Photocurable composition having high silicon content and high stability

Abstract

To provide a photocurable composition having high stability with a stability coefficient of 14 or more.SOLUTION: A photocurable composition of the present invention can include a polymerizable material, a fluorine-free release agent, and a photopolymerization initiator, where the polymerizable material includes at least one silicon-containing monomer having a structure represented by the formula (1) below, an amount of silicon (Si) in the photocurable composition is at least 15 mass% based on the total mass of the polymerizable material, and the fluorine-free release agent can include an acetylenediol.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to photocurable compositions, particularly photocurable compositions for nanoimprint lithography (NIL) and inkjet adaptive planarization (IAP). [Background technology]

[0002] Imprint resists with a high silicon content are suitable for forming photocurable layers with high etching resistance. However, photocurable compositions with a silicon content of more than 15% by weight have the disadvantage of becoming unstable due to phase separation.

[0003] There is a need for improved photocurable compositions for IAP and NIL processes, particularly for sub-20 nm CD device fabrication, that have high stability, low viscosity, and high cure speed, and that result in photocured layers with high etch resistance. Summary of the Invention

[0004] In one embodiment, the photocurable composition may include a polymerizable material, a fluorine-free release agent, and a photopolymerization initiator, and the polymerizable material may include at least one silicon-containing monomer having a structure represented by formula (1): [ka] In formula (1), R1 and R2 each independently represent -O-Si(CH3)3, an alkyl group, an aryl group, or an alkylaryl group; R3 and R4 each independently represent -O-Si(CH3)3, an alkyl group, an aryl group, or an alkylaryl group; R5 represents a C1 to C5 alkyl group, an aryl group, or an alkylaryl group; R6 represents -R5-X, X, -O-Si(CH3)3, an alkyl group, an aryl group, or an alkylaryl group; X represents an acrylate or methacrylate; and n represents a number from 0 to 4. The amount of silicon (Si) in the photocurable composition can be at least 15% by mass based on the total mass of the polymerizable material. The fluorine-free release agent can include an acetylenic diol.

[0005] In one embodiment of the photocurable composition, the acetylenic diol can have a structure represented by the following formula (2) or a structure represented by the following formula (3). [ka] [ka] In formula (2) and formula (3), R1, R3, R5, and R7 each independently represent a C1 to C3 alkyl group, and R2, R4, R6, and R8 each independently represent a C4 to C 12 X represents a hydrogen atom or a C1-C 10 and m and n each independently represent a number from 1 to 40.

[0006] In some embodiments, the acetylenic diol can include a structure represented by formula (4): [ka]

[0007] In another embodiment of the photocurable composition, the acetylenic diol can be an ethoxylated acetylenic diol having a structure represented by formula (5) or a structure represented by formula (6): [ka] [ka] In the formulas (5) and (6), m and n each independently represent a number from 1 to 40.

[0008] In one embodiment of the photocurable composition, the amount of Si can be at least 20 wt. % based on the total weight of the photocurable composition. In a particular embodiment, the amount of Si can be at least 25 wt. % based on the total weight of the photocurable composition.

[0009] In one embodiment of the photocurable composition, the molecular weight of the silicon-containing monomer can be 100 g / mol or more and 800 g / mol or less.

[0010] In another embodiment of the photocurable composition, the amount of the at least one silicon-containing monomer can be at least 45% by weight, based on the total weight of the polymerizable material.

[0011] In one embodiment, the photocurable composition can further include at least one mold release agent that is not an acetylenic diol.

[0012] In a further embodiment, the viscosity of the photocurable composition can be 30 mPa·s or less.

[0013] In one embodiment of the photocurable composition, the amount of polymerizable material can be at least 90% by weight, based on the total weight of the photocurable composition.

[0014] In one embodiment, the at least one silicon-containing monomer of the photocurable composition can include at least two different silicon-containing monomers.

[0015] In some embodiments of the photocurable composition, at least one silicon-containing monomer is selected from the following group: methacryloxymethyltris(trimethylsiloxy)silane (SiM1), 1,3-bis(3-methacryloxypropyl)tetrakis(trimethylsiloxy)disiloxane (SiM2) 3-acryloxypropyl-tris(trimethylsiloxy)silane (SiM3), (Methacryloxymethyl)bis(trimethylsiloxy)methylsilane (SiM4), 3-methacryloxypropylbis(trimethylsiloxy)methylsilane (SiM5), (3-acryloxypropyl)methylbis(trimethylsiloxy)silane (SiM6), methacryloxypropyltris(trimethylsiloxy)silane (SiM7), Acryloxymethyltrimethylsilane (SiM8), acryloxymethyltris(trimethylsiloxy)silane (SiM9), 1,3-bis[(acryloxymethyl)phenethyl]tetramethyldisiloxane (SiM10), methacryloxypropyl-terminated polydimethylsiloxane (SiM11), and any combination thereof.

[0016] In another embodiment of the photocurable composition, the amount of non-fluorine-containing release agent (surfactant) can be at least 2% by weight.

[0017] In one embodiment, the photocurable composition may have a stability factor (SF) of at least 14, where the stability factor is defined as the number of days that the photocurable composition does not exhibit phase separation at room temperature.

