not have a substituent.
  • Substituents having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, etc.
  • An alkyl group is mentioned.
  • Examples of the monovalent aromatic group include a phenyl group, a tolyl group (o-, m-, p-), a naphthyl group (1-, 2-), a phenanthryl group, and an anthranyl group.
  • examples of the group having a monovalent heterocyclic structure include monovalent groups derived from heterocyclic rings such as indole, pyrimidine, piperidine, morpholine, pyran, furan, piperazine, and pyridine.
  • R 10 in the formula (9) include the following various groups.
  • the bonding positions of R 9 with respect to R 10 are only examples, and are not limited to these bonding positions, and are each other bonding positions. May be.
  • the content ratio of the structural unit represented by the formula (8) in the polymer (3A) is preferably 30 to 90 mol% with respect to 100 mol% in total of all the structural units constituting the polymer (3A). It is more preferably 35 to 80 mol%, still more preferably 40 to 75 mol%.
  • Examples of the alicyclic hydrocarbon group having 4 to 20 carbon atoms as R 11 in the formula (10) include norbornane, tricyclodecane, tetracyclododecane, adamantane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and cyclooctane. And divalent groups having an alicyclic ring derived from cycloalkanes and the like. These alicyclic hydrocarbon groups may or may not have a substituent.
  • Substituents having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, etc.
  • An alkyl group is mentioned.
  • Examples of the monomer that gives the structural unit represented by the formula (10) include dicyclopentadiene, bicyclo (4,3,0) nona-3,7-diene, 4-vinylcyclohexene, norbornadiene, 5-vinylnorborna- Examples thereof include unsaturated alicyclic hydrocarbon compounds such as 2-ene, ⁇ -pinene, ⁇ -pinene and limonene. These monomers may use only 1 type and may use 2 or more types together. In the case where isomers exist in these monomers, any isomer may be used, or only one isomer may be used, and a mixture of two or more isomers may be used. It may be used.
  • the content of the structural unit represented by the formula (10) in the polymer (3A) is preferably 9 to 60 mol% with respect to a total of 100 mol% of all the structural units constituting the polymer (3A). 10 to 50 mol% is more preferable, and 15 to 45 mol% is still more preferable.
  • the polystyrene equivalent weight average molecular weight (Mw) of the polymer (3A) measured by gel permeation chromatography is preferably 1500 to 200000, more preferably 2000 to 10000.
  • the method for preparing this polymer (3A) is not particularly limited. Usually, after preparing a copolymer containing the above formula (7) and the above formula (10), the above formula contained in the obtained copolymer is used. It can be obtained by introducing the group represented by the formula (9) into the structural unit of (7) using a compound represented by [HO—R 9 -R 10 ].
  • the (2B) acid generator can be applied as it is, and further, bis-O- (p-toluenesulfonyl) - ⁇ -dimethylglyoxime, bis-O- (camphorsulfonyl) Glyoxime derivatives such as - ⁇ -dimethylglyoxime can be used.
  • These acid generators (3B) may use only 1 type, and may use 2 or more types together.
  • the blending amount of the acid generator (3B) is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and 0.5 to 3 parts by mass with respect to 100 parts by mass of the polymer (3A). Is more preferable.
  • the (1C) crosslinking agent can be applied as it is to the (3C) crosslinking agent.
  • the amount of the crosslinking agent (3C) is preferably 1 to 100 parts by weight and more preferably 5 to 50 parts by weight with respect to 100 parts by weight of the polymer (3A).
  • it is the same as the composition (1) that it can contain at least one of an adhesion assistant (1D), a surfactant (1E), a solvent (1F) and the like which will be described later.
  • the adhesion aid (1D) is not particularly limited as long as it is a component that can improve the adhesion between the first resin layer and the substrate.
  • the adhesion assistant (1D) include a functional silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group.
  • trimethoxysilylbenzoic acid ⁇ -methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, ⁇ -isocyanatopropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 1,3,5-N-tris (trimethoxysilylpropyl) isocyanurate and the like.
  • adhesion assistants may be used alone or in combination of two or more.
  • the blending amount thereof is the alkali-soluble resin (1A) of the composition (1), the polymer (2A) of the composition (2), or the weight of the composition (3).
  • the amount is preferably 0.2 to 10 parts by mass, more preferably 0.5 to 8 parts by mass with respect to 100 parts by mass of the combined (3A).
  • the surfactant (1E) is not particularly limited as long as it can adjust coating properties, striations, wettability, developability, and the like.
