TW201946105A - Underlayer film forming composition for imprinting and practical application thereof - Google Patents

Abstract

The present invention provides a composition for forming an underlayer film for imprint, which includes a polymer and a solvent, and the polymer includes a constituent unit derived from a monomer having a pKa of 4.0 or less and a polymerizable group. In addition, the present invention relates to a set related to the underlayer film-forming composition for imprint, a hardenable composition for imprint, a laminate, a method for producing a laminate, a method for forming a laminate, and a method for producing a semiconductor device.

Description

Underlayer film forming composition for imprint, kit, hardening composition for imprint, laminated body, method for producing laminated body, pattern forming method, and method for producing semiconductor device

The present invention relates to an underlayer film-forming composition for imprinting, a kit, a hardening composition for imprinting, a laminated body, a method for producing a laminated body, a pattern forming method, and a method for producing a semiconductor device.

The imprint method is a method of transferring a pattern of a mold to form a desired structure on a resin layer. Among them, by a light imprint method, light is irradiated through a light-transmitting mold or a light-transmitting substrate to light-harden a curable composition, and then a fine pattern can be transferred to the light-hardened object by peeling the mold. In this method, since embossing can be performed at room temperature, it can be applied to the field of precision processing of ultra-fine patterns such as the production of semiconductor integrated circuits. Recently, new developments such as a nano casting method combining these advantages or a reverse embossing method for making a three-dimensional laminated structure have also been reported.
As a coating method of the curable composition for imprint, inkjet coating is being studied (for example, Patent Document 1). The curable composition for imprinting is usually added as a droplet of about 1 to 100 pL on a substrate. By using inkjet coating, the coating amount can be adjusted in accordance with the thickness of the imprint pattern, and a uniform imprint pattern can be ensured. Here is an example: In order to further enhance the adhesion between the imprinted layer formed from the hardenable composition for imprint and the substrate, an underlayer film formed from the imprinted lower film-forming composition is applied between the two (patent Documents 2 and 3) or adhesive layers (Patent Documents 4 and 5).
[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2005-533393
[Patent Document 2] Japanese Patent Laid-Open No. 2013-093552
[Patent Document 3] Japanese Patent Laid-Open No. 2014-093385
[Patent Document 4] Japanese Patent Laid-Open No. 2016-146468
[Patent Document 5] Japanese Patent Laid-Open No. 2017-206695

In the photoimprint method, as described above, the surface of the substrate is coated with a hardening composition for imprinting, and the surface is formed to irradiate light in a state in contact with the mold to harden the hardening composition for imprinting. Into an embossed layer. Then, the process including peeling the mold is included. During the process of peeling the mold, the imprint layer (hardened material) may be peeled from the substrate and adhered to the mold. It is considered that one of the reasons is that the adhesion between the substrate and the imprint layer is not very high compared to the adhesion between the mold and the imprint layer. In order to solve such a problem, for example, the technologies described in the aforementioned Patent Documents 2 to 5 have been proposed, thereby achieving a certain degree of resolution. However, with the expansion of the use of the imprint method and the active development of products using this, in addition to ensuring the adhesion between the substrate and the imprint layer, it is also important to ensure the adhesion to various substrates.
Therefore, an object of the present invention is to provide an underlayer film-forming composition for imprint, which can ensure sufficient adhesion to various substrates, a kit using the underlayer film-forming composition for imprint, and a hardening composition for imprint. Material, multilayer body, method for manufacturing multilayer body, pattern forming method, and method for manufacturing semiconductor device.

Based on the above-mentioned problems, the present inventors have studied a technique for forming a composition using an underlayer film for imprinting in an imprinting method. In addition, it was found that the polymer contained in the underlayer film-forming composition for imprinting can solve the above-mentioned problems by using a polymer having a polymerizable group and a low acidity partial structure. Specifically, the above-mentioned problem is solved by the following mechanism of <1> and the mechanisms of <2> to <23> which are its preferred embodiments.

<1> An underlayer film-forming composition for imprint, comprising a polymer and a solvent, the polymer including a constituent unit derived from a monomer having a pKa of 4.0 or less and a polymerizable group.
<2> The underlayer film-forming composition for imprinting according to <1>, wherein the polymer is an acrylic resin.
<3> The underlayer film-forming composition for imprinting according to <1> or <2>, wherein the polymer has a weight average molecular weight of 2,000 or more.
<4> The underlayer film-forming composition for imprinting according to any one of <1> to <3>, wherein the polymerizable group of the polymer is a (meth) acrylfluorenyl group.
<5> The underlayer film-forming composition for imprinting according to any one of <1> to <4>, wherein the constituent unit of the polymer derived from a monomer having a pKa of 4.0 or less is derived from pKa A constituent unit of a monomer of 3.0 or less.
<6> The underlayer film-forming composition for imprinting according to any one of <1> to <5>, wherein the constituent unit derived from the monomer having a pKa of 4.0 or less has a member selected from the group consisting of a hydroxyl group, a carboxyl group, and sulfur At least one of a group of a carboxylic acid group, a dithiocarboxylic acid group, a sulfonic acid group, a phosphate monoester group, a phosphate diester group, and a phosphate group.
<7> The underlayer film-forming composition for imprinting according to any one of <1> to <6>, wherein 99.0% by mass or more of the underlayer film-forming composition for imprinting is a solvent.
<8> The underlayer film-forming composition for imprinting according to any one of <1> to <7>, wherein the polymer has a structural unit containing a polymerizable group.
<9> A set comprising the underlayer film-forming composition for imprinting and the curable composition for imprinting according to any one of <1> to <8>.
<10> A curable composition for imprinting, which is used for the kit according to <9>.
<11> A laminated body comprising a substrate, an underlying film formed of the imprinting underlying film forming composition according to any one of <1> to <8>, and a substrate located on the surface of the substrate, and An embossed layer formed by a curable composition for imprint on the surface of a film.
<12> The laminated body according to <11>, wherein a substrate having an organic layer as an outermost layer is used as the substrate.
<13> The laminated body according to <11> or <12>, wherein the substrate having a basic layer is used as the substrate on the outermost surface as the substrate.
<14> A method for manufacturing a laminated body, comprising: a process for applying the underlayer film-forming composition according to any one of <1> to <8> to the surface of a substrate to form an underlayer film for imprinting; ; And a process of applying a hardening composition for imprint on the surface of the above-mentioned underlayer film.
<15> The method for producing a laminated body according to <14>, wherein a substrate having an organic layer as an outermost layer is used as the substrate.
<16> The method for producing a multilayer body according to <14> or <15>, wherein the substrate having a basic layer is used as the outermost substrate as the substrate.
<17> A pattern forming method, comprising: a process for forming an underlayer film on a substrate surface using the underlayer film forming composition for imprinting according to any one of <1> to <8>; Process for forming a lower-layer film-forming composition for imprint to form a hardenable composition layer for imprinting; process for bringing a mold into contact with the hardenable composition layer for imprinting; hardening the above-mentioned imprinting state while in contact with the mold A process of exposing the conductive composition layer; and a process of peeling the mold from the exposed curable composition layer for imprinting.
<18> The pattern forming method according to <17>, wherein a substrate having an organic layer as an outermost layer is used as the substrate.
<19> The pattern forming method according to <17> or <18>, wherein the substrate having a basic layer is used as the substrate on the outermost surface as the substrate.
<20> The pattern forming method according to any one of <17> to <19>, wherein the underlayer film-forming composition for imprint is applied to a substrate surface by a spin coating method.
<21> The pattern forming method according to any one of <17> to <20>, wherein the curable composition for imprint is applied to an underlayer film by an inkjet method.
<22> A method for manufacturing a semiconductor device, comprising the pattern forming method according to any one of <17> to <21>.
[Inventive effect]

The underlayer film-forming composition for imprint of the present invention can ensure sufficient adhesion to various substrates. In addition, it is possible to provide a kit using the underlayer film-forming composition for imprint, a curable composition for imprint, a laminate, a method for producing a laminate, a method for forming a pattern, and a method for producing a semiconductor device.

Hereinafter, the content of this invention is demonstrated in detail. In addition, in this specification, "-" means using the value contained before and after as a lower limit value and an upper limit value.
In this specification, "(meth) acrylate" means an acrylate and a methacrylate.
In this specification, "imprint" means a pattern transfer having a size of preferably 1 nm to 10 mm, and more preferably means a pattern transfer having a size of approximately 10 nm to 100 µm (nano imprint).
In the description of the group (atomic group) in the present specification, the unrepresented and unsubstituted marks include those having no substituent and those having a substituent. For example, "alkyl" includes not only alkyl groups (unsubstituted alkyl groups) having no substituents, but also alkyl groups (substituted alkyl groups) having substituents.
In this specification, "light" includes not only light or electromagnetic waves with wavelengths in the ultraviolet, near-ultraviolet, far-ultraviolet, visible, or infrared regions, but also radiation. The radiation includes, for example, microwaves, electron beams, extreme ultraviolet (EUV), and X-rays. In addition, laser light such as a 248 nm excimer laser, a 193 nm excimer laser, and a 172 nm excimer laser can also be used. The light may be a monochromatic light (single-wavelength light) passing through a filter or a light (composite light) having a plurality of different wavelengths.
When the weight average molecular weight (Mw) in the present invention is not specifically described, it refers to a person measured by gel permeation chromatography (GPC).
When the temperature in the present invention is not particularly described, it is set to 23 ° C.
The boiling point in the present invention refers to the boiling point in 1 atmosphere (1atm = 1013.25hPa).

