Method for producing composition, cured product, method for producing pattern, method for inspecting composition, and composition

Abstract

Provided are: a method for producing a composition, said method comprising a step in which a composition for forming an imprint pattern is used and a component contained in the composition is detected by light absorption, and a step in which a component contained in the composition is detected according to a method that includes a step for charging the composition or particles obtained from the composition; a cured product of the composition obtained according to the production method; a method for producing a pattern using the composition obtained according to the the production method; a method for inspecting a composition; and a composition.

Description

Method for producing a composition, a cured product, a method for producing a pattern, a method for inspecting a composition, and a method for inspecting a composition

[0001] The present invention relates to a method for producing a composition, a method for producing a cured product, a method for producing a pattern, a method for inspecting a composition, and the composition.

[0002] Imprinting is a technique for transferring a fine pattern onto a material by pressing a patterned metal mold (commonly called a mold or stamper) onto the material. Since the imprinting method makes it possible to easily create precise fine patterns, it has been expected to be applied in a variety of fields in recent years. In particular, nanoimprinting technology, which can form fine patterns at the nano-order level, has attracted attention.

[0003] Patent Document 1 describes a curable composition that satisfies the following formula (1) in a cured state: １ / Er ２ ≧1.10 (1) (where Er １ indicates the composite elastic modulus (GPa) of the cured surface, and Er ２ indicates the composite elastic modulus (GPa) inside the cured product.

[0004] JP 2016-029138 A

[0005] As imprinting methods, methods known as thermal imprinting and curing imprinting have been proposed based on the transfer method. In thermal imprinting, a mold is pressed into a thermoplastic resin heated to or above its glass transition temperature (hereinafter sometimes referred to as "Tg"), and then the mold is released after cooling to form a fine pattern. This method allows for the selection of a variety of materials, but it also has problems such as the difficulty of forming fine patterns due to the need for high pressure during pressing and reduced dimensional accuracy caused by thermal shrinkage, etc. On the other hand, in curing imprinting, for example, a film formed from an imprint pattern-forming composition is photo-cured or thermally cured while pressed against the mold, and then the mold is released. Since imprinting is performed on an uncured material, the application of high pressure and high-temperature heating can be partially or completely omitted, making it possible to easily create fine patterns. Another advantage is that dimensional variation before and after curing is small, allowing for the accurate formation of fine patterns. Recently, new developments have been reported, such as nanocasting, which combines the advantages of both thermal imprinting and curing imprinting, and reversal imprinting, which produces three-dimensional layered structures.

[0006] In the curing imprinting method, an imprint pattern-forming composition is applied to a support (the surface of which may be subjected to an adhesion treatment, if necessary) to form a film, and then a mold made of a light-transmitting material such as quartz is pressed against the support. The imprint pattern-forming composition is cured by light irradiation or heating while the mold is pressed against the support, and the mold is then released to produce a cured product with the desired pattern transferred. Methods for applying the imprint pattern-forming composition to a support include spin coating and inkjet printing. In particular, inkjet printing has attracted attention in recent years due to its low loss of the imprint pattern-forming composition. Spin coating is an application method with excellent productivity due to its high throughput. Furthermore, a method of performing microfabrication using a transferred imprint pattern as a mask is called nanoimprint lithography (NIL), and is being developed as a next-generation lithography technology. NIL allows for the formation of complex two-dimensional and three-dimensional pattern circuits in a single process, which would require multiple exposures in photolithography, thereby reducing the number of steps. Furthermore, the composition is required to be capable of resolving ultrafine patterns with a minimum line width of 20 nm or less, and to have high etching resistance as a mask when microfabricating an object to be processed. Specific examples of compositions for imprint pattern formation intended for use as a mask include those described in Japanese Patent No. 5426814, JP 2015-009171 A, JP 2015-185798 A, JP 2015-070145 A, JP 2015-128134 A, etc.

[0007] Conventionally, in the production of compositions for imprint pattern formation, detection of contained components by light absorption or the like has been performed for quality inspection. Performing such quality inspections to detect missing or incorrectly added components, loss due to volatilization, or alteration within the composition is extremely important industrially for ensuring the quality of the composition. However, conventional detection of contained components by light absorption has the problem of being limited in the types of components that can be used, such as being unable to detect components with very low light absorption. The present invention aims to provide a method for producing a composition, a method for producing a cured product and a pattern, and a method for inspecting a composition, which can be used while detecting a wide variety of compounds. Another object of the present invention is to provide a composition containing a wide variety of compounds.

[0008] Representative embodiments of the present invention are described below. <1> A method for producing a composition, comprising the steps of: using a composition for imprint pattern formation, and detecting components contained in the composition by light absorption; and detecting the components contained in the composition by a method comprising the step of charging the composition or particles obtained from the composition. <2> A method for producing a composition according to <1>, wherein the composition for imprint pattern formation contains a polymerizable compound. <3> The composition for imprint pattern formation has a maximum molar absorption coefficient of 100 L mol at a wavelength of 190 to 400 nm. －１ ・cm －１<4> A method for producing the composition according to <1> or <2>, which contains a compound that satisfies at least one of the following conditions: a molecular weight of 300 or more and a boiling point of 300°C or more. <5> A method for producing the composition according to <4>, in which the molecular weight of the compound is 500 or more. <6> A method for producing the composition according to <4>, in which the boiling point of the compound is 350°C or more. <7> A method for producing the composition according to any one of <1> to <6>, in which the detection of the contained components by light absorption is detection using ultraviolet light. <8> A method for producing the composition according to any one of <1> to <7>, in which the detection by a method comprising a step of charging the composition or particles obtained from the composition is a charged particle detection method. <9> A method for producing the composition according to any one of <1> to <7>, in which the detection by a method comprising a step of charging the composition or particles obtained from the composition is detection by electrospray ionization. <10> The method for producing the composition according to any one of <1> to <9>, wherein the content of the solvent relative to the total mass of the composition for imprint pattern formation is less than 0.1 mass %. <11> A cured product obtained by curing the composition obtained by the method for producing a composition according to any one of <1> to <10>. <12> A method for producing a pattern, comprising applying the composition obtained by the method for producing a composition according to any one of <1> to <10> onto a substrate or a mold, and irradiating the composition for imprint pattern formation with light while sandwiched between the mold and the substrate. <13> The method for producing a pattern according to <12>, wherein the pattern has a shape of any one of lines, holes, and pillars with a size of 100 nm or less. <14> A method for inspecting a composition, using a composition for imprint pattern formation, comprising the steps of: detecting components contained in the composition by light absorption; and detecting components contained in the composition by a method comprising the step of charging the composition or particles obtained from the composition. <15> Polymerizable compound, having a maximum molar absorption coefficient of 100 L mol in the wavelength range of 190 to 400 nm －１ ・cm －１and a compound that satisfies at least one of the following conditions: a molecular weight of 300 or more and a boiling point of 300°C or more.

[0009] According to the present invention, there are provided a method for producing a composition that can be used while detecting a wide variety of compounds, a method for producing a cured product or a pattern, and a method for inspecting the composition. The present invention also provides a composition containing a wide variety of compounds.

[0010] The present invention will be described in detail below. In this specification, the term "to" is used to mean that the numerical values ​​before and after the term are included as the lower and upper limits. In this specification, "(meth)acrylate" refers to acrylate and methacrylate, "(meth)acrylic" refers to acrylic and methacrylic, and "(meth)acryloyl" refers to acryloyl and methacryloyl. "(meth)acryloyloxy" refers to acryloyloxy and methacryloyloxy. In this specification, "imprint" preferably refers to pattern transfer having a size of 1 nm to 10 mm, and more preferably refers to pattern transfer having a size of approximately 10 nm to 100 μm (nanoimprint). In the description of groups (atomic groups) in this specification, a notation that does not specify whether they are substituted or unsubstituted encompasses both unsubstituted and substituted groups. For example, the term "alkyl group" encompasses not only alkyl groups without a substituent (unsubstituted alkyl groups) but also alkyl groups with a substituent (substituted alkyl groups). As used herein, "light" includes not only light with wavelengths in the ultraviolet, near-ultraviolet, far-ultraviolet, visible, and infrared regions, and electromagnetic waves, but also radiation. Radiation includes, for example, microwaves, electron beams, extreme ultraviolet (EUV), and X-rays. Laser light such as a 248 nm excimer laser, a 193 nm excimer laser, and a 172 nm excimer laser can also be used. This light may be monochrome light (single wavelength light) filtered through an optical filter, or light of multiple different wavelengths (complex light). In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are defined as polystyrene equivalent values ​​measured by gel permeation chromatography (GPC measurement) unless otherwise specified. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220 (manufactured by Tosoh Corporation) and a guard column such as HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, or TSKgel Super HZ2000 (manufactured by Tosoh Corporation) as a column.Unless otherwise specified, measurements were performed using THF (tetrahydrofuran) as the eluent. Furthermore, unless otherwise specified, detection was performed using a 254 nm UV (ultraviolet) detector. Unless otherwise specified, the temperature was 23°C, the pressure was 101,325 Pa (1 atmosphere), and the relative humidity was 50% RH. The term "process" as used herein refers not only to an independent process, but also to a process that cannot be clearly distinguished from other processes, as long as the intended effect of the process is achieved. As used herein, the term "total solids" refers to the total mass of all components of a composition excluding the solvent. Furthermore, as used herein, the term "solids concentration" refers to the mass percentage of the components excluding the solvent relative to the total mass of the composition. In this specification, a combination of preferred embodiments is a more preferred embodiment.