  • this surfactant (1E) polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene-n-octylphenyl ether, polyoxyethylene-n-nonylphenyl ether, polyethylene glycol Nonionic surfactants such as dilaurate and polyethylene glycol distearate, and the following trade names: KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no.
  • surfactants (1E) may be used alone or in combination of two or more.
  • the blending amount thereof is the alkali-soluble resin (1A) of the composition (1), the polymer (2A) of the composition (2), or the weight of the composition (3).
  • the amount is preferably 15 parts by mass or less and more preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of the combined (3A).
  • the solvent (1F) is not particularly limited as long as it can dissolve the components constituting the first resin layer forming composition.
  • the solvent (1F) include ethylene glycol monoalkyl ethers, ethylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, triethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol Monoalkyl ether acetates, lactic acid esters, aliphatic carboxylic acid esters, other esters (ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate) Methyl 3-methoxypropionate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutylpropionate, methyl acetoacetate, Methyl binate, etc.), aromatic hydrocarbons (tolu
  • solvent (1F) may use only 1 type, and may use 2 or more types together.
  • the blending amount thereof is the alkali-soluble resin (1A) of the composition (1), the polymer (2A) of the composition (2) or the polymer (2) of the composition (3) ( 3A)
  • the amount is preferably 100 to 3000 parts by mass, more preferably 200 to 2000 parts by mass with respect to 100 parts by mass.
  • the material of the substrate is not particularly limited, and may be made of only one kind of material, or may be a laminate in which two or more layers of different materials are laminated.
  • Examples of the material constituting the substrate include silicon, various metals (such as aluminum), various metal (such as aluminum) sputtered films, alumina, glass epoxy, paper phenol, and glass.
  • the thickness of the substrate is not particularly limited, but is usually 1000 to 10,000 nm. Further, the surface of the substrate may be subjected to surface modification or the like as necessary.
  • the thickness of the first resin layer formed on the substrate is not particularly limited, but is usually 1 to 1000 nm, preferably 5 to 500 nm, and more preferably 10 to 100 nm.
  • substrate is not specifically limited, For example, appropriate means, such as spin coating, cast coating, roll coating, are mentioned. Furthermore, you may volatilize the solvent in a coating film by prebaking (PB) as needed.
  • PB prebaking
  • the heating conditions for this prebaking are appropriately selected depending on the composition of the first resin layer forming composition, but the heating temperature is usually about 100 to 400 ° C., preferably 150 to 250 ° C. Further, the heating time is usually 10 to 300 seconds, preferably 30 to 90 seconds.
  • the “second resin layer forming step (2)” [PR (2) in FIG. 1] is a step of forming the second resin layer 32 mainly composed of an organic polymer on the surface of the first resin layer 31. is there.
  • the second resin layer is a resin layer containing an organic polymer as a main component.
  • the main component of the organic polymer means that the organic polymer is contained in an amount of 95% by mass or more (or 100% by mass) when the entire second resin layer is 100% by mass. . That is, in other words, it means that the inorganic polymer described later is not contained, or even if it is contained, it is less than 5% by mass.
  • the second resin layer is a layer that can follow the surface shape of the stamped stamper and transfer the shape. Other properties are not limited, but a radiation-sensitive resin layer can be used.
  • this 2nd resin layer the 2nd resin formed on the 1st resin layer using the composition for 2nd resin layer formation containing a polymerizable unsaturated compound and a radiation sensitive polymerization initiator A layer is preferred.
  • the polymerizable unsaturated compound may be an unsaturated compound that can be polymerized by exposure in the presence of a radiation-sensitive polymerization initiator, and the type thereof is not particularly limited, but (meth) acrylic acid esters are preferable. These (meth) acrylic acid esters may be monofunctional, bifunctional, or trifunctional or higher, and these may be used alone or in combination of two or more.
  • Examples of the monofunctional (meth) acrylic acid esters include 2-hydroxyethyl (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, isobornyl (meth) acrylate, butyl (meth) acrylate, and 3-methoxybutyl (meth) Acrylate, (2- (meth) acryloyloxyethyl) (2-hydroxypropyl) phthalate and the like. These may use only 1 type and may use 2 or more types together.
  • bifunctional (meth) acrylic acid esters examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1 , 9-nonanediol di (meth) acrylate, bisphenoxyethanol full orange (meth) acrylate, polyester both-end (meth) acryl-modified compound, polypropylene glycol both-end (meth) acryl-modified compound, polytetramethylene glycol both-end (meth) An acrylic modified compound etc. are mentioned. These may use only 1 type and may use 2 or more types together.
  • trifunctional or higher functional (meth) acrylic acid esters examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Examples include pentaerythritol hexa (meth) acrylate, tri (2- (meth) acryloyloxyethyl) phosphate, and the like. These may use only 1 type and may use 2 or more types together.
