Photocurable components

Abstract

A photocurable composition comprising a polymerizable material, an evaporative diluent, and a photopolymerization initiator, wherein the polymerizable material may contain at least 80 wt% of at least one first polymerizable monomer having a boiling point of 250°C or higher at 1 atm, the evaporative diluent may have a boiling point of 200°C or lower at 1 atm, the amount of the evaporative diluent may be 5 wt% or more and 40 wt%, the vapor pressure of the evaporative diluent may be 5 times or more the vapor pressure of the at least one polymerizable monomer, the difference between the surface tension of the evaporative diluent and the surface tension of the photocurable composition may be 5 mN / m or less, and the viscosity of the photocurable composition may be 20 mPa·s or less.

Description

Technical Field

[0001] The present disclosure relates to a photocurable composition, particularly a photocurable composition suitable for forming a photocurable layer in the field of inkjet adaptable planarization (IAP).

Background Art

[0002] Inkjet adaptable planarization (IAP) is a process of planarizing the surface of a substrate, such as a wafer including an electronic circuit, by ejecting droplets of a curable composition onto the surface of the substrate and bringing the added flat superstrate into direct contact with the liquid to form a flat liquid layer. The flat liquid layer is usually solidified under UV light irradiation, and after removing the superstrate, a flat surface can be obtained that can undergo subsequent processing steps such as baking (bake treatment), etching, and / or further film-forming processes. In order to produce a photocurable layer having good strength, high etching resistance, and high thermal stability, an improved photocurable composition for IAP is required that can sufficiently control and dispense the photocurable composition onto the substrate.

Summary of the Invention

[0003] In one embodiment, the photocurable composition can include a polymerizable material, a volatile diluent, and a photoinitiator, where the polymerizable material includes at least one first polymerizable monomer having a boiling point of 250 °C or higher at 1 atm in an amount of at least 80 wt% based on the total mass of the polymerizable material, the volatile diluent has a boiling point of 200 °C or lower at 1 atm, the amount of the volatile diluent is 5 wt% or more and 40 wt% or less based on the total mass of the photocurable composition, the vapor pressure of the volatile diluent is 5 times or more the vapor pressure of the at least one polymerizable monomer, the difference between the surface tension of the volatile diluent and the surface tension of the photocurable composition is 5 mN / m or less, and the viscosity of the photocurable composition is 20 mPa·s or less.

[0004] In one embodiment of the photocurable composition, the contact angle (CA-FS) of the photocurable composition with respect to a fused silica template can be 8 degrees or more and 30 degrees or less, the contact angle (CA-SI) of the photocurable composition with respect to a pre-treated silicon substrate can be 2.0 degrees or more and 15 degrees or less, and CA-FS may be 3 degrees or more greater than CA-SI.

[0005] In another embodiment of the photocurable composition, at least one first polymerizable monomer of the polymerizable material may include at least one monofunctional acrylate monomer, at least one polyfunctional acrylate monomer, or a combination thereof.

[0006] In one embodiment, at least one first polymerizable monomer may include a polyfunctional acrylate monomer. In a particular embodiment, at least one first polymerizable monomer may have at least one polyfunctional acrylate monomer as its main component.

[0007] In another aspect, at least one polyfunctional acrylate monomer may include an aromatic polyfunctional acrylate monomer.

[0008] In some embodiments, at least one polyfunctional acrylate monomer may include trimethylolpropane triacrylate (TMPTA), 9,9-bis[4-(2-acryloxyethoxy)phenyl]fluorene (A-BPEF), neopentyl glycol diacrylate (A-NPG), diethylene glycol diacrylate, tricyclodecanedimethanol diacrylate (A-DCP), ethoxylated trimethylolpropane triacrylate, trimethylolpropane (PO)6 triacrylate, trimethylolpropane (EO)9 triacrylate, polyethylene glycol 600 diacrylate, trimethylolpropane (EO)15 triacrylate, pentaerythritol tetraacrylate, 1,3-adamantanediol diacrylate, dibenzyl-1,3-propane diacrylate, 1,8-naphthalenediyl diacrylate, 2,2-hexafluorobis(4-hydroxyphenyl)propane diacrylate, or any combination thereof.

[0009] In one embodiment of the photocurable composition, the evaporative diluent may include acetonitrile, propylene glycol methyl ether (PGME), cyclohexanone, n-hexyl acrylate (nHA), or any combination thereof. In certain embodiments, the evaporative diluent may be acetonitrile.