[0018] In one embodiment, the polymerizable material of the photocurable composition can further include at least one non-silicon-containing polymerizable monomer. In certain embodiments, the non-silicon-containing polymerizable monomer can include an acrylate monomer. In particular, in certain embodiments, the amount of the acrylate monomer can be at least 20% by weight.

[0019] In another embodiment, a laminate can include a substrate and a photocurable layer overlying the substrate, the photocurable layer can be formed from the photocurable composition described above.

[0020] In one embodiment, a method of forming a photocurable layer on a substrate includes applying a layer of a photocurable composition onto a substrate, wherein the photocurable composition comprises a polymerizable material, a non-fluorine-containing release agent, and at least one photoinitiator, and the polymerizable material comprises at least one silicon-containing monomer having a structure represented by formula (1): [ka] In formula (1), R1 and R2 each independently represent -O-Si(CH3)3, an alkyl group, an aryl group, or an alkylaryl group; R3 and R4 each independently represent -O-Si(CH3)3, an alkyl group, an aryl group, or an alkylaryl group; R5 represents a C1-C5 alkyl group, an aryl group, or an alkylaryl group; R6 represents -R5-X, X, -O-Si(CH3)3, an alkyl group, an aryl group, or an alkylaryl group; X represents an acrylate or methacrylate; n represents a number from 0 to 4; the amount of silicon (Si) in the photocurable composition is at least 15 wt% based on the total weight of the polymerizable material; and the fluorine-free release agent comprises an acetylenic diol. The method may include the steps of contacting the photocurable composition with a template or superstrate; irradiating the photocurable composition with light to form a photocured layer; and removing the template or superstrate from the photocured layer.

[0021] In another embodiment, a method for making an article includes applying a layer of a photocurable composition onto a substrate, wherein the photocurable composition comprises a polymerizable material, a non-fluorine-containing release agent, and at least one photoinitiator, and the polymerizable material comprises at least one silicon-containing monomer having a structure represented by Formula (1): [ka] In formula (1), R1 and R2 each independently represent -O-Si(CH3)3, an alkyl group, an aryl group, or an alkylaryl group; R3 and R4 each independently represent -O-Si(CH3)3, an alkyl group, an aryl group, or an alkylaryl group; R5 represents a C1 to C5 alkyl group, an aryl group, or an alkylaryl group; R6 represents -R5-X, X, -O-Si(CH3)3, an alkyl group, an aryl group, or an alkylaryl group; X represents an acrylate or methacrylate; n represents a number of 0 to 4; and The amount of (Si) is at least 15 wt % based on the total weight of the polymerizable material, and the fluorine-free release agent comprises an acetylenic diol, and the method can include contacting the photocurable composition with a template or superstrate, irradiating the photocurable composition with light to form a photocured layer, removing the template or superstrate from the photocured layer, forming a pattern on the substrate, treating the patterned substrate in the pattern forming step, and producing an article from the treated substrate in the substrate treating step. DETAILED DESCRIPTION OF THE INVENTION

[0022] The following description is provided to aid in understanding the teachings disclosed herein and focuses on particular implementations and embodiments of the teachings. This focus is provided to aid in explaining the teachings and should not be construed as a limitation on the scope or applicability of the teachings.

[0023] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The materials, methods, and examples are merely illustrative and are not intended to be limiting. Unless described herein, many details regarding specific materials and processing acts are conventional and can be found in textbooks and other sources in the imprint and lithography arts.

[0024] As used herein, the terms "comprises," "having," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of features is not necessarily limited to only those features, but may include other features not expressly listed or inherent in such process, method, article, or apparatus.

[0025] In this specification, unless expressly stated to the contrary, "or" refers to an inclusive or rather than an exclusive or. For example, condition A or B is satisfied by either A being true (or present) and B being false (or not present), A being false (or not present) and B being true (or present), or both A and B being true (or present).

[0026] Additionally, the use of the singular is used to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one, and the singular also includes the plural unless it is clear that otherwise is intended.

[0027] The present disclosure is directed to a photocurable composition comprising a polymerizable material, a fluorine-free release agent, and a photopolymerization initiator, wherein the polymerizable material comprises at least one silicon-containing monomer having a structure represented by formula (1): [ka] In formula (1), R1 and R2 each independently represent -O-Si(CH3)3, an alkyl group, an aryl group, or an alkylaryl group; R3 and R4 each independently represent -O-Si(CH3)3, an alkyl group, an aryl group, or an alkylaryl group; R5 represents a C1 to C5 alkyl group, an aryl group, or an alkylaryl group; R6 represents -R5-X, X, -O-Si(CH3)3, an alkyl group, an aryl group, or an alkylaryl group; X represents an acrylate or methacrylate; and n represents a number from 0 to 4. The amount of silicon (Si) in the photocurable composition can be at least 15% by weight based on the total weight of the polymerizable material, and the fluorine-free release agent can include an acetylenic diol.

[0028] As used herein, unless otherwise specified, the term "silicon-containing monomer" refers to a monomer having a structure represented by formula (1). Although formula (1) has a repeating unit, if the molecular weight is 800 g / mol or less, it is referred to as a "monomer" in this specification.

[0029] Surprisingly, it has been found that when acetylene diol is used as a release agent, photocurable compositions with a silicon content of more than 15% by weight can be prepared with high stability.The photocurable compositions are suitable for, for example, mask replication processes with CDs of less than 19 nm.

[0030] In one aspect, the acetylenic diol can be an ethoxylated acetylenic diol.