  • the kind of the radiation sensitive polymerization initiator is not particularly limited.
  • Examples of the radiation sensitive polymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1-hydroxy-cyclohexylphenyl.
  • the blending amount of the radiation-sensitive polymerization initiator is not particularly limited, but is preferably 0.01 to 30% by mass, more preferably 0.1 to 20% by mass with respect to the entire second resin film forming composition. More preferred is 15% by mass.
  • the thickness of the second resin layer formed on the first resin layer is not particularly limited, but is usually 1 to 1000 nm, preferably 5 to 500 nm, and more preferably 10 to 100 nm.
  • coating the composition for 2nd resin layer formation on the 1st resin layer is not specifically limited, For example, appropriate means, such as spin coating, cast coating, roll coating, are mentioned. Furthermore, you may volatilize the solvent in a coating film by prebaking (PB) as needed.
  • the prebaking heating conditions are appropriately selected depending on the composition of the second resin layer forming composition, but the heating temperature is usually about 30 to 150 ° C, preferably 50 to 130 ° C. Further, the heating time is usually 10 to 300 seconds, preferably 30 to 90 seconds.
  • the stamper 10 having the convex portion 11 is pressed and detached from the second resin layer 32, and then the second step. This is a step of forming a recess 321 in the resin layer 32.
  • the second resin layer may or may not be penetrated by the pressure contact of the stamper, but among these, it is preferable not to penetrate the second resin layer.
  • the adhesion surface between the first resin layer and the second resin layer is increased, and the adhesion between them is increased, The resist peeling between the first resin film and the second resin film can be suppressed.
  • the thickness (remaining film thickness) of the bottom of the recess to be formed is not particularly limited, but is preferably 1 nm or more, more preferably 3 to 500 nm, and further preferably 5 to 150 nm.
  • the press contact and desorption conditions of the stamper with respect to the second resin layer are not particularly limited as long as the recess can be formed in the second resin layer, but the press contact pressure is preferably 0.1 MPa or more (100 MPa or less), 0.1 ⁇ 50 MPa is more preferable. Further, the pressing time is preferably 1 second or more (600 seconds or less), more preferably 1 to 300 seconds. Moreover, the said press-contact and desorption should just be able to form a recessed part in a 2nd resin layer, may be performed only once, and may be performed twice or more.
  • the “stamper (10)” has a convex portion 11 for transfer on the surface thereof, and after pressing the stamper 10 against the second resin layer 32, the stamper 10 is detached so as to correspond to the convex portion 11 of the stamper 10.
  • the recessed portion 321 thus formed can be formed (transferred) on the surface of the second resin layer 32.
  • This stamper 10 may or may not be transparent to radiation.
  • the stamper 10 is exposed in a state of being pressed against the second resin layer 32 [in FIG. PR (3-2 ′) exposure step can be provided], whereby the convex portion 11 of the stamper 10 can be more easily transferred to the second resin layer 32.
  • the transmittance for radiation is not particularly limited, but the transmittance is preferably 70% or more with respect to desired radiation (the radiation that the radiation-sensitive polymerization initiator can function), and is preferably 75 to 100%. Is more preferable, and 80 to 100% is still more preferable.
  • the second resin layer 32 may be completely cured by exposure. Further, after being incompletely cured, complete curing may be performed by heating in a later step.
  • the type of radiation used for exposure is not particularly limited, and radiation such as charged particle beams such as visible light, ultraviolet light, far ultraviolet light, X-rays, and electron beams ⁇ ArF excimer laser (wavelength 193 nm) or KrF excimer laser (wavelength 248 nm), etc. Including ⁇ can be used.
  • This stamper only needs to have mechanical properties as a stamper, and can further have transparency to radiation as described above. From such a viewpoint, a light-transmitting inorganic material is particularly preferable as the material constituting the stamper.
  • a quartz material ⁇ quartz (single crystal, polycrystal), various glasses (quartz glass, fluoride glass, calcium phosphate glass, borate glass, borosilicate glass, etc.) ⁇ , Silicon, spinel, corundum, sapphire and the like.
  • a functional layer can be provided on the surface of the stamper (surface having a convex portion) as necessary.
  • a release layer As the functional layer, a release layer, an ionization suppressing layer, an adhesion improving layer ⁇ a layer for improving adhesion between various layers (such as an interlayer between a stamper and a translucent electrode layer) ⁇ , a thermal diffusion layer, various optical functions Examples include a layer ⁇ reflection suppression, a refractive index control layer, a light transmission improving layer (made of silicon oxide), etc. ⁇ , an insulating layer, and the like. These various layers may use only 1 type and may use 2 or more types together. That is, for example, each layer may have only one layer or may have a multilayer structure of two or more layers.