The underlayer film-forming composition for imprint of the present invention is characterized in that it includes a polymer and a solvent, and the polymer includes a constituent unit of a monomer having an atom pKa of 4.0 or less and a polymerizable group (in this specification, the polymer Called a specific polymer). This makes it possible to achieve good adhesion between the imprint layer and the substrate. In particular, with its preferred embodiment, it is possible to realize a low-defect imprinting program without depending on the type of substrate.

＜ Specific polymer ＞
The specific polymer used in the present invention includes a constituent unit of a monomer having an atom pKa of 4.0 or less.
The pKa of the monomer is preferably 3.0 or less, more preferably 2.5 or less, and even more preferably 2.0 or less. The lower limit is actually -3.0 or more, and further 1.0 or more.

In this specification, pKa means pKa in an aqueous solution, and it is set to the value calculated by the method described in the Example mentioned later.

A constituent unit of a monomer having an atom pKa 4.0 or lower includes a hydroxyl group (alcoholic hydroxyl group, phenolic hydroxyl group), a carboxyl group, amidino group, amidino group, a urea group, a carbamate group, a cyano group, Ether group (preferably polyalkyleneoxy), cyclic ether group, lactone group, sulfofluorenyl group, sulfonyl group, sulfonamido group, sulfonamido group, phosphate group, phosphate group and butyronitrile At least one of the groups (hereinafter, sometimes simply referred to as "acid group") is preferred. Among them, it is preferable to have at least one selected from the group consisting of a hydroxyl group, a carboxyl group, a thiocarboxylic acid group, a dithiocarboxylic acid group, a sulfonic acid group, a phosphate monoester group, a phosphodiester group, and a phosphate group. At least one selected from the group consisting of a sulfonic acid group, a phosphate monoester group, a phosphodiester group, and a phosphate group is further preferred.

Among the monomers having a pKa of 4.0 or less, a molecular weight of 50 or more is preferable, 100 or more is more preferable, 150 or more is further preferable, and 200 or more is further preferable. In addition, the molecular weight is preferably 1,000 or less, more preferably 800 or less, even more preferably below, and still more preferably 600 or less. By setting it as such a range, the effect of the improvement of film formability and the improvement of adhesiveness can be exhibited more effectively.

Examples of the polymerizable group possessed by the monomers having a pKa 4.0 or lower include (meth) acrylfluorenyl, epoxy, oxetanyl, methylol, methylol ether, and vinyl ether. Base etc. From the viewpoint of ease of polymerization, a (meth) acrylfluorenyl group is particularly preferable. In the present specification, the polymerizable group defined and exemplified herein is referred to as a polymerizable group Ps.

It is preferable that the monomer having pKa 4.0 or less has a structure represented by an acid group-linking group-polymerizable group. Here, the linking group is exemplified by a linking group L described later.

In the specific polymer, the proportion of the constituent units derived from monomers having a pKa of 4.0 or less in all the constituent units is based on the mole ratio when each constituent unit is used as a monomer, preferably 0.5% by mass or more, and 1% by mass. The above is more preferable, and 3% by mass or more is more preferable. The upper limit is preferably 50% by mass or less, more preferably 30% by mass or less, and even more preferably 15% by mass or less.
The specific polymer may include only one type of constituent unit derived from a monomer having a pKa of 4.0 or less, or may include two or more types of constituent units. When two or more kinds are included, the total measurement is preferably within the above range.

The specific polymer has a polymerizable group.
The polymerizable group may be bonded to a side chain of a specific polymer, or may be bonded to a terminal. In the present invention, the specific polymer preferably has a structural unit containing a polymerizable group. In addition, as for the specific polymer, the constituent unit derived from the monomer having a pKa 4.0 or lower may have a polymerizable group, or may be different from the constituent unit derived from a monomer having a pKa 4.0 or lower, including a polymerizable group. The constituent unit is different from a constituent unit derived from a monomer having a pKa of 4.0 or lower, and it is preferable to include a constituent unit having a polymerizable group.
Specific examples of the polymerizable group include a polymerizable group Ps, and a (meth) acrylfluorenyl group is particularly preferred. The polymerizable group is preferably introduced into the polymer in the form of a structural unit. The above-mentioned specific polymer has a polymerizable group, so that the underlayer film for imprinting forms a crosslinked structure, can prevent agglomeration and destruction of the underlayer film at the time of peeling, and can ensure more effective adhesion.
In the specific polymer, the proportion of the constituent units having a polymerizable group in all the constituent units is based on a molar ratio when each constituent unit is used as a monomer, preferably 50% by mass or more, and more preferably 70% by mass or more. 85 mass% or more is more preferable. The upper limit is preferably 99.5 mass% or less, more preferably 99 mass% or less, and still more preferably 97 mass% or less.
The specific polymer may contain only one kind of structural unit having a polymerizable group, or may contain two or more kinds. When two or more kinds are included, the total measurement is preferably within the above range.

In the specific polymer, the total ratio of the constituent units having an acid group to the constituent units having a polymerizable group in all the constituent units is 90% by mass or more based on the molar ratio when each constituent unit is a monomer. Preferably, 95 mass% or more is more preferable, and 97 mass% or more is more preferable. The upper limit may be 100% by mass.

The specific polymer is preferably at least one selected from the group consisting of acrylic resin, novolac resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, and melamine resin. Acrylic resin, polyester resin, and novolac At least one of the resin groups is more preferable, and acrylic resin is more preferable.

Acrylic resins generally refer to polymers of acrylic acid, acrylates, and methacrylates or to monomers that have these as the main component and can be copolymerized with them, such as styrene, vinyl methyl, vinyl acetate, and acrylonitrile. Copolymer resin. The acrylic resin can be synthesized by addition polymerization of an acrylic monomer. Addition polymerization is caused by free radicals, cations, and anions, and is called radical polymerization, cationic polymerization, and anionic polymerization, respectively. The most industrially used is free radical polymerization. Examples of the acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate , Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) ) Lauryl acrylate.

Phenolic resins are produced by the reaction of phenol as a trifunctional monomer (the substituted phenol may be difunctional or monofunctional in some cases) and formaldehyde as a bifunctional monomer under an acid or basic catalyst. The one obtained by the acid catalyst is referred to as novolac, and the one obtained by the alkaline catalyst is referred to as resol. The soluble phenolic resin is self-hardened by heating. Novolac is hardened when heated with a hardener such as hexamethylenetetramine (HMTA). Examples of the raw materials include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, and 2,6-xylenol. Phenol, 3,4-xylenol, 3,5-xylenol, resorcinol, p-tert-butylphenol, p-nonylphenol, bisphenol, etc.
Melamine resin is a thermosetting synthetic resin obtained by the addition and condensation of melamine (2,4,6-triamine-1,3,5-tri) and formaldehyde. Since an amine group (-NH2) is used as a reactive group together with a urea resin or the like, it can be counted as one of the amine resin. It is excellent in transparency, hardness, colorability, heat resistance, arc resistance, etc., and therefore has a wide range of uses such as molding materials, decorative boards, and coatings. Melamine uses an amine group as a reactive group and reacts with formaldehyde to form methylolmelamine. Methylolmelamine From monomethylolmelamine to hexamethylolmelamine, all substituents can be easily obtained as a mixture.

An epoxy resin is a general term for a compound having two or more epoxy groups in one molecule. Generally, it does not harden even if it can be heated by itself, and a hardener or catalyst is required to obtain a cured product. Addition of a hardening agent causes an addition reaction to result in an insoluble and infusible thermosetting resin, so that volatiles do not occur and processability is good. As the hardener, various first amines, second amines, acid anhydrides, and phenol resins can be used. The production of an epoxy resin is performed by two methods based on the reaction of a compound having active hydrogen with epichlorohydrin and the oxidation of a compound having a double bond. Examples of the compound having active hydrogen include 2,2-bis (4-hydroxyphenyl) propane (alias bisphenol A), 4,4'-dihydroxydiphenylmethane (alias bisphenol F), 2, 2-bis (3,5-dibromo-4-hydroxyphenyl) propane (also known as tetrabromobisphenol A), o-cresol, hexahydrophthalic acid, m-aminophenol, p-aminophenol. As other epoxy resin raw materials, novolac-type phenol resins, dimer acids, polybutadiene, soybean oil, alicyclic compounds, tetrahydrophthalic acid, p-hydroxybenzoic acid, m-xylylenediamine, Hydantoin compound, cyanuric acid, etc.

Polyester resin is obtained by the polycondensation reaction of a dibasic acid and a diol, and the main chain has an ester bond (-COO-). Examples of the dibasic acid include terephthalic acid, naphthalenedicarboxylic acid, cyclohexanedicarboxylic acid, adipic acid, maleic anhydride, fumaric acid, and itaconic acid. As the polybasic acid polyol, propylene glycol, ethylene glycol, and diethylene glycol are often used. Among them, other glycols are also appropriately distinguished and used according to the properties of the resin. As a polyester commonly used as a plastic material, in addition to PET (polyethylene terephthalate), there is a polybutylene terephthalate in which the ethylene glycol component of PET is replaced with tetramethylene glycol. Esters (PBT) or cyclohexane dimethyl terephthalate (PCT) substituted with cyclohexanedimethanol. Also known are polymers in which terephthalic acid is replaced with 2,6-naphthalenedicarboxylic acid. 2,6-naphthalene dicarboxylate (PEN), etc.

Polyurethane (PU) is a group of polymers having a urethane bond (urethane bond) obtained by the reaction of polyisocyanate and a polyol. In the case where any of the compounds to be reacted is also difunctional, a thermoplastic PU can be obtained as it is, and a PU having a network structure is formed when at least one of the compounds is trifunctional or more or a side chain reaction is caused.

Regarding the resins mentioned above, please refer to "Asakura Publishing Co., Ltd." edited by Kei Miyasaka and others.