[0031] In another embodiment, the acetylenic diol can have a structure represented by formula (2) below or a structure represented by formula (3) below. [ka] [ka] In the formula, R1, R3, R5, and R7 each independently represent a C1 to C3 alkyl group, and R2, R4, R6, and R8 each independently represent a C4 to C12 X represents a hydrogen atom or a C1-C 10 and m and n each independently represent a number from 1 to 40.

[0032] In a specific embodiment, the acetylenic diol can have a structure represented by the following formula (4), a structure represented by the following formula (5), or a structure represented by the following formula (6). [ka] [ka] [ka] In the formulas (4) to (6), n and m may be the same or different and each independently represent a number from 1 to 40, particularly from 1 to 20. The amount of the fluorine-free release agent may be at least 2% by mass based on the total mass of the photocurable composition.

[0033] In certain embodiments, the amount of silicon (Si) in the photocurable composition can be at least 16 wt.%, e.g., at least 17 wt.%, at least 18 wt.%, at least 19 wt.%, at least 20 wt.%, at least 23 wt.%, at least 25 wt.%, or at least 28 wt.%, based on the total weight of the polymerizable material. In other embodiments, the amount of silicon in the photocurable composition can be 33 wt.% or less, 30 wt.% or less, 28 wt.% or less, or 26 wt.% or less.

[0034] In certain embodiments, the molecular weight of the silicon-containing monomer of the polymerizable material can be 100 g / mol or more and 800 g / mol or less. The molecular weight of the silicon-containing monomer of the polymerizable material can be at least 100 g / mol, at least 200 g / mol, at least 300 g / mol, or at least 400 g / mol. In other embodiments, the molecular weight of the silicon-containing monomer can be 800 g / mol or less, 700 g / mol or less, 600 g / mol or less, 500 g / mol or less, or 400 g / mol or less.

[0035] In a further embodiment, the amount of at least one silicon-containing monomer can be at least 45% by weight, or at least 60% by weight, for example, at least 65% by weight, at least 70% by weight, at least 80% by weight, at least 90% by weight, at least 95% by weight, or 100% by weight, based on the total weight of the polymerizable material. In another embodiment, the amount of silicon-containing monomer can be 99% by weight or less, 95% by weight or less, 90% by weight or less, or 85% by weight or less, based on the total weight of the polymerizable material. In a particular embodiment, the amount of silicon-containing monomer can be 60% by weight or more and 85% by weight or less, based on the total weight of the polymerizable material.

[0036] Non-limiting examples of polymerizable monomers corresponding to the structure represented by formula (1) of the silicon-containing monomer include: Methacryloxymethyltris(trimethylsiloxy)silane (SiM1): [ka] 1,3-bis(3-methacryloxypropyl)tetrakis(trimethylsiloxy)disiloxane (SiM2): [ka] 3-acryloxypropyl-tris(trimethylsiloxy)silane (SiM3): [ka] (Methacryloxymethyl)bis(trimethylsiloxy)methylsilane (SiM4): [ka] 3-Methacryloxypropylbis(trimethylsiloxy)methylsilane (SiM5): [ka] (3-acryloxypropyl)methylbis(trimethylsiloxy)silane (SiM6): [ka] Methacryloxypropyltris(trimethylsiloxy)silane (SiM7): [ka] Acryloxymethyltrimethylsilane (SiM8): [ka] Acryloxymethyltris(trimethylsiloxy)silane (SiM9): [ka] 1,3-bis[(acryloxymethyl)phenethyl]tetramethyldisiloxane (SiM10): [ka] and methacryloxypropyl-terminated polydimethylsiloxane (SiM11): [ka] In the formula, n is a number of 1 to 4. The at least one silicon-containing monomer may include at least two different silicon-containing monomers.

[0037] The photocurable compositions of the present disclosure can be designed to have low viscosities prior to curing. In one embodiment, the viscosity of the photocurable composition can be 30 mPa·s or less, 25 mPa·s or less, 20 mPa·s or less, 15 mPa·s or less, or 10 mPa·s or less. In another specific embodiment, the viscosity can be at least 3 mPa·s or at least 5 mPa·s. In particularly preferred aspects, the photocurable composition can have a viscosity of 5 mPa·s or more and 20 mPa·s or less. All viscosity values ​​herein relate to viscosities measured at 23°C by the Brookfield method using a Brookfield viscometer.

[0038] In one embodiment, the polymerizable material of the photocurable composition can further include at least one non-silicon-containing polymerizable monomer, such as one or more monofunctional and / or one or more multifunctional polymerizable monomers.

[0039] In one embodiment, the non-silicon-containing polymerizable monomer can include an acrylate monomer. As used herein, the term acrylate monomer includes both unsubstituted acrylates and alkyl-substituted acrylates, such as methacrylates. Non-limiting examples of acrylate monomers include benzyl acrylate (BA), isobornyl acrylate (IBXA), 1,5-pentanediol diacrylate (MPDA), dihydrodicyclopentadienyl acrylate (DCPA), tricyclodecane dimethanol diacrylate (A-DCP), phenylethanediol diacrylate (PHEDA), bisphenol A dimethacrylate, m-xylylene diacrylate (mxDA), neopentyl glycol diacrylate, and any combination thereof.

