WO2020066442A1 - Composition de formation de film de sous-couche d'impression, film de sous-couche, procédé de formation de motif et procédé de fabrication d'élément semi-conducteur - Google Patents

Composition de formation de film de sous-couche d'impression, film de sous-couche, procédé de formation de motif et procédé de fabrication d'élément semi-conducteur Download PDF

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Publication number
WO2020066442A1
WO2020066442A1 PCT/JP2019/033723 JP2019033723W WO2020066442A1 WO 2020066442 A1 WO2020066442 A1 WO 2020066442A1 JP 2019033723 W JP2019033723 W JP 2019033723W WO 2020066442 A1 WO2020066442 A1 WO 2020066442A1
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Prior art keywords
group
composition
underlayer film
forming
acid
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Japanese (ja)
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旺弘 袴田
雄一郎 後藤
直也 下重
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Fujifilm Corp
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Fujifilm Corp
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography

Definitions

  • the present invention relates to a composition for forming an underlayer film for imprint, and an underlayer film using the composition for forming an underlayer film for imprint, a pattern forming method, and a method for manufacturing a semiconductor device.
  • the imprint method is a method of transferring a pattern of a mold to form a desired structure in a resin layer.
  • an optical imprinting method utilizing curing of a resin by exposure, light is irradiated through a light-transmitting mold or a light-transmitting substrate to light-cur the curable composition. Thereafter, the fine pattern can be transferred to the photo-cured product by removing the mold.
  • This method enables imprinting at room temperature, so that it can be applied to the field of precision processing of ultra-fine patterns such as fabrication of semiconductor integrated circuits. Recently, new developments such as a nanocasting method combining these advantages and a reversal imprint method for producing a three-dimensional laminated structure have been reported.
  • Patent Document 1 As a method for applying the curable composition for imprints, inkjet coating has been studied (for example, Patent Document 1). There, the curable composition for imprints is often dropped on a substrate as droplets of about 1 to 100 pL (Patent Documents 2 to 5). By employing inkjet coating, the amount of application can be adjusted according to the density of the imprint pattern, and a uniform imprint pattern can be secured.
  • the problem of adhesion between the substrate and the curable composition for imprint has come to be regarded as a problem.
  • the curable composition for imprints was applied to the surface of the substrate, and the curable composition for imprints was cured by irradiating light with the mold in contact with the surface. Thereafter, the mold is peeled off. In the step of removing the mold, the cured product may peel off from the substrate and adhere to the mold. This is probably because the adhesion between the substrate and the cured product is lower than the adhesion between the mold and the cured product.
  • Patent Document 6 discloses a polymer having a predetermined structure having an alkynyl group in a naphthalene structure and having a polystyrene-equivalent weight average molecular weight of 3,000 or more and 10,000 or less, and a solvent. There is disclosed a composition for forming a resist underlayer film.
  • Patent Document 7 discloses an adhesive film containing a compound having the following structural units (X and Y are integers).
  • An object of the present invention is to solve such a problem, and a composition for forming an underlayer film for imprinting having excellent adhesion to various substrates, and a composition for forming an underlayer film for imprinting are provided. It is an object of the present invention to provide a used lower layer film, a pattern forming method, and a method of manufacturing a semiconductor device.
  • a composition for forming an underlayer film for imprinting comprising: a solvent; ⁇ 2> The composition for forming an underlayer film for imprints according to ⁇ 1>, wherein the polymer is at least one of a (meth) acrylic resin, a vinyl resin, and a novolak resin.
  • ⁇ 3> The composition for forming an underlayer film for imprint according to ⁇ 1> or ⁇ 2>, wherein the polymer has a weight average molecular weight of 4000 or more.
  • ⁇ 4> The composition for forming an underlayer film for imprint according to any one of ⁇ 1> to ⁇ 3>, wherein the low molecular compound has a pKa in the range of -5 to 5.
  • ⁇ 5> The composition for forming an underlayer film for imprint according to any one of ⁇ 1> to ⁇ 4>, wherein the low-molecular compound has a molecular weight of 600 or less.
  • the polymer has a functional group capable of binding to the functional group of the low-molecular compound
  • the combination of the functional group of the polymer and the functional group of the low-molecular compound may be ethylenically unsaturated groups, an amino group and an acid group or an acid anhydride group, an amino group and a crosslinkable group, and a hydroxyl group and a crosslinkable group.
  • the low molecular compound is an acid group selected from the group consisting of a carboxylic acid group, a thiocarboxylic acid group, a dithiocarboxylic acid group, a sulfonic acid group, a phosphate monoester group, a phosphate diester group, and a phosphate group.
  • the polymer has a functional group capable of binding to the functional group of the low-molecular compound,
  • ⁇ 10> The formation of an underlayer film for imprint according to any one of ⁇ 1> to ⁇ 9>, wherein the low-molecular compound is contained at a ratio of 0.01 to 0.03% by mass of the solid content of the composition.
  • Composition. ⁇ 11> The composition for forming an underlayer film for imprint according to any one of ⁇ 1> to ⁇ 10>, wherein 99% by mass or more of the composition is a solvent.
  • ⁇ 12> The composition for forming an underlayer film for imprint according to any one of ⁇ 1> to ⁇ 11>, wherein the low-molecular compound is an acid having a pKa of 5 or less.
  • ⁇ 14> a step of applying the composition for forming an underlayer film for imprint according to any one of ⁇ 1> to ⁇ 12> to a substrate to form an underlayer film for imprint;
  • a step of applying the curable composition for imprint on the underlayer film for imprint, A pattern forming method, comprising: exposing the curable composition for imprints to light while the mold is in contact with the curable composition for imprints; and removing the mold.
  • ⁇ 15> The pattern forming method according to ⁇ 14>, wherein a substrate having a carbon content of 70% by mass or more in a region from the surface to a thickness of 10 nm is used.
  • ⁇ 16> The pattern forming method according to ⁇ 14> or ⁇ 15>, wherein the step of forming the imprint underlayer film includes a spin coating method.
  • ⁇ 17> The pattern forming method according to any one of ⁇ 14> to ⁇ 16>, including a step of forming a liquid film on the lower layer film for imprint.
  • ⁇ 18> The pattern forming method according to any one of ⁇ 14> to ⁇ 17>, wherein the step of applying the curable composition for imprints includes an inkjet method.
  • a method for manufacturing a semiconductor device comprising the method for forming a pattern according to any one of ⁇ 14> to ⁇ 18>.
  • imprint preferably refers to a pattern transfer having a size of 1 nm to 10 mm, more preferably a pattern transfer having a size of about 10 nm to 100 ⁇ m (nanoimprint).
  • the notation of not indicating substituted or unsubstituted includes not only a group having no substituent but also a group having a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • light includes not only light having a wavelength in the ultraviolet, near-ultraviolet, far-ultraviolet, visible, and infrared regions, and electromagnetic waves, but also radiation. Radiation includes, for example, microwaves, electron beams, extreme ultraviolet (EUV), and X-rays. Alternatively, laser light such as a 248 nm excimer laser, a 193 nm excimer laser, or a 172 nm excimer laser can be used. These lights may be monochrome light (single-wavelength light) that has passed through an optical filter, or may be light having different wavelengths (composite light).
  • the pressure at the time of measuring the boiling point in the present invention is 1013.25 hPa (1 atm) unless otherwise specified.
  • the temperature in the present invention is 23 ° C., unless otherwise specified.
  • the term "step" is included not only in an independent step but also in the case where the intended action of the step is achieved even if it cannot be clearly distinguished from other steps. .
  • the composition for forming an underlayer film for imprinting of the present invention includes a polymer (hereinafter, may be referred to as a specific polymer) and a pKa of 5 or less.