[0011] (Method for Producing Composition) The method for producing a composition of the present invention includes a step of detecting components contained in the composition by light absorption using a composition for imprint pattern formation (hereinafter also referred to as a "detection step by light absorption"), and a step of detecting components contained in the composition by a method including a step of charging the composition or particles obtained from the composition (hereinafter also referred to as a "detection step by charging").

[0012] The method for producing a composition of the present invention allows the detection and use of a wide variety of compounds. The reason for the above-mentioned effect is believed to be as follows. The method for producing a composition of the present invention includes a step of detecting components contained in the composition by light absorption, and a step of detecting components contained in the composition by a method including charging the composition or particles obtained from the composition. A production method including such a method is believed to expand the types of components that can be used in the composition, since components with very low light absorption can be detected by a method including charging the composition or particles obtained from the composition. The present invention will be described in detail below.

[0013] <Detection Step by Light Absorption> The method for producing a composition of the present invention includes a step of detecting components contained in the composition for imprint pattern formation by light absorption (detection step by light absorption). Details of the composition for imprint pattern formation will be described later.

[0014] The detection of the contained components by light absorption is preferably detection using ultraviolet light, more preferably detection by ultraviolet light absorbance measurement. The wavelength of the ultraviolet light is not particularly limited, but is preferably 190 to 400 nm, more preferably 210 to 370 nm, and even more preferably 230 to 340 nm. Furthermore, the detection of the contained components by light absorption may be detection using ultraviolet light and visible light, more preferably detection by ultraviolet light and visible light absorbance measurement. In this case, the wavelength of the visible light is preferably greater than 400 nm and less than or equal to 800 nm.

[0015] The detection of components by light absorption is preferably carried out using at least a portion of the composition for imprint pattern formation as a sample. The sample may be prepared by diluting the composition for imprint pattern formation, for example, about 2 to 1000 times. The solvent used for dilution is not particularly limited, and may be appropriately selected from those that have low reactivity with the components in the composition for imprint pattern formation and do not inhibit detection. Examples of the solvent include alcohols such as methanol and ethanol, and organic solvents such as acetonitrile.

[0016] The detection of components by light absorption is also preferably carried out by separating the components in the composition for imprint pattern formation by liquid chromatography such as HPLC (high performance liquid chromatography). For example, in HPLC measurement, the components can be detected by light absorption using an ultraviolet (UV) detector, an ultraviolet-visible (UV-VIS) detector, a photodiode array (PDA) detector, or the like. Furthermore, in HPLC measurement, each component can be quantified by preparing samples of known concentrations of each component in the composition for imprint pattern formation and creating a calibration curve. Measurement conditions for HPLC measurement, such as the type of column, mobile phase, flow rate, amount of sample used, and column temperature, may be set with reference to conventional methods so as to separate the components in the composition for imprint pattern formation.

[0017] <Detection Step by Charging> The method for producing a composition of the present invention includes a step of detecting contained components by a method including a step of charging the composition for imprint pattern formation or particles obtained from the composition (detection step by charging).

[0018] The detection step based on electric charge is preferably a step of quantifying the contained components, which makes it possible to determine whether the content of the contained components has become different from the designed value due to volatilization, denaturation, etc. of the contained components.

[0019] The detection by the method including the step of charging the composition or particles obtained from the composition is preferably detection by a charged particle detection method. The charged particle detection method may be a conventional method, but is preferably a method including, for example, the following (A-1) to (A-4): (A-1) spraying the composition for imprint pattern formation with nitrogen gas to form fine droplets; (A-2) vaporizing the solvent in the droplets by heating to obtain desolvated particles; (A-3) causing charged nitrogen gas to collide with the particles to impart a positive charge to the particle surface; and (A-4) discharging the charge and detecting the current value. Detection by the charged particle detection method involves spraying an eluate to form fine particles of the sample in the same manner as in an ELSD (evaporative light scattering detector), and then discharging the charged N ２It uses gas ionization and electrical detection, but has the advantage of being able to detect with higher sensitivity than ELSD, with small sensitivity differences depending on the component. It also has the advantage of being easy to analyze the results and easy to maintain the device.

[0020] Furthermore, detection by a method including a step of charging the composition or particles obtained from the composition is preferably detection by electrospray ionization. The electrospray ionization method may be a conventional method, but is preferably a method including, for example, the following steps (B-1) to (B-4): (B-1) applying a high voltage between the composition for imprint pattern formation at the end of a capillary and a counter electrode to form a Taylor cone; (B-2) releasing charged droplets from the tip of the Taylor cone by evaporation of the solvent; (B-3) further evaporation of the solvent in the droplets increases the charge density (concentration), and the droplets become even smaller due to the electrostatic force of like charges; (B-4) repeating this process, ultimately causing ions to desorb from the droplets and be ionized. Detection by electrospray ionization has the advantage of being highly sensitive and capable of detecting a wide range of compounds.

[0021] The detection in the charge-based detection step is preferably carried out using at least a portion of the composition for imprint pattern formation as a sample. The sample may be prepared by diluting the composition for imprint pattern formation, for example, about 2 to 1000 times. The solvent used for dilution is not particularly limited, and may be appropriately selected from those that have low reactivity with the components in the composition for imprint pattern formation and do not inhibit detection. Examples of the solvent include alcohols such as methanol and ethanol, and organic solvents such as acetonitrile.

[0022] The detection of components in the charge-based detection step is also preferably carried out by separating the components in the imprint pattern-forming composition using liquid chromatography such as HPLC (high-performance liquid chromatography). For example, the detection of components in the charge-based detection step can be carried out by methods such as HPLC measurement using a charged aerosol detector (CAD) for detection (LC / CAD) or liquid chromatography / electrospray ionization mass spectrometry (LC / ESI-MS). Furthermore, in these measurements, each component can be quantified by preparing samples with known concentrations of each component in the imprint pattern-forming composition and creating a calibration curve. Measurement conditions for HPLC measurement, LC / ESI-MS, etc., such as the type of column, mobile phase, flow rate, amount of sample used, and column temperature, can be set with reference to conventional methods to ensure separation of the components in the imprint pattern-forming composition.

[0023] The detection step based on charge may make it possible to detect and even quantify components such as a release agent, which will be described later, that are difficult to detect in a detection step based on light absorption.

[0024] The light absorption detection step and the charge detection step may be carried out separately, or may be carried out consecutively, for example, by using an ultraviolet detector and a charged particle detector in combination as detectors for a single HPLC.

[0025] <Other Detection Steps> The method for producing a composition of the present invention may further include other detection steps in addition to the above-mentioned light absorption detection step and charge detection step. For example, when the composition for imprint pattern formation contains a component that has fluorescence, detection by fluorescence measurement may also be performed. Furthermore, when the composition for imprint pattern formation contains a component with a large refractive index, detection by differential refractive index measurement may also be performed. These detection methods can be performed by using a fluorescence (RF) detector, a differential refractive index (RI) detector, an ELSD (evaporative light scattering detector), or the like as a detector in the above-mentioned HPLC.

[0026] <Step of Preparing the Composition for Imprint Pattern Formation> The method for producing a composition of the present invention may further include a step of preparing the composition for imprint pattern formation (preparation step). For example, the composition for imprint pattern formation can be prepared by appropriately mixing the components contained in the composition for imprint pattern formation described below, and stirring by a known method as necessary. In preparing the composition, some of the components contained in the composition may be mixed first to form a solution, mixture, suspension, or the like, and then mixed with the other components. Preparation can also be performed in a clean room or the like. When preparation is performed in a clean room, if the composition for imprint pattern formation contains a component that is solid under the preparation environment (e.g., 23°C and 1 atmosphere), the component that is solid under the preparation environment (e.g., 23°C and 1 atmosphere) and at least some of the components that are liquid under the preparation environment can be mixed outside the clean room to prepare a mixed solution, and the mixed solution can then be moved into the clean room and mixed with the other components. The solid components do not need to be completely dissolved in the mixed solution; they may be in a dispersion or suspension state.

[0027] The composition for imprint pattern formation may be filtered through a filter. ２ It is preferable to pass the solution through a filter having an effective filtration area of ​​at least one time. An example of such an embodiment is the method described in paragraphs 0019 to 0028 of JP 2012-094821 A. The above description is incorporated herein by reference.