[0040] In further embodiments, the amount of the at least one non-silicon-containing monomer (e.g., acrylate monomer) can be at least 5 wt.%, at least 10 wt.%, at least 15 wt.%, at least 20 wt.%, or at least 25 wt.%, based on the total weight of the polymerizable material. In other embodiments, the amount of the non-silicon-containing monomer can be no more than 40 wt.%, no more than 35 wt.%, no more than 30 wt.%, no more than 25 wt.%, or no more than 20 wt.%, based on the total weight of the polymerizable material.

[0041] The amount of polymerizable material in the photocurable composition can be at least 60% by weight, e.g., at least 70%, at least 80%, at least 85%, at least 90%, or at least 95% by weight, based on the total weight of the photocurable composition. In another embodiment, the amount of polymerizable material can be 99% by weight or less, e.g., 97% by weight or less, 95% by weight or less, 90% by weight or less, 85% by weight or less, 80% by weight or less, or 70% by weight or less. The amount of polymerizable material can be any value between the minimum and maximum values ​​listed above. In a specific embodiment, the amount of polymerizable material can be 70% by weight or more and 98% by weight or less.

[0042] In a further embodiment, the photocurable composition can further comprise at least one second release agent that is not an acetylenic diol (the acetylenic diol is also referred to herein as the "first release agent").

[0043] In one embodiment, the second release agent can be a nonionic ethoxylated fluorosurfactant. Non-limiting examples of ethoxylated fluorosurfactants include structures represented by the following formula (7), the following formula (8), and the following formula (9): [ka] In formula (7), x represents a number from 2 to 8, and y represents a number from 2 to 40; [ka] In formula (8), x represents a number from 5 to 15, and y represents a number from 20 to 40; [ka] In formula (9), x represents a number from 2 to 30, and y represents a number from 15 to 40.

[0044] In yet another embodiment, the second release agent can be a fluorine-free ethoxylated surfactant. A non-limiting example of the fluorine-free ethoxylated surfactant can be a structure represented by the following formula (10): [ka] In formula (10), x represents a number from 5 to 15, and y represents a number from 10 to 40.

[0045] In another embodiment, the second release agent may be a surfactant containing fluorine and silicon. Non-limiting examples include a surfactant represented by the following formula (11) and a surfactant represented by the following formula (12). [ka] [ka]

[0046] In yet another embodiment, the second release agent can be a polymer containing silicon and fluorine and having a molecular weight between 280 and 26,000 g / mol. Here, this is referred to as a Si / F release agent. Non-limiting examples of Si / F release agents include polymers having at least one of the following structures: a structure represented by formula (13), a structure represented by formula (14), a structure represented by formula (15), a structure represented by formula (16), and a structure represented by formula (17). [ka] [ka] [ka] [ka] [ka] In formulas (13) to (17), X can represent a C1 to C7 alkyl group or -CH=CH2. m represents a number from 0 to 80, n represents a number from 1 to 80, u represents a number from 1 to 6, y and z each independently represent a number from 0 to 40, p represents a number from 1 to 6, and q can represent a number from 3 to 13. L represents an oxygen atom, a nitrogen atom, a sulfur atom, or a C1 to C6 alkylene group, and R can represent an oxygen atom, a nitrogen atom, a sulfur atom, or an organic substituent having at least one carbon.

[0047] In certain embodiments, the second release agent has a low contact angle (CA T ) is the contact angle (CA S The contact angles of the photocurable composition on the pretreated template and the surface-coated substrate can be adjusted so that the contact angle is greater than 1 / 2. As used herein, the term "pretreated template" refers to a template (e.g., a quartz slide) that has been pretreated (primed) with the photocurable composition before testing the contact angle, while the surface-coated substrate is a silicon substrate coated with an adhesion layer coating.

[0048] In a non-limiting example, the adhesive layer coating can be a combination of Isorad 501 and hexamethoxymethylmelamine. The structure of Isorad 501 is represented by formula (18): [ka] In formula (18), n1 and n2 each independently represent a number from 1 to 12.

[0049] In one embodiment, CA T and CAS can be 15° or less, e.g., 12° or less, 10° or less, 8° or less, or 6° or less. T and CA S can be at least 1°, at least 2°, or at least 3°.

[0050] In certain embodiments, the contact angle with respect to the template can be greater than the contact angle with respect to the substrate (CA T >CA S ), where the difference in contact angles (ΔCA) can be at least 0.1°, at least 0.2°, at least 0.3°, at least 0.5°, at least 1°, at least 2°, or at least 3°. In alternative embodiments, ΔCA can be 6° or less, 5° or less, 3° or less, or 1° or less.

[0051] In one embodiment, the amount of the second release agent can be at least 0.1 wt.%, at least 0.2 wt.%, at least 0.3 wt.%, at least 0.5 wt.%, at least 0.7 wt.%, at least 1 wt.%, at least 1.5 wt.%, or at least 2 wt.%, based on the total weight of the photocurable composition. In another embodiment, the amount of the second release agent can be 10 wt.% or less, 5 wt.% or less, 2 wt.% or less, 1 wt.% or less, or 0.5 wt.% or less.

[0052] In one embodiment, the weight percent ratio of the first release agent (acetylenic diol) to the second release agent can be from 10:1 to 1:1, particularly from 10:1 to 3:1.