  • a polymer hereinafter, may be referred to as a specific polymer
  • a low molecular weight compound selected from an acid and an acid generator capable of generating an acid having a pKa of 5 or less and having a functional group capable of binding to the polymer and having a molecular weight of 1000 or less hereinafter, a specific low molecular weight compound
  • a solvent With such a configuration, a composition having excellent adhesion to the substrate and the curable composition for imprints can be obtained.
  • a composition for forming an underlayer film which exhibits excellent adhesion to various substrates can be obtained.
  • the reason why such an effect is obtained includes unknown points, but is presumed as follows. That is, in the underlayer film formed using the composition for forming an underlayer film for imprint, the specific low-molecular compound binds to the specific polymer. On the other hand, it is considered that the polarity generated when the specific low-molecular compound is an acid or an acid generator interacts with the upper layer of the curable composition layer for imprints and the lower layer of the substrate.
  • the configuration of the present invention will be described in detail.
  • the specific polymer used in the present invention is usually a main component of the lower layer film, and known polymers can be widely used.
  • the specific polymer include (meth) acrylic resin, vinyl resin, novolak resin, epoxy resin, polyurethane resin, phenol resin, polyester resin and melamine resin, and at least one of (meth) acrylic resin, vinyl resin and novolak resin It is preferred that
  • the weight average molecular weight of the polymer is preferably 4000 or more, more preferably 6000 or more, and further preferably 8000 or more.
  • the upper limit is preferably 100,000 or less, and may be 50,000 or less.
  • the molecular weight of the polymer a value measured based on a method described in Examples described later is employed.
  • the polymer preferably has a functional group.
  • This functional group is preferably capable of bonding to a functional group of a low-molecular compound described below.
  • the functional group of the specific polymer is more preferably an ethylenically unsaturated group, an amino group, a crosslinkable group, or a hydroxy group.
  • Examples of the ethylenically unsaturated group include (meth) acryloyl group, (meth) acryloyloxy group, (meth) acryloylamino group, vinyl group, vinyloxy group, allyl group, methylallyl group, propenyl group, butenyl group, and vinylphenyl And a cyclohexenyl group, and a (meth) acryloyl group and a vinyl group are preferred.
  • the ethylenically unsaturated group defined here is called Et.
  • Examples of the crosslinkable group include an isocyanate group, a methylol group (hydroxymethyl group), and an epoxy group (oxirane group).
  • the crosslinkable group defined here is called Bd.
  • the functional group of the specific polymer defined here is referred to as a functional group Q1, and may be distinguished from the functional group Q2 of the specific low-molecular compound in some cases.
  • Specific combinations of the functional group of the specific polymer and the functional group of the specific low-molecular compound are as described in Table 3 below.
  • the specific polymer preferably has at least one structural unit of the following formulas (1) to (3).
  • R 1 and R 2 are each independently a hydrogen atom or a methyl group.
  • R 21 and R 3 are each independently a substituent T described later.
  • n2 is an integer of 0 to 4.
  • n3 is an integer of 0 to 3.
  • L 1 , L 2 and L 3 are each independently a single bond or a linking group L described below. Among them, a single bond or an alkylene group or (oligo) alkyleneoxy group defined by the linking group L is preferable. However, the presence or absence of the oxygen atom at the terminal of the (oligo) alkyleneoxy group may be adjusted depending on the structure of the preceding group.
  • Q 1 is a functional group of the specific polymer, examples of the above functional groups Q1 and the like.
  • R 21 s When there are a plurality of R 21 s , they may be connected to each other to form a cyclic structure.
  • linkage is intended to include, in addition to a continuous form of bonding, a form in which some atoms are lost and condensed (condensed).
  • an oxygen atom, a sulfur atom, or a nitrogen atom (amino group) may be interposed in the connection.
  • cyclic structure formed examples include an aliphatic hydrocarbon ring (referred to as ring Cf) (for example, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cyclopropene ring, cyclobutene ring, cyclopentene ring, cyclohexene ring) Etc.), aromatic hydrocarbon rings (referred to as rings Cr) (benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, etc.), nitrogen-containing heterocyclic rings (referred to as rings Cn) (for example, pyrrole ring, imidazole Ring, pyrazole ring, pyridine ring, pyrroline ring, pyrrolidine ring, imidazolidine ring, pyrazolidine ring, piperidine ring, piperazine ring, morpholine ring, etc.), oxygen-containing heterocycle (referred to
  • R 3 When there are a plurality of R 3 , they may be connected to each other to form a cyclic structure.
  • Examples of the formed cyclic structure include ring Cf, ring Cr, ring Cn, ring Co, and ring Cs.
  • the above specific polymer may be a copolymer having a structural unit other than the structural units of the above formulas (1) to (3).
  • Other structural units include the following (11), (21) and (31).
  • the structural unit (11) is preferably combined with the structural unit (1)
  • the structural unit (21) is preferably combined with the structural unit (2)
  • (31) is preferably combined with the structural unit (3).
  • R 11 and R 22 are each independently a hydrogen atom or a methyl group.
  • R 31 is a substituent T described later, and n31 is an integer of 0 to 3.
  • R 31 s When there are a plurality of R 31 s , they may be connected to each other to form a cyclic structure. Examples of the formed cyclic structure include a ring Cf, a ring Cr, a ring Cn, a ring Co, and a ring Cs.
  • R 17 is an organic group or a hydrogen atom that forms an ester structure with the carbonyloxy group in the formula.
  • the organic group include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably having 1 to 12 carbon atoms, and still more preferably having 1 to 6 carbon atoms; which may be linear or cyclic, and may be linear or branched); The number 6 to 22, preferably 6 to 18, more preferably 6 to 10, and an arylalkyl group (preferably 7 to 23, more preferably 7 to 19, and still more preferably 7 to 11; an alkyl group
  • the moiety may be linear or cyclic, and may be linear or branched), or a group consisting of an aromatic heterocyclic ring in which an oxygen atom is bonded to a carbon atom (in the case of a cyclic structure, a pyrrole ring, an imidazole ring, A pyrazole ring, a pyridine ring, a furan ring, a thiophen
  • R 27 is a substituent T described later, and n21 is an integer of 0 to 5.
  • R 27 When R 27 is in plurality, they may form a cyclic structure via connection to each other. Examples of the formed cyclic structure include a ring Cf, a ring Cr, a ring Cn, a ring Co, and a ring Cs.
  • substituent T examples include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 6), and an arylalkyl group (preferably having 7 to 21 carbon atoms, more preferably 7 to 15 carbon atoms).
  • an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably having 2 to 12 carbon atoms, still more preferably being 2 to 6), a hydroxy group and an amino group (-NR N 2 ) (having 0 carbon atoms)
  • a sulfanyl group preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 10 carbon atoms.
  • An alkoxy group preferably having 1 to 12 carbon atoms, more preferably 1 to 6, more preferably 1 to 3
  • an aryloxy group preferably having 6 to 22 carbon atoms, 8, more preferably 6 to 10
  • an acyl group preferably having 2 to 12 carbon atoms, more preferably 2 to 6 and still more preferably 2 to 3
  • an acyloxy group preferably having 2 to 12 carbon atoms, 2 to 6, more preferably 2 to 3
  • an aryloyl group preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and still more preferably 7 to 11
  • an aryloyloxy group having 7 to 11 carbon atoms.
  • 7 to 19 are more preferable
  • 7 to 11 are more preferable
  • a carbamoyl group preferably having 1 to 12 carbon atoms, more preferably 1 to 6 is more preferable
  • a sulfamoyl group having a carbon number of 1 to 3. 0-12 are preferable, 0-6 are more preferable, 0-3 are more preferable), a sulfo group, a sulfooxy group, a phosphono group, a phosphonooxy group, and an alkyl sulfo group.