[0028] <Composition for Imprint Pattern Formation> The composition for imprint pattern formation may be in the form of a solution, a mixture, a suspension, etc. The composition for imprint pattern formation has a maximum molar absorption coefficient of 100 L mol at wavelengths of 190 to 400 nm. －１ ・cm －１ It is preferable that the compound contains a compound having a molar absorption coefficient of 80 L mol or less. －１ ・cm －１ It is preferable that the concentration is 60 L mol or less. －１ ・cm －１It is more preferable that the composition of the present invention is one of the following: Since the method for producing the composition of the present invention includes a detection step based on electric charge, even when the composition contains such a compound with low light absorption, it can be detected by the detection step based on electric charge. Examples of such a compound with low light absorption include a release agent, which will be described later.

[0029] The composition for imprint pattern formation preferably contains a compound that satisfies at least one of the conditions of a molecular weight of 300 or more and a boiling point of 300°C or more. Such a compound is considered to be easily detected in a detection step based on charge. A compound that satisfies at least one of the conditions of a molecular weight of 300 or more and a boiling point of 300°C or more has a maximum molar absorption coefficient of 100 L mol at the wavelength of 190 to 400 nm as described above. －１ ・cm －１ The molecular weight is preferably 400 or more, more preferably 500 or more. The upper limit of the molecular weight is not particularly limited, but is preferably, for example, 100,000 or less. It can also be 10,000 or less, or 2,000 or less. The boiling point is preferably 320°C or more, more preferably 350°C or more. The upper limit of the boiling point is not particularly limited, but is preferably, for example, 1,000°C or less.

[0030] [Polymerizable Compound] The composition for imprint pattern formation preferably contains a polymerizable compound. The polymerizable compound used in the present invention is preferably liquid at 25°C. By using a compound that is liquid at 25°C, the composition for imprint pattern formation can be configured to be substantially free of solvent. Here, "substantially free of solvent" means, for example, that the content of solvent in the composition for imprint pattern formation is 3% by mass or less, further 1% by mass, particularly 0.5% by mass or less, and preferably 0.1% by mass or less. A compound that is liquid at 25°C is preferably stored at a temperature above its freezing point before preparation, more preferably stored at a temperature above its freezing point but below 25°C before preparation, and even more preferably stored at a temperature above its freezing point but below 23°C before preparation.

[0031] The polymerizable compound may be either a monofunctional polymerizable compound having only one polymerizable group or a polyfunctional polymerizable compound having two or more polymerizable groups. An embodiment in which the composition for imprint pattern formation contains a monofunctional polymerizable compound and a polyfunctional polymerizable compound is also one of the preferred embodiments of the present invention.

[0032] -Monofunctional Polymerizable Compound- The type of monofunctional polymerizable compound used in the present invention is not particularly limited as long as it does not deviate from the spirit of the present invention. The monofunctional polymerizable compound used in the present invention preferably has a plastic structure. The present invention may contain only one type of monofunctional polymerizable compound, or may contain two or more types. The molecular weight of the monofunctional polymerizable compound used in the present invention is preferably 1,000 or less, more preferably 800 or less. The lower limit of the molecular weight is not particularly limited, but can be, for example, 100 or more. The boiling point at 101,325 Pa of the monofunctional polymerizable compound used in the present invention is preferably 85°C or higher, more preferably 90°C or higher. The upper limit of the boiling point is not particularly limited, but can be, for example, 400°C or lower. The type of polymerizable group possessed by the monofunctional polymerizable compound used in the present invention is not particularly limited, but examples include an ethylenically unsaturated bond-containing group and an epoxy group, with an ethylenically unsaturated bond-containing group being preferred. Examples of the ethylenically unsaturated bond-containing group include a group containing a (meth)acrylic group, a vinyl group, a vinyl ether group, etc., with a group containing a (meth)acrylic group being more preferred, and a group containing an acrylic group being even more preferred. Furthermore, the group containing a (meth)acrylic group is preferably a (meth)acryloyloxy group. That is, in the present invention, the monofunctional polymerizable compound is preferably a (meth)acrylate. The type of atoms constituting the monofunctional polymerizable compound used in the present invention is not particularly limited, but is preferably composed only of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, silicon atoms, and halogen atoms, more preferably composed only of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, and halogen atoms, and even more preferably composed only of atoms selected from carbon atoms, oxygen atoms, and hydrogen atoms. The Onishi parameter of the monofunctional polymerizable compound used in the present invention is preferably 4.0 or less, more preferably 3.8 or less. The lower limit of the Onishi parameter is not particularly limited, but can be, for example, 2.2 or more.

[0033] The monofunctional polymerizable compound used in the present invention preferably has a plastic structure. For example, at least one of the monofunctional polymerizable compounds used in the present invention preferably contains one group selected from the group consisting of the following (1) to (3): (1) a group containing at least one of an alkyl chain and an alkenyl chain, and at least one of an alicyclic structure and an aromatic ring structure, and having a total carbon number of 8 or more (hereinafter sometimes referred to as "group (1)"); (2) a group containing an alkyl chain having 4 or more carbon atoms (hereinafter sometimes referred to as "group (2)"); and (3) a group containing an alkenyl chain having 4 or more carbon atoms (hereinafter sometimes referred to as "group (3)"). This configuration makes it possible to efficiently reduce the elastic modulus of the cured film while reducing the amount of monofunctional polymerizable compound added to the imprint pattern-forming composition. Furthermore, the interfacial energy with the mold is reduced, thereby greatly reducing the mold release force (improving mold releasability). The alkyl chain and alkenyl chain in the above groups (1) to (3) may be linear, branched, or cyclic, and are preferably linear or branched. Furthermore, the above groups (1) to (3) preferably have the alkyl chain and / or alkenyl chain at the terminal of the monofunctional polymerizable compound, i.e., as an alkyl group and / or alkenyl group. This structure can further improve mold releasability. The alkyl chain and alkenyl chain may each independently contain an ether group (—O—) in the chain, but from the perspective of improving mold releasability, it is preferable that they do not contain an ether group. <<Group (1)>> The above group (1) has a total carbon number of 8 or more, preferably 10 or more. There is no particular upper limit on the total carbon number, but it is preferably 35 or less. Furthermore, the number of carbon atoms constituting the alkyl chain and / or alkenyl chain is preferably 5 or more, more preferably 6 or more, and even more preferably 8 or more. The upper limit of the number of carbon atoms constituting the alkyl chain and / or alkenyl chain is not particularly limited, but can be, for example, 25 or less. The cyclic structure is preferably a 3- to 8-membered monocyclic or fused ring.The number of rings constituting the fused ring is preferably two or three. The cyclic structure is more preferably a five- or six-membered ring, and even more preferably a six-membered ring. Furthermore, a monocyclic ring is more preferable. As the cyclic structure in the group (1), a cyclohexane ring, a benzene ring, or a naphthalene ring is more preferable, and a benzene ring is particularly preferable. Furthermore, the cyclic structure is preferably an aromatic ring structure. The number of cyclic structures in the group (1) may be one or two or more, but one or two is preferable, and one is more preferable. In the case of a fused ring, the fused ring is considered as one cyclic structure. The group (1) preferably has a structure represented by cyclic structure-alkyl chain or alkenyl chain-*, or *-cyclic structure-alkyl or alkenyl group, and more preferably a structure represented by *-cyclic structure-alkyl or alkenyl group. Here, * indicates the bonding position to another moiety. <<Group (2)>> The group (2) is a group containing an alkyl chain having 4 or more carbon atoms, and is preferably a group consisting only of an alkyl chain having 4 or more carbon atoms (i.e., an alkyl group). The number of carbon atoms in the alkyl chain is preferably 7 or more, and more preferably 9 or more. The upper limit of the number of carbon atoms in the alkyl chain is not particularly limited, but can be, for example, 25 or less. <<Group (3)>> The group (3) is a group containing an alkenyl chain having 4 or more carbon atoms, and is preferably a group consisting only of an alkenyl chain having 4 or more carbon atoms (i.e., an alkylene group). The number of carbon atoms in the alkenyl chain is preferably 7 or more, and more preferably 9 or more. The upper limit of the number of carbon atoms in the alkenyl chain is not particularly limited, but can be, for example, 25 or less. The monofunctional polymerizable compound used in the present invention is preferably a compound in which a polymerizable group is bonded to one or more of the groups (1) to (3) above, either directly or via a linking group, and more preferably a compound in which a polymerizable group is bonded directly to one of the groups (1) to (3). Examples of the linking group include -O-, -C(=O)-, and -CH. ２Examples of monofunctional polymerizable compounds preferably used in the present invention are listed below. However, it goes without saying that the present invention is not limited to these. The first group is most preferable, followed by the second and third groups. 2nd group 3rd group

[0034] As a commercially available monofunctional polymerizable compound, a compound having the above structure is sold by Shin-Nakamura Chemical Co., Ltd. and the like. The amount of the monofunctional polymerizable compound used in the present invention relative to the total polymerizable compounds in the composition for imprint pattern formation is preferably 5 to 30% by mass. The lower limit is preferably 8% by mass or more, more preferably 10% by mass or more. The upper limit is preferably 29% by mass or less, more preferably 28% by mass or less, and even more preferably 25% by mass or less. By setting the lower limit of the content to 5% by mass or more, mold releasability tends to be improved, and defects and mold breakage during mold release can be more effectively suppressed. Furthermore, by setting the upper limit of the content to 30% by mass or less, the pattern strength of the composition for imprint pattern formation can be maintained and pattern collapse can be suppressed when transferring a pattern of 20 nm or less. In the composition for imprint pattern formation, the mass ratio of the monofunctional polymerizable compound to the bifunctional polymerizable compound is preferably 1:18 to 1:3.