[0053] In one embodiment, the photocurable composition of the present disclosure can be essentially solvent-free. As used herein, unless otherwise specified, the term "solvent" refers to a compound that can dissolve or disperse polymerizable monomers but does not itself polymerize during photocuring of the photocurable composition. The term "essentially solvent-free" as used herein refers to an amount of solvent of 5% by weight or less, based on the total weight of the photocurable composition. In certain aspects, the amount of solvent can be 3% by weight or less, 2% by weight or less, or 1% by weight or less, based on the total weight of the photocurable composition, or the photocurable composition can be solvent-free except for unavoidable impurities.

[0054] In another specific embodiment, the photocurable composition can include a solvent in an amount of at least 5%, at least 8%, at least 10%, at least 15%, or at least 20% by weight, based on the total weight of the photocurable composition. In another embodiment, the amount of solvent can be 30% or less, 20% or less, 15% or less, 10% or less, 5% or less, or 3% or less by weight, based on the total weight of the photocurable composition.

[0055] The photocurable composition may include one or more photoinitiators to initiate photocuring of the composition upon exposure to light. In some embodiments, curing may be achieved by a combination of photocuring and thermal curing.

[0056] The photocurable composition may further include one or more optional additives, non-limiting examples of which include stabilizers, dispersants, solvents, surfactants, inhibitors, and any combination thereof.

[0057] In another embodiment, the photocurable composition of the present disclosure can be essentially free of particles, such as pigment particles. As used herein, essentially free of particles means that the photocurable composition contains no more than 50 particles per ml having a size of at least 200 nm, no more than 50 particles per ml having a size of at least 150 nm, no more than 50 particles per ml having a size of at least 100 nm, no more than 50 particles per ml having a size of at least 50 nm, no more than 50 particles per ml having a size of at least 20 nm, or no more than 50 particles per ml having a size of at least 15 nm.

[0058] In yet another embodiment, the photocurable composition of the present disclosure may be free of epoxy group-containing monomers, epoxy group-containing oligomers, acrylamides, or polyurethanes.

[0059] The photocurable compositions of the present disclosure can be adapted for use in inkjet adaptive planarization (IAP) or nanoimprint lithography (NIL).

[0060] A surprising advantage of the photocurable compositions of the present disclosure is their high stability. In one embodiment, the photocurable composition may have a stability factor (SF) of at least 14. Here, the stability factor is defined as the number of days that the photocurable composition does not exhibit phase separation at room temperature. In certain aspects, the stability factor may be at least 20, at least 30, or at least 50. As used herein, "phase separation" means that the photocurable composition splits into two separate phases or becomes turbid. To confirm phase separation, a light beam from a flashlight is irradiated onto a glass vial containing the photocurable composition. If the light beam passes through the glass vial without light scattering, no phase separation is observed, whereas if the light beam from the flashlight is scattered according to the Tyndall effect, phase separation is present. A more obvious indicator of phase separation (instability of the photocurable composition), without the need for light testing, is the observation of solid precipitate particles at the bottom of the glass vial or the formation of two liquid layers.

[0061] In one embodiment, the photocurable composition can be applied onto a substrate to form a photocurable layer. The combination of the substrate and the photocurable layer overlying the substrate is referred to herein as a laminate.

[0062] The present disclosure further relates to a method of forming a photocurable layer, which method may include applying a layer of the above-described photocurable composition onto a surface of a substrate, contacting the photocurable composition with a template or superstrate, irradiating the photocurable composition with light to form the photocurable layer, and removing the template or superstrate from the photocurable layer.

[0063] The substrate and solidified layer may undergo additional processing, such as, for example, an etching process, to transfer an image into the substrate that corresponds to the pattern in one or both of the solidified layer and / or the patterned layer underlying the solidified layer. The substrate may be subjected to further known steps and processes for device (article) manufacturing, including, for example, curing, oxidation, layer formation, deposition, doping, planarization, etching, molding material removal, dicing, bonding, and packaging.

[0064] The photocurable layer can also be used as an interlayer insulating film in semiconductor devices such as LSI, system LSI, DRAM, SDRAM, RDRAM, or D-RDRAM, or as a resist film used in the semiconductor manufacturing process. [Example]

[0065] The following non-limiting examples illustrate the concepts described herein.

[0066] Example 1 The photocurable compositions were prepared with the goal of obtaining a photocurable composition that has a high silicon content (at least 15% by weight of Si content) and is a clear, stable solution in the presence of a release agent (surfactant). A photocurable composition is herein considered to be a stable solution if all components dissolve to form a clear solution, and no phase separation or turbidity is observed after standing at room temperature for 14 days.