  • the thickness of each functional layer is not particularly limited, but the thickness of each layer is preferably 1 to 100 nm, more preferably 1 to 50 nm, and particularly preferably 1 to 20 nm.
  • the release layer is a layer for facilitating separation of the stamper and the second resin film.
  • the release layer it is preferable that the release layer is disposed on a part or the entire surface of the convex portion of the stamper.
  • a silane compound having a halogenated organic group such as a halogenated alkyl group
  • a release layer composed of an organic monomolecular film self-assembled so that the halogenated organic group is located on the surface can be obtained.
  • silane compound examples include 3,3,3-trifluoropropyl group, tridecafluoro-1,1,2,2-tetrahydrooctyl group, heptadecafluoro-1,1,2,2-tetrahydrodecyl group, Examples include trichlorosilane and trialkoxysilane (such as trimethoxysilane and triethoxysilane) having various halogenated organic groups such as 3,3,4,4,5,5,6,6,6-nonafluorohexyl group.
  • perfluorodecyltrichlorosilane, octadecyltrichlorosilane, dimethyldichlorosilane, and the like can be given. These may use only 1 type and may use 2 or more types together.
  • the ionization suppressing layer can be formed of a light-transmitting inorganic material such as a nitride, an oxide, an oxynitride, or a hydrogenated nitride.
  • a light-transmitting inorganic material such as a nitride, an oxide, an oxynitride, or a hydrogenated nitride.
  • nitrides silicon nitride, aluminum nitride, indium nitride, gallium nitride, tin nitride, boron nitride, chromium nitride, silicon nitride carbide, etc .; as oxides, indium oxide, tin oxide, indium tin oxide, aluminum oxide, oxide Germanium, silicon oxide, zinc oxide, zirconium oxide, titanium oxide, yttrium oxide, erbium oxide, cerium oxide, tantalum oxide, hafnium oxide, etc .; oxy
  • the “filling portion forming step (4)” (PR (4-1) to (4-2) in FIG. 2) is a step of forming the filling portion 33 mainly composed of an inorganic polymer in the recess 321. .
  • This filling part is a part mainly composed of an inorganic polymer.
  • the phrase “mainly composed of an inorganic polymer” means that the inorganic polymer is contained in an amount of 90% by mass or more (or 100% by mass) when the entire filling portion is 100% by mass. That is, in other words, it means that the organic polymer is not contained, or even if it is contained, it is less than 10% by mass.
  • This filling portion is a portion having an etching selectivity with respect to the first resin layer and the second resin layer mainly containing an organic polymer by containing an inorganic polymer as a main component. .
  • the inorganic polymer constituting the filling portion is a polymer whose skeleton is formed of an inorganic element.
  • inorganic elements examples include Si, Ti, Al, Zr and the like. Of these, Si is preferable, and the inorganic polymer is more preferably polysiloxane.
  • a filling part formed by using a composition for forming a filling part containing a polysiloxane containing a structural unit represented by the following formula (12) and a structural unit represented by the following formula (13) and a solvent Preferably there is.
  • R 1 represents an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 4.
  • the alkyl group having 1 to 4 carbon atoms of R 1 in the formula (12) may be linear or branched.
  • R 1 in the formula (12) is, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, etc. Can be mentioned.
  • Examples of the monomer that gives the structural unit represented by the formula (12) include silane compounds represented by the following formula (14).
  • R 1 represents an alkyl group having 1 to 4 carbon atoms
  • R 2 represents an alkyl group having 1 to 4 carbon atoms
  • n is an integer of 1 to 4.
  • R 1 in the formula (12) can be applied as it is to R 1 in the formula (14).
  • R 1 and R 2 may be the same or different.
  • the three R 2 in the formula (14) may be the same or different from each other.
  • Examples of the silane compound represented by the formula (14) include 3- (trimethoxysilyl) propyl methacrylate, 3- (triethoxysilyl) propyl methacrylate, N-3- (methacryloxy-2-hydroxypropyl) -3-amino.
  • Examples of the monomer that gives the structural unit represented by the formula (13) include a silane compound represented by the following formula (15). Si (OR 1 ) 4 (15) In [Equation (15), R 1 represents a monovalent organic group. ]
  • Examples of the monovalent organic group for R 1 in the formula (15) include an alkyl group and an aromatic group.
  • the four R 1 s in the formula (15) may be the same as or different from each other.