[0010] In one embodiment of the photocurable composition, at least one polyfunctional acrylate monomer may include trimethylolpropane triacrylate (TMPTA), 9,9-bis[4-(2-acryloxyethoxy)phenyl]fluorene (A-BPEF), neopentyl glycol diacrylate (A-NPG), or any combination thereof, and the evaporative diluent may include acetonitrile.

[0011] In a further embodiment of the photocurable composition, the difference between the surface tension of the evaporative diluent and the surface tension of the photocurable composition may be 3 mN / m or less.

[0012] In yet another embodiment of the photocurable composition, the viscosity of the photocurable composition may be 15 mPa·s or less.

[0013] In another embodiment of the photocurable composition, the surface tension of the photocurable composition may be 28 mN / m or more and 35 mN / m or less.

[0014] In one embodiment of the photocurable composition, the amount of evaporative diluent may be 5 wt% or more and 30 wt% or less relative to the total mass of the photocurable composition.

[0015] In yet another embodiment of the photocurable composition, the amount of polymerizable material may be 55 wt% or more of the total mass of the photocurable composition. In one embodiment, the amount of polymerizable material may be 65 wt% or more of the total mass of the photocurable composition.

[0016] In one embodiment, the laminate may include a substrate and a photocurable layer superimposed on the substrate, and the photocurable layer may be formed from the above-described photocurable composition.

[0017] In another embodiment, a method for manufacturing an article comprises the steps of coating a layer of a photocurable composition onto a substrate, wherein the photocurable composition comprises a polymerizable material, an evaporative diluent, and a photopolymerization initiator, wherein the polymerizable material contains at least 80 wt% of the total mass of the polymerizable material of at least one first polymerizable monomer having a boiling point of 250°C or higher at 1 atm, the evaporative diluent has a boiling point of 200°C or lower at 1 atm, the amount of the evaporative diluent is 5 wt% to 40 wt% of the total mass of the photocurable composition, and the vapor pressure of the evaporative diluent is 5 times the vapor pressure of the at least one polymerizable monomer. The above is true, wherein the difference between the surface tension of the evaporative diluent and the surface tension of the photocurable composition is 5 mN / m or less, and the viscosity of the photocurable composition is 20 mPa·s or less, and the method may include the steps of: contacting the photocurable composition with a template or superstraight; irradiating the photocurable composition with light to form a photocurable layer; removing the template or substrate from the photocurable layer; forming a pattern on the substrate; processing the superstraight on which the pattern was formed in the forming step; and manufacturing an article from the substrate processed in the processing step.

[0018] In one embodiment of the method, the difference between the surface tension of the evaporative diluent and the surface tension of the photocurable composition may be 3 mN / m or less.

[0019] In another embodiment of the method, the surface tension of the photocurable composition may be 28 mN / m or more and 35 mN / m or less. [Modes for carrying out the invention]

[0020] The following description is provided to aid in understanding the teachings disclosed herein and focuses on specific embodiments and examples of these teachings. This focus is provided to assist in the description of these teachings and should not be construed as limiting the scope or applicability of these teachings.

[0021] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which the present invention pertains. Materials, methods, and examples are illustrative and not intended to limit the scope. Many details relating to specific materials and processing procedures, beyond what is described herein, are conventional and can be found in textbooks and other sources of information on imprint and lithography techniques.

[0022] In this specification, the terms “including,” “having,” or any other variation thereof are intended to cover non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of features is not necessarily limited to those features and may include other features not expressly described in or inherent to such process, method, article, or apparatus.

[0023] In this specification, unless expressly stated otherwise, “or” means inclusive OR and not exclusive OR. For example, condition A or B is satisfied by one of the following: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0024] Furthermore, the use of the singular form is used to describe the elements and components described herein. This is done solely for convenience and to give a general sense of the scope of the invention. This description should be read as including one or at least one, and the singular form also includes the plural form unless it becomes clear that it has another meaning.