[0035] -Bifunctional Polymerizable Compound- The imprint pattern forming composition preferably contains a bifunctional polymerizable compound. The types of atoms constituting the bifunctional polymerizable compound used in the present invention are not particularly limited, but the bifunctional polymerizable compound is preferably composed only of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, and halogen atoms, and more preferably composed only of atoms selected from carbon atoms, oxygen atoms, and hydrogen atoms.

[0036] The type of polymerizable group in the bifunctional polymerizable compound is not particularly limited, but examples thereof include an ethylenically unsaturated bond-containing group and an epoxy group, with an ethylenically unsaturated bond-containing group being preferred. Examples of the ethylenically unsaturated bond-containing group include a group containing a (meth)acrylic group, a vinyl group, a vinyl ether group, etc., with a group containing a (meth)acrylic group being more preferred, and a group containing an acrylic group being more preferred. Furthermore, the group containing a (meth)acrylic group is preferably a (meth)acryloyloxy group. Examples of the polymerizable group in the present invention include a vinyl group, a (meth)acryloyloxy group, a (meth)acryloylamide group, an epoxy group, and a vinyl ether group. The bifunctional polymerizable compound used in the present invention may contain two different types of polymerizable groups, or may contain two of the same type of polymerizable groups.

[0037] The lower limit of the content of the bifunctional polymerizable compound in the composition for imprint pattern formation is preferably 70% by mass or more, more preferably 73% by mass or more, of the total polymerizable compounds, and the upper limit of the content is preferably 95% by mass or less, more preferably 93% by mass or less.

[0038] In the imprint pattern formation composition, preferably, 40% by mass or more of all polymerizable compounds contained in the composition contain at least one of an alicyclic structure and an aromatic ring structure, more preferably 40 to 100% by mass of at least one of an alicyclic structure and an aromatic ring structure, and even more preferably 40 to 90% by mass of at least one of an alicyclic structure and an aromatic ring structure. This configuration tends to lower the Onishi parameter and further improve etching resistance. The Onishi parameter is a value expressed as N / (NC-NO), where N is the total number of atoms, NC is the total number of carbon atoms, and NO is the total number of oxygen atoms. The cyclic structure is preferably a hydrocarbon group. The hydrocarbon group may be an aromatic hydrocarbon group or an alicyclic hydrocarbon group. The cyclic structure is preferably a five-membered or six-membered ring, or a fused ring thereof. The number of cyclic structures per molecule is preferably one. As described above, in the case of a fused ring, the fused ring is considered to be one cyclic structure.

[0039] Furthermore, the viscosity at 25°C of the bifunctional polymerizable compound containing at least one of an alicyclic structure and an aromatic ring structure is preferably 125 mPa·s or less, more preferably 50 mPa·s or less, even more preferably 30 mPa·s or less, and even more preferably 25 mPa·s or less. Such a configuration tends to improve mold filling. The lower limit of the viscosity is preferably 1 mPa·s or more, more preferably 5 mPa·s or more. Setting the viscosity within this range tends to improve etching resistance. The bifunctional polymerizable compound containing at least one of an alicyclic structure and an aromatic ring structure may be a bifunctional polymerizable compound having two or less atoms connecting two polymerizable groups, a bifunctional polymerizable compound having three or more atoms connecting two polymerizable groups, and / or a bifunctional polymerizable compound having two polymerizable groups containing an ethylenically unsaturated bond and having six or less atoms connecting the ethylenically unsaturated bonds. Hereinafter, more preferred ranges will be explained by dividing the compounds into bifunctional polymerizable compounds in which the number of atoms linking two polymerizable groups is 2 or less and / or bifunctional polymerizable compounds in which two polymerizable groups containing an ethylenically unsaturated bond are contained and the number of atoms linking the ethylenically unsaturated bonds is 6 or less (hereinafter sometimes referred to as "short-chain bifunctional compounds"), and bifunctional polymerizable compounds in which the number of atoms linking two polymerizable groups is 3 or more (hereinafter sometimes referred to as "long-chain bifunctional compounds").

[0040] <<Bifunctional Polymerizable Compound Having Two or Fewer Atoms Linking Two Polymerizable Groups>> The bifunctional polymerizable compound used in the present invention preferably includes a bifunctional polymerizable compound having two or fewer atoms linking two polymerizable groups and / or a bifunctional polymerizable compound (short-chain bifunctional compound) containing two polymerizable groups containing ethylenically unsaturated bonds and having six or fewer atoms linking the ethylenically unsaturated bonds. The use of the short-chain bifunctional compound can suppress pattern elongation during tension. This suppresses pattern deformation during mold release, and is presumed to prevent pattern collapse even during transfer of ultrafine patterns of 20 nm or less. Here, the number of atoms linking the two polymerizable groups refers to the smallest number of atoms connecting the polymerizable groups. For example, in the compound below, the portion surrounded by a square (acryloyloxy group) is the polymerizable group, and the atoms linking the polymerizable groups are the two carbon atoms indicated by 1 and 2 below. The number of atoms linking the ethylenically unsaturated bonds together is also considered in the same manner as above. For example, in the case of the above compound, the atoms linking the ethylenically unsaturated bonds together are six atoms: a carbon atom adjacent to the ethylenically unsaturated bond, an oxygen atom, the carbon atom shown in 1 above, the carbon atom shown in 2 above, an oxygen atom, and a carbon atom adjacent to the ethylenically unsaturated bond.

[0041] The atom linking the polymerizable groups in the short-chain bifunctional compound is preferably a carbon atom, a sulfur atom, an oxygen atom, a nitrogen atom or a silicon atom, more preferably a carbon atom.

[0042] The short-chain bifunctional compound used in the present invention has a polymerizable group -CR ２ -CR ２-polymerizable group (each R is independently a hydrogen atom or a substituent). Each R is preferably independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and even more preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. The hydrocarbon group is preferably an alkyl group or an aryl group, more preferably a linear or branched alkyl group, and even more preferably a linear alkyl group. The short-chain bifunctional compound used in the present invention is preferably a compound having a polymerizable group -CHR １ -CHR １ -Polymerizable group (R １ each independently represents a hydrocarbon group), a polymerizable group -CH ２ -CHR １ -Polymerizable group (R １ is a hydrocarbon group), or a polymerizable group —CH ２ -CH ２ -polymerizable group, and the polymerizable group -CHR １ -CHR １ -Polymerizable group (R １ are each independently a hydrocarbon group).

[0043] The short-chain bifunctional compound used in the present invention may contain a cyclic structure as a side chain, i.e., as a substituent bonded to the atom connecting two polymerizable groups. However, since the inclusion of a cyclic structure increases the viscosity of the compound, it is preferable that the compound does not contain a cyclic structure from the viewpoint of reducing viscosity. The viscosity of the short-chain bifunctional compound used in the present invention at 25°C is preferably 30 mPa·s or less, more preferably 10 mPa·s or less, even more preferably 7 mPa·s or less, and even more preferably 5 mPa·s or less. The lower limit of the viscosity is not particularly limited, but may be 1 mPa·s or more. From the viewpoint of residual film uniformity, the boiling point of the short-chain bifunctional compound used in the present invention at 101,325 Pa (1 atmosphere) is preferably 210°C or more, more preferably 230°C or more, and even more preferably 240°C or more. The upper limit of the boiling point of the short-chain bifunctional compound is not particularly limited, but for example, even 500°C or less is sufficiently practical. The Onishi parameter of the short-chain bifunctional compound used in the present invention is preferably 5.5 or less, more preferably 5.0 or less. The lower limit of the Onishi parameter is not particularly limited, but may be, for example, 3.0 or more, or even 4.0 or more.

[0044] Examples of short-chain bifunctional compounds that can be used in the present invention are listed below, but it goes without saying that the present invention is not limited to these.

[0045] The content of the short-chain bifunctional compound in all polymerizable compounds contained in the composition for imprint pattern formation is preferably 1 to 80 mass %, more preferably 10 to 40 mass %, and even more preferably 10 to 20 mass %. The composition for imprint pattern formation may contain only one type of short-chain bifunctional compound, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.