[0067] The following components were used to prepare the photocurable compositions: a) Silicon-containing polymerizable monomers: methacryloxymethyltris(trimethylsiloxy)silane (SiM1); 1,3-bis(3-methacryloxypropyl)tetrakis(trimethylsiloxy)disiloxane (SiM2); 3-acryloxypropyltris(trimethylsiloxy)silane (SiM3); methacryloxypropyltris(trimethylsiloxy)silane (SiM7); 1,3-bis[(acryloxymethyl)phenethyl]tetramethyldisiloxane (SiM10); and Methacryloxypropyl-terminated polydimethylsiloxane (SiM11) b) Silicon-free polymerizable monomers: Isobornyl acrylate (IBXA), benzyl acrylate (BA), dihydrodicyclopentadienyl acrylate (DCPA), m-xylylene diacrylate (mxDA), tricyclodecane dimethanol diacrylate (A-DCP), dipentaerythritol penta / hexaacrylate (DPHPA), 1-phenyl-1,2-ethanediyl ester (PHEDA), and 3-methyl-1,5-pentanediol diacrylate (MPDA). c) Release agent: D810 (Dynol (trademark) 810) from Air Products, an ethoxylated acetylenic diol having a structure represented by formula (5), wherein n and m each independently represent a number from 2 to 3; D604 (Dynol™ 604) from Air Products, an ethoxylated acetylenic diol having a structure represented by formula (5), where n and m are 4; S554 from Chemguard, a fluorine-containing surfactant having a structure represented by formula (7), where x=6, y<10, and molecular weight is 750 g / mol; FS2000M1, a fluorine-containing surfactant having a structure represented by formula (9), in which x and y are 9 and 21, respectively, manufactured by Wonda Science; FS2000M2, a fluorine-free surfactant having a structure represented by formula (10), wherein x = 9 and y = 21, manufactured by Wonda Science; MFR-M15, a surfactant containing fluorine and silicon and having a structure represented by formula (11), wherein n is a number from 15 to 40, manufactured by Gelest; A surfactant containing fluorine and silicon having a structure represented by formula (12), where n is a number from 15 to 40, is FMS C32 manufactured by Gelest. d) Photoinitiator: As photopolymerization initiators, Irgacure TPO, Irgacure 4265 and Irgacure 907, all manufactured by BASF, were used.

[0068] The first set of comparative photocurable compositions is summarized in Tables 1 and 2. These samples demonstrate that stable, clear solutions can be prepared with Si contents up to about 14.5 wt. % when containing conventional release agents commonly used in resists for NIL or AIP processing. However, it was not possible to obtain stable solutions with Si contents above 15 wt. % even when the type of polymerizable monomer was varied.

[0069] Tables 3 and 4 summarize photocurable compositions according to the present disclosure. All of these compositions contain acetylenic diol as a release agent. Surprisingly, it has been observed that the use of acetylenic diol as a release agent results in clear, stable solutions of photocurable compositions up to a silicon content of about 30 wt. % based on the total weight of the photocurable composition.

[0070] In Tables 1-4, the term "solubility" refers to the stability of the photocurable composition, with "Y" meaning that a clear photocurable composition was formed and maintained its clarity for at least 14 days, and "N" meaning that the photocurable composition was not a clear solution or underwent phase separation within 14 days.

[0071] [Table 1]

[0072] [Table 2]

[0073] [Table 3]

[0074] [Table 4]

[0075] Example 2 Two contact angle measurements were performed on the photocurable compositions containing the acetylenic diol described in Example 1 as a release agent: 1) the contact angle (CA) against a pretreated template, which was a quartz slide primed with the photocurable composition being tested. T 2) Contact angle (CA) on a substrate that is a silicon wafer coated with an adhesion layer coating SThe adhesive layer coating was a copolymer made from a mixture of Isorad 501 (Schenectady International, Schenectady, USA), see formula (18) above, and hexamethoxymethylmelamine (Cymel 303, Cytec Corporation, CA). T and CA S For both the template and the substrate, it is desirable to have a low contact angle that allows easy spreading of the photocurable composition. Here, the contact angle with the template must be larger than the contact angle with the substrate. That is, CA T >CA S is.

[0076] A summary of the contact angle measurements for samples S9 and S10 is shown in Table 5. Both compositions S9 and S10 had low contact angles with the template and substrate, but the contact angle with the template (CA T ) is the contact angle (CA S ) is lower than that.

[0077] For photocurable compositions S9 and S10, the contact angle was adjusted and improved by further adding various amounts of the fluorine-containing surfactant FS2000M1 (see Equation 9). As can be seen from Table 5, the addition of surfactant FS2000M1 increased the contact angle with the template and decreased the contact angle with the substrate (see samples S9-1 to S9-4 and S10-1 to S10-4). Therefore, the addition of 0.25 mass % of FS2000M1 made the contact angle with the template larger than the contact angle with the substrate (CA T >CA S The maximum amount of surfactant FS2000M1 added was 0.75% by weight, and at higher amounts, the photocurable composition was no longer stable and phase separation, indicated by "NS," occurred.

[0078] [Table 5]

[0079] A similar trend in contact angle measurements was observed for photocurable compositions S15 and S16. For these measurements, the additional surfactant added next to the acetylenic diol was the fluorine-containing surfactant S554, represented by formula (7) above. As shown in Table 6, the contact angles for both the template and the substrate were low for all photocurable compositions. However, when the photocurable composition contained only acetylenic diol (D810) as a release agent, the contact angle for the substrate was larger than the contact angle for the template. By adding 0.5% or 1.0% by weight of the release agent S554 in addition to the acetylenic diol, the contact angle could be adjusted, and the contact angle for the template was larger than the contact angle for the substrate (CA). T >CA S ) (see samples S15-1, S15-2 and S16-1, S16-2).

[0080] Furthermore, when 2% by mass of the release agent FS2KM2 (a fluorine-free surfactant) was added as a third release agent (see S16-3), the contact angles for the template and substrate increased further, but the increase in the contact angle for the template was much greater, and the CA T >CA S The relationship was maintained, with a difference of 4.6°.