  • These monovalent organic groups may be substituted or unsubstituted.
  • Examples of the monovalent alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
  • examples of the substituted monovalent alkyl group include ⁇ -aminopropyl group, ⁇ -glycidoxypropyl group, and ⁇ -trifluoropropyl group.
  • Examples of the monovalent aromatic group include a phenyl group and a benzyl group.
  • Examples of the silane compound represented by the formula (15) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra -Tert-butoxysilane, tetraphenoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraisocyanatosilane, tetrakis (butoxyethoxyethoxy) silane, tetrakis (dimethylsiloxy) silane, tetrakis (ethoxyethoxy) silane, tetrakis (2-ethylhexyl) Siloxy) silane, tetrakis (2-methacryloxyethoxy) silane, tetrakis (methoxy
  • the polysiloxane constituting the filling portion forming composition may contain other structural units in addition to the structural unit represented by the formula (12) and the structural unit represented by the formula (13). .
  • the structural unit represented by following formula (16) and the structural unit represented by following formula (17) are mentioned. These structural units may contain only 1 type and may contain 2 or more types.
  • R 1 represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, or —OR 2
  • R 2 represents an alkyl group having 1 to 5 carbon atoms.
  • R 1 represents an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group having 1 to 5 carbon atoms in R 1 of the formula (16) may be linear or branched.
  • Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, a t-butyl group, and a pentyl group.
  • R 1 is —OR 2
  • R 1 in the same formula can be applied as it is as the alkyl group having 1 to 5 carbon atoms of R 2 .
  • R 1 and R 2 may be the same or different.
  • the structural unit represented by the formula (16) may be contained in the polysiloxane only in one kind or in two or more kinds.
  • Examples of the monomer that gives the structural unit represented by the formula (16) include a silane compound represented by the following formula (18).
  • R 1 represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, or —OR 2
  • R 2 represents an alkyl group having 1 to 5 carbon atoms
  • R 3 represents Represents a monovalent organic group.
  • R 1 and R 2 in the formula (18) the description of R 1 and R 2 in the formula (16) can be applied as it is. Furthermore, the explanation of R 1 in the formula (15) can be applied as it is to R 3 in the formula (18).
  • silane compound represented by the formula (18) examples include 2-methylphenyltrimethoxysilane, 2-methylphenyltriethoxysilane, 2-methylphenyltri-n-propoxysilane, 2-methylphenyltri-iso-propoxy.
  • Silane 2-methylphenyltri-n-butoxysilane, 2-methylphenyltri-sec-butoxysilane, 2-methylphenyltri-tert-butoxysilane, 2-methylphenyltrichlorosilane, 2-methylphenyltriacetoxysilane, 4-methylphenyltrimethoxysilane, 4-methylphenyltriethoxysilane, 4-methylphenyltri-n-propoxysilane, 4-methylphenyltri-iso-propoxysilane, 4-methylphenyltri-n-butoxysilane, 4 -Methylph Nyltri-sec-butoxysilane, 4-methylphenyltri-tert-butoxysilane, 4-methylphenyltrichlorosilane, 4-methylphenyltriacetoxysilane, 2-ethylphenyltrimethoxysilane, 2-ethylphenyltriethoxysilane, 2 -Ethylphenyltri-n
  • the alkyl group having 1 to 4 carbon atoms in R 1 of the formula (17) may be linear or branched.
  • Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-methylpropyl group, a 1-methylpropyl group, a t-butyl group, and a pentyl group.
  • the structural unit represented by Formula (17) may be contained in polysiloxane only by 1 type, and may be contained 2 or more types.
  • Examples of the monomer that gives the structural unit represented by the formula (17) include a silane compound represented by the following formula (19).
  • R 1 Si (OR 2 ) 3 (19) [In the formula (19), R 1 represents a linear or branched alkyl group having 1 to 4 carbon atoms, and R 2 represents a monovalent organic group. ]
  • R 1 in the formula (19) the description of R 1 in the formula (16) can be applied as it is.
  • R 3 in the formula (18) can be applied to R 2 in the formula (19) as it is.
  • Examples of the silane compound represented by the formula (19) include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxy.
  • silane compounds methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, methyltri-n-butoxysilane, methyltri-sec-butoxysilane, ethyltrimethoxysilane , Ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, ethyltri-n-butoxysilane, ethyltri-sec-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n- Propyltri-n-propoxysilane, n-propyltri-iso-propoxysilane, n-propyltri-n-butoxysilane, n-propyltri-sec-butoxysilane
  • the polysiloxane constituting the filling portion forming composition may be other A structural unit can be further included.