[0025] The present disclosure is directed to a photocurable composition comprising a polymerizable material, a volatile diluent, and a photoinitiator. The photocurable composition can include: a) the polymerizable material can include at least one first polymerizable monomer having a boiling point of 250 °C or higher at 1 atm in an amount of at least 80 wt% based on the total mass of the polymerizable material; b) the volatile diluent can have a boiling point of 200 °C or lower at 1 atm; c) the amount of the volatile diluent can be 5 wt% or more and 40 wt% or less based on the total mass of the photocurable composition; d) the vapor pressure of the volatile diluent can be 5 times or more the vapor pressure of at least one polymerizable monomer; e) the difference between the surface tension of the volatile diluent and the surface tension of the photocurable composition can be 5 mN / m or less; f) the viscosity of the photocurable composition can be 20 mPa·s or less, and can include a combination of such features.

[0026] The photocurable composition of the present disclosure can have a desired dispensing behavior suitable for IAP processing while forming a solid layer after photocuring that has high etching resistance and good mechanical strength. Two main properties that affect the flow of a fluid are the viscosity and surface tension of the composition. Surprisingly, it has been found that the presence of a small amount of the selected volatile diluent only slightly affects the surface tension and can significantly reduce the viscosity of the photocurable composition compared to the same composition without the volatile diluent. This makes it possible to improve photocurable compositions that are known to form layers with high thermal stability and high etching resistance after curing but have the drawback of high viscosity. The addition of a small amount of the selected volatile solvent can reduce the viscosity without causing an undesirable change in the surface tension, thereby making such a photocurable composition suitable for IAP processing.

[0027] As used herein, the term "volatile diluent" means a solvent that only slightly changes the surface tension of the photocurable composition and significantly reduces the viscosity of the photocurable composition.

[0028] The photocurable composition of the present disclosure can form droplets with a very fine size of less than picoliter. After disposing the droplets on a substrate and before merging the droplets, it can be designed such that less than 1% of the volatile residues remain by evaporating the evaporative diluent from the photocurable composition. Thereby, it is possible to ensure the low shrinkage of the photocured layer desired in the IAP process during the downstream heating step.

[0029] In one aspect, the evaporative diluent can be a solvent that does not react with the monomers of the polymerizable material. In another aspect, the evaporative diluent can react with the polymerizable monomer and be integrated into the formed polymer matrix.

[0030] The photocurable composition of the present disclosure can be designed to have a viscosity of 20 mPa·s or less, 18 mPa·s or less, 15 mPa·s or less, 12 mPa·s or less, or 10 mPa·s or less. In another aspect, the viscosity may be 2 mPa·s or more, 3 mPa·s or more, or 5 mPa·s or more. In a specific aspect, the viscosity may be 15 mPa·s or less. In this specification, all viscosity values are related to the viscosity measured at a temperature of 23 °C by the Brookfield method using a Brookfield viscometer.

[0031] In one embodiment, the amount of the evaporative diluent may be 40 wt% or less, for example, 35 wt% or less, 30 wt% or less, 25 wt% or less, 20 wt% or less, 15 wt% or less, or 12 wt% or less, based on the total mass of the photocurable composition. In another aspect, the amount of the evaporative diluent can be 5 wt% or more, 8 wt% or more, 10 wt% or more, 12 wt% or more, or 15 wt% or more. In one aspect, the amount of the evaporative diluent can be 5 wt% or more and 15 wt% or less based on the total mass of the photocurable composition. The amount of the evaporative diluent can be any value between the above maximum and minimum values.

[0032] In one embodiment, the presence of an evaporative diluent can cause a viscosity reduction of 40% or more, 50% or more, 55% or more, 60% or more, or 65% or more, where the viscosity reduction rate is defined as the percentage reduction in viscosity between a photocurable composition without an evaporative diluent and the corresponding photocurable composition containing an evaporative diluent.

[0033] In a further embodiment, the vapor pressure of the evaporative diluent can be five times or more the vapor pressure of the polymerizable monomer having the highest vapor pressure among the polymerizable materials, for example, seven times or more, ten times or more, twenty times or more, thirty times or more, or fifty times or more.

[0034] In one embodiment, the vapor pressure of the evaporative diluent may be 0.05 mmHg or higher at 25°C, for example, 0.1 mmHg or higher, 0.5 mmHg or higher, 1 mmHg or higher, 5 mmHg or higher, 10 mmHg or higher, 50 mmHg or higher, or 80 mmHg or higher. In another embodiment, the vapor pressure may be 150 mmHg or less, 130 mmHg or less, or 100 mmHg or less at 25°C.