[0081] [Table 6]

[0082] Contact angle measurement Contact angles were measured at room temperature using a Dropmaster DM-701 contact angle meter (Kyowa Interface Science Co., Ltd.). For each contact angle measurement, 2 ml of test sample was added to a syringe, from which a 2 μl droplet was mechanically applied to the target surface. Images of the droplet were continuously captured with a CCD camera from the time the droplet contacted the target surface. Contact angles were automatically calculated by the software associated with the Dropmaster DM-701 contact angle meter. The data shown in Tables 5 and 6 are contact angles measured 3 seconds after contact with the target surface.

[0083] viscosity The measured viscosities for all samples shown in Table 1 show very low viscosities below 10 mPa·s, even for representative samples S1, S2 and S3.

[0084] Viscosity was measured at 23°C using a Brookfield Viscometer LVDV-II+Pro at 200 rpm with a #18 spindle. For viscosity tests, approximately 6-7 mL of sample liquid was added to the sample chamber, enough to cover the spindle head. For all viscosity tests, at least three measurements were taken and the average value was calculated.

[0085] The viscosities of the photocurable compositions S1 to S16 were 4 mPa·s to 25 mPa·s.

[0086] Stability testing of photocurable compositions : Stability testing of each photocurable composition was performed by mixing all components in an 8 ml glass vial and mixing for approximately 1-2 minutes using a Corning™ Vortex Mixer. The vial was then capped and placed on a roller mixer to continue mixing the sample. Roll mixing continued until the mixture was free of solids or liquid phase separation was no longer observable. After mixing, the glass vials containing the photocurable compositions were stored on a shelf at room temperature. The photocurable compositions in the glass vials were visually inspected every 24 hours to observe the formation of precipitates or liquid phase separation. Phase separation was evaluated using an Energizer flashlight, which was placed on the outer wall of the glass vial and turned on. If the light beam could pass through the glass vial unobstructed, it was considered a clear solution. If light scattering (Tyndall effect) was visually observed, phase separation occurred, meaning the sample was unstable and unusable. Another clear indicator of phase separation (instability) was the visual observation of particles settling out at the bottom of the glass vial or the formation of two liquid layers.

[0087] Silicon Content Calculation The silicon content of the polymerizable material of the photocurable composition was calculated according to the following formula: Si [wt%] = [Σw i (n i M Si ) / M i )]×100%, where M Si is the molecular weight of silicon, M i is the molecular weight of each complete monomer, n i is the molar amount of Si in each monomer, w i is the molar amount of each monomer in the complete composition, e.g., w i =0.5 means that each monomer contributes 50% by weight to the composition.

[0088] The specification and drawings of the embodiments described in this disclosure are intended to provide a general understanding of the structure of various embodiments. The specification and drawings are not intended to serve as an exhaustive and comprehensive description of all elements and features of apparatus and systems that use the structures or methods described herein. Individual embodiments may be provided in combination in a single embodiment, and conversely, various features that are described for brevity in the context of a single embodiment may also be provided individually or in any combination. Furthermore, reference to numerical ranges includes each and every value within that range. Many other embodiments may be apparent to those skilled in the art only after reading this specification. Other embodiments can be used and derived from this disclosure, such that structural substitutions, logical substitutions, or other changes can be made without departing from the scope of the disclosure. Accordingly, the disclosure should be considered illustrative and not restrictive.

Claims

1. A photocurable composition comprising a polymerizable material, a non-fluorine-containing release agent, and a photopolymerization initiator, The polymerizable material contains at least one silicon-containing monomer having a structure represented by the following formula (1): 【Chemistry 1】 In formula (1), R1 and R2 each independently represent —O—Si(CH ３ ) ３ , an alkyl group, an aryl group, or an alkylaryl group; R3 and R4 each independently represent —O—Si(CH ３ ) ３ , an alkyl group, an aryl group, or an alkylaryl group; R5 is C １ ~C ５ represents an alkyl group, an aryl group, or an alkylaryl group represented by the formula: R6 is -R5-X, X, -O-Si(CH ３ ) ３ , an alkyl group, an aryl group, or an alkylaryl group; X represents an acrylate or methacrylate; n represents a number from 0 to 4, the amount of silicon (Si) in the photocurable composition is at least 15% by weight, based on the total weight of the polymerizable material; The photocurable composition, wherein the fluorine-free release agent comprises an acetylenic diol.

2. The photocurable composition according to claim 1 , wherein the acetylenic diol has a structure represented by the following formula (2) or a structure represented by the following formula (3): 【Chemistry 2】 【Transformation 3】 In formula (2) and formula (3), R1, R3, R5, and R7 each independently represent C １ ~C ３ R2, R4, R6, and R8 each independently represent an alkyl group of the formula C ４ ~C １２ X represents a hydrogen atom or a C １ ~C １０ and m and n each independently represent a number from 1 to 40.

3. The photocurable composition according to claim 2 , wherein the acetylenic diol comprises a structure represented by the following formula (4): 【Chemistry 4】

4. The photocurable composition according to claim 2, wherein the acetylenic diol is an ethoxylated acetylenic diol having a structure represented by the following formula (5) or a structure represented by the following formula (6): 【Transformation 5】 【Transformation 6】

5. 2. The photocurable composition of claim 1, wherein the amount of Si is at least 20% by weight, based on the total weight of the photocurable composition.