  • each structural unit which uses the following each compound as a monomer is mentioned. These other structural units may be used alone or in combination of two or more. Examples of the compound that gives another structural unit include dimethyldimethoxysilane, diethyldimethoxysilane, dipropyldimethoxysilane, diphenyldimethoxysilane, (3-acryloxypropyl) methyldimethoxysilane, di-tert-butyldichlorosilane, and diethoxy.
  • the content ratio of the structural unit represented by the formula (12) is, when the total of all the structural units included in the polysiloxane is 100 mol%,
  • the content is preferably 1 to 50 mol%, more preferably 1 to 30 mol%, still more preferably 5 to 10 mol%.
  • the filling portion has excellent adhesion, and also has excellent durability when used as a mask.
  • the content ratio of the structural unit represented by the formula (13) is, when the total of all the structural units included in the polysiloxane is 100 mol%, It is preferably 50 to 99 mol%, more preferably 50 to 80 mol%, still more preferably 50 to 60 mol%. In this range, the durability when used as a mask is excellent, and the storage stability of the filling portion forming composition is also excellent.
  • the content ratio of the structural unit represented by the formula (16) in the polysiloxane constituting the filling portion forming composition is, when the total of all the structural units included in the polysiloxane is 100 mol%, It is preferably 10 mol% or less, more preferably 0 to 7 mol%, still more preferably 0 to 5 mol%.
  • the content of the structural unit represented by the formula (17) in the polysiloxane constituting the filling portion forming composition is preferably 50 mol% or less, more preferably 1 to 40 mol%, and further Preferably, it is 1 to 30 mol%.
  • the content ratio of the other structural units is 10 mol% or less when the total of all the structural units contained in the polysiloxane is 100 mol%. It is preferably 1 to 8 mol%, more preferably 1 to 5 mol%.
  • the weight average molecular weight in terms of polystyrene measured by GPC of the polysiloxane constituting the filling portion forming composition is preferably 500 to 100,000, more preferably 1,000 to 50,000, and still more preferably 1,000 to 10,000.
  • the silanol abundance ratio in the polysiloxane constituting the filling portion forming composition is preferably 1 to 2 times, more preferably 1 to 2 times the Si—O—Si bond in the inorganic polymer. 1.7 times, more preferably 1 to 1.5 times. When the silanol abundance ratio is 1 to 2 times, the storage stability is particularly good.
  • the silanol abundance ratio is measured by Si 29 -NMR.
  • the polysiloxane which comprises the said various composition for filling part formation may be contained only 1 type in the composition for filling part formation, and may be contained 2 or more types.
  • the solvent constituting the filling portion forming composition is not particularly limited as long as it can dissolve the polysiloxane and does not dissolve the second resin layer.
  • alcohols, ethers, esters, and the like, and those containing these are preferable, and alcohols are particularly preferable.
  • these solvents may use only 1 type and may use 2 or more types together.
  • the blending amount of the solvent is not particularly limited, but is preferably 20 to 10,000 parts by mass, more preferably 30 to 5000 parts by mass with respect to 100 parts by mass of the polysiloxane.
  • the alcohol is preferably an alcohol having 2 to 10 carbon atoms.
  • the alcohol having 2 to 10 carbon atoms may be linear or branched.
  • Examples of the alcohol include 1-butanol, 2-butanol, pentanol, cyclopentanol, hexanol, cyclohexanol, 4-methyl-2-pentanol, heptanol, cycloheptanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether And propylene glycol monopropyl ether.
  • the ether include diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diisopentyl ether and the like.
  • the ester examples include methyl lactate, ethyl lactate, and propylene glycol monomethyl ether acetate.
  • the filler forming composition may contain other additives such as a surfactant and a crosslinking agent.
  • the method for forming the filling portion is not particularly limited, but usually, the filling portion forming composition is applied onto the second resin layer having the recesses to form a film.
  • the coating method in this case is not particularly limited, and examples thereof include appropriate means such as spin coating, cast coating, and roll coating. Furthermore, you may volatilize the solvent in a coating film by prebaking (PB) as needed.
  • PB prebaking
  • the heating conditions for this pre-baking are appropriately selected depending on the composition of the filling portion forming composition, but the heating temperature is usually about 60 to 180 ° C., preferably 80 to 150 ° C. Further, the heating time is usually 10 to 300 seconds, preferably 30 to 180 seconds.
  • a step of removing a part of the surface of the filling portion (step of flattening) [PR (4-2) in FIG. 2] is performed in order to reveal the pattern of the second resin layer 32.
  • the removal method is not particularly limited, but an etching method such as dry etch back or wet etch back, a CMP method, or the like can be used. Of these, dry etch back and CMP are preferable.