[0046] <<Bifunctional Polymerizable Compound in Which the Number of Atoms Linking Two Polymerizable Groups is Three or More>> The bifunctional polymerizable compound used in the present invention may contain a bifunctional compound other than the above-described short-chain bifunctional compound. Examples of bifunctional compounds other than short-chain bifunctional compounds include bifunctional polymerizable compounds (long-chain bifunctional compounds) in Which the number of atoms linking two polymerizable groups is three or more. By incorporating such a compound, volatilization of the composition is suppressed, and the residual film uniformity of the cured pattern after imprinting is improved. The number of atoms linking the polymerizable groups in the long-chain bifunctional compound is preferably 3 to 12, more preferably 3 to 9, and even more preferably 3 to 5.

[0047] The viscosity of the long-chain bifunctional compound used in the present invention at 25°C is preferably 130 mPa·s or less, more preferably 20 mPa·s or less, and even more preferably 10 mPa·s or less. The lower limit of the viscosity is not particularly limited, but may be 1 mPa·s or more. From the viewpoint of residual film uniformity, the boiling point of the long-chain bifunctional compound used in the present invention is preferably 230°C or more, more preferably 250°C or more, and even more preferably 258°C or more at 101,325 Pa (1 atmosphere). The upper limit of the boiling point of the long-chain bifunctional compound is not particularly limited, but for example, a boiling point of 300°C or less is sufficiently practical. The Onishi parameter of the long-chain bifunctional compound used in the present invention is preferably 4.5 or less. The lower limit of the Onishi parameter is not particularly limited, but may be, for example, 3.0 or more, or even 3.1 or more.

[0048] The long-chain bifunctional compound of the present invention may have a cyclic structure (alicyclic structure and / or aromatic ring structure), or may not contain a cyclic structure. In addition, the cyclic structure may be partly an atom connecting two polymerizable groups, or may contain a cyclic structure as a substituent bonded to an atom connecting two polymerizable groups.

[0049] When the composition for imprint pattern formation contains a long-chain bifunctional compound, the content thereof is preferably 30 to 80% by mass, more preferably 35 to 75% by mass, even more preferably 40 to 75% by mass, and even more preferably 60 to 75% by mass, of all polymerizable compounds. The composition for imprint pattern formation may contain only one long-chain bifunctional compound, or may contain two or more long-chain bifunctional compounds. When two or more long-chain bifunctional compounds are contained, the total amount is preferably within the above-mentioned range. Furthermore, in the present invention, the composition for imprint pattern formation may be configured to be substantially free of a long-chain bifunctional compound. "Substantially free" means that the content is 1% by mass or less of all polymerizable compounds contained in the composition for imprint pattern formation.

[0050] Hereinafter, more preferred ranges will be explained by dividing the compounds into bifunctional polymerizable compounds that contain at least one of an alicyclic structure and an aromatic ring structure and have three or more atoms connecting two polymerizable groups (hereinafter, may be referred to as a "long-chain cyclic group-containing bifunctional compound") and bifunctional polymerizable compounds that do not contain an alicyclic structure or an aromatic ring structure and have three or more atoms connecting two polymerizable groups (hereinafter, may be referred to as a "long-chain cyclic group-free bifunctional compound").

[0051] <<<Bifunctional Polymerizable Compound Having At Least an Alicyclic Structure and an Aromatic Ring Structure, and Having Three or More Atoms Linking Two Polymerizable Groups>>> A long-chain bifunctional compound having at least an alicyclic structure and an aromatic ring structure, and having three or more atoms linking two polymerizable groups, will be described below. The long-chain cyclic group-containing bifunctional compound is preferably represented by polymerizable group-L-cyclic structure-L-polymerizable group (each L is independently a single bond or a linking group). When L is a linking group, it is preferably an alkylene group, more preferably an alkylene group having 1 to 3 carbon atoms, and even more preferably an alkylene group having 1 or 2 carbon atoms. The long-chain cyclic group-containing bifunctional compound is preferably a (meth)acrylate.

[0052] The viscosity at 25°C of the long-chain cyclic group-containing bifunctional compound used in the present invention is preferably 130 mPa·s or less, more preferably 20 mPa·s or less, and even more preferably 10 mPa·s or less. The lower limit of the viscosity is not particularly limited, but is preferably 1 mPa·s or more. From the viewpoint of residual film uniformity, the boiling point of the long-chain cyclic group-containing bifunctional compound used in the present invention is preferably 255°C or more, more preferably 260°C or more, at 101,325 Pa (1 atmosphere). The upper limit of the boiling point of the long-chain cyclic group-containing bifunctional compound is not particularly limited, but for example, 320°C or less is sufficiently practical. The Onishi parameter of the long-chain cyclic group-containing bifunctional compound used in the present invention is preferably 4.3 or less. The lower limit of the Onishi parameter is not particularly limited, but may be, for example, 3.0 or more, or even 3.1 or more.

[0053] Examples of the long-chain cyclic group-containing bifunctional compound are shown below, but it goes without saying that the long-chain cyclic group-containing bifunctional compound of the present invention is not limited to these.

[0054] When the composition for imprint pattern formation contains a long-chain cyclic group-containing bifunctional compound, the content thereof is preferably 10 to 80 mass %, more preferably 40 to 75 mass %, and even more preferably 60 to 75 mass %, of all polymerizable compounds. The composition for imprint pattern formation may contain only one type of long-chain cyclic group-containing bifunctional compound, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range. On the other hand, in the present invention, the composition for imprint pattern formation may also be configured so that it is substantially free of a long-chain cyclic group-containing bifunctional compound. "Substantially free" means that the content is 1 mass % or less of all polymerizable compounds contained in the composition for imprint pattern formation.

[0055] <<<Bifunctional Polymerizable Compounds Free of Alicyclic and Aromatic Structures, and Having Three or More Atoms Linking Two Polymerizable Groups>>> A long-chain bifunctional compound free of alicyclic and aromatic structures, and having three or more atoms linking two polymerizable groups, will now be described (long-chain cyclic group-free bifunctional compounds). The long-chain cyclic group-free bifunctional compound is preferably represented by a polymerizable group-linear or branched hydrocarbon group-polymerizable group structure. The hydrocarbon group is preferably an alkylene group, more preferably an alkylene group having 3 to 10 carbon atoms. The alkylene group is preferably a linear or branched alkylene group. In the case of a branched alkylene group, the branched chain of the alkylene group is preferably a methyl group. The long-chain cyclic group-free bifunctional compound is preferably a (meth)acrylate.

[0056] The viscosity of the long-chain cyclic group-free bifunctional compound at 25°C is preferably 50 mPa·s or less, more preferably 20 mPa·s or less, and even more preferably 10 mPa·s or less. The lower limit of the viscosity is not particularly limited, but may be, for example, 1 mPa·s or more, or even 3 mPa·s or more. From the viewpoint of residual film uniformity, the boiling point of the long-chain cyclic group-free bifunctional compound used in the present invention is preferably 230°C or more, more preferably 260°C or more, at 101,325 Pa (1 atmosphere). The upper limit of the boiling point of the long-chain cyclic group-free bifunctional compound is not particularly limited, but for example, 300°C or less is sufficiently practical. The Onishi parameter of the long-chain cyclic group-free bifunctional compound used in the present invention is preferably 4.5 or less. The lower limit of the Onishi parameter is not particularly limited, but may be, for example, 3.0 or more, or even 3.5 or more.

[0057] Examples of the long-chain cyclic group-free bifunctional compound are shown below. It goes without saying that the long-chain cyclic group-free bifunctional compound of the present invention is not limited to these.

[0058] When the imprint pattern-forming composition contains a bifunctional compound not containing a long-chain cyclic group, the lower limit of the content of the bifunctional compound not containing a long-chain cyclic group in all polymerizable compounds is preferably 1% by mass or more, more preferably 5% by mass or more. Furthermore, the upper limit of the content of the bifunctional compound not containing a long-chain cyclic group is preferably 30% by mass or less, more preferably 15% by mass or less, of all polymerizable compounds contained in the imprint pattern-forming composition. The imprint pattern-forming composition may contain only one type of bifunctional compound not containing a long-chain cyclic group, or may contain two or more types. When two or more types are contained, the total amount is within the above-mentioned range. On the other hand, in the present invention, the imprint pattern-forming composition may be configured to be substantially free of a bifunctional compound not containing a long-chain cyclic group. For example, the content of the bifunctional compound not containing a long-chain cyclic group in all polymerizable compounds may be 3% by mass or less, or may be 1% by mass or less.

[0059] <<Trifunctional or Higher Functional Polymerizable Compounds>> The composition for imprint pattern formation may or may not contain a trifunctional or higher functional polymerizable compound. In the present invention, the content of trifunctional or higher functional polymerizable compounds among all polymerizable compounds contained in the composition for imprint pattern formation is preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass or less. By setting the content within such a range, it becomes possible to suppress an increase in the viscosity of the composition and maintain good filling properties. Furthermore, the total amount of polymerizable compounds relative to the total solid content of the composition for imprint pattern formation is preferably 90% by mass or more. Furthermore, the upper limit of the above total amount is preferably 99% by mass or less.