  • an arylsulfonyl group (preferably having 6 to 22 carbon atoms, more preferably having 6 to 18 carbon atoms, and still more preferably having 6 to 10 carbon atoms).
  • a heterocyclic group (containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom; preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 2 to 5;
  • a (meth) acryloyl group, a (meth) acryloyloxy group, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an oxo group ((O), an imino group ( NRNR N ), an alkylidene group ( C (R N ) 2 ) and the like.
  • R N is a hydrogen atom, an alkyl group of the substituent T, an alkenyl group of the substituent T, an aryl group of the substituent T, an arylalkyl group of the substituent T, or a heterocyclic group of the substituent T.
  • the alkyl and alkenyl moieties contained in each substituent may be linear or cyclic, and may be linear or branched.
  • the substituent T is a group that can take a substituent, it may further have a substituent T.
  • the alkyl group may be a hydroxyalkyl group in which a hydroxy group is substituted.
  • linking group L examples include an alkylene group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 6), and an alkenylene group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6; (2 to 3 are more preferable), (oligo) alkyleneoxy group (the number of carbon atoms of the alkylene group in one structural unit is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 to 3; Preferably 1 to 50, more preferably 1 to 40, still more preferably 1 to 30, an arylene group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10), an oxygen atom,
  • the linking group include a sulfur atom, a sulfonyl group, a carbonyl group, a thiocarbonyl group, -NR N- , and a combination thereof.
  • the alkylene group, alkenylene group, and alkyleneoxy group may have the above substituent T.
  • the alkylene group may have a hydroxy group.
  • the connecting chain length of the connecting group L is preferably 1 to 24, more preferably 1 to 12, and further preferably 1 to 6.
  • the alkylene group, alkenylene group, and (oligo) alkyleneoxy group defined by the linking group L may be linear or cyclic, and may be linear or branched.
  • the atoms constituting the linking group L are preferably those containing a carbon atom and a hydrogen atom, and if necessary, a hetero atom (at least one selected from an oxygen atom, a nitrogen atom and a sulfur atom).
  • the number of carbon atoms in the linking group is preferably 1 to 24, more preferably 1 to 12, and still more preferably 1 to 6.
  • the number of hydrogen atoms may be determined according to the number of carbon atoms and the like.
  • the number of hetero atoms is preferably from 0 to 12, more preferably from 0 to 6, and even more preferably from 0 to 3, for each of oxygen, nitrogen and sulfur atoms.
  • the synthesis of the specific polymer may be carried out by a conventional method.
  • a known method relating to addition polymerization of an olefin can be appropriately employed.
  • a known method relating to addition polymerization of styrene can be appropriately employed.
  • a known method for synthesizing a phenol resin can be appropriately employed.
  • the compounding amount of the specific polymer is not particularly limited, but in the composition for forming an underlayer film for imprinting, it is preferable to occupy a majority in the solid content, more preferably 70% by mass or more in the solid content, More preferably, the content is 80% by mass or more in a minute.
  • the upper limit is not particularly limited, but is practically 99.0% by mass or less.
  • the content of the specific polymer in the composition for forming an underlayer film for imprint (including the solvent) is not particularly limited, but is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more. Is more preferable, and the content is more preferably 0.1% by mass or more.
  • the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 1% by mass or less, and even more preferably less than 1% by mass.
  • One of the above polymers may be used, or a plurality thereof may be used. When a plurality of materials are used, the total amount falls within the above range.
  • the composition for forming an underlayer film for imprinting of the present invention is selected from an acid having a pKa of 5 or less and an acid generator capable of generating an acid with a pKa of 5 or less in combination with the specific polymer, and the polymer And a low-molecular compound (specific low-molecular compound) having a functional group capable of binding to and having a molecular weight of 1,000 or less.
  • the pKa of the acid related to the specific low-molecular compound is 5 or less, but is preferably 4.5 or less, more preferably 4.2 or less.
  • the lower limit is preferably -5 or more, more preferably -4 or more, and still more preferably -3.5 or more.
  • the pKa of a low-molecular compound refers to pKa in an aqueous solution, for example, those described in Chemical Handbook (II) (4th revised edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.)
  • the pKa in the aqueous solution can be specifically measured by measuring the acid dissociation constant at 23 ° C. using an infinitely diluted aqueous solution. If measurement is not possible, a value based on a database of Hammett's substituent constants and known literature values can be obtained by calculation using the following software package 1. All pKa values in this specification indicate values obtained by calculation using this software package 1.
  • Software Package 1 Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).
  • the molecular weight of the specific low-molecular compound is 1,000 or less, preferably 800 or less, more preferably 700 or less, and even more preferably 600 or less.
  • the lower limit is not particularly limited, but is, for example, 80 or more, and may be 100 or more.
  • the acid group include a carboxylic acid group, a sulfonic acid group, a phenolic hydroxy group, a phosphoric acid group, a thiocarboxylic acid group, and a dithiocarboxylic acid group.
  • the acid group is preferably a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group.
  • the acid generator include an embodiment in which an acid group is a group capable of generating the acid group.
  • the group capable of generating an acid group include a carboxylic acid ester group, a thiocarboxylic acid ester group, a dithiocarboxylic acid ester group, a sulfonic acid ester group, a phosphoric acid monoester group, a phosphoric acid diester group, and a dicarboxylic acid anhydride.
  • the organic group constituting the ester include an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3), and an aryl group (preferably having 6 to 22 carbon atoms and 6 to 18 carbon atoms).
  • the alkyl group constituting the ester is preferably a tertiary alkyl group (preferably having 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and still more preferably 4 to 8 carbon atoms).
  • a tertiary alkyl group in which the groups are linked to each other to form a cyclic structure preferably a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, or a cyclohexane ring
  • the above acid groups or groups capable of generating an acid group are collectively referred to as an acid group or the like Ac.
  • the specific low-molecular compound is an acid generator
  • examples of the acid generator include a photoacid generator and a thermal acid generator.
  • the photoacid generator is preferable.
  • the acid generated from the acid generator is the same as the above-mentioned acid having a pKa of 5 or less.
  • the protecting group for protecting the acid group of an acid having a pKa of 5 or less a triphenylsulfonium group and a diazo group are preferable. As described above, by using an acid as an acid generator, there is an advantage that a specific low-molecular compound can be handled in a stable form in which an acid group site is protected.
  • the functional group of the specific low molecular compound is not particularly limited as long as it reacts with and binds to the functional group of the specific polymer.
  • Examples include an ethylenically unsaturated group, an acid group or an acid anhydride group, and a crosslinkable group.
  • Examples of the ethylenically unsaturated group include the aforementioned ethylenically unsaturated group Et.
  • Examples of the acid group or the acid anhydride group include the above-described Ac group such as the acid group.
  • the crosslinkable group include the above-described examples of the crosslinkable group Bd.
  • the functional group of the specific low-molecular compound defined here is referred to as a functional group Q2, and may be distinguished from the functional group Q1 of the specific polymer.
  • Table 3 shows specific combinations of the functional group of the specific polymer and the functional group of the specific low-molecular compound.
  • the acid of the specific low-molecular compound may be an inorganic acid or an organic acid, but is preferably an organic acid.
  • examples of the inorganic acid include sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, and boric acid.
  • the specific low molecular weight compound is an organic acid
  • it is preferably a compound represented by the formula (4).
  • Q 2 is a functional group Q2 as defined above.
  • Ac 4 is Ac such as an acid group defined above.
  • n41 is an integer of 1 to 4.
  • n42 is an integer of 1 to 4.
  • L 4 represents a single bond or a linking group of the L (when n41 + n42 is 3 or more is replaced as trivalent or more connecting group).