  • the “etching step (5)” [PR (5-1) to (5-2) in FIG. 2] is a step of etching the first resin layer 31 and the second resin layer 32 using the filling portion 33 as a mask. is there.
  • etching may be performed in any way, but dry etching (a method of physically or chemically etching under reduced pressure) is preferable, and further, reactive ion etching (RIE). Is more preferable.
  • the first resin layer and the second resin layer are mainly composed of an organic polymer, whereas the filling portion is composed mainly of an inorganic polymer, so that the etching rate in dry etching can be varied.
  • the filling portion can function as a mask for the first resin layer and the second resin layer.
  • the source gas for dry etching is not particularly limited, but includes oxygen atoms such as O 2 , CO, and CO 2 , inert gases such as He, N 2 , and Ar, and chlorine atoms such as Cl 2 and BCl 2.
  • oxygen atoms such as O 2 , CO, and CO 2
  • inert gases such as He, N 2 , and Ar
  • chlorine atoms such as Cl 2 and BCl 2.
  • a gas containing hydrogen, H 2 , NH 2 gas, or the like can be used. These gases may use only 1 type and may use 2 or more types together.
  • the etching rate for each of the first resin layer and the second resin layer is not particularly limited, and each etching rate may be the same or different. If they are different, either etching rate may be high, but the etching rate of the first resin layer is slower than the etching rate of the second resin layer [PR (5-1) to (5 in FIG. -2)] is preferred. In this case, when processing the substrate to be processed, it is possible to form a pattern (mask) having better etching resistance (mask resistance).
  • Etch rate ratio the can be a suitably the composition and use of the etching technique of each resin layer, in particular, the etch rate was S 1 for the first resin layer, the etching rate for the second resin layer was S 2
  • S 1 / S 2 is preferably 1 to 3, more preferably 1.5 to 3, and more preferably 2 to 3. It is particularly preferred.
  • the etching rate is a value measured by the following method. That is, the first resin film and the second resin film are formed with an arbitrary film thickness (film thickness before processing), and etching is performed based on a difference from a film thickness (film thickness after processing) after etching is performed under arbitrary conditions. Measure by calculating the speed.
  • the first resin layer forming step (1), the second resin layer forming step (2), the concave portion forming step (3), the filling portion forming step (4), and the etching step (5) can be provided.
  • a mask removing step (7) [PR (7) in FIG. 3] for removing the mask (filling portion, second resin layer and first resin layer) can be provided.
  • Each of these other processes may use only 1 type and may use 2 or more types together.
  • Preparation Example 1 Preparation of first resin layer forming composition 100 parts by mass of an alkali-soluble resin (1A) having the following phenolic hydroxyl group, 1.0 part by mass of a thermal acid generator (1B), and 25 crosslinker (1C) A composition for forming the first resin layer is prepared by dissolving, in 400 parts by mass of the solvent (1F), 2.5 parts by mass of the adhesion promoter (1D) and 0.2 parts by mass of the surfactant (1E). Prepared.
  • Preparation Example 2 Preparation of second resin film forming composition 100 parts by weight of butyl methacrylate, 50 parts by weight of 1,6-hexanediol dimethacrylate, 25 parts by weight of 2,4,6-trimethylbenzoyl-phenyl-phosphine oxide Were mixed and stirred uniformly to obtain a second resin film-forming composition.
  • Preparation Example 3 Preparation of filling portion forming composition 0.54 g of maleic anhydride was dissolved by heating in 10.8 g of water to prepare an aqueous maleic acid solution. Next, 18.71 g of tetraethoxysilane and 53.5 g of propylene glycol monopropyl ether were placed in the flask. A cooling tube and a dropping funnel containing the previously prepared maleic acid aqueous solution were set in the flask, heated at 100 ° C. in an oil bath, and then slowly dropped with the maleic acid aqueous solution at 4 ° C. Reacted for hours.
  • reaction product polysiloxane having a weight average molecular weight of 2100.
  • the solid content in the obtained reaction product was 15.7% as a result of measurement by a firing method.
  • the weight average molecular weight of the obtained product was 2100. 14.89 g of the reaction product obtained as described above was dissolved in 30.79 g of propylene glycol monoethyl ether, and this solution was further filtered through a filter having a pore size of 0.2 ⁇ m to obtain a filling part forming composition. It was.
  • the weight average molecular weight of the product was measured by a size exclusion chromatography (SEC) method.