The specific polymer preferably has a main chain represented by a constitutional unit represented by any one of the following formulae (1) to (6).
[Chemical Formula 1]

R ¹ is a hydrogen atom or a methyl group, and a methyl group is preferred.
X ^R is an oxygen atom or NH, and an oxygen atom is preferred.
n is an integer of 1 to 3, 1 or 2 is preferable, and 1 is more preferable.
m is an integer of 1 to 5, 1 or 2 is preferable, and 1 is more preferable.
R is preferably a partial structure (acid group) of pKa 4.0 or less. When R in the formulae (1) to (6) is two or more, plural Rs may be bonded to each other to form a ring. The preferred acid group is the same as the acid group possessed by the monomer having a pKa of 4.0 or lower.
In the formulae (1) to (6), the main chain or the benzene ring may have a substituent T described later within a range in which the effects of the present invention are exhibited. In addition, R or a substituent T may be bonded to the main chain to form a ring.

The specific polymer-based copolymers described above are also preferable. It is preferable that the copolymerization component includes at least one of the structural units represented by any one of the following formulae (1-1) to (1-6) together with the structural units of the formulae (1) to (6).
[Chemical Formula 2]

R ¹ is a hydrogen atom or a methyl group, and a methyl group is preferred.
X ^R is an oxygen atom or NH, and an oxygen atom is preferred.
n is an integer of 1 to 3, 1 or 2 is preferable, and 1 is more preferable.
m is an integer of 1 to 5, 1 or 2 is preferable, and 1 is more preferable.
R ² is a substituent each independently including a polymerizable group. It is preferable that the polymerizable group contained in R ² is the aforementioned Ps. When R ^{2 in} Formulas (1-1) to (1-6) is two or more, plural R ² may be bonded to each other to form a ring. The main chain and the benzene ring in the formula (1-1) to the formula (1-6) may be substituted with the substituent T within the range where the effects of the present invention are exhibited.
As R ² , the following formula (T2) is preferred. The formula of R ² is more preferably 80 or more and 1000 or less, more preferably 100 or more and 800 or less, and more preferably 150 or more and 600 or less.
-(L ⁴ ) _n6- (P) _n7 …… (T2)
L ⁴ is the following linking group L, of which alkylene, arylene, (oligomeric) alkoxy, carbonyl, oxygen atom, and a combination of these are preferred. n6 is 0 or 1, and 1 is preferred. P is a group containing a polymerizable group, and Ps or Ps and a group consisting of a linking group L are preferable. n7 is an integer of 1 to 6, and 1 or 2 is preferable. In addition, when n7 is 2 or more, L ^{4 may} be a trivalent or more valent linking group. For example, a group containing a trivalent or more alkane structure (carbon number of 1 to 12 is preferred, and 1 to 6 is more preferred) 1 to 3 are further preferred), an olefin structured base (carbon number 2 to 12 is preferred, 2 to 6 is more preferred, 2 to 3 is more preferred), or an aryl structured base (carbon number 6 22 is more preferred, 6 to 18 is more preferred, and 6 to 10 is more preferred. Furthermore, the (oligomeric) alkoxy group may be a mono-alkoxy group or an oligo-alkoxy group. The number of connected atoms of L ⁴ is preferably from 1 to 24, more preferably from 1 to 12, and even more preferably from 1 to 6.
The specific polymer contains a structural unit represented by the formula (1), and when it is a copolymer, it is preferable to include a structural unit represented by the formula (1-1). Regarding formulas (2) to (6), it is also preferable to include constituent units represented by formulas (1-2) to (1-6), respectively.

It is also preferable that the specific polymer further includes a constitutional unit (sometimes referred to as "another constitutional unit") without an acid group and a polymerizable group. It is preferable that the other constituent units have a skeleton of the above formulae (1-1) to (1-6). Wherein the substituent R ² does not become an acid group and a polymerizable group of the substituent group R ^3. As long as the effect of the present invention is exerted, other main chains or benzene rings may be substituted with a substituent T. R ³ or substituent T may be bonded to the main chain to form a ring.
R ³ is preferably represented by the following formula (T3). The formula of R ³ is more preferably 80 or more and 1000 or less, more preferably 100 or more and 800 or less, and more preferably 150 or more and 600 or less.
-(L ⁵ ) _n8- (T1) _n9 …… (T3)
L ⁵ is a linker L described later, and among them, alkylene, aryl, (oligomeric) alkoxy, carbonyl, oxygen atom, and a combination of these are preferred. The number of connected atoms of L ⁵ is preferably from 1 to 24, more preferably from 1 to 12, and even more preferably from 1 to 6. n8 is 0 or 1. T ¹ is a substituent T described below. Among them, an alkyl group substituted with a halogen atom, an aryl group substituted with a halogen atom, and an arylalkyl group substituted with a halogen atom are preferred. n9 is an integer of 1 to 6, and 1 or 2 is preferable. When n9 is 2 or more, L ^{5 may} be a trivalent or more linking group. For example, a group containing an alkane structure of trivalent or more (a carbon number of 1 to 12 is preferred, 1 to 6 is more preferred, 1 ～ 3 is further preferred), a base of an olefin structure (2 to 12 carbons is preferred, 2 to 6 is more preferred, 2 to 3 is more preferred), or a base of an aryl structure (6 to 22 carbons is Preferably, 6 to 18 is more preferred, and 6 to 10 is even more preferred) a linking group.

Examples of the substituent T include an alkyl group (carbon number 1 to 24 is preferred, 1 to 12 is more preferred, and 1 to 6 is more preferred), and an arylalkyl group (carbon number 7 to 21 is preferred, 7 to 15 are more preferred, 7 to 11 are further preferred), alkenyl (2 to 24 carbons are preferred, 2 to 12 are more preferred, 2 to 6 are more preferred), alkynyl (2 to 6 carbons) -12 is preferred, 2-6 is more preferred, 2-3 is more preferred), hydroxyl and amine groups (carbon number 0-24 is preferred, 0-12 is more preferred, 0-6 is further preferred ), Thiol group, carboxyl group, aryl group (carbon number 6 to 22 is preferred, 6 to 18 is more preferred, 6 to 10 is more preferred), heteroaryl group (carbon number 1 to 22 is preferred, 1 -16 is more preferred, 1-12 is further preferred), alkoxy (carbon number 1-12 is preferred, 1-6 is more preferred, 1-3 is further preferred), aryloxy (carbon number 6 to 22 is preferred, 6 to 18 is more preferred, 6 to 10 is further preferred), fluorenyl (carbon number 2 to 12 is preferred, 2 to 6 is more preferred, 2 to 3 is further preferred) , Fluorenyl group (carbon number 2-12 is preferred, 2-6 is more preferred, 2-3 is more preferred), arylfluorenyl group (carbon number 7-23 is preferred, 7-19) More preferably, 7 to 11 are further preferred), arylfluorenyloxy (carbon number 7 to 23 is preferred, 7 to 19 is more preferred, 7 to 11 is further preferred), carbamoyl (carbon number 1 -12 is preferred, 1 to 6 is more preferred, 1 to 3 is more preferred), sulfamoyl (carbon number 0 to 12 is preferred, 0 to 6 is more preferred, 0 to 3 is further preferred ), Sulfonic acid group, alkylsulfonyl group (carbon number 1 to 12 is preferred, 1 to 6 is more preferred, 1 to 3 is more preferred), arylsulfonyl group (carbon number 6 to 22 is more preferred) 6 to 18 are more preferred, 6 to 10 are more preferred), heterocyclic groups (carbon numbers of 1 to 12 are preferred, 1 to 8 are more preferred, 2 to 5 are further preferred, and 5-membered rings are included Or 6-membered ring is preferred), (meth) acrylfluorenyl, (meth) acrylfluorenyl, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), oxo group (= O ), Imino (= NR ^N ), alkylene (= C (R ^N ) ₂ ), etc.
R ^N is a hydrogen atom, an alkyl group (carbon number 1 to 12 is preferred, 1 to 6 is more preferred, 1 to 3 is more preferred), an alkenyl group (carbon number 2 to 12 is preferred, 2 to 6 is More preferably, 2 to 3 are further preferred), alkynyl (2 to 12 carbons are preferred, 2 to 6 are more preferred, 2 to 3 are more preferred), and aryl (6 to 22 carbons are more preferred) 6 to 18 are more preferred, 6 to 10 are further preferred), heteroaryl (carbon number 1 to 22 is preferred, 1 to 16 is more preferred, 1 to 12 are further preferred), of which hydrogen Atom, methyl, ethyl or propyl are preferred. R ^N may have each group specified by the substituent T within the range in which the effect of the present invention is exhibited.
The alkyl moiety, alkenyl moiety, and alkynyl moiety contained in each substituent may be chained, cyclic, or linear or branched. When the substituent T is a group capable of obtaining a substituent, it may further have a substituent T. For example, the alkyl group may be a halogenated alkyl group, or may be a (meth) acryloxyalkyl group, an aminoalkyl group, or a carboxyalkyl group.