[0035] In another embodiment, the surface tension of the evaporative diluent may be 23 mN / m or more, 25 mN / m or more, 27 mN / m or more, or 30 mN / m or more. In a further embodiment, the surface tension may be 40 mN / m or less, 37 mN / m or less, 35 mN / m or less, or 32 mN / m or less.

[0036] In a further embodiment, the difference between the surface tension of the evaporative diluent and the surface tension of the photocurable composition may be 5 mN / m or less, 4 mN / m or less, 3 mN / m or less, or 2 mN / m or less.

[0037] In some embodiments, the evaporative diluent may include acetonitrile, propylene glycol methyl ether (PGME), cyclohexanone, n-hexyl acrylate (nHA), or any combination thereof. In certain embodiments, the evaporative diluent may include acetonitrile. In certain embodiments, the evaporative diluent may be primarily composed of acetonitrile. In this specification, "primarily composed of acetonitrile" means 99 wt% or more, or the evaporative diluent is acetonitrile.

[0038] The polymerizable material of the photocurable composition of the present disclosure can be designed to form a high-temperature stable layer having high etching resistance. In one embodiment, the polymerizable material of the photocurable composition may contain at least 80 wt% of at least one first polymerizable monomer having a boiling point of 250°C or higher at 1 atm.

[0039] In one embodiment, at least one first polymerizable monomer may include at least one monofunctional acrylate monomer, at least one polyfunctional acrylate monomer, or a combination thereof. In a particular embodiment, the polymerizable material may include at least one polyfunctional acrylate monomer. In a particular embodiment, at least one first polymerizable monomer may be primarily composed of a polyfunctional acrylate monomer. In another particular embodiment, the polyfunctional acrylate monomer may be an aromatic polyfunctional acrylate monomer. In this specification, the phrase "at least one first polymerizable monomer primarily composed of a polyfunctional acrylate monomer" means that 99 wt% or more of the first polymerizable monomer is a polyfunctional acrylate monomer.

[0040] In another embodiment, at least one first polymerizable monomer may have a vapor pressure of 0.01 mmHg or less, 0.005 mmHg or less, 0.001 mmHg or less, 0.0005 mmHg or less, or 0.0003 mmHg or less at a temperature of 25°C.

[0041] Non-limiting examples of polyfunctional acrylate monomers of the first polymerizable monomer include bisphenol A dimethacrylate, m-xylylenediacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, trimethylolpropane triacrylate (TMPTA), 9,9-bis[4-(2-acryloxyethoxy)phenyl]fluorene (A-BPEF), neopentyl glycol diacrylate (A-NPG), diethylene glycol diacrylate, and tricyclodecane dimethyl diacrylate. It may be acrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane (EO) 9 triacrylate, polyethylene glycol 600 diacrylate, trimethylolpropane (EO) 15 triacrylate, pentaerythritol tetraacrylate, 1,3-adamantanediol diacrylate, dibenzyl-1,3-propane diacrylate, 1,8-naphthalenediyl diacrylate, or 2,2-hexafluorobis(4-hydroxyphenyl)propane diacrylate, or any combination thereof.

[0042] The polymerizable material may further contain at least one second polymerizable monomer in an amount up to 20 wt% of the total mass of the polymerizable material, wherein at least one second polymerizable monomer may have a boiling point of less than 250°C.

[0043] At least one second monomer can be a monofunctional monomer or a polyfunctional monomer. In certain non-limiting examples, at least the second polymerizable monomer can be benzyl acrylate, divinylbenzene, trivinylbenzene, cyclohexyl acrylate, 2-methoxyethyl acrylate, tetrahydrofurfuryl acrylate, or 1H,1H-heptafluorobutyl acrylate, 1,4-butanediol diacrylate.

[0044] In another embodiment, the polymerizable material may include one or more polymerizable oligomers or polymers, insofar as they can satisfy the viscosity requirements of the photocurable composition.

[0045] In certain embodiments of the photocurable compositions of the present disclosure, at least one polyfunctional acrylate monomer may include trimethylolpropane triacrylate (TMPTA), 9,9-bis[4-(2-acryloxyethoxy)phenyl]fluorene (A-BPEF), neopentyl glycol diacrylate (A-NPG), or a combination thereof, and the evaporative diluent may include acetonitrile.