  • L 4 is a single bond, an alkylene group defined by the linking group L or a trivalent or higher linking group having the structure thereof, an arylene group or a trivalent or higher linking group having the structure thereof, an (oligo) alkyleneoxy group or A trivalent or higher-valent linking group having the structure, or a linking group obtained by combining them is preferable.
  • the presence or absence of the oxygen atom at the terminal of the (oligo) alkyleneoxy group may be adjusted depending on the structure of the preceding group.
  • the synthesis of the specific low-molecular compound may be performed by a conventional method.
  • B-8 and B-9 are acid generators, and pKa is the pKa of the generated acid.
  • the amount of the specific low-molecular compound is not particularly limited, but in the composition for forming an underlayer film for imprinting, the content is preferably 1% by mass or more in solid content, and more preferably 5% by mass or more in solid content. More preferably, it is more preferably at least 8% by mass in the solid content.
  • the upper limit is not particularly limited, but is preferably 20% by mass or less in the solid content, and may be 15% by mass or less.
  • the content of the specific low-molecular compound in the composition for forming an underlayer film for imprint (including the solvent) is not particularly limited, but is preferably 0.001% by mass or more, and more preferably 0.005% by mass or more. More preferably, it is still more preferably 0.01% by mass or more.
  • the upper limit is preferably 5% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less, even more preferably 0.8% by mass or less. It is even more preferred that the content is not more than 0.5% by mass.
  • the ratio of the specific low-molecular compound to the specific polymer is 1 part by mass or more with respect to 100 parts by mass of the specific polymer, from the viewpoint of sufficiently extracting the effect thereof and avoiding a problem that the amount becomes excessive. It is more preferably at least 2 parts by mass, and still more preferably at least 5 parts by mass.
  • the upper limit is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 20 parts by mass or less.
  • One or more specific low molecular weight compounds may be used. When a plurality of materials are used, the total amount falls within the above range.
  • the combination of the functional group Q1 of the specific polymer and the functional group Q2 of the specific low-molecular compound includes (i) ethylenically unsaturated groups, (ii) an amino group and an acid group or an acid anhydride. It is preferably selected from the group consisting of (iii) an amino group and a crosslinkable group, (iv) a hydroxy group and a crosslinkable group, and (vi) a combination of a crosslinkable group and an acid group or an acid anhydride group.
  • the acid anhydride group include an anhydride group of a dicarboxylic acid (a carbonyloxycarbonyl group bonded to a carbon atom to form a cyclic structure).
  • Examples of the ethylenically unsaturated group include an ethylenically unsaturated group Et, and examples of the acid group or acid anhydride include Ac such as an acid group.
  • Examples of the crosslinkable group include the examples of the crosslinkable group Bd.
  • the combination of the functional group Q1 of the specific polymer and the functional group Q2 of the specific low-molecular compound is more preferably as shown in the following table.
  • the composition for forming an underlayer film for imprint contains a solvent (hereinafter, may be referred to as a "solvent for an underlayer film").
  • the solvent is preferably a compound which is liquid at 23 ° C. and has a boiling point of 250 ° C. or less.
  • the non-volatile components ultimately form the underlying film.
  • the composition for forming an underlayer film for imprinting preferably contains 99.0% by mass or more of a solvent for an underlayer film, more preferably 99.5% by mass or more, and may be 99.6% by mass or more. .
  • the ratio of the solvent is in the above range, the film thickness at the time of film formation is kept small, which leads to improvement of pattern formability at the time of etching.
  • the solvent may be contained alone or in combination of two or more in the composition for forming an underlayer film for imprint. When two or more kinds are included, the total amount is preferably in the above range.
  • the boiling point of the solvent for the lower layer film is preferably 230 ° C. or lower, more preferably 200 ° C. or lower, further preferably 180 ° C. or lower, further preferably 160 ° C. or lower, and more preferably 130 ° C. or lower. Is even more preferable. Although the lower limit is practically 23 ° C., it is more practical that the lower limit is 60 ° C. or higher. By setting the boiling point within the above range, the solvent can be easily removed from the lower layer film, which is preferable.
  • the solvent for the lower layer film is preferably an organic solvent.
  • the solvent is preferably a solvent having at least one of an alkylcarbonyl group, a carbonyl group, a hydroxy group and an ether group. Among them, it is preferable to use an aprotic polar solvent.
  • alkoxy alcohol propylene glycol monoalkyl ether carboxylate, propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate.
  • alkoxy alcohol examples include methoxyethanol, ethoxyethanol, methoxypropanol (eg, 1-methoxy-2-propanol), ethoxypropanol (eg, 1-ethoxy-2-propanol), and propoxypropanol (eg, 1-propoxy-2-propanol).
  • Propanol methoxybutanol (eg, 1-methoxy-2-butanol, 1-methoxy-3-butanol), ethoxybutanol (eg, 1-ethoxy-2-butanol, 1-ethoxy-3-butanol), methylpentanol (Eg, 4-methyl-2-pentanol).
  • the propylene glycol monoalkyl ether carboxylate is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, and propylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate ( PGMEA) is particularly preferred.
  • propylene glycol monoalkyl ether propylene glycol monomethyl ether (PGME) or propylene glycol monoethyl ether is preferable.
  • lactate ethyl lactate, butyl lactate, or propyl lactate is preferred.
  • acetate methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate are preferred.
  • alkoxypropionate methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferable.
  • chain ketones include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, Acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone or methyl amyl ketone is preferred.
  • cyclic ketone methylcyclohexanone, isophorone or cyclohexanone is preferable.
  • lactone ⁇ -butyrolactone ( ⁇ BL) is preferable.
  • alkylene carbonate propylene carbonate is preferred.
  • an ester solvent having 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, and still more preferably 7 to 10), and having 2 or less hetero atoms.
  • ester solvent having 7 or more carbon atoms and 2 or less heteroatoms include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, butyl propionate, Examples thereof include isobutyl isobutyrate, heptyl propionate, and butyl butanoate. It is particularly preferable to use isoamyl acetate.
  • a solvent having a flash point (hereinafter, also referred to as a p component) of 30 ° C or higher.
  • Such components include propylene glycol monomethyl ether (p component: 47 ° C.), ethyl lactate (p component: 53 ° C.), ethyl 3-ethoxypropionate (p component: 49 ° C.), and methyl amyl ketone (p component: 42 ° C.), cyclohexanone (p component: 30 ° C.), pentyl acetate (p component: 45 ° C.), methyl 2-hydroxyisobutyrate (p component: 45 ° C.), ⁇ -butyrolactone (p component: 101 ° C.) or propylene carbonate (P component: 132 ° C.) is preferred.
  • propylene glycol monoethyl ether, ethyl lactate, pentyl acetate or cyclohexanone is more preferred, and propylene glycol monoethyl ether or ethyl lactate is particularly preferred.
  • solvents particularly preferred as the solvent for the lower layer film alkoxy alcohol, propylene glycol monoalkyl ether carboxylate, propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, chain ketone, cyclic ketone, lactone, and alkylene Carbonates.
  • the composition for forming an underlayer film for imprint contains, in addition to the above, one or more of an alkylene glycol compound, a polymerization initiator, a polymerization inhibitor, an antioxidant, a leveling agent, a thickener, a surfactant, and the like. You may go out.
  • a thermal polymerization initiator and the like each component described in JP-A-2013-036027, JP-A-2014-090133, and JP-A-2013-189537 can be used.
  • the description in the above publication can be referred to.
  • the composition for forming an underlayer film for imprinting may include an alkylene glycol compound.
  • the alkylene glycol compound preferably has from 3 to 1,000 alkylene glycol structural units, more preferably from 4 to 500, still more preferably from 5 to 100. It is more preferable to have 50.