Examples of the linking group L include an alkylene group (carbon number 1 to 24 is preferred, 1 to 12 is more preferred, and 1 to 6 is more preferred), and an alkenyl group (carbon number 2 to 12 is more preferred) , 2 to 6 are more preferred, 2 to 3 are further preferred), alkynyl (carbon number of 2 to 12 is preferred, 2 to 6 is more preferred, 2 to 3 are further preferred), (oligomeric) Alkoxy group (The number of carbons of the alkylene group in one constituent unit is preferably from 1 to 12, more preferably from 1 to 6, and even more preferably from 1 to 3; the number of repetitions is preferably from 1 to 50. 1 to 40 is more preferred, 1 to 30 is further preferred), aryl (carbon number 6 to 22 is preferred, 6 to 18 is more preferred, 6 to 10 is further preferred), oxygen atom, sulfur atom , Sulfonyl, carbonyl, thiocarbonyl, -NR ^N -and combinations of these. The alkylene group may have the following substituent T. For example, the alkylene group may have a hydroxyl group. The number of atoms contained in the linking group L is preferably 1 to 50 in addition to the hydrogen atom, more preferably 1 to 40, and still more preferably 1 to 30. The number of connected atoms refers to the number of atoms in the shortest distance in the group of atoms participating in the connection. For example, when -CH _2- (C = O) -O-, the number of atoms involved in the connection is six, and in addition to hydrogen atoms, there are also four. On the other hand, the shortest atom participating in the connection is -CCO-, which becomes three. The number of connecting atoms is preferably from 1 to 24, more preferably from 1 to 12, and even more preferably from 1 to 6. The above-mentioned alkylene, alkenyl, alkynyl, and (oligomeric) alkoxy may be linear, cyclic, or linear or branched.

The weight-average molecular weight of the specific polymer is preferably 2,000 or more, more preferably 3,000 or more, even more preferably 4,000 or more, even more preferably 6,000 or more, further preferably 10,000 or more, and even more preferably 15,000 or more. The upper limit of the weight average molecular weight is not particularly limited. For example, it is preferably 200,000 or less, more preferably 100,000 or less, more preferably 70,000 or less, even more preferably 50,000 or less, and may be 35,000 or less. By setting the weight-average molecular weight to be equal to or more than the above-mentioned lower limit value, the stability of the film during the baking process is improved, and the planarity at the time of forming the imprint underlayer film can be further improved. In addition, by setting the weight average molecular weight to be equal to or less than the above-mentioned upper limit value, the solubility in a solvent becomes high, and application by spin coating or the like becomes easier. The wettability of the curable composition for imprint is improved by maintaining the fluidity by setting the molecular weight within an appropriate range.
The dispersion (Mw / Mn) of the specific polymer is preferably 3.0 or less, and more preferably 2.5 or less. The lower limit of the degree of dispersion may be 1.0, but even if it is 1.5 or more, it is a sufficiently practical level.

The content of the specific polymer in the underlayer film-forming composition for imprint is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and more preferably 0.1% by mass or more. As the upper limit, 10% by mass or less is preferred, 7% by mass is more preferred, 5% by mass is further preferred, 4% by mass or less is more preferred, 3% by mass or less is further preferred, and 1% by mass may be preferred. It may be 0.7 mass% or less.
The content of the non-volatile components of the specific polymer (referred to as components other than the solvent in the composition, the same below) is preferably 5 mass% or more, more preferably 20 mass% or more, and 30 mass% or more To be more preferable, 50% by mass or more is more preferable, 80% by mass or more is more preferable, 90% by mass or more is still more preferable, and 95% by mass or more may be 99% by mass or more. The upper limit may be 100% by mass.
By setting the amount to be equal to or more than the above-mentioned lower limit value, the effect due to the polymer blend can be appropriately exhibited, and a uniform film can be easily produced. On the other hand, by setting it to the above-mentioned upper limit value or less, the effect of using a solvent is appropriately exhibited, and a uniform film is easily formed over a wide area.
The specific polymer may be used alone or in combination of two or more. When two or more kinds are used, it is preferable that the total measurement falls within the above range.

As examples of the specific polymer, the following polymers can be mentioned, but the present invention is not limited thereto and is to be interpreted. The crosslinkable units in the table correspond to the constituent units (for example, formulae (1-1) to (1-6)) having the polymerizable group Ps, and the acidic units correspond to those derived from the pKa 4.0 or lower. The constituent units of the monomer (for example, formulas (1) to (6)) correspond.


[Table 1]



[Table 2]


[table 3]



[Table 4]

<Solvent>
The underlayer film-forming composition for imprint contains a solvent (hereinafter, sometimes 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 lower. Generally, the non-volatile components eventually form an underlayer film. The underlayer film-forming composition for imprinting preferably contains 99.0% by mass or more of the solvent for the underlayer film, more preferably contains 99.5% by mass or more, and may be 99.6% by mass or more. In the present invention, the liquid system means that the viscosity at 23 ° C is 100,000 mPa ･ s or less. By setting the ratio of the solvent to the above range, the film thickness at the time of film formation is kept thin, so that the pattern formability at the time of etching processing is improved.
The solvent may contain only one kind in the underlayer film-forming composition for imprint, or two or more kinds. When two or more kinds are included, the total measurement is preferably within the above range.
The boiling point of the solvent for the lower film is preferably 230 ° C or lower, more preferably 200 ° C or lower, more preferably 180 ° C or lower, more preferably 160 ° C or lower, and 130 ° C or lower. The lower limit is actually 23 ° C, but it is more practical above 60 ° C. By setting the boiling point to the above range, the solvent can be easily removed from the lower layer film, which is preferable.

A solvent-based organic solvent for the underlayer film is preferred. The solvent is preferably a solvent having any one or more of an ester group, a carbonyl group, a hydroxyl group, and an ether group. Among them, it is preferable to use an aprotic polar solvent.

As specific examples, alkoxy alcohol, propylene glycol monoalkyl ether carboxylate, propylene glycol monoalkyl ether, lactate, acetate, alkoxypropionate, chain ketone, cyclic ketone, and lactone are selected. And alkylene carbonate.

Examples of the alkoxy alcohol include methoxyethanol, ethoxyethanol, methoxypropanol (for example, 1-methoxy-2-propanol), and ethoxypropanol (for example, 1-ethoxy). 2-propanol), propoxypropanol (for example, 1-propoxy-2-propanol), methoxybutanol (for example, 1-methoxy-2-butanol, 1-methyl Oxy-3-butanol), ethoxybutanol (for example, 1-ethoxy-2-butanol, 1-ethoxy-3-butanol), methylpentanol (for example, 4-methyl 2-pentyl alcohol) and the like.

The propylene glycol monoalkyl ether carboxylic acid ester 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. Methyl ether acetate (PGMEA) is particularly preferred.

As the propylene glycol monoalkyl ether, propylene glycol monomethyl ether (PGME) or propylene glycol monoethyl ether is preferable.
As the lactate, ethyl lactate, butyl lactate or propyl lactate is preferred.
As the 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 is preferred.
As the alkoxypropionate, methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferred.
As the chain ketone, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutanone, phenylacetone , Methyl ethyl ketone, methyl isobutyl ketone, acetoacetone, acetone acetone, ionone, diacetone alcohol, acetomethanol, acetophenone, methylnaphthyl ketone, methylpentyl Ketones are preferred.
As the cyclic ketone, methylcyclohexanone, isophorone or cyclohexanone is preferred.
As the lactone, γ-butyrolactone (γBL) is preferred.
As the alkylene carbonate, propylene carbonate is preferable.

In addition to the above components, it is preferable to use an ester-based solvent having a carbon number of 7 or more (7 to 14 is preferred, 7 to 12 is more preferred, 7 to 10 is more preferred) and a hetero atom number is 2 or less.

Preferable examples of the ester-based solvent having 7 or more carbon atoms and 2 or less heteroatoms include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, and propyl acetate. Amyl acetate, hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate, butyl butyrate, etc. It is particularly preferred to use isoamyl acetate.

It is also preferable to use a solvent having a flash point (hereinafter, also referred to as p component) of 30 ° C or higher. As such a component, propylene glycol monomethyl ether (p component: 47 ° C), ethyl lactate (p component: 53 ° C), ethyl 3-ethoxypropionate (p component: 49 ° C), methylpentyl ketone (P component: 42 ° C), cyclohexanone (p component: 30 ° C), amyl acetate (p component: 45 ° C), methyl 2-hydroxyisobutyrate (p component: 45 ° C), γ-butane Ester (p component: 101 ° C) or propylene carbonate (p component: 132 ° C) is preferred. Among these, propylene glycol monoethyl ether, ethyl lactate, amyl acetate, or cyclohexanone is more preferable, and propylene glycol monoethyl ether or ethyl lactate is particularly preferable.

Examples of the solvent for the lower film include alkoxy alcohol, propylene glycol monoalkyl ether carboxylic acid ester, propylene glycol monoalkyl ether, lactate, acetate, alkoxypropionate, and chain. Ketones, cyclic ketones, lactones and alkylene carbonates.

＜ Other ingredients ＞
As for the underlayer film-forming composition for imprint, in addition to the above, one or two or more alkylene glycol compounds, a polymerization initiator, a polymerization inhibitor, an antioxidant, a leveling agent, a tackifier, Surfactants and so on.
Regarding the thermal polymerization initiator, the components described in Japanese Patent Application Laid-Open No. 2013-036027, Japanese Patent Application Laid-Open No. 2014-090133, and Japanese Patent Application Laid-Open No. 2013-189537 can be used. Regarding the content and the like, it is also possible to refer to the description in the aforementioned publication.

<<< Alkanyl glycol compound >>
The underlayer film-forming composition for imprint may include an alkylene glycol compound. The alkylene glycol compound preferably has 3 to 1,000 alkylene glycol constituent units, more preferably 4 to 500 units, more preferably 5 to 100 units, and even more preferably 5 to 50 units. . 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, more preferably from 300 to 3,000, and even more preferably from 300 to 1,000.
The alkylene glycol compound is exemplified by polyethylene glycol, polypropylene glycol, such mono- or dimethyl ethers, mono- or dioctyl ether, mono- or dinonyl ether, mono- or didecyl ether, monostearate, Monoesters, monoadipates, and monosuccinates are preferred. Polyethylene glycol and polypropylene glycol are preferred.
The surface tension of the alkylene glycol compound at 23 ° C is preferably 38.0 mN / m or more, and more preferably 40.0 mN / m or more. The upper limit of the surface tension is not particularly limited, and is, for example, 48.0 mN / m or less. By blending the compounds as described above, the wettability of the hardening composition for imprint provided directly above the lower film can be improved.
The surface tension was measured using a surface tension meter SURFACE TENS-IOMETER CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd, and measured at 23 ° C using a glass plate. The unit is expressed in mN / m. Two samples were made for each level and measured three times. The arithmetic average of 6 times in total was adopted as the evaluation value.