[0046] The amount of polymerizable material in the photocurable composition may be 30 wt% or more relative to the total mass of the photocurable composition, for example, 40 wt% or more, 50 wt% or more, 60 wt% or more, 70 wt% or more, or 80 wt% or more. In another embodiment, the amount of polymerizable material may be 90 wt% or less, for example, 85 wt% or less, 80 wt% or less, 70 wt% or less, or 60 wt% or less. The amount of polymerizable material may be any value between the above minimum and maximum values. In a particular embodiment, the amount of polymerizable material may be 50 wt% or more and 85 wt% or less relative to the total mass of the photocurable composition.

[0047] A more important aspect of the IAP process is that the contact angle of the photocurable composition with respect to the template must be greater than the contact angle with respect to the substrate. Furthermore, a lower contact angle with respect to the substrate is desirable to facilitate the spreading of the liquid resist composition. In one embodiment, the contact angle of the photocurable composition with respect to the fused silica template (CA-FS) can be 3 degrees or more greater than the contact angle of the photocurable composition with respect to the pre-treated silicon substrate (CA-SI). In one embodiment, the contact angle with respect to the fused silica template (CA-FS) can be between 8 degrees and 30 degrees, while the contact angle with respect to the silicon substrate (CA-SI) can be between 2.0 degrees and 15 degrees. In this specification, the term "pre-treated silicon substrate" means a silicon substrate having a layer of acryloxymethyltrimethoxysilane deposited on its outer surface by vapor deposition.

[0048] The photocurable composition can be adapted so that the photocured layer formed from the photocurable composition has high thermal stability. In one embodiment, the onset temperature of thermal decomposition of the photocured layer may be above 250°C, above 300°C, above 350°C, above 375°C, or above 400°C. In this specification, the onset temperature of thermal decomposition is also called the "thermal decomposition temperature" and refers to the temperature at which the TGA curve first shows a deviation from a nearly linear flat region to a curve, shortly before the rapid decomposition decrease of the sample.

[0049] To initiate photocuring of the photocurable composition when exposed to light, one or more photopolymerization initiators may be included in the photocurable composition.

[0050] In some embodiments, curing can be achieved by combining photocuring and thermal curing.

[0051] The photocurable composition may further contain one or more optional additives. Non-limiting examples of optional additives may be stabilizers, dispersants, solvents, surfactants, inhibitors, or any combination thereof.

[0052] The photocurable compositions disclosed herein can be adapted for use in inkjet-adaptive planarization (IAP).

[0053] In one embodiment, a photocurable composition can be applied to a substrate to form a photocurable layer. In this specification, the combination of a substrate and a photocurable layer superimposed on the substrate is referred to as a laminate.

[0054] This disclosure further relates to a method for forming a photocurable layer. This method may include steps of: coating a layer of the above-mentioned photocurable composition onto a substrate; contacting the photocurable composition with a template or superstraight; irradiating the photocurable composition with light to form a photocurable layer; and removing the template or superstraight from the photocurable layer.

[0055] The substrate and solidified layer may undergo additional processing, such as etching, to transfer an image onto the substrate that corresponds to the pattern of one or both of the patterns of the solidified layer and / or the patterned layer beneath the solidified layer. The substrate may further undergo known processes and treatments for the manufacture of apparatus (articles), including, for example, curing, oxidation, layer formation, film deposition, doping (impurity introduction), planarization, etching, formation material removal, dicing (chip formation), bonding, and packaging.

[0056] The photocured layer may further be used as an interlayer insulating film for semiconductor devices such as LSIs, system LSIs, DRAMs, SDRAMs, RDRAMs, or D-RDRAMs, or as a resist film used in semiconductor manufacturing processes.

[0057] As further demonstrated in the examples, by including a small amount of a suitable evaporative diluent, the viscosity of the photocurable composition can be significantly reduced while maintaining high surface tension. This improves the dispersibility of the photocurable composition, enabling the formation of a high-quality layer suitable for IAP treatment, such as one with high etching resistance and high thermal stability. [Examples]

[0058] The following non-limiting examples illustrate the concepts described herein.

[0059] Example 1

[0060] Table 1 lists solvents known to be used in photocurable compositions. The solvents are listed in descending order of their boiling point (at 1 atmosphere). Furthermore, Table 1 lists the viscosity, vapor pressure, and surface tension of each solvent at 23°C.

[0061] For the photocurable compositions of this disclosure, as shown in the following examples, only acetonitrile (ACN), propylene glycol methyl ether (PGME), cyclohexanone, and nHA are suitable as evaporative diluents from the solvents listed in Table 1.