  • the weight average molecular weight (Mw) of the alkylene glycol compound is preferably from 150 to 10,000, more preferably from 200 to 5,000, further preferably from 300 to 3,000, and still more preferably from 300 to 1,000.
  • Alkylene glycol compounds include polyethylene glycol, polypropylene glycol, their mono or dimethyl ether, mono or dioctyl ether, mono or dinonyl ether, mono or didecyl ether, monostearate, monooleate, monoadipate, and monosuccinate. Acid esters are exemplified, and polyethylene glycol and polypropylene glycol are preferred.
  • the surface tension at 23 ° C. of the alkylene glycol compound is preferably at least 38.0 mN / m, more preferably at least 40.0 mN / m. Although the upper limit of the surface tension is not particularly limited, it is, for example, 48.0 mN / m or less.
  • the wettability of the curable composition for imprints provided immediately above the lower layer film can be further improved.
  • the surface tension is measured at 23 ° C. using a glass plate using a surface tension meter SURFACE TENS-IOMETER CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd. The unit is indicated by mN / m. Two samples are prepared for each level, and each sample is measured three times. An arithmetic average value of a total of six times is adopted as the evaluation value.
  • the content is 40% by mass or less of the nonvolatile component, preferably 30% by mass or less, more preferably 20% by mass or less, and preferably 1 to 15% by mass. More preferred. Only one alkylene glycol compound may be used, or two or more alkylene glycol compounds may be used. When two or more kinds are used, the total amount is preferably within the above range.
  • the composition for forming an underlayer film for imprints may contain a polymerization initiator, and preferably contains at least one of a thermal polymerization initiator and a photopolymerization initiator.
  • a photopolymerization initiator By including the polymerization initiator, the reaction of the polymerizable group contained in the composition for forming an underlayer film for imprinting is promoted, and the adhesion tends to be improved.
  • a photopolymerization initiator is preferable.
  • the photopolymerization initiator a radical polymerization initiator and a cationic polymerization initiator are preferable, and a radical polymerization initiator is more preferable.
  • a plurality of photopolymerization initiators may be used in combination.
  • a known compound can be arbitrarily used.
  • halogenated hydrocarbon derivatives eg, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
  • acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives, etc.
  • the description in paragraphs 0165 to 182 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated in the present specification.
  • Examples of the acylphosphine compound include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
  • commercially available products such as IRGACURE-819, IRGACURE 1173, and IRGACURE-TPO (all trade names: manufactured by BASF) can be used.
  • the content of the photopolymerization initiator used in the composition for forming an underlayer film for imprinting is, for example, 0.0001 to 5% by mass, preferably 0.0005 to 3% by mass of the non-volatile component. %, More preferably 0.01 to 1% by mass. When two or more photopolymerization initiators are used, the total amount falls within the above range.
  • the surface free energy of the imprint underlayer film formed from the composition for forming an imprint underlayer film of the present invention is preferably 30 mN / m or more, more preferably 40 mN / m or more, and 50 mN / m. More preferably, it is the above.
  • the upper limit is preferably 200 mN / m or more, more preferably 150 mN / m or more, and even more preferably 100 mN / m or more.
  • the surface free energy can be measured using a surface tension meter SURFACE TENS-IOMETER CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd. at 23 ° C. using a glass plate.
  • the composition for forming an underlayer film of the present invention is generally used as a composition for forming an underlayer film for a curable composition for imprints.
  • the composition of the curable composition for imprints is not particularly limited, but preferably contains a polymerizable compound.
  • the curable composition for imprints preferably contains a polymerizable compound, and it is more preferable that the polymerizable compound constitute the maximum amount component.
  • the polymerizable compound may have one polymerizable group in one molecule, or may have two or more polymerizable groups.
  • At least one of the polymerizable compounds contained in the curable composition for imprints preferably contains 2 to 5 polymerizable groups in one molecule, more preferably 2 to 4 polymerizable groups, and more preferably 2 or 3 polymerizable groups. More preferably, it contains three more preferably.
  • At least one of the polymerizable compounds contained in the curable composition for imprints preferably has a cyclic structure.
  • Examples of this cyclic structure include an aliphatic hydrocarbon ring Cf and an aromatic hydrocarbon ring Cr.
  • the polymerizable compound preferably has an aromatic hydrocarbon ring Cr, and more preferably has a benzene ring.
  • the molecular weight of the polymerizable compound is preferably from 100 to 900. It is preferable that at least one of the polymerizable compounds is represented by the following formula (I-1).
  • L 20 is a 1 + q divalent linking group, for example, a linking group having a cyclic structure.
  • Examples of the ring structure include the above-mentioned ring Cf, ring Cr, ring Cn, ring Co, and ring Cs.
  • R 21 and R 22 each independently represent a hydrogen atom or a methyl group.
  • L 21 and L 22 each independently represent a single bond or the above-mentioned linking group L.
  • L 20 and L 21 or L 22 may be bonded via a linking group L or not to form a ring.
  • L 20 , L 21 and L 22 may have the substituent T described above.
  • a plurality of substituents T may combine to form a ring. When there are a plurality of substituents T, they may be the same or different.
  • q2 is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and still more preferably 0 or 1.
  • Examples of the polymerizable compound include the compounds used in the following examples, the compounds described in paragraphs 0017 to 0024 of JP-A-2014-90133 and the compounds described in the examples, and the compounds described in paragraphs 0024 to 0089 of JP-A-2015-9171.
  • Compounds, compounds described in paragraphs 0023 to 0037 of JP-A-2015-70145, and compounds described in paragraphs 0012 to 0039 of WO2016 / 152597 can be exemplified, but the present invention is limited thereby. Not to be interpreted.
  • the polymerizable compound is preferably contained in the curable composition for imprints in an amount of 30% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, still more preferably 55% by mass or more, and 60% by mass. %, Or 70% by mass or more. Further, the upper limit is preferably less than 99% by mass, more preferably 98% by mass or less, and can be 97% by mass or less.
  • the boiling point of the polymerizable compound is preferably set and formulated in relation to the specific compound contained in the composition for forming an underlayer film for imprint described above.
  • the boiling point of the polymerizable compound is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, and further preferably 400 ° C. or lower.
  • the lower limit is preferably 200 ° C. or higher, more preferably 220 ° C. or higher, even more preferably 240 ° C. or higher.
  • the curable composition for imprints may contain additives other than the polymerizable compound.
  • Other additives may include a polymerization initiator, a surfactant, a sensitizer, a release agent, an antioxidant, a polymerization inhibitor, and the like.
  • Specific examples of the curable composition for imprints that can be used in the present invention include the compositions described in JP-A-2013-036027, JP-A-2014-090133, and JP-A-2013-189537. And their contents are incorporated herein.
  • the preparation of the curable composition for imprints and the method of forming a film (pattern forming layer) can also be referred to the description in the above-mentioned publication, and the contents thereof are incorporated herein.
  • the content of the solvent in the curable composition for imprints is preferably 5% by mass or less, more preferably 3% by mass or less, and more preferably 1% by mass of the curable composition for imprints. It is more preferred that:
  • the curable composition for imprints may also be in an embodiment substantially not containing a polymer (preferably having a weight average molecular weight of more than 1,000, more preferably having a weight average molecular weight of more than 2,000).
  • the phrase "contains substantially no polymer” means that, for example, the content of the polymer is 0.01% by mass or less of the curable composition for imprints, preferably 0.005% by mass or less, and not containing at all. Is more preferred.
  • the curable composition for imprints preferably has a viscosity of 20.0 mPa ⁇ s or less, more preferably 15.0 mPa ⁇ s or less, further preferably 11.0 mPa ⁇ s or less, and 9 More preferably, it is not more than 0.0 mPa ⁇ s.