When the alkylene glycol compound is contained, it is 40% by mass or less of the nonvolatile component, 30% by mass or less is preferable, 20% by mass or less is more preferable, and 1 to 15% by mass is further more preferable.
The alkylene glycol compound may be used alone or in combination of two or more. When two or more kinds are used, it is preferable that the total measurement falls within the above range.

<< polymerization initiator
The lower-layer film-forming composition for imprinting may contain a polymerization initiator, and it is preferable to include at least one of a thermal polymerization initiator and a photopolymerization initiator. By including a polymerization initiator, there is a tendency that the reaction of the polymerizable group contained in the underlayer film-forming composition for imprinting is promoted and the adhesion is improved. From the viewpoint of improving the cross-linking reactivity with the curable composition for imprint, a photopolymerization initiator is preferred. As the photopolymerization initiator, a radical polymerization initiator and a cationic polymerization initiator are preferable, and a radical polymerization initiator is more preferable. In the present invention, a plurality of photopolymerization initiators may be used in combination.

As the photoradical polymerization initiator, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), fluorenylphosphine compounds such as a fluorenylphosphine oxide, and hexaaryl Oxime compounds such as bisimidazole, oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo-based compounds Compounds, azide compounds, metallocene compounds, organoboron compounds, iron-arene complexes, and the like. For details of these, refer to the descriptions in paragraphs 0165 to 0182 of Japanese Patent Application Laid-Open No. 2016-027357, which are incorporated into this specification.
Examples of the fluorenylphosphine compound include 2,4,6-trimethylbenzylfluorenyl-diphenyl-phosphine oxide and the like. In addition, IRGACURE-819, IRGACURE1173, and IRGACURE-TPO (product names: all manufactured by BASF) can be used as commercially available products.

When the content of the photopolymerization initiator used in the above-mentioned underlayer film-forming composition for imprinting is blended, the nonvolatile component is, for example, 0.0001 to 5% by mass, preferably 0.0005 to 3% by mass, and 0.01 -1 mass% is more preferable. When two or more kinds of photopolymerization initiators are used, the total amount is within the above range.

<Container>
As a storage container for the underlayer film-forming composition for imprint, a conventionally known storage container can be used. In addition, as a storage container, in order to prevent impurities from being mixed into the raw materials or the composition, it is also preferable to use a multi-layer bottle composed of six kinds of six-layer resin or a bottle having six resins in a seven-layer structure. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

＜ Surface free energy ＞
The surface free energy of the imprint underlayer film formed from the imprint underlayer film forming composition of the present invention is preferably 30 mN / m or more, more preferably 40 mN / m or more, and more preferably 50 mN / m or more. As an upper limit, 200 mN / m or more is preferable, 150 mN / m or more is more preferable, and 100 mN / m or more is more preferable.
The surface free energy can be measured using a surface tension meter SURFACE TENS-IOMETER CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd. and using a glass plate at 23 ° C.

＜ curable composition for imprinting ＞
The underlayer film-forming composition of the present invention is generally used as a composition for forming an underlayer film for a curable composition for imprint.
The composition and the like of the curable composition for imprint are not particularly limited, and it is preferable to include a polymerizable compound.

<<< Polymerizable Compound >>
It is preferable that the curable composition for imprint contains a polymerizable compound, and it is more preferable that the polymerizable compound constitute a maximum amount of the component. The polymerizable compound may have one polymerizable group in one molecule, or may have two or more polymerizable groups. It is preferred that at least one of the polymerizable compounds contained in the curable composition for imprinting contains 2 to 5 polymerizable groups in one molecule, 2 to 4 is more preferred, and 2 or 3 is contained. For further preference, it is further preferred to include three.
At least one of the polymerizable compounds contained in the curable composition for imprint contains an aromatic ring (carbon number 6 to 22 is more preferable, 6 to 18 is more preferable, 6 to 10 is more preferable) and an alicyclic ring (The number of carbon atoms is preferably 3 to 24, 3 to 18 is more preferable, and 3 to 6 are more preferable.) At least one of them is preferable, and an aromatic ring is more preferable. An aromatic ring-based benzene ring is preferred.
The molecular weight of the polymerizable compound is preferably 100 to 900.
At least one type of the polymerizable compound is preferably represented by the following formula (I-1).
[Chemical Formula 3]

L ²⁰ is a 1 + q2 valent linking group, for example, a alkane structure of 1 + q2 valence (carbon number 1-12 is more preferable, 1-6 is more preferable, 1 to 3 is more preferable), Groups with olefin structure (carbon numbers 2-12 are preferred, 2-6 are more preferred, 2-3 are more preferred), groups with aryl structures (carbon numbers 6-22 are preferred, 6-18 More preferably, 6 to 10 are further preferred), and a group having a heteroaryl structure (carbon number of 1 to 22 is preferred, 1 to 18 is more preferred, 1 to 10 is further preferred, and as a hetero atom, it may be Examples include a nitrogen atom, a sulfur atom, and an oxygen atom, and a 5-membered ring, a 6-membered ring, and a 7-membered ring are preferred) or a linking group containing a combination of these. Examples of the group in which two aryl groups are combined include groups having a structure such as biphenyl or diphenylalkane, biphenylene, and indene. Examples of a combination of a heteroaryl structure group and an aryl structure group include groups having a structure such as indole, benzimidazole, quinoxaline, and carbazole.
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, and among them, a linking group having a hetero atom is preferred. L ²⁰ and L ²¹ or L ²² may form a ring by bonding with or without a linker L. L ²⁰ , L ²¹ and L ²² may have the above-mentioned substituent T. A plurality of substituents T may be bonded to form a ring. When there are a plurality of substituents T, they may be the same as or different from each other.
q2 is an integer from 0 to 5, an integer from 0 to 3 is preferred, an integer from 0 to 2 is more preferred, and 0 or 1 is further preferred.

Examples of the polymerizable compound include compounds used in the following examples, paragraphs 0017 to 0024 of Japanese Patent Application Laid-Open No. 2014-090133 and the compounds described in the examples, and Japanese Patent Laid-Open No. 2015-009171. The compounds described in paragraphs 0024 to 0089, the compounds described in paragraphs 0223 to 0037 of Japanese Patent Application Laid-Open No. 2015-070145, and the compounds described in paragraphs 0012 to 0039 of International Publication No. 2016/152597. However, the present invention It is not explained by this limitation.

It is preferable that the polymerizable compound contains 30% by mass or more in the curable composition for imprinting, more preferably 45% by mass or more, more preferably 50% by mass or more, more preferably 55% by mass or more, and may be 60 It may be 70% by mass or more. The upper limit value is preferably less than 99% by mass, more preferably 98% by mass or less, and can be 97% by mass or less.

It is preferable that the boiling point of the polymerizable compound is designed by using the relationship setting with the specific compound contained in the above-mentioned underlayer film-forming composition for imprinting. 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, and still more preferably 240 ° C or higher.

＜＜ Other Ingredients ＞＞
The curable composition for imprint may contain additives other than a 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 hardenable composition for imprint that can be used in the present invention are described in Japanese Patent Application Laid-Open No. 2013-036027, Japanese Patent Application Laid-Open No. 2014-090133, and Japanese Patent Application Laid-Open No. 2013-189537. Composition, and incorporates these contents into this specification. Regarding the method for preparing the curable composition for imprint and the method for forming the film (pattern-forming layer), it is also possible to refer to the description of the above-mentioned publication and incorporate the contents into this specification.

In the present invention, the content of the solvent in the embossable curable composition is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less.
The curable composition for imprinting can also be made substantially free of polymers (preferably having a weight average molecular weight greater than 1,000, more preferably having a weight average molecular weight greater than 2,000, and even more preferably a polymer having a weight average molecular weight greater than 10,000) Like this. The fact that the polymer is not substantially contained means, for example, that the content of the polymer is 0.01% by mass or less of the curable composition for imprint, preferably 0.005% by mass or less, and more preferably not contained at all.

＜ Physical properties and other values ＞＞
The viscosity of the curable composition for imprinting is preferably 20.0 mPa ･ s or less, more preferably 15.0 mPa ･ s or less, even more preferably 11.0 mPa ･ s or less, and even more preferably 9.0 mPa ･ s or less. The lower limit of the viscosity is not particularly limited, and it can be, for example, 5.0 mPa ･ s or more. The viscosity is measured in the following manner.
The viscosity was measured using an E-type rotary viscosity meter RE85L made by TOKI SANGYO CO., LTD, and a standard conical rotor (1 ° 34 '× R24). The temperature of the sample cup was adjusted to 23 ° C. The unit is expressed by mPa ･ s. Other details about the measurement are based on JISZ8803: 2011. Two samples were made for each level and measured three times. The arithmetic average of 6 times in total was adopted as the evaluation value.

The surface tension (γResist) of the hardening composition for imprint 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. By using a hardenable composition for imprint having a high surface tension, the capillary force is increased, and high-speed filling of the hardenable composition for imprint into a mold pattern can be performed. The upper limit value of the surface tension is not particularly limited. From the viewpoint of imparting the relationship with the underlayer film and the inkjet adaptability, 40.0 mN / m or less is preferable, and 38.0 mN / m or less is more preferable. It is 36.0 mN / m or less. The surface tension of the curable composition for imprint was measured by the following method.