[0062] [Table 1]

[0063] Example 2

[0064] Photocurable compositions were prepared (C1 and S1) containing the polymerizable monomers 9,9-bis[4-(2-acryloxyethoxy)phenyl]fluorene (A-BPEF) and benzyl acrylate (BA), two photopolymerization initiators, and one surfactant. See Table 2 for the exact compositions. The difference between C1 and S1 is the addition of 10 parts acetonitrile to sample S1. It can be seen that the viscosity decreased significantly from 33 mPa·s to 11.9 mPa·s with the addition of only 10 parts acetonitrile, while the surface tension remained almost the same.

[0065] [Table 2]

[0066] Example 3

[0067] Photocurable compositions were prepared (C2, S2, and S3) containing the polymerizable monomers tricyclodecanedimethanol diacrylate (A-DCP), dicyclopentenyl acrylate (DCPA), and isobornyl acrylate (IBXA), two photopolymerization initiators, and one surfactant. See Table 3 for the exact compositions. The difference between composition C2 and compositions S2 and S3 is the addition of acetonitrile: 10 parts to S2 and 20 parts to S3. The addition of just 10 parts acetonitrile significantly reduced the viscosity from 26.1 mPa·s to 10.4 mPa·s (a 61.5% decrease), while the surface tension remained the same. Adding 20 parts acetonitrile further reduced the viscosity to 8 mPa·s (a 70% decrease), and the surface tension only slightly changed from 32.1 mN / m to 30.6 mN / m.

[0068] [Table 3]

[0069] Example 4

[0070] Photocurable compositions were prepared (S4, C3, and C4) containing the polymerizable monomer neopentyl glycol diacrylate (A-NPG), an evaporative diluent, a photopolymerization initiator, and a surfactant. The exact compositions are summarized in Table 4. The composition differed depending on the type of evaporative diluent used: composition S4 used acetonitrile (surface tension 31 mN / m), composition C3 used DMSO (surface tension 49.2 mN / m), and composition C4 used IPA (surface tension 21.8 mN / m).

[0071] Although all compositions had low viscosity in the range of 2–6 mPa·s, the contact angle measurements with respect to the surface of the fused silica material (template simulation) and the surface of the pre-treated silicon material (substrate simulation) showed very different properties among the three compositions.

[0072] Only composition S4 formed a contact angle such that, as desired in the IAP process, the contact angle with respect to the template was 3 degrees or more greater than the contact angle with respect to the substrate, and the minimum contact angle with respect to the substrate was 2 degrees or more.

[0073] As further as can be seen from the data summarized in Table 4, when DMSO with a surface tension of 49.2 mN / m is included, the surface tension of the final composition C3 is 41 mN / m, which is much higher than that of composition S4 containing acetonitrile with a surface tension of 31 mN / m.

[0074] [Table 4]

[0075] The data in Table 4 further indicates that samples C3 and C4 are not suitable for IAP processing. When the contact angle to the template and the contact angle to the substrate are very similar, as in sample C3, it can lead to undesirable imprint performance. Furthermore, when the contact angle to the substrate is very low (less than 2 degrees), problems may occur during extrusion.

[0076] Example 5

[0077] Measurement of evaporation rate

[0078] An evaporation experiment was conducted to compare the evaporation rates of samples C1 and S1 (from Example 2) and samples C2, S2, and S3 (from Example 3).

[0079] Each test was performed by coating the first slide glass with an adhesion promoter and measuring the mass of the first slide glass. Then, three drops of the photocurable composition under test (hereinafter also referred to as the "test composition") were added to the second slide glass (without the adhesion promoter coating) so that the initial mass of the test composition added to the second slide glass was 0.033 g. Immediately after placing the three drops on the second slide glass, the second slide glass was covered with the first slide glass. After the test composition had spread sufficiently, the first and second slide glass glasses were separated again, and a thin layer of the test composition remained on the first slide glass, and its evaporation rate was measured.

[0080] To measure the evaporation rate, the mass loss of the first glass slide containing the test composition layer was measured after a first time interval of 5 minutes (T1) and after a second time interval of 30 minutes (T2).

[0081] [Table 5]

[0082] The data in Table 5 show that representative samples S1, S2, and S3 of this disclosure exhibit significantly higher mass loss than comparative samples C1 and C2. This mass loss is desirable in the photocurable composition and is related to the evaporation of the added evaporative diluent. In actual IAP treatment, since the droplet size is within the picoliter range, it is expected that the evaporative diluent will evaporate very quickly before the droplets merge together. Rapid evaporation can be concluded particularly from samples S5 and S6, and no difference was observed even when the time was extended from 5 to 10 minutes.