  • the lower limit of the viscosity is not particularly limited, but may be, for example, 5.0 mPa ⁇ s or more.
  • the viscosity is measured according to the following method. The viscosity is measured by adjusting the temperature of the sample cup to 23 ° C. using an E-type rotary viscometer RE85L manufactured by Toki Sangyo Co., Ltd.
  • the surface tension ( ⁇ Resist) of the curable composition for imprints is preferably 28.0 mN / m or more, more preferably 30.0 mN / m or more, and may be 32.0 mN / m or more. .
  • the upper limit of the surface tension is not particularly limited, but is preferably 40.0 mN / m or less, and 38.0 mN / m or less from the viewpoint of the relationship with the underlayer film and imparting inkjet suitability. Or less, and may be 36.0 mN / m or less.
  • the surface tension of the curable composition for imprints is measured according to the same method as the above-mentioned method for the alkylene glycol compound.
  • the Onishi parameter of the curable composition for imprints is preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.7 or less.
  • the lower limit value of the Onishi parameter of the curable composition for imprints is not particularly limited, it may be, for example, 1.0 or more, or even 2.0 or more.
  • a conventionally known storage container can be used as the storage container for the curable composition for imprints used in the present invention.
  • the inner wall of the container is formed into a multi-layer bottle composed of six types and six layers of resin, or six types of resin is formed into a seven-layer structure. It is also preferred to use a bottle that has been used. Examples of such a container include a container described in JP-A-2015-123351.
  • the method for forming a pattern includes a step of forming an underlayer film on the substrate surface using the composition for forming an underlayer film for imprinting of the present invention (underlayer film forming step); Forming a curable composition layer for imprint by applying the composition for forming an underlayer film for imprint (preferably, the surface of an underlayer film) (curable composition layer for imprint); A step of contacting a mold with the curable composition layer for printing, a step of exposing the curable composition layer for imprint in a state where the mold is in contact, and the curable composition for imprinting, where the mold is exposed. And a step of peeling off from the material layer.
  • underlayer film forming step Forming a curable composition layer for imprint by applying the composition for forming an underlayer film for imprint (preferably, the surface of an underlayer film) (curable composition layer for imprint); A step of contacting a mold with the curable composition layer for printing, a step of exposing the curable composition layer for imprint in a state where
  • Lower-layer film formation step >>>
  • the lower film 2 is formed on the surface of the substrate 1 as shown in FIGS.
  • the underlayer film is preferably formed by applying the composition for forming an underlayer film for imprint on a substrate in a layered manner.
  • the substrate 1 may have an undercoat layer or an adhesion layer in addition to the case of a single layer.
  • the method for applying the composition for forming an underlayer film for imprinting on the surface of a substrate is not particularly limited, and a generally well-known application method can be employed.
  • the application method include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spin coating method, a slit scanning method, and an inkjet method.
  • a spin coating method is preferred.
  • the solvent is volatilized (dried) by heat to form an underlayer film as a thin film.
  • the thickness of the lower film 2 is preferably 2 nm or more, more preferably 3 nm or more, still more preferably 4 nm or more, and may be 5 nm or more, or may be 7 nm or more. It may be 10 nm or more. Further, the thickness of the lower layer film is preferably 40 nm or less, more preferably 30 nm or less, further preferably 20 nm or less, and may be 15 nm or less.
  • the film thickness is equal to or more than the lower limit, the expandability (wettability) of the curable composition for imprint on the lower layer film is improved, and a uniform residual film can be formed after imprint.
  • the film thickness is equal to or less than the upper limit, the residual film after imprinting becomes thin, unevenness of the film thickness hardly occurs, and the uniformity of the residual film tends to be improved.
  • a silicon substrate a glass substrate, a quartz substrate, a sapphire substrate, a silicon carbide (silicon carbide) substrate, a gallium nitride substrate, an aluminum substrate, an amorphous aluminum oxide substrate, a polycrystalline aluminum oxide substrate, an SOC (spin-on carbon), an SOG ( Spin-on-glass), silicon nitride, silicon oxynitride, and a substrate composed of GaAsP, GaP, AlGaAs, InGaN, GaN, AlGaN, ZnSe, AlGa, InP, or ZnO.
  • the material of the glass substrate include aluminosilicate glass, aluminoborosilicate glass, and barium borosilicate glass.
  • a silicon substrate and a substrate coated with SOC are preferable.
  • a silicon substrate whose surface is appropriately modified can be used.
  • the carbon content in a region from the surface of the substrate to a thickness of 10 nm (more preferably, a thickness of 100 nm) is 70% by mass or more (preferably 80 to 100%). Mass%) may be used.
  • a substrate having a 200-nm-thick SOC (Spin on Carbon) film obtained by applying various spin-on carbon films to a silicon substrate by a spin coating method and performing baking at 240 ° C.
  • a substrate having an organic layer as the outermost layer.
  • the organic layer of the substrate include an amorphous carbon film formed by CVD (Chemical Vapor Deposition) and a spin-on carbon film formed by dissolving a high carbon material in an organic solvent and spin coating.
  • spin-on carbon film examples include nortricyclene copolymer, hydrogenated naphthol novolak resin, naphthol dicyclopentadiene copolymer, phenoldicyclopentadiene copolymer, fluorenebisphenol novolak described in JP-A-2005-128509, Acenaphthylene copolymer and indene copolymer described in 2005-250434, fullerene having a phenol group described in JP-A-2006-227391, bisphenol compound and its novolak resin, dibisphenol compound and its novolak resin, adamantane phenol Compound novolak resin, hydroxyvinylnaphthalene copolymer, bisnaphthol compound described in JP-A-2007-199653, and this novolak resin, R MP, the resin compound shown in tricyclopentadiene copolymers thereof.
  • SOC As an example of the SOC, reference can be made to the description in paragraph 0126 of JP
  • the contact angle of the substrate surface with water is preferably 20 ° or more, more preferably 40 ° or more, and even more preferably 60 ° or more. It is practical that the upper limit is 90 ° or less.
  • the contact angle is measured according to the method described in Examples described later.
  • a substrate having a basic layer as the outermost layer (hereinafter, referred to as a basic substrate).
  • the basic substrate include a substrate containing a basic organic compound (for example, an amine compound or an ammonium compound) and an inorganic substrate containing a nitrogen atom.
  • Curable composition layer forming step for imprint In the application step, for example, as shown in FIG. 1C, the curable composition for imprint 3 is applied to the surface of the lower layer film 2.
  • the method of applying the curable composition for imprints is not particularly limited, and the description in paragraph 0102 of JP2010-109092A (the publication number of the corresponding US application is US2011 / 183127) can be referred to. Is incorporated herein. It is preferable that the curable composition for imprints is applied to the surface of the underlayer film by an inkjet method. Further, the curable composition for imprints may be applied by multiple coating.
  • the amount of the droplets is preferably about 1 to 20 pL, and it is preferable that the droplets are arranged on the surface of the underlayer film at intervals of the droplets.
  • the interval between droplets is preferably 10 to 1000 ⁇ m.
  • the interval between the droplets is the interval between the nozzles of the inkjet.
  • the volume ratio of the lower layer film 2 to the film-like curable composition for imprint 3 applied on the lower layer film is preferably 1: 1 to 500, and more preferably 1:10 to 300. More preferably, the ratio is 1:50 to 200.
  • a method for producing a laminate according to a preferred embodiment of the present invention is a method for producing a laminate using a kit containing a curable composition for imprinting and a composition for forming an underlayer film for imprinting, wherein the imprinting is performed. Applying the curable composition for imprints to the surface of an underlayer film formed from the composition for forming an underlayer film for use. Further, the method for manufacturing a laminate according to a preferred embodiment of the present invention includes a step of applying the composition for forming an underlayer film for imprint in a layer on a substrate, and forming the layer for imprint applied in the layer.