The Ohnishi parameter of the hardenable composition for imprint 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 Ohnishi parameter of the hardening composition for imprint is not particularly limited, and may be, for example, 1.0 or more, and further 2.0 or more.
For the polymerizable compound of the curable composition for imprint, the number of carbon atoms, hydrogen atoms, and oxygen atoms of the total constituent components can be substituted into the following formula to obtain the Ohnishi parameter.
Ohnishi parameter = sum of the number of carbon atoms, hydrogen atoms and oxygen atoms / (number of carbon atoms-number of oxygen atoms)

＜＜ Storage Container ＞＞
As a storage container for the imprintable curable composition used in the present invention, a conventionally known storage container can be used. In addition, as a storage container, in order to prevent impurities from being mixed into the raw materials or the composition, it is also preferable to use a multi-layer bottle composed of six kinds of six-layer resin or a bottle having six resins in a seven-layer structure. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

<Pattern and pattern formation method>
A method for forming a pattern according to a preferred embodiment of the present invention includes: a process for forming an underlayer film on a substrate surface using the underlayer film forming composition for imprinting according to the present invention (underlayer film forming process); The surface is preferred.) A process for forming a hardenable composition layer for imprinting (a hardenable composition layer formation process for imprinting) by applying an underlayer film-forming composition for imprinting, and applying a mold to the hardenable composition for imprinting A process of contacting the layers; a process of exposing the hardenable composition layer for imprinting in a state in contact with the mold; and a process of peeling the mold from the hardenable composition layer for imprinting of the exposure.
Hereinafter, a pattern forming method (a method of manufacturing a cured product pattern) will be described with reference to (1) to (7) of FIG. 1. Obviously, the structure of the present invention is not limited to the illustration.

＜〈 Underlayer Film Formation Process 〉＞
As shown in (1) and (2) of FIG. 1, in the lower-layer film forming process, the lower-layer film 2 is formed on the surface of the substrate 1. The underlayer film is preferably formed on a substrate by applying an underlayer film-forming composition for imprinting to a layer. The substrate 1 may have an undercoat layer or an adhesive film, except for a case where the substrate 1 is composed of a single layer.

A method for applying the underlayer film-forming composition for imprint to a substrate is not particularly limited, and a generally known and applicable method can be adopted. Specifically, examples of the applicable method include a dip coating method, a pneumatic coating method, a curtain coating method, a wire bar coat method, a gravure coating method, an extrusion coating method, and a spin. The coating method, the slit scanning method, or the inkjet method is preferably a spin coating method.
Furthermore, after the imprinting underlayer film-forming composition is applied to a substrate on a substrate, the solvent is evaporated (dried) by heat to form an underlayer film as a thin film.

The thickness of the lower layer film 2 is preferably 2 nm or more, more preferably 3 nm or more, and even more preferably 4 nm or more, and may be 5 nm or more, 7 nm or more, and 10 nm or more. The thickness of the lower layer film is preferably 40 nm or less, more preferably 30 nm, and even more preferably 20 nm, and may be 15 nm or less. By setting the film thickness to be greater than the above-mentioned lower limit value, the spreadability (wetability) of the curable composition for imprint on the underlayer film is improved, and a uniform residual film can be formed after imprinting. By setting the film thickness to be equal to or less than the above-mentioned upper limit value, there is a tendency that the residual film after embossing becomes thin, uneven film thickness is unlikely to occur, and the uniformity of the residual film is improved.

The material of the substrate is not particularly limited, and reference can be made to the description in paragraph 0103 of Japanese Patent Application Laid-Open No. 2010-109092, and these contents are incorporated into this specification. In the present invention, 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 alumina substrate, a polycrystalline alumina substrate, and a SOC (Spin-coated carbon), SOG (spin-coated glass), silicon nitride, silicon oxynitride, and GaAsP, GaP, AlGaAs, InGaN, GaN, AlGaN, ZnSe, AlGa, InP, or ZnO. Specific examples of the material of the glass substrate include aluminosilicate glass, aluminoborosilicate glass, and barium borosilicate glass. In the present invention, a silicon substrate and a substrate coated with SOC (spin-coated carbon) are preferred.

In the present invention, it is preferable to use a substrate having an organic layer as the outermost layer.
Examples of the organic layer of the substrate include an amorphous carbon film formed by CVD (Chemical Vapor Deposition) or a spin coating type carbon film formed by dissolving a high carbon material in an organic solvent and spin coating. Examples of the spin-coated carbon film include a tricyclone copolymer, a hydronaphthol novolac resin, a naphthol dicyclopentadiene copolymer, a phenol dicyclopentadiene copolymer, and Japanese Patent Application Laid-Open No. 2005- Amidene bisphenol novolak described in JP 128509, a pinene copolymer, an indene copolymer described in JP 2005-250434, and a fullerene having a phenol group described in JP 2006-227391 Bisphenol compound and the novolac resin, dibisphenol compound and the novolac resin, novolac resin of the adamantane phenol compound, hydroxyvinyl naphthalene copolymer, bisnaphthol described in JP 2007-199653 The compound and the novolak resin, ROMP, and a resin compound shown as a tricyclopentadiene copolymer.
As an example of the SOC, the description in paragraph 0126 of Japanese Patent Application Laid-Open No. 2011-164345 can be referred to, and the content is incorporated into this specification.

The contact angle of water on the substrate surface is preferably 20 ° or more, more preferably 40 ° or more, and more preferably 60 ° or more. The upper limit is actually 90 ° or less. The contact angle is measured by a method described in Examples described later.

In the present invention, it is preferable to use a substrate (hereinafter, referred to as an alkaline substrate) having an alkaline layer as the outermost layer. Examples of the basic substrate include a substrate containing a basic organic compound (for example, an amine compound or an ammonium compound) or an inorganic substrate containing a nitrogen atom.

＜ Process for forming hardening composition layer for imprinting ＞＞
In the applicable process, for example, as shown in (3) of FIG. 1, the curable composition 3 for imprint is applied to the surface of the lower layer film 2.
The method for applying the curable composition for imprinting is not particularly limited, and reference can be made to paragraph 0102 of Japanese Patent Application Laid-Open No. 2010-109092 (the publication number corresponding to the US application is US Patent Application Publication No. 2011/0183127). This content is incorporated into this specification. The curable composition for imprint is preferably applied to the surface of the underlayer film by an inkjet method. Moreover, the hardening composition for imprints can be applied by multiple application. In the method of arranging droplets on the surface of the lower film by an inkjet method or the like, the amount of the droplets is preferably about 1 to 20 pL, and the droplets are preferably arranged on the surface of the lower film at intervals. The droplet interval is preferably an interval of 10 to 1000 μm. In the case of the inkjet method, the droplet interval is set as the arrangement interval of the nozzles for inkjet.
Further, the volume ratio of the lower layer film 2 to the film-like imprintable curable composition 3 applied to the lower layer film is preferably 1: 1 to 500, more preferably 1:10 to 300, and 1:50 to 200. Is even better.
In addition, a method for manufacturing a laminated body according to a preferred embodiment of the present invention is a method for manufacturing a kit using the present invention. The method includes applying an imprint on a surface of an underlayer film formed from the above-mentioned underlayer film forming composition for imprinting. Process for hardening composition. Furthermore, a method for manufacturing a laminated body according to a preferred embodiment of the present invention includes a process for applying the above-mentioned lower-layer film-forming composition for imprinting to a substrate on a substrate, and further includes applying the lower-layer film for imprinting applicable to the above-mentioned layer. The forming composition is preferably at 100 to 300 ° C, more preferably at 130 to 260 ° C, even more preferably at 150 to 230 ° C, and the process of heating (baking) is more preferred. The heating time is preferably 30 seconds to 5 minutes.

＜〈 Mold contact process 〉＞
For example, as shown in (4) of FIG. 1, in the mold contact process, the hardening composition 3 for imprint is brought into contact with a mold 4 having a pattern for transferring a shape of a pattern. Through this process, a desired hardened pattern (embossed pattern) is obtained.
Specifically, in order to transfer a desired pattern to the film-like embossable curable composition, the surface of the film-like embossable curable composition 3 is covered with the mold 4.

The mold may be a light-transmitting mold or a non-light-transmitting mold. When using a light-transmitting mold, it is preferable to irradiate light to the curable composition 3 for imprint from the mold side. In the present invention, it is more preferable to use a light-transmitting mold and irradiate light from the mold side.
The mold which can be used in the present invention is a mold having a pattern for transfer. The pattern possessed by the mold can be formed, for example, by photolithography, electron beam scanning, or the like with a desired processing accuracy. However, in the present invention, the method for producing a mold pattern is not particularly limited. The pattern formed by the method for manufacturing a cured product pattern according to the preferred embodiment of the present invention can also be used as a mold.
The material constituting the light-transmitting mold used in the present invention is not particularly limited, and examples thereof include light-transmitting resins such as glass, quartz, polymethyl methacrylate (PMMA), polycarbonate resin, transparent metal vapor-deposited films, and polymer materials. For soft films such as dimethylsilane, light-hardened films, metal films, and the like, quartz is preferred.
The non-light-transmitting mold material used when the light-transmitting substrate is used in the present invention is not particularly limited as long as it has a predetermined strength. Specific examples include ceramic materials, vapor-deposited films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, substrates such as SiC, silicon, silicon nitride, polycrystalline silicon, silicon oxide, and amorphous silicon. It is not particularly limited.