[0083] Viscosity measurement

[0084] The viscosity of samples C1-C4 and S16-S18 was measured using a Brookfield DV-11+Pro viscometer with spindle #18. For each viscosity measurement, 6-7 ml of the sample was taken, added to the sample chamber, and allowed to equilibrate for 15-20 minutes until the target temperature of 23°C was reached. Viscosity was measured at a speed of 135 rpm using spindle #18. For each sample, the measurement was repeated three times, and the average value was calculated.

[0085] Measurement of surface tension

[0086] The surface tension of the composition was measured using the pendant drop method with a DM-701 contact angle meter manufactured by Kyowa Interface Science Co., Ltd. (Japan). For measurement, a syringe containing the liquid test composition was placed in the syringe holder of the DM-701, and the pendant drop measurement program on the control panel was started. The DM-701 enables automatic liquid dispensing and droplet size control. Droplet images were taken, and the droplet shape was analyzed using the Young-Laplace theory with software. In the case of a two-component system, the surface tension of the mixture can be calculated by summing the products of the surface tension and mole fraction of each component.

[0087] Measurement of contact angle

[0088] The contact angle (CA) was measured using a Drop Master DM-701 contact angle meter manufactured by Kyowa Interface Science Co., Ltd. (Japan).

[0089] For testing the contact angle (CA-FS) with respect to the fused silica template, a fused silica slide was used to simulate the template surface during the actual imprint process.

[0090] To measure the contact angle (CA-SI) with respect to the silicon substrate, a pre-treated silicon wafer containing a silane layer (acryloxymethyltrimethoxysilane) deposited by vapor deposition as an adhesion promoter was used to simulate the substrate surface ("CA on the substrate") during the actual imprint process.

[0091] The actual contact angle measurement was initiated by adding 2 ml of test sample to a syringe, with 2 μl of the sample per test being added to the target surface by machine. Droplet images were continuously captured by a CCD camera from the moment the sample droplet contacted the surface. The contact angle was automatically calculated by software based on image analysis.

[0092] The specifications and drawings of the embodiments described herein are intended to provide a general understanding of the structures of various embodiments. The specifications and drawings are not intended to serve as a comprehensive and exhaustive description of all elements and features of apparatus and systems using the structures or methods described herein. Individual embodiments may be provided in combination within a single embodiment, and conversely, various features described in the context of a single embodiment for brevity may also be provided individually or in any subcombination. Furthermore, references to numerical ranges include each and all values ​​within that range. Many other embodiments will be apparent to those skilled in the art only after reading this specification. Other embodiments can be used and derived from this disclosure so as to allow for structural substitution, logical substitution, or other modifications without departing from the scope of this disclosure. Therefore, this disclosure should be considered illustrative rather than restrictive.

Claims

1. A photocurable composition comprising a polymerizable material, an evaporative diluent, and a photopolymerization initiator, The polymerizable material contains at least one first polymerizable monomer having a boiling point of 250°C or higher at 1 atmosphere, in an amount of at least 80 wt% of the total mass of the polymerizable material. The evaporative diluent has a boiling point of 200°C or less at 1 atmosphere. The amount of the evaporative diluent is 5 wt% or more and 40 wt% or less relative to the total mass of the photocurable composition. The vapor pressure of the evaporative diluent is five times or more the vapor pressure of the at least one polymerizable monomer. The difference between the surface tension of the evaporative diluent and the surface tension of the photocurable composition is 5 mN / m or less, and The photocurable composition having a viscosity of 20 mPa·s or less.

2. The photocurable composition according to claim 1, wherein the contact angle (CA-FS) of the photocurable composition with respect to a fused silica template is 8 degrees or more and 30 degrees or less, the contact angle (CA-SI) of the photocurable composition with respect to a pre-treated silicon substrate is 2.0 degrees or more and 15 degrees or less, and the CA-FS is 3 degrees or more greater than the CA-SI.

3. The photocurable composition according to claim 1, wherein the at least one first polymerizable monomer comprises at least one monofunctional acrylate monomer, at least one polyfunctional acrylate monomer, or a combination thereof.