[0060] [Photopolymerization initiator] The composition for imprint pattern formation preferably contains a photopolymerization initiator. As the photopolymerization initiator used in the present invention, any compound can be used as long as it generates an active species that polymerizes the above-mentioned polymerizable compound upon irradiation with light. As the photopolymerization initiator, a radical photopolymerization initiator or a cationic photopolymerization initiator is preferred, and a radical photopolymerization initiator is more preferred.

[0061] The radical photopolymerization initiator used in the present invention may be, for example, a commercially available initiator. Examples of such initiators that can be preferably used include those described in paragraph 0091 of JP-A-2008-105414. Among these, acetophenone-based compounds, acylphosphine oxide-based compounds, and oxime ester-based compounds are particularly preferred from the viewpoints of curing sensitivity and absorption characteristics.

[0062] Specifically, the following photopolymerization initiators can be mentioned.

[0063] The photopolymerization initiator may be used alone, but it is also preferable to use two or more types in combination. When two or more types are used in combination, it is more preferable to use two or more types of radical photopolymerization initiators in combination.

[0064] The content of the photopolymerization initiator used in the present invention is preferably 0.01 to 15% by mass, more preferably 0.1 to 10% by mass, even more preferably 0.5 to 7% by mass, and even more preferably 1 to 5% by mass, based on the total composition excluding the solvent. When two or more photopolymerization initiators are used, the total amount falls within the above range. A photopolymerization initiator content of 0.01% by mass or more tends to further improve sensitivity (fast curing), resolution, line edge roughness, and coating strength, and is therefore preferred. Furthermore, a photopolymerization initiator content of 15% by mass or less tends to further improve light transmittance, colorability, handleability, and the like, and is therefore preferred.

[0065] [Release Agent] The composition for imprint pattern formation preferably further contains a release agent. The type of release agent used in the present invention is not particularly limited as long as it does not deviate from the spirit of the present invention, but it is preferably an additive that is unevenly distributed at the interface with the mold and has the function of facilitating release from the mold. Specific examples include surfactants and non-polymerizable compounds that have a polyalkylene glycol structure having at least one hydroxyl group at the terminal or in which the terminal hydroxyl group is etherified, and that are substantially free of fluorine atoms and silicon atoms (hereinafter sometimes referred to as "non-polymerizable compounds with releasability").

[0066] The release agent may be contained in one kind or in two or more kinds. When the release agent is contained, the total content is preferably 0.1 to 20 mass % of the total solid content.

[0067] <<Surfactant>> The surfactant is preferably a nonionic surfactant. A nonionic surfactant is a compound having at least one hydrophobic moiety and at least one nonionic hydrophilic moiety. The hydrophobic moiety and the hydrophilic moiety may be located at the end or inside of the molecule. The hydrophobic moiety is composed of a hydrophobic group selected from a hydrocarbon group, a fluorine-containing group, and a Si-containing group, and the number of carbon atoms in the hydrophobic moiety is preferably 1 to 25, more preferably 2 to 15, even more preferably 4 to 10, and most preferably 5 to 8. The nonionic hydrophilic moiety preferably has at least one group selected from the group consisting of an alcoholic hydroxyl group, a phenolic hydroxyl group, an ether group (preferably a polyoxyalkylene group or a cyclic ether group), an amide group, an imide group, a ureido group, a urethane group, a cyano group, a sulfonamide group, a lactone group, a lactam group, and a cyclocarbonate group. The nonionic surfactant may be any of hydrocarbon-based, fluorine-based, Si-based, or fluorine / Si-based nonionic surfactants, but fluorine-based or Si-based surfactants are more preferred, and fluorine-based surfactants are even more preferred. Here, the term "fluorine / Si-based surfactant" refers to a surfactant that has the functions of both a fluorine-based surfactant and a Si-based surfactant. Commercially available fluorine-based nonionic surfactants include Fluorad FC-4430 and FC-4431 manufactured by Sumitomo 3M Limited, Surflon S-241, S-242, and S-243 manufactured by Asahi Glass Co., Ltd., Eftop EF-PN31M-03, EF-PN31M-04, EF-PN31M-05, EF-PN31M-06, and MF-100 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., Polyfox PF-636, PF-6320, PF-656, and PF-6520 manufactured by OMNOVA, and Futergent 250, 251, 222F, and 212M manufactured by Neos Corporation. Examples of such a solvent include DFX-18 manufactured by Daikin Industries, Ltd., Unidyne DS-401, DS-403, DS-406, DS-451, and DSN-403N manufactured by DIC Corporation, Megafac F-430, F-444, F-477, F-553, F-556, F-557, F-559, F-562, F-565, F-567, F-569, and R-40 manufactured by DuPont, and Capstone FS-3100 and ZONYL FSO-100 manufactured by DuPont.When the composition for imprint pattern formation contains a surfactant, the content of the surfactant is preferably 0.1 to 10 mass %, more preferably 0.2 to 5 mass %, and even more preferably 0.5 to 5 mass %, of the total composition excluding the solvent. The composition for imprint pattern formation may contain only one type of surfactant, or may contain two or more types. When two or more types are contained, the total amount thereof preferably falls within the above range.

[0068] <<Non-polymerizable Compound Having Mold-Releasability>> The composition for imprint pattern formation may contain a non-polymerizable compound having at least one hydroxyl group at its terminal or a polyalkylene glycol structure in which the terminal hydroxyl group has been etherified, and substantially containing no fluorine atoms or silicon atoms. Here, the term "non-polymerizable compound" refers to a compound having no polymerizable groups. Furthermore, "substantially containing no fluorine atoms or silicon atoms" means, for example, that the total content of fluorine atoms and silicon atoms in the non-polymerizable compound is 1% by mass or less, preferably 0.1% by mass or less, and more preferably no fluorine atoms or silicon atoms at all. The absence of fluorine atoms or silicon atoms improves compatibility with polymerizable compounds, resulting in improved coating uniformity, pattern formability during imprinting, and line edge roughness after dry etching, particularly in a solvent-free composition for imprint pattern formation. The polyalkylene glycol structure contained in the non-polymerizable compound having mold releasability is preferably a polyalkylene glycol structure containing an alkylene group having 1 to 6 carbon atoms, more preferably a polyethylene glycol structure, a polypropylene glycol structure, a polybutylene glycol structure, or a mixed structure thereof, still more preferably a polyethylene glycol structure, a polypropylene glycol structure, or a mixed structure thereof, and particularly preferably a polypropylene glycol structure.

[0069] Furthermore, the compound may be substantially composed of only a polyalkylene glycol structure, excluding the terminal substituent. Here, "substantially" refers to the content of components other than the polyalkylene glycol structure being 5% by mass or less of the total, preferably 1% by mass or less. In particular, it is preferable that the non-polymerizable compound having mold-releasability contains a compound substantially composed of only a polypropylene glycol structure. The polyalkylene glycol structure preferably has 3 to 100 alkylene glycol structural units, more preferably 4 to 50, even more preferably 5 to 30, and particularly preferably 6 to 20. The non-polymerizable compound having mold-releasability preferably has at least one terminal hydroxyl group or an etherified terminal hydroxyl group. As long as the compound has at least one terminal hydroxyl group or the terminal hydroxyl group is etherified, the remaining terminal may be a hydroxyl group, or the hydrogen atom of the terminal hydroxyl group may be substituted. Examples of groups whose terminal hydroxyl groups may be substituted with hydrogen atoms include alkyl groups (i.e., polyalkylene glycol alkyl ethers) and acyl groups (i.e., polyalkylene glycol esters). Polyalkylene glycols in which all terminals are hydroxyl groups are more preferred. Compounds having multiple (preferably two or three) polyalkylene glycol chains via linking groups can also be preferably used, but polyalkylene glycol chains with a straight chain structure, without branching, are preferred. Diol-type polyalkylene glycols are particularly preferred. Specific preferred examples of non-polymerizable compounds with releasability include polyethylene glycol, polypropylene glycol (e.g., manufactured by Wako Pure Chemical Industries, Ltd.), their mono- or dimethyl ethers, mono- or dibutyl ethers, mono- or dioctyl ethers, mono- or dicetyl ethers, monostearate esters, monooleate esters, polyoxyethylene glyceryl ethers, polyoxypropylene glyceryl ethers, and trimethyl ethers thereof. The weight-average molecular weight of the non-polymerizable compound with releasability is preferably 150 to 6,000, more preferably 200 to 3,000, even more preferably 250 to 2,000, and even more preferably 300 to 1,200.

[0070] Further, examples of the non-polymerizable compound having releasability that can be used in the present invention include a non-polymerizable compound having a releasability and having an acetylene diol structure. Examples of commercially available products of such non-polymerizable compounds having releasability include Olfine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.).

[0071] Specific examples of non-polymerizable compounds having releasability that are preferably used in the present invention include the following compounds: In the following structural formula, n, a, b, and c each represent the number of repeats, n is 5 to 15, and a+b+c is 11.