In the manufacturing method of the said hardened | cured material pattern, when imprint lithography is performed using the hardenable composition for imprinting, it is preferable to set the mold pressure to 10 atmospheres or less. When the mold pressure is set to 10 atmospheres or less, there is a tendency that the mold or the substrate is not easily deformed and the pattern accuracy is improved. Further, it is also preferable from the viewpoint that the device can be downsized due to low pressure. The mold pressure is reduced from the residual film of the curable composition for imprint which touches the convex part of the mold, and the range capable of ensuring the uniformity of the mold transfer is preferably selected.
It is also preferable to contact the hardening composition for imprint and the mold in an atmosphere containing helium or a condensable gas, or an atmosphere containing both helium and a condensable gas.

＜＜ Light irradiation process ＞＞
In the light irradiation process, the hardening composition for imprint is irradiated with light to form a hardened material. The irradiation amount of light irradiation in the light irradiation process may be sufficiently larger than the minimum irradiation amount required for curing. The amount of irradiation required for curing is appropriately determined by investigating the consumption of unsaturated bonds in the curable composition for imprint and the like.
The type of light to be irradiated is not particularly limited, and ultraviolet light is exemplified.
Moreover, in the imprint lithography applied to the present invention, the substrate temperature during light irradiation is usually set to room temperature, but in order to improve reactivity, light irradiation may be performed while heating. When the vacuum state is used as the preparation stage for light irradiation, it is effective in preventing the inclusion of bubbles, suppressing the decrease in the reactivity caused by the incorporation of oxygen, and improving the adhesion between the mold and the hardening composition for imprinting. Light irradiation was performed in a vacuum state. Moreover, in the said hardened | cured material pattern manufacturing method, the preferable vacuum degree at the time of light irradiation is the range of ^10-1 Pa to normal pressure.
When exposed, the exposure illuminance is set to 1 ~ 500mW / cm ² and is preferred, to 10 ~ 400mW / cm ² more preferably in the range of. The exposure time is not particularly limited, but is preferably 0.01 to 10 seconds, and more preferably 0.5 to 1 second. The exposure amount is preferably in the range of 5 to 1000 mJ / cm ² , and more preferably in the range of 10 to 500 mJ / cm ² .
In the above-mentioned method for manufacturing a cured product pattern, after curing the film-shaped imprintable curable composition (pattern-forming layer) by light, the process may further include a process of heating and curing the cured pattern as necessary. The temperature for heating and hardening the curable composition for imprinting after light irradiation is preferably 150 to 280 ° C, and more preferably 200 to 250 ° C. The time for applying heat is preferably 5 to 60 minutes, and more preferably 15 to 45 minutes.

＜＜ Release Process ＞＞
In the demolding process, the hardened material and the mold are separated ((5) in FIG. 1). The obtained hardened material pattern can be used in various applications as described later.
That is, in the present invention, there is disclosed a laminated body further having a hardened pattern formed of a hardenable composition for imprint on the surface of the underlayer film. Moreover, although the film thickness of the pattern formation layer containing the hardening composition for imprints used by this invention differs depending on the use used, it is about 0.01 micrometer-30 micrometers.
In addition, as described later, etching and the like can be performed.

＜ The hardened pattern and its application ＞
As described above, the hardened pattern formed by the method for manufacturing a hardened pattern can be used as a permanent film used in a liquid crystal display device (LCD), etc., or as an etching resist (mask for lithography) for semiconductor device manufacturing. ). In particular, this specification discloses a method for manufacturing a semiconductor device (circuit board), which method includes a process of obtaining a hardened pattern by a method for manufacturing a hardened pattern according to a preferred embodiment of the present invention. Furthermore, the method for manufacturing a semiconductor device according to a preferred embodiment of the present invention may include a process and formation of etching or ion implantation on a substrate using the hardened pattern obtained by the above-mentioned hardened pattern manufacturing method as a mask. Process of electronic components. The semiconductor device is preferably a semiconductor element. That is, in this specification, a method for manufacturing a semiconductor device including the above-described pattern forming method is disclosed. Furthermore, in this specification, a method for manufacturing an electronic device is disclosed. The method includes a process for obtaining a semiconductor device by the method for manufacturing the semiconductor device and a process for connecting the semiconductor device to a control mechanism that controls the semiconductor device.
In addition, a grid pattern is formed on the glass substrate of the liquid crystal display device by using the pattern formed by the above-mentioned hardened pattern manufacturing method, thereby making it possible to inexpensively manufacture a large screen size (eg, 55 inches, greater than 60 inches with less reflection or absorption). Inch) polarizer. For example, a polarizing plate described in Japanese Patent Application Laid-Open No. 2015-132825 or International Publication No. 2011/132649 can be manufactured.
As shown in FIG. 1 (6) and FIG. 1 (7), the hardened | cured material pattern formed by this invention is also useful as an etching resist (mask for lithography). When a hardened pattern is used as an etching resist, first, a nano or micron-level fine hardened pattern is formed on a substrate by the above-mentioned hardened pattern manufacturing method. In the present invention, it is particularly effective to form a nano-scale fine pattern, and it is also possible to form a pattern having a size of 50 nm or less, especially 30 nm or less. The lower limit value of the size of the hardened | cured material pattern formed by the said hardened | cured material pattern manufacturing method is not specifically limited, For example, it can be 1 nm or more.
In addition, the present invention also discloses a method for manufacturing a mold for imprinting, which method includes a process for obtaining a hardened pattern on a substrate by a method for manufacturing a hardened pattern according to a preferred embodiment of the present invention, and the above-mentioned hardening obtained by using the method. An object pattern is etched on the substrate.
In wet etching, etching is performed using hydrogen fluoride or the like, and in dry etching, etching gas such as CF ₄ is used to form a desired hardened pattern on the substrate. The hardened material pattern is particularly excellent in etching resistance against dry etching. That is, the pattern formed by the above-mentioned hardened pattern manufacturing method is preferably used as a mask for lithography.

Specifically, the pattern formed by the present invention can be preferably used for the production of a guide pattern or the like, which is used to form a self-organized fine pattern (directed self-assembly, DSA (directed self-assembly)) ), That is, recording media such as magnetic disks, light-receiving elements such as solid-state imaging elements, light-emitting elements such as LED (light emitting diode) or organic EL (organic electroluminescence), optical devices such as liquid crystal display devices (LCD), Optical components such as diffraction gratings, relief holograms, optical waveguides, filters, microlens arrays, thin film transistors, organic transistors, color filters, anti-reflection films, polarizers, polarizers, optical films, pillars, and other flat panel display components Nano-devices, immunoassay wafers, DNA separation wafers, microreactors, photonic liquid crystals, block copolymers.
[Example]

The following examples further illustrate the present invention. The materials, usage amounts, proportions, processing contents, processing sequence, and the like shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Synthesis of A-1 / B-1 (90/10) copolymer>
100 g of water was added to the flask as a solvent, and the temperature was raised to 90 ° C. under a nitrogen atmosphere. To this water, 16.0 g (0.16 mol) of epoxy methacrylate (FUJIFILM Wako Pure Chemical Corporation), the following disodium phosphate 2-propenyloxyethyl; 1.8 g (7 mmol) FUJIFILM Wako Pure Chemical Corporation), 2,2'-azobis (2- (2-imidazolin-2-yl) propane dihydrochloride) (VA-044); 1.0 g (3 mmol) (FUJIFILM Wako Pure Chemical Corporation), water; 50 g of the mixed liquid was added dropwise for 2 hours. After completion of the dropwise addition, a copolymer was obtained by further stirring at 90 ° C for 4 hours.
To the solution of the above copolymer was added acrylic acid; 11.6 g (0.16 mol) (FUJIFILM Wako Pure Chemical Corporation), tetraethylammonium bromide (TEAB); 2.1 g (FUJIFILM Wako Pure Chemical Corporation), 4-hydroxy-tetramethyl Piperidin-1-oxy (4-HO-TEMPO); 50 mg (FUJIFILM Wako Pure Chemical Corporation), reacted at 90 ° C for 8 hours, and it was confirmed that acrylic acid disappeared from H-NMR by the reaction, thereby obtaining an aqueous resin solution . The reaction scheme is shown below.
1N hydrochloric acid was added to the aqueous solution, and the precipitate was purified by washing with water to obtain a resin A-1 / B-1 powder.
The other copolymers were similarly synthesized.

[Chemical Formula 4]

Disodium phosphate 2-propenyloxyethyl (molecular weight 254.2)

[Chemical Formula 5]

The resin was dissolved in PGMEA to obtain a PGMEA solution.
The weight-average molecular weight (Mw, polystyrene equivalent) determined by gel permeation chromatography (GPC) of the obtained resin was 20,000, and the degree of dispersion (Mw / Mn) = 2.2.
＜ Method of measuring molecular weight ＞
The weight average molecular weight (Mw) of the resin is defined as a polystyrene conversion value by gel permeation chromatography (GPC measurement). HLC-8220 (manufactured by TOSOH CORPORATION) was used for the apparatus, and protective column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) were used as the column. As the eluent, THF (tetrahydrofuran) was used. Detection was performed using an RI detector.

<Preparation of the Underlayer Film-forming Composition>
A solution containing the ingredients shown in the following table was prepared. This was filtered using a 0.02 μm nylon filter and a 0.010 μm PTFE (polytetrafluoroethylene) filter to prepare the preparation of the underlying film-forming composition shown in the examples and comparative examples.

<Preparation of hardening composition for imprinting>
The various compounds described in the following table were mixed, and 4-hydroxy-2,2,6,6-tetramethyl was further added as a polymerization inhibitor so that the total amount of the polymerizable compound was 200 mass ppm (0.02 mass%). Prepared from piperidine-1-oxy radical (manufactured by Tokyo Chemical Industry Co., Ltd.). This was filtered through a 0.02 μm nylon filter and a 0.001 μm PTFE filter to prepare a curable composition for imprint.