4. The photocurable composition according to claim 3, wherein the at least one first polymerizable monomer comprises a polyfunctional acrylate monomer.

5. The photocurable composition according to claim 4, wherein the at least one first polymerizable monomer comprises the at least one polyfunctional acrylate monomer as a main component.

6. The photocurable composition according to claim 3, wherein the at least one polyfunctional acrylate monomer comprises an aromatic polyfunctional acrylate monomer.

7. The photocurable composition according to claim 3, wherein the at least one polyfunctional acrylate monomer comprises trimethylolpropane triacrylate, 9,9-bis[4-(2-acryloxyethoxy)phenyl]fluorene, neopentyl glycol diacrylate, diethylene glycol diacrylate, tricyclodecanedimethanol diacrylate, ethoxylated trimethylolpropane triacrylate, trimethylolpropane(PO)6 triacrylate, trimethylolpropane(EO)9 triacrylate, polyethylene glycol 600 diacrylate, trimethylolpropane(EO)15 triacrylate, pentaerythritol tetraacrylate, 1,3-adamantanediol diacrylate, dibenzyl-1,3-propane diacrylate, 1,8-naphthalenediyl diacrylate, or 2,2-hexafluorobis(4-hydroxyphenyl)propane diacrylate, or any combination thereof.

8. The photocurable composition according to claim 1, wherein the evaporative diluent comprises acetonitrile, propylene glycol methyl ether, cyclohexanone, n-hexyl acrylate, or any combination thereof.

9. The photocurable composition according to claim 8, wherein the evaporative diluent comprises acetonitrile.

10. The photocurable composition according to claim 7, wherein the at least one polyfunctional acrylate monomer comprises trimethylolpropane triacrylate, 9,9-bis[4-(2-acryloxyethoxy)phenyl]fluorene, neopentyl glycol diacrylate, or a combination thereof, and the evaporative diluent comprises acetonitrile.

11. The photocurable composition according to claim 1, wherein the difference between the surface tension of the evaporative diluent and the surface tension of the photocurable composition is 3 mN / m or less.

12. The photocurable composition according to claim 1, wherein the viscosity of the photocurable composition is 15 mPa·s or less.

13. The photocurable composition according to claim 1, wherein the surface tension of the photocurable composition is 28 mN / m or more and 35 mN / m or less.

14. The photocurable composition according to claim 1, wherein the amount of the evaporative diluent is 5 wt% or more and 30 wt% or less with respect to the total mass of the photocurable composition.

15. The photocurable composition according to claim 1, wherein the amount of the polymerizable material is 55 wt% or more of the total mass of the photocurable composition.

16. The photocurable composition according to claim 1, wherein the amount of the polymerizable material is 65 wt% or more of the total mass of the photocurable composition.

17. A laminate comprising a substrate and a photocurable layer superimposed on the substrate, wherein the photocurable layer is formed from the photocurable composition described in claim 1.

18. A method for manufacturing articles, A step of coating a layer of a photocurable composition onto a substrate, wherein the photocurable composition comprises a polymerizable material, an evaporative diluent, and a photopolymerization initiator. The polymerizable material contains at least one first polymerizable monomer having a boiling point of 250°C or higher at 1 atmosphere, in an amount of at least 80 wt% of the total mass of the polymerizable material. The evaporative diluent has a boiling point of 200°C or less at 1 atmosphere. The amount of the evaporative diluent is 5 wt% or more and 40 wt% or less relative to the total mass of the photocurable composition. The vapor pressure of the evaporative diluent is five times or more the vapor pressure of the at least one polymerizable monomer. The difference between the surface tension of the evaporative diluent and the surface tension of the photocurable composition is 5 mN / m or less, and The viscosity of the aforementioned photocurable composition is 20 mPa·s or less. A step of bringing the photocurable composition into contact with a template or superstraight, A step of irradiating the photocurable composition with light to form a photocurable layer, A step of removing the template or the superstraight from the light-cured layer, A step of forming a pattern on the substrate, A step of processing the substrate on which the pattern has been formed in the forming step, and A method comprising the step of manufacturing an article from the substrate processed in the processing step.

19. The method according to claim 18, wherein the difference between the surface tension of the evaporative diluent and the surface tension of the photocurable composition is 3 mN / m or less.

20. The photocurable composition according to claim 1, wherein the surface tension of the photocurable composition is 28 mN / m or more and 35 mN / m or less.

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