  • the method includes heating (baking) the composition for use at preferably 100 to 300 ° C, more preferably 130 to 260 ° C, and still more preferably 150 to 230 ° C.
  • the heating time is preferably 30 seconds to 5 minutes.
  • a liquid film may be formed on the substrate.
  • the formation of the liquid film may be performed by a conventional method. For example, it may be formed by applying a composition containing a crosslinkable monomer (the examples of the polymerizable compound is liquid at a temperature of 23 ° C.) on a substrate.
  • Mold contact process for example, as shown in FIG. 1 (4), the curable composition for imprint 3 is brought into contact with a mold 4 having a pattern for transferring a pattern shape. Through these steps, a desired pattern (imprint pattern) is obtained. Specifically, the mold 4 is pressed against the surface of the film-like curable composition for imprints 3 in order to transfer a desired pattern to the film-like curable composition for imprints.
  • the mold may be a light transmissive mold or a light non-transmissive mold.
  • a light transmitting mold it is preferable to irradiate the curable composition 3 with light from the mold side.
  • a mold that can be used in the present invention is a mold having a pattern to be transferred.
  • the pattern of the mold can be formed according to desired processing accuracy by, for example, photolithography or electron beam lithography, but in the present invention, the method of forming the mold pattern is not particularly limited. Further, a pattern formed by the pattern forming method according to the preferred embodiment of the present invention can be used as a mold.
  • the material constituting the light-transmitting mold used in the present invention is not particularly limited, but may be a light-transmitting resin such as glass, quartz, polymethyl methacrylate (PMMA), or a polycarbonate resin, a transparent metal vapor-deposited film, or polydimethylsiloxane. Examples thereof include a flexible film, a photocurable film, and a metal film, and quartz is preferable.
  • the non-light-transmitting mold material used when a light-transmitting substrate is used in the present invention is not particularly limited, but may be any material having a predetermined strength.
  • Specific examples include ceramic materials, vapor-deposited films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, and substrates such as SiC, silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon. And are not specifically restricted.
  • the surface of the substrate may be appropriately processed by an ordinary method. For example, by forming an OH group on the surface of the substrate by UV ozone treatment or the like, and increasing the polarity of the substrate surface, the adhesion is further improved. Is also good.
  • the mold pressure be 10 atm or less.
  • the mold pressure is preferably selected from a range in which the remaining film of the curable composition for imprints corresponding to the mold projections is reduced, while uniformity of mold transfer can be ensured.
  • the contact between the curable composition for imprinting and the mold is performed in an atmosphere containing helium gas or condensable gas, or both helium gas and condensable gas.
  • Light irradiation step the curable composition for imprints is irradiated with light to form a cured product.
  • the irradiation amount of light irradiation in the light irradiation step may be sufficiently larger than the minimum irradiation amount necessary for curing.
  • the irradiation amount required for curing is appropriately determined by examining the consumption of unsaturated bonds of the curable composition for imprints.
  • the type of light to be applied is not particularly limited, but is exemplified by ultraviolet light.
  • the substrate temperature during light irradiation is usually room temperature, but light irradiation may be performed while heating to increase reactivity.
  • a vacuum state As a stage prior to light irradiation, if a vacuum state is set, it is effective in preventing air bubbles from entering, suppressing a decrease in reactivity due to oxygen mixing, and improving the adhesion between the mold and the curable composition for imprints.
  • Light irradiation may be performed.
  • a preferable degree of vacuum during light irradiation is in a range of 10 -1 Pa to normal pressure.
  • the exposure illuminance is preferably in the range of 1 to 500 mW / cm 2 , and more preferably in the range of 10 to 400 mW / cm 2 .
  • the exposure time is not particularly limited, but is preferably 0.01 to 10 seconds, and more preferably 0.5 to 1 second. Exposure amount is preferably in a range of 5 ⁇ 1000mJ / cm 2, and more preferably in the range of 10 ⁇ 500mJ / cm 2.
  • a step of curing the film-shaped curable composition for imprints (pattern forming layer) by light irradiation and, if necessary, further applying heat to the cured pattern to further cure the pattern. May be included.
  • the temperature for heating and curing the curable composition for imprints after light irradiation is preferably from 150 to 280 ° C, more preferably from 200 to 250 ° C.
  • the time for applying heat is preferably from 5 to 60 minutes, more preferably from 15 to 45 minutes.
  • the present invention discloses a laminate having a pattern formed from the curable composition for imprints on the surface of the underlayer film.
  • the thickness of the pattern forming layer comprising the curable composition for imprints used in the present invention is about 0.01 ⁇ m to 30 ⁇ m, although it varies depending on the use. Further, as described later, etching or the like can be performed.
  • the pattern formed by the above-described pattern (cured product pattern) forming method is used as a permanent film used for a liquid crystal display (LCD) or the like, or as an etching resist (lithography mask) for manufacturing a semiconductor element.
  • this specification discloses a method for manufacturing a semiconductor device (circuit board) including a step of obtaining a pattern by a pattern forming method according to a preferred embodiment of the present invention.
  • the step of performing etching or ion implantation on the substrate using the pattern obtained by the pattern forming method as a mask, and the step of forming an electronic member You may have.
  • the semiconductor device is preferably a semiconductor element. That is, this specification discloses a method of manufacturing a semiconductor device including the above-described pattern forming method. Further, the present specification discloses a method of manufacturing an electronic device, comprising: a step of obtaining a semiconductor device by the method of manufacturing a semiconductor device; and a step of connecting the semiconductor device and a control mechanism that controls the semiconductor device. .
  • a grid pattern is formed on a glass substrate of a liquid crystal display device by using a pattern formed by the above-described pattern forming method, so that reflection and absorption are reduced, and a large screen size (for example, 55 inches, 60 inches, (1 inch is 2.54 cm))) can be manufactured at low cost.
  • a polarizing plate described in JP-A-2015-132825 or WO 2011/132649 can be manufactured.
  • the pattern formed by the present invention is also useful as an etching resist (lithography mask) as shown in FIGS.
  • a pattern is used as an etching resist, first, a fine pattern of, for example, nano or micron order is formed on a substrate by the above-described pattern forming method.
  • the present invention is particularly advantageous in that a fine pattern on the order of nanometers can be formed, and a pattern having a size of 50 nm or less, particularly 30 nm or less can be formed.
  • the lower limit of the size of the pattern formed by the above-described pattern forming method is not particularly limited, but may be, for example, 1 nm or more.
  • the present invention also includes a step of obtaining a pattern on a substrate by a pattern forming method according to a preferred embodiment of the present invention, and a step of etching the substrate using the obtained pattern. A method for manufacturing a printing mold is also disclosed.
  • a desired pattern can be formed on the substrate by etching with an etching gas such as hydrogen fluoride in the case of wet etching or CF 4 in the case of dry etching.
  • the pattern has particularly good etching resistance to dry etching. That is, the pattern formed by the above pattern forming method is preferably used as a lithography mask.
  • the pattern formed by the present invention is specifically, a recording medium such as a magnetic disk, a light receiving element such as a solid-state imaging device, a light emitting element such as an LED (light emitting diode) or an organic EL (organic electroluminescence), a liquid crystal display.
  • Optical devices such as devices (LCD), diffraction gratings, relief holograms, optical waveguides, optical filters, optical components such as microlens arrays, thin film transistors, organic transistors, color filters, antireflection films, polarizing plates, polarizing elements, optical films, Columns and other flat panel display members, nanobiodevices, immunoassay chips, deoxyribonucleic acid (DNA) separation chips, microreactors, photonic liquid crystals, micropattern formation using self-assembly of block copolymers (directed @ self-assembly, DSA) It can be preferably used for producing a guide pattern or the like.