6. 2. The photocurable composition according to claim 1, wherein the silicon-containing monomer has a molecular weight of 100 g / mol or more and 800 g / mol or less.

7. 10. The photocurable composition of claim 1, wherein the amount of the at least one silicon-containing monomer is at least 45% by weight, based on the total weight of the polymerizable material.

8. The photocurable composition of claim 1 , wherein the photocurable composition further comprises at least one mold release agent that is not an acetylenic diol.

9. The photocurable composition according to claim 1, which has a viscosity of 30 mPa·s or less.

10. The photocurable composition of claim 1 , wherein the amount of the polymerizable material is at least 90% by weight, based on the total weight of the photocurable composition.

11. The photocurable composition of claim 1 , wherein the at least one silicon-containing monomer comprises at least two different silicon-containing monomers.

12. The at least one silicon-containing monomer is selected from the following group: methacryloxymethyltris(trimethylsiloxy)silane (SiM1), 1,3-bis(3-methacryloxypropyl)tetrakis(trimethylsiloxy)disiloxane (SiM2) 3-acryloxypropyl-tris(trimethylsiloxy)silane (SiM3), (methacryloxymethyl)bis(trimethylsiloxy)methylsilane (SiM4), 3-methacryloxypropylbis(trimethylsiloxy)methylsilane (SiM5), (3-acryloxypropyl)methylbis(trimethylsiloxy)silane (SiM6), methacryloxypropyltris(trimethylsiloxy)silane (SiM7), acryloxymethyltrimethylsilane (SiM8), acryloxymethyltris(trimethylsiloxy)silane (SiM9), 1,3-bis[(acryloxymethyl)phenethyl]tetramethyldisiloxane (SiM10), methacryloxypropyl-terminated polydimethylsiloxane (SiM11), and any combination thereof.

13. 2. The photocurable composition of claim 1, wherein the amount of the fluorine-free release agent is at least 2% by weight.

14. 10. The photocurable composition of claim 1, wherein the photocurable composition has a stability factor (SF) of at least 14, the stability factor being defined as the number of days the photocurable composition does not exhibit phase separation at room temperature.

15. The photocurable composition of claim 1 , wherein the polymerizable material further comprises at least one non-silicon-containing polymerizable monomer.

16. 16. The photocurable composition of claim 15, wherein the non-silicon-containing polymerizable monomer comprises an acrylate monomer.

17. 17. The photocurable composition of claim 16, wherein the amount of the acrylate monomer is at least 20% by weight.

18. 18. A laminate comprising a substrate and a photocurable layer overlying the substrate, the photocurable layer being formed from the photocurable composition of claim 1.

19. 1. A method for forming a photocurable layer on a substrate, comprising: applying a layer of a photocurable composition onto a substrate, wherein the photocurable composition comprises a polymerizable material, a non-fluorine-containing release agent, and at least one photoinitiator; The polymerizable material contains at least one silicon-containing monomer having a structure represented by the following formula (1): 【Transformation 7】 In formula (1), R1 and R2 each independently represent —O—Si(CH ３ ) ３ , an alkyl group, an aryl group, or an alkylaryl group; R3 and R4 each independently represent —O—Si(CH ３ ) ３ , an alkyl group, an aryl group, or an alkylaryl group; R5 is C １ ~C ５ represents an alkyl group, an aryl group, or an alkylaryl group represented by the formula: R6 is -R5-X, X, -O-Si(CH ３ ) ３ , an alkyl group, an aryl group, or an alkylaryl group; X represents an acrylate or methacrylate; n represents a number from 0 to 4, the amount of silicon (Si) in the photocurable composition is at least 15% by weight, based on the total weight of the polymerizable material; The fluorine-free release agent comprises an acetylenic diol, contacting the photocurable composition with a template or superstrate; a step of irradiating the photocurable composition with light to form a photocured layer; and removing the template or the superstrate from the photocurable layer.

20. 1. A method for manufacturing an article, comprising: applying a layer of a photocurable composition onto a substrate, wherein the photocurable composition comprises a polymerizable material, a non-fluorine-containing release agent, and at least one photoinitiator; The polymerizable material contains at least one silicon-containing monomer having a structure represented by the following formula (1): 【Transformation 8】 In formula (1), R1 and R2 each independently represent —O—Si(CH ３ ) ３ , an alkyl group, an aryl group, or an alkylaryl group; R3 and R4 each independently represent —O—Si(CH ３ ) ３ , an alkyl group, an aryl group, or an alkylaryl group; R5 is C １ ~C ５ represents an alkyl group, an aryl group, or an alkylaryl group represented by the formula: R6 is -R5-X, X, -O-Si(CH ３ ) ３ , an alkyl group, an aryl group, or an alkylaryl group; X represents an acrylate or methacrylate; n represents a number from 0 to 4, the amount of silicon (Si) in the photocurable composition is at least 15% by weight, based on the total weight of the polymerizable material; The fluorine-free release agent comprises an acetylenic diol, contacting the photocurable composition with a template or superstrate; a step of irradiating the photocurable composition with light to form a photocured layer; removing the template or the superstrate from the photocurable layer; forming a pattern on the substrate; a step of treating the substrate on which the pattern has been formed in the step of forming the pattern; and The method includes manufacturing an article from the substrate processed in the step of processing the substrate.

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