  • SEC size exclusion chromatography
  • a 2-methoxyethanol solution of LiBr—H 3 PO 4 having a concentration of 10 mmol / L was used as a solvent, and 0.1 g of the product was added to 100 cc of 10 mmol / L LiBr—H 3 PO 4 in 2-methoxyethanol. What was dissolved in was used.
  • Standard sample polystyrene (manufactured by WAKO), apparatus: high-speed GPC apparatus “HLC-8120GPC” (model name), manufactured by Tosoh Corporation, column: 15 cm long aqueous / polar organic solvent-based GPC column “TSK-GEL SUPER” AWM-H "(manufactured by Tosoh Corporation) is connected in series, and the measurement temperature is 40 ° C., the flow rate is 0.6 ml / min. , Detector: RI (built in the high-speed GPC device).
  • Example 1 Example Using First Resin Layer (1) First Resin Layer Forming Step A first resin layer forming composition prepared above is spin-coated on a 6-inch silicon wafer (substrate). Then, heating was performed at 180 ° C. for 1 minute and at 300 ° C. for 1 minute using a hot plate to form a 300 nm-thick first resin layer.
  • Second resin layer forming step 10 ⁇ L of the second resin layer forming composition prepared previously is dropped onto the first resin layer obtained up to the above (1), and the second resin layer is formed by spin coating. Formed.
  • the second resin layer obtained up to the above (2) has a concavo-convex pattern of 70 nm line (convex width) / 140 nm space (aspect ratio: 1) (that is, convex part of 70 nm line)
  • a quartz stamper is pressed at a pressure of 0.4 MPa for 120 seconds, irradiated with light of illuminance of 2.5 mW / cm with a high-pressure mercury lamp for 30 seconds, and then the stamper is detached to remove the second resin layer.
  • a recess was formed on the surface.
  • the concave portions having a substantially square cross section with a width of 70 nm and a depth of 70 nm were arranged at intervals of 140 nm.
  • the concavo-convex pattern arranged in (1) was formed.
  • the remaining film thickness (distance from the bottom surface of the recess to the bottom surface of the second resin layer) was 100 nm.
  • Etching Step The second resin layer and the first resin layer were etched by reactive ion etching (RIE) under oxygen conditions using the filling portion obtained up to (4) as a mask to form a pattern.
  • RIE reactive ion etching
  • a cross section of the obtained pattern was observed with a scanning electron microscope (manufactured by Hitachi Keiki Service Co., Ltd., model “S9380”), a concave / convex pattern in which concave portions having a width of 70 nm ⁇ depth of 70 nm were arranged at intervals of 140 nm was obtained. I was able to get it.
  • RIE reactive ion etching

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WO2013191118A1 (ja) * 2012-06-18 2013-12-27 富士フイルム株式会社 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
WO2014157226A1 (ja) * 2013-03-26 2014-10-02 富士フイルム株式会社 インプリント用下層膜形成組成物およびパターン形成方法
JP2015065443A (ja) * 2009-08-17 2015-04-09 Jsr株式会社 パターン形成方法
WO2015103232A1 (en) * 2013-12-30 2015-07-09 Canon Nanotechnologies, Inc. Methods for uniform imprint pattern transfer of sub-20 nm features

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KR101901330B1 (ko) * 2012-09-19 2018-09-27 삼성디스플레이 주식회사 유기전계발광 표시장치의 제조 방법
KR20160017222A (ko) 2014-08-01 2016-02-16 박두우 짜장소스 제조방법과 이를 통해 제조된 짜장소스 및 이를 이용한 짜장면
JP2018187879A (ja) * 2017-05-10 2018-11-29 株式会社金陽社 オフセット印刷用ブランケットゴム層の製造方法、及びオフセット印刷用ゴムブランケットの製造方法
WO2019198668A1 (ja) * 2018-04-09 2019-10-17 大日本印刷株式会社 ナノインプリント用テンプレート及びその製造方法、並びに、２段メサブランクス及びその製造方法

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JP2015065443A (ja) * 2009-08-17 2015-04-09 Jsr株式会社 パターン形成方法
WO2013154075A1 (ja) * 2012-04-09 2013-10-17 旭硝子株式会社 微細パターンを表面に有する物品の製造方法
WO2013191118A1 (ja) * 2012-06-18 2013-12-27 富士フイルム株式会社 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
JP2014003123A (ja) * 2012-06-18 2014-01-09 Fujifilm Corp 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
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JP2014192178A (ja) * 2013-03-26 2014-10-06 Fujifilm Corp インプリント用下層膜形成組成物およびパターン形成方法
WO2015103232A1 (en) * 2013-12-30 2015-07-09 Canon Nanotechnologies, Inc. Methods for uniform imprint pattern transfer of sub-20 nm features
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