[0072] When the composition for imprint pattern formation contains a non-polymerizable compound having releasability, the content of the non-polymerizable compound having releasability is preferably 0.1 to 20 mass %, more preferably 0.2 to 15 mass %, even more preferably 0.5 to 10 mass %, even more preferably 0.5 to 5 mass %, and still more preferably 0.5 to 4 mass % of the total composition excluding the solvent. The composition for imprint pattern formation may contain only one type of non-polymerizable compound having releasability, or may contain two or more types. When two or more types are contained, the total amount thereof preferably falls within the above range.

[0073] <Other Components> The composition for imprint pattern formation used in the present invention may contain other components in addition to those described above, provided that they do not deviate from the spirit of the present invention. Examples of other components include sensitizers, antioxidants, polymerization inhibitors (e.g., 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical), ultraviolet absorbers, solvents, etc. These compounds may each be contained alone or in combination of two or more. For details of these compounds, please refer to the descriptions in paragraphs

[0061] to

[0064] of JP 2014-170949 A, the contents of which are incorporated herein by reference.

[0074] Preferably, the imprint pattern-forming composition is substantially free of a solvent. Thus, the imprint pattern-forming composition does not necessarily contain a solvent, but a solvent may be optionally added, for example, when fine-tuning the viscosity of the composition. The types of solvents that can be preferably used in the composition of the present invention are those commonly used in photoimprint pattern-forming compositions and photoresists, and are not particularly limited as long as they dissolve and uniformly disperse the compounds used in the present invention and do not react with these components. Examples of solvents that can be used in the present invention include those described in paragraph

[0088] of JP 2008-105414 A, the contents of which are incorporated herein by reference. Furthermore, the imprint pattern-forming composition is preferably substantially free of components with a molecular weight of 2,000 or more. "Substantially free" means that the content is 3% by mass or less of the total solids content of the imprint pattern-forming composition, preferably 1% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0.1% by mass or less. The lower limit of the content is not particularly limited, and may be 0% by mass.

[0075] <Characteristics of the Imprint Pattern Formation Composition> The Onishi parameter of the imprint pattern formation composition is preferably 5.0 or less, more preferably 4.0 or less, even more preferably 3.9 or less, even more preferably 3.7 or less, and even more preferably 3.6 or less. By adjusting the Onishi parameter to 5.0 or less, etching resistance tends to be further improved. The lower limit of the Onishi parameter may be 3.0 or more, or even 3.5 or more. The viscosity of the imprint pattern formation composition at 23°C is preferably 20 mPa·s or less, more preferably 10 mPa·s or less, and even more preferably 8 mPa·s or less. The lower limit of the viscosity is not particularly limited, but can be, for example, 5 mPa·s or more. By adjusting the viscosity within this range, the imprint pattern formation composition can easily penetrate into the mold, thereby shortening the mold filling time. Furthermore, it is possible to improve pattern formability and throughput.

[0076] (Method for inspecting a composition) The method for inspecting a composition of the present invention comprises the steps of using a composition for imprint pattern formation to detect components contained in the composition by light absorption, and detecting components contained in the composition by a method comprising a step of charging the composition or particles obtained from the composition. Preferred aspects of the composition for imprint pattern formation, the step of detecting components contained in the composition by light absorption, and the step of detecting components contained in the composition by a method comprising a step of charging the composition or particles obtained from the composition, in the method for inspecting a composition of the present invention, are all the same as the preferred aspects of the method for producing a composition of the present invention.

[0077] (Cured Product and Method for Producing a Pattern) The present invention also discloses a cured product obtained by curing the imprint pattern-forming composition. The cured product is preferably provided on a silicon substrate. The pattern-producing method of the present invention includes applying the imprint pattern-forming composition to a substrate or a mold, and irradiating the imprint pattern-forming composition with light while sandwiched between the mold and the substrate. When the imprint pattern-forming composition is applied to a substrate, an intermediate layer may be further formed on the surface of the substrate to which the imprint pattern-forming composition is applied. Forming an intermediate layer may increase adhesion between the cured product and the substrate, thereby suppressing peeling of the cured product from the substrate when released from the mold. The intermediate layer is not particularly limited and any intermediate layer known in the art may be used, such as the intermediate layers described in paragraphs 0013 to 0073 of WO 2021 / 166992. Furthermore, a liquid film may be further provided on the surface of the intermediate layer opposite the substrate (i.e., the surface to which the imprint pattern-forming composition is applied). The liquid film preferably contains a radically polymerizable compound that is liquid at 23°C and 1 atmosphere. Examples of such a liquid film and a liquid film-forming composition used to form such a liquid film include those described in paragraphs 0135 to 0159 of WO 2021 / 166992. The disclosures of these specifications are incorporated herein by reference.

[0078] The pattern formed by the pattern manufacturing method of the present invention is also useful as an etching resist (lithography mask). When using the pattern as an etching resist, first, a substrate made of, for example, SiO ２ Using a silicon substrate (e.g., silicon wafer) on which a thin film such as silicon dioxide is formed, a fine pattern, for example, on the nano- or micro-order, is formed on the substrate by the pattern manufacturing method of the present invention. The present invention is particularly advantageous in that it can form fine patterns on the nano-order, and can even form patterns with sizes of 100 nm or less, further 25 nm or less, and particularly 20 nm or less. The lower limit of the pattern size formed by the pattern manufacturing method of the present invention is not particularly limited, but can be, for example, 10 nm or more. Here, the pattern size refers to the smallest dimension of the pattern formed by the pattern manufacturing method of the present invention. In the case of a line pattern, it refers to the line width of the pattern, and in the case of a pillar / hole pattern, it refers to the diameter of the pattern. Furthermore, the imprint pattern preferably includes any of the shapes of lines, holes, and pillars. Among these, an imprint pattern including any of the shapes of lines, holes, and pillars with sizes of 100 nm or less is more preferred, and an imprint pattern including any of the shapes of lines, holes, and pillars with sizes of 25 nm or less is even more preferred. Subsequently, the imprint pattern is etched with hydrogen fluoride or the like in the case of wet etching, or CF4 in the case of dry etching. ４ and CHF ３ / CF ４ By etching using an etching gas such as a Ar / Ar mixed gas, a desired pattern can be formed on the substrate. The pattern has good etching resistance, particularly against dry etching. That is, the pattern obtained by the manufacturing method of the present invention is preferably used as a lithography mask. For details of the pattern manufacturing method, please refer to paragraphs 0057 to 0071 of JP 2015-185798 A, the contents of which are incorporated herein by reference.

[0079] The above-described pattern can also be used as an etching mask to manufacture a semiconductor device. Specifically, a substrate is processed using the above-described pattern as an etching mask. For example, dry etching is performed using the pattern as an etching mask to selectively remove an upper layer portion of the substrate. By repeating such processing on the substrate, a semiconductor device can be obtained. The semiconductor device is, for example, an LSI (large scale integrated circuit).

[0080] (Composition) The composition of the present invention comprises a polymerizable compound, a polymerizable compound having a maximum molar absorption coefficient of 100 L·mol at wavelengths of 190 to 400 nm, and a polymerizable compound having a maximum molar absorption coefficient of 100 L·mol at wavelengths of 190 to 400 nm. －１ ・cm －１ or below, and compounds that satisfy at least one of the conditions of having a molecular weight of 300 or more and a boiling point of 300°C or more. The composition of the present invention is preferably a composition produced by the method for producing a composition of the present invention. The composition of the present invention is preferably a composition to be subjected to the method for testing a composition of the present invention.

[0081] The composition of the present invention comprises a polymerizable compound and a polymerizable compound having a maximum molar absorption coefficient of 100 L mol in the wavelength range of 190 to 400 nm. －１ ・cm －１ Polymerizable compounds can generally be detected by detecting the components contained therein through light absorption (for example, detection using ultraviolet light). However, compounds with a maximum molar absorption coefficient of 100 L mol or less at wavelengths of 190 to 400 nm are also included. －１ ・cm －１The compounds described below are components with very low light absorption, and are difficult to detect by detecting components by light absorption (e.g., detection by ultraviolet light). Furthermore, the composition for imprint pattern formation contains a compound that satisfies at least one of the conditions of a molecular weight of 300 or more and a boiling point of 300°C or more. It is believed that such compounds are easily detected by a detection process using electrical charge. In other words, the composition of the present invention can be quality-tested for the first time by using the composition inspection method of the present invention to detect components that should be contained, such as missing components, incorrect addition amounts, loss due to volatilization, or denaturation in the composition.

[0082] The composition of the present invention is preferably a composition used to form an imprint pattern, and more preferably a composition used as a composition for forming an imprint pattern in the pattern manufacturing method of the present invention. －１ ・cm －１ or below, and the compound satisfying at least one of the conditions of having a molecular weight of 300 or more and a boiling point of 300° C. or more are the same as the preferred aspects of these components in the composition for imprint pattern formation used in the method for producing a composition of the present invention described above. Other preferred aspects of the composition of the present invention are the same as the preferred aspects of the composition for imprint pattern formation used in the method for producing a composition of the present invention described above.

[0083] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

[0084] <Preparation of Composition> A method for preparing a composition for imprint pattern formation will be described below. Details of each component used in preparing the composition are shown in the table below. Components in the columns marked with "-" in the table were not used.