＜ Calculation of pKa ＞
Use the following software package and calculate it.
Package software: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs)

<Formation of Underlayer Film / Evaluation of Film Thickness>
On the substrates shown in the following table, an underlayer film-forming composition for imprinting described in the table was spin-coated, and an underlayer film was formed by heating with a hot plate under the baking conditions described in the table. The film thickness of the lower film was measured by an ellipsometer.

＜ Evaluation of close contact force ＞
On the surface of the underlayer film obtained as described above, an inkjet printer DMP-2831 manufactured by FUJIFILM Dimatix was used to print a hardening composition for imprint with a droplet discharge temperature of 23 pC per nozzle and a temperature of 23 ° C. The lower layer film was coated so as to have a square array with a spacing of about 100 μm, and was used as a pattern forming layer. Next, in a He environment (replacement rate of 90% or more), the pattern forming layer is covered with a quartz wafer spin-coated with the composition for forming an adhesive layer shown in Example 6 of Japanese Patent Application Laid-Open No. 2014-024322. In addition, a curable composition for imprinting is sealed. At a time of 10 seconds after the sealing, exposure was performed under the condition of 150 mJ / cm ² using a high-pressure mercury lamp from the mold side. The force required to peel the exposed sample was measured, and the adhesion force of the lower layer film was set to F.
A: F≥30N
B: 25N≤F ＜ 30N
C: 20N≤F ＜ 25N
D: F <20N

<Flat shape (evaluation of peeling defects)>
On the surface of the underlayer film obtained as described above, an inkjet printer DMP-2831 manufactured by FUJIFILM Dimatix was used to print a hardenable composition for imprint with a droplet discharge temperature of 6 pL per nozzle at 25 ° C. The lower layer film was coated so as to have a square array with a spacing of about 100 μm, and was used as a pattern forming layer. Next, a quartz mold (a line pattern with a line width of 28 nm and a depth of 60 nm) was covered on the pattern forming layer under a He environment (a substitution rate of 90% or more), and the mold was filled with a hardening composition for imprinting. Ten seconds after the seal was passed, a high-pressure mercury lamp was used from the mold side and exposure was performed under the conditions of 150 mJ / cm ² , and then the pattern was transferred on the pattern forming layer by peeling the mold. The presence or absence of peeling of the transferred pattern was confirmed with an optical microscope observation (macro observation) and an SEM observation (micro observation).
A: No pattern peeling was observed
B: No peeling was observed under macro observation, but pattern peeling was confirmed under micro observation
C: Macroscopic observation confirmed the presence of peeling in a localized area (the end of the mold release)
D: Peeling was confirmed across the front surface of the transfer area under macro observation

In Tables 5 and 6 below, A-1 / B-1 of the polymer means a copolymer having a constitutional unit of A-1 and a constitutional unit of B-1. 90/10 represents a copolymerization ratio (molar ratio), and refers to the ratio of the left constituent unit and the right constituent unit, respectively. The pKa of the monomer is a value of pKa of a monomer having a pKa of 4.0 or less among the monomers constituting the polymer. The meanings of the abbreviations in the table are as follows.
PGMEA: propylene glycol monomethyl ether acetate
PGME: propylene glycol monomethyl ether γBL: γ-butyrolactone
Mw: weight average molecular weight
[table 5]


[TABLE 6]


[TABLE 7]

The unit of the blending amount is the mass part. The unit of the boiling point is ℃ (1013.25hPa).

[TABLE 8]



[TABLE 9]

<Substrate>
Substrate Si: Silicon wafer with a diameter of 8 inches (1 inch is 2.54 cm). Substrate 1: Spin-coated carbon film ODL-102 (Shin) coated on a silicon wafer with a diameter of 8 inches by spin coating. -Etsu Chemical Co., Ltd.) and baked at 240 ° C for 60 seconds to form a substrate with a SOC (Spin on Carbon) film with a thickness of 200 nm.
Substrate 2: Spin-coated carbon film ODL-50 (Shin-Etsu Chemical Co., Ltd.) was coated on a silicon nitride wafer with a diameter of 8 inches by spin coating, and baked at 240 ° C for 60 minutes. In seconds, a substrate with a SOC (Spin on Carbon) film having a thickness of 200 nm is formed.
Substrate 3: SOC NCA9053EH (Nissan Chemical Industries, Ltd.) was applied on a 8-inch diameter silicon wafer by spin coating, and baked at 240 ° C for 60 seconds to form a 200 nm SOC (Spin on Carbon) film substrate.
Substrate SOG: OCD T-12 (Tokyo Ohka Kogyo Co., Ltd.) was coated on a silicon wafer with a diameter of 8 inches by spin coating, and UV ozone treatment was performed for 120 seconds to form a SOG with a thickness of 200 nm. Film substrate.

From the above results, it is clear that if an underlayer film is formed by using an underlayer film forming composition for imprinting using a polymer derived from monomer-derived constituent units and polymerizable groups of pKa 4.0 or less, a hardening composition for imprinting can be achieved Excellent adhesion (Examples 1 to 15). In particular, it can be seen that these underlayer film-forming compositions for imprinting are materials that achieve good adhesion to various substrates such as substrates having different carbon contents or SOG substrates and are highly versatile. In any of the samples of the examples, the imprint layer formed on the surface of the lower layer film had a good surface shape.
On the other hand, when the specific polymer is not used (Comparative Example 1), the result is poor adhesion.

1‧‧‧ substrate

2‧‧‧ lower film

3‧‧‧curable composition for imprinting

4‧‧‧ mold

(1)-(7) of FIG. 1 are process explanatory drawings which show an example of the formation of a hardened | cured material pattern, and an example of the manufacturing process at the time of using the obtained hardened | cured material pattern for the process by a substrate by etching.

Claims (22)

An underlayer film-forming composition for imprinting includes a polymer and a solvent, and the polymer includes a constituent unit derived from a monomer having a pKa of 4.0 or less and a polymerizable group. The underlayer film-forming composition for imprinting according to item 1 of the patent application scope, wherein The polymer is an acrylic resin. The underlayer film-forming composition for imprinting as described in item 1 or 2 of the patent application scope, wherein The weight average molecular weight of this polymer is 2,000 or more. The underlayer film-forming composition for imprinting as described in item 1 or 2 of the patent application scope, wherein The polymerizable group of the polymer is a (meth) acrylfluorenyl group. The underlayer film-forming composition for imprinting as described in item 1 or 2 of the patent application scope, wherein The constituent unit derived from the monomer having a pKa of 4.0 or less is a constituent unit derived from the monomer having a pKa of 3.0 or less. The underlayer film-forming composition for imprinting as described in item 1 or 2 of the patent application scope, wherein The constituent unit derived from the monomer having a pKa of 4.0 or less has a member selected from the group consisting of a hydroxyl group, a carboxyl group, a thiocarboxylic acid group, a dithiocarboxylic acid group, a sulfonic acid group, a phosphoric acid monoester group, a phosphoric acid diester group, and a phosphoric acid group. At least one of the group. The underlayer film-forming composition for imprinting as described in item 1 or 2 of the patent application scope, wherein 99.0% by mass or more of the underlayer film-forming composition for imprint is a solvent. The underlayer film-forming composition for imprinting as described in item 1 or 2 of the patent application scope, wherein This polymer has a structural unit containing a polymerizable group. A kit comprising the underlayer film-forming composition for imprinting and the hardening composition for imprinting according to any one of claims 1 to 8 in the scope of patent application. A hardenable composition for embossing, which is used in the set described in claim 9 of the scope of patent application. A laminated body comprising a substrate, an underlayer film formed on the surface of the substrate and formed by the underlayer film forming composition according to any one of claims 1 to 8 of the scope of patent application, and an underlayer film formed on the underlayer. An embossed layer formed by a curable composition for imprint on the surface of a film. The laminated body described in item 11 of the scope of patent application, wherein As the substrate, a substrate having an organic layer as the outermost layer was used. The laminated body according to item 11 or item 12 of the scope of patent application, wherein As the substrate, a substrate having a basic layer was used as the outermost layer. A method for manufacturing a laminated body includes: A process for forming the underlayer film for imprinting by applying the underlayer film-forming composition for imprinting according to any one of claims 1 to 8 to the surface of a substrate; and A process for applying a curable composition for imprint to the surface of the underlayer film. The method for manufacturing a laminated body according to item 14 of the scope of patent application, wherein As the substrate, a substrate having an organic layer as the outermost layer was used. The method for manufacturing a laminated body according to item 14 or item 15 of the scope of patent application, wherein As the substrate, a substrate having a basic layer was used as the outermost layer. A pattern forming method includes: A process for forming an underlayer film on a substrate surface by using the underlayer film forming composition for imprinting described in any one of claims 1 to 8 of the scope of patent application; A process of applying an underlayer film-forming composition for imprinting on the underlayer film to form a hardenable composition layer for imprinting; A process of bringing a mold into contact with the hardening composition layer for imprinting; A process of exposing the hardenable composition layer for imprinting in contact with the mold; and A process of peeling the mold from the exposed curable composition layer for imprinting. The pattern forming method described in item 17 of the scope of patent application, wherein As the substrate, a substrate having an organic layer as the outermost layer was used. The pattern forming method described in item 17 or 18 of the scope of patent application, wherein As the substrate, a substrate having a basic layer was used as the outermost layer. The pattern forming method described in item 17 or 18 of the scope of patent application, wherein The underlayer film-forming composition for imprint was applied to the substrate surface by a spin coating method. The pattern forming method described in item 17 or 18 of the scope of patent application, wherein This curable composition for imprint was applied to an underlayer film by an inkjet method. A method for manufacturing a semiconductor device, including the pattern forming method described in any one of the 17th to the 21st patent applications.