  • LCD liquid crystals
  • DSA self-assembly
  • composition for forming underlayer film for imprint Solutions containing the components shown in Tables 4 and 5 below were prepared. This was filtered through a nylon filter having a pore size of 0.02 ⁇ m and a PTFE (polytetrafluoroethylene) filter having a pore size of 0.010 ⁇ m to prepare the composition for forming an underlayer film for imprint shown in Examples and Comparative Examples.
  • the weight average molecular weight (Mw) of the polymer was defined as a value in terms of polystyrene according to gel permeation chromatography (GPC measurement).
  • the apparatus used was HLC-8220 (manufactured by Tosoh Corporation), and the columns used were a guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by Tosoh Corporation).
  • the eluent used was THF (tetrahydrofuran). For detection, an RI detector was used.
  • the chemical structure is identified by a conventional method such as LC-MS, NMR, IR, etc.
  • the molecular weight was determined from the chemical formula.
  • Example 10 a composition for forming an underlayer film for imprinting was formed on a substrate as described below, and a liquid film was applied thereon. Specifically, the following compound (AB) was diluted to 0.3% by mass with 1-methoxy-2-propanol (propylene glycol monomethyl ether) to prepare a coating solution (AB). A coating solution (AB) was spin-coated on the surface of each substrate so as to have a thickness of 8 nm, and heated at 60 ° C. for 1 minute using a hot plate to form a liquid film.
  • AB 1-methoxy-2-propanol
  • a coating solution (AB) was spin-coated on the surface of each substrate so as to have a thickness of 8 nm, and heated at 60 ° C. for 1 minute using a hot plate to form a liquid film.
  • Curable composition for imprint The unit of the blending amount is parts by mass and the unit of boiling point is ° C (1013.25 hPa).
  • SOC-1 A spin-on carbon film ODL-102 (manufactured by Shin-Etsu Chemical Co., Ltd.) is applied on a silicon wafer having a diameter of 8 inches by a spin coat method, baked at 240 ° C. for 60 seconds, and a 200 nm-thick SOC (Spin on carbon) is applied. Substrate on which a Carbon film is formed. The contact angle with water became 45 °.
  • SOC-2 A spin-on carbon film ODL-50 (manufactured by Shin-Etsu Chemical Co., Ltd.) is applied on a silicon nitride wafer having a diameter of 8 inches by a spin coat method, baked at 240 ° C.
  • SOC-3 SOC NCA9053EH (manufactured by Nissan Chemical Industries, Ltd.) is applied on a silicon wafer having a diameter of 8 inches by spin coating, and baked at 240 ° C. for 60 seconds to form a 200 nm thick SOC (Spin on Carbon) film. Substrate. The contact angle with water became 75 °.
  • Si (Si substrate) 8 inch diameter silicon wafer. The contact angle with water was 30 °.
  • O 3 treated Si (ozone treated Si substrate): A substrate obtained by irradiating an 8-inch silicon wafer with UV for 5 minutes using a UV irradiator (PL21-200-4, manufactured by Sen Special Light Source Co., Ltd.) The contact angle with water became 5 °.
  • the composition for forming an underlayer film for imprinting containing a specific polymer and a specific low-molecular compound has not only a general Si substrate but also a different carbon content and a different contact angle to water. Good adhesion to various substrates such as an SOC substrate and a substrate obtained by treating a Si substrate with ozone was realized, and it was found that the material was highly versatile (Examples 1 to 11). Furthermore, the composition for forming an underlayer film for imprinting of the present invention may be formed by forming a liquid film of a (meth) acrylate compound on a substrate and applying the liquid film thereon to form an underlayer film.
  • the surface of the layer of the curable composition for imprints formed on the lower layer film was excellent (Example 10).
  • the composition for forming an underlayer film for imprinting which does not use a low-molecular compound, could not obtain sufficient adhesion to a water-repellent (hydrophobic) SOC substrate having a particularly high contact angle (Comparative Example 1). ).
  • the compound having no polymerizable group (C-1), the compound having a too high pKa (C-3), and the compound having no acid group (C-4) have different degrees of hydrophilicity.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Shaping Of Tube Ends By Bending Or Straightening (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Dans le but d'améliorer l'adhésivité entre un substrat et un produit durci, une composition de formation de film de sous-couche d'impression est appliquée à un processus d'impression, la composition comprenant : un polymère ; un composé de faible poids moléculaire qui est choisi parmi un acide ayant un pKa inférieur ou égal à 5 et un agent de génération d'acide capable de générer un acide ayant un pKa inférieur ou égal à 5, qui a un groupe fonctionnel qui peut se lier au polymère, et qui a un poids moléculaire inférieur ou égal à 1000 ; et un solvant.
PCT/JP2019/033723 2018-09-27 2019-08-28 Composition de formation de film de sous-couche d'impression, film de sous-couche, procédé de formation de motif et procédé de fabrication d'élément semi-conducteur Ceased WO2020066442A1 (fr)

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JP2020155506A (ja) * 2019-03-19 2020-09-24 キオクシア株式会社 インプリント方法および半導体装置の製造方法
WO2022015681A1 (fr) * 2020-07-15 2022-01-20 Croda, Inc. Composés d'ester de phosphate de polyéther, compositions et utilisations

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WO2014007079A1 (fr) * 2012-07-02 2014-01-09 日産化学工業株式会社 Procédé de fabrication de dispositif à semi-conducteurs à l'aide de composition de formation de film de sous-couche organique pour processus de lithographie à développement de solvant
JP2014024322A (ja) * 2012-06-18 2014-02-06 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
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WO2016152600A1 (fr) * 2015-03-24 2016-09-29 富士フイルム株式会社 Composition de résine pour la formation de film de sous-couche, stratifié, procédé de formation de motif, kit de formation d'empreinte, et procédé de fabrication de dispositif
WO2018092713A1 (fr) * 2016-11-16 2018-05-24 キヤノン株式会社 Composition formant couche adhésive et procédé de production d'un article

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JP2009158729A (ja) * 2007-12-27 2009-07-16 Hitachi Ltd インプリント用基板
WO2011013630A1 (fr) * 2009-07-29 2011-02-03 日産化学工業株式会社 Composition permettant de former une couche primaire de résist pour lithographie par nano-impression
JP2013093552A (ja) * 2011-10-07 2013-05-16 Fujifilm Corp インプリント用下層膜組成物およびこれを用いたパターン形成方法
JP2014024322A (ja) * 2012-06-18 2014-02-06 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
WO2014007079A1 (fr) * 2012-07-02 2014-01-09 日産化学工業株式会社 Procédé de fabrication de dispositif à semi-conducteurs à l'aide de composition de formation de film de sous-couche organique pour processus de lithographie à développement de solvant
JP2016028419A (ja) * 2014-07-08 2016-02-25 キヤノン株式会社 密着層組成物、ナノインプリントによる膜の製造方法、光学部品の製造方法、回路基板の製造方法、および電子機器の製造方法
WO2016152600A1 (fr) * 2015-03-24 2016-09-29 富士フイルム株式会社 Composition de résine pour la formation de film de sous-couche, stratifié, procédé de formation de motif, kit de formation d'empreinte, et procédé de fabrication de dispositif
WO2018092713A1 (fr) * 2016-11-16 2018-05-24 キヤノン株式会社 Composition formant couche adhésive et procédé de production d'un article

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020155506A (ja) * 2019-03-19 2020-09-24 キオクシア株式会社 インプリント方法および半導体装置の製造方法
WO2022015681A1 (fr) * 2020-07-15 2022-01-20 Croda, Inc. Composés d'ester de phosphate de polyéther, compositions et utilisations

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