[0085] [Preparation of Imprint Pattern Forming Composition S-1] Outside a clean room, 10% by mass of A-1 (total amount used: 43 parts by mass) and 2 parts by mass of C-1 were mixed in a container to form a suspension. In a clean room, 7.5% by mass of A-1 (total amount used: 43 parts by mass) and another 7.5% by mass of A-1 (43 parts by mass) were each transferred into a clean bottle. 75% by mass of A-1 (total amount used: 43 parts by mass) was mixed with 30 parts by mass of A-2, 20 parts by mass of B-1, 2 parts by mass of C-2, and 3 parts by mass of D-1 in a mixing container in the clean room. This mixture was used as a main mixture. The suspension was added to the main mixture. 7.5% by mass of A-1, which had been transferred using a clean bottle, was added to the container containing the suspension, stirred, and then added to the main mixture. This process was repeated twice to prepare a composition. The above composition was filtered using a composite filter consisting of a nylon filter with a pore size of 0.02 μm and a UPE filter with a pore size of 0.003 μm connected in this order to prepare composition for forming an imprint pattern S-1.

[0086] [Preparation of Composition S-2 for Imprint Pattern Formation] Composition S-2 for imprint pattern formation was prepared in the same manner as in the preparation of Composition S-1 for imprint pattern formation, except that A-3 was used instead of A-1 and the other components were changed as shown in the table below.

[0087]

[0088]

[0089] The structures of the compounds listed in the table are as follows:

[0090] [Polymerizable compounds] A-1: ​​Phenylethylene glycol diacrylate A-2: Benzyl acrylate A-3: m-Xylene diacrylate A-4: Naphthyl methyl acrylate A-5: NPGDA (neopentyl glycol diacrylate) A-6: Isobornyl acrylate A-7: 1,4-cis-butenediol diacrylate A-8: Stearyl acrylate A-9: 1,6-hexanediol diacrylate A-10: Dimethylol tricyclodecane diacrylate

[0091] [Polymerization initiator] ・B-1: Omnirad 819 (manufactured by IGM Resins BV) ・B-2: Omnirad TPO (manufactured by IGM Resins BV) ・B-3: Omnirad TPO-L (manufactured by IGM Resins BV)・B-4: Omnirad 1173 (manufactured by IGM Resins BV) ・B-5: Omnirad 369 (manufactured by IGM Resins BV) ・B-6: Omnirad 379 (manufactured by IGM Resins BV) ・B-7: Omnirad 907 (manufactured by IGM Resins BV) ・B-8: Omnirad 651 (manufactured by IGM Resins BV) B-9: Irgacure OXE01 (manufactured by BASF) B-10: Irgacure OXE02 (manufactured by BASF)

[0092] [Release agents] C-1: Polyoxyethylene stearyl ether SR-705 (manufactured by BLAUNON) C-2: SR-730 (manufactured by BLAUNON) C-3: Emulgen 320P (manufactured by Kao Chemicals) C-4: PPO (polypropylene oxide) C-5: Compound having the following structure, where l+m+n=11 C-6: Compound having the following structure C-7: Futergent 212M

[0093] [Sensitizers] D-1: Compounds having the following structures D-2: Dibutoxyanthracene D-3: 4,4'-bis(diethylamino)benzophenone D-4: 2-isopropylthioxanthone

[0094] [Polymerization inhibitors] E-1: BHT (dibutylhydroxytoluene), E-2: MEHQ (hydroquinone monomethyl ether), E-3: 4-OH-TEMPO (4-hydroxy-TEMPO free radical), E-4: Cupferron (ammonium nitrosophenylhydroxylamine)

[0095] <Detection> [Sample Preparation] 1 g of each composition for imprint pattern formation was weighed out, and 99 g of acetonitrile was added to dilute it 100 times to prepare a sample.

[0096] [Detection of contained components by a method including a step of charging a composition or particles obtained from the composition (MS)] Each sample was subjected to LC / MS (liquid chromatography mass spectrometry) under the following measurement conditions to detect contained components. - Measurement conditions - Apparatus: Agilent LC / MS G1956B Column: TOSOH ODS-80Ts 5 mm 2.0 mmf × 150 mm Eluent A: MQ water (10 mM CH3COONH4) Eluent B: MeOH (10 mM CH3COONH4) Gradient: In a mixture of eluent A and eluent B, the proportion of eluent B was varied linearly from 50% (0 min), 100% (30 min), and 100% (45 min) Flow rate: 0.2 mL / min Injection volume: 2 mL Oven temperature: 40°C Detection: ESI-Posi-SIM mode

[0097] [Detection of contained components by light absorption, or detection of contained components by a method including a step of charging the composition or particles obtained from the composition (CAD)] Each sample was subjected to HPLC-Corona CAD (high performance liquid chromatography charged aerosol detection) under the following measurement conditions to detect the contained components. -Measurement conditions- Equipment: U-3000 + Corona Veo (Thermo Fisher) Column: Hypresil gold 1.7mm 2.1 x 100 mm (Thermo) Eluent A: MQ water (10mM AcONH4) Eluent B: Acetonitrile Gradient: In a mixture of eluent A and eluent B, the proportion of eluent B was varied linearly from 15% (0 min), 100% (10 min), 100% (15 min), 15% (15.01 min), and 15% (20 min) Flow rate: 0.5mL / min Injection volume: 2mL Column oven temperature: 35°C Detection: UV254nm / CAD (55°C) When UV254nm is used as the detection method, the contained components are detected by light absorption, and when CAD (55°C) is used, detection is performed by charged aerosol detection. For example, in Example 1, the detection results when UV254 nm is used as the detection method and the detection results by the above-mentioned "detection of components by a method including a step of charging a composition or particles obtained from the composition (MS)" are used.

[0098] [Evaluation] In each example and comparative example, the analyses described in the table below were performed, and examples in which quantitative testing of all components was possible are marked with "pass" in the table below, and examples in which quantitative testing of all components was not possible are marked with "fail" in the table below. "UV" means that the sample was analyzed using only "UV". "UV+MS" means that the sample was analyzed using "UV" and "MS". "UV+CAD" means that the sample was analyzed using "UV" and "CAD".

[0099]

[0100]

[0101] As can be seen from the above results, the method for producing a composition of the present invention makes it possible to detect all components used in the composition, and it can be said that a wide variety of components can be used in the composition. In comparison, the method for producing a composition of Comparative Example 1, which only performs detection by UV, cannot detect some components, and it can be said that the components that can be used in the composition are limited.

Claims

1. A method for producing a composition, comprising: a step of using a composition for imprint pattern formation, and detecting components contained in the composition by light absorption; and a step of detecting components contained in the composition by a method comprising a step of charging the composition or particles obtained from the composition.

2. The method for producing a composition according to claim 1, wherein the composition for imprint pattern formation contains a polymerizable compound.

3. The composition for imprint pattern formation has a maximum molar absorption coefficient of 100 L mol at wavelengths of 190 to 400 nm. －１ ・cm －１ 3. A method for producing the composition of claim 1 or 2, comprising a compound that is:

4. A method for producing the composition according to claim 1 or 2, which contains a compound that satisfies at least one of the following conditions: a molecular weight of 300 or more and a boiling point of 300°C or more.

5. The method for producing the composition according to claim 4, wherein the molecular weight of the compound is 500 or more.

6. The method for producing the composition according to claim 4, wherein the boiling point of the compound is 350°C or higher.

7. The method for producing a composition according to claim 1 or 2, wherein the detection of the contained components by light absorption is detection by ultraviolet light.

8. A method for producing a composition according to claim 1 or 2, wherein the detection by a method including a step of charging the composition or particles obtained from the composition is a charged particle detection method.

9. The method for producing a composition according to claim 1 or 2, wherein the detection by a method comprising a step of charging the composition or particles obtained from the composition is detection by electrospray ionization.

10. The method for producing a composition according to claim 1 or 2, wherein the content of the solvent relative to the total mass of the composition for imprint pattern formation is less than 0.1 mass %.

11. A cured product obtained by curing a composition obtained by the method for producing a composition according to claim 1 or 2.

12. A method for producing a pattern, comprising applying a composition obtained by the method for producing a composition according to claim 1 or 2 onto a substrate or a mold, and irradiating the composition for forming an imprint pattern with light while sandwiched between the mold and the substrate.

13. The method for producing a pattern according to claim 12, wherein the pattern includes any one of a line, a hole, and a pillar having a size of 100 nm or less.

14. A method for inspecting a composition, comprising: using a composition for imprint pattern formation, detecting components contained in the composition by light absorption; and detecting components contained in the composition by a method comprising a step of charging the composition or particles obtained from the composition.

15. Polymerizable compound, the maximum molar absorption coefficient in the wavelength range of 190 to 400 nm is 100 L mol －１ ・cm －１ and a compound that satisfies at least one of the following conditions: a molecular weight of 300 or more and a boiling point of 300°C or more.

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