Curable composition

Abstract

The present invention relates to a curable composition, preferably a photocurable composition, comprising at least a first monomer compound and a polymerization initiator.

Description

Technical Field

[0001] This invention relates to a curable composition (preferably a photocurable composition), a method for preparing the curable composition, a method for preparing a cured layer, a cured layer, and a stacked layer. Background Technology

[0002] In the semiconductor industry, miniaturization has been a continuous trend in order to improve the performance of microchips. However, achieving 7-nanometer and smaller node technologies significantly increases complexity and requires some new process and material solutions.

[0003] Inkjet adaptive planarization technology can be used to planarize the surface of a substrate. This involves printing droplets of a photocurable composition onto the substrate surface. The droplet pattern can be customized to the existing surface morphology. A superstrate is brought into direct contact with the liquid to form a planar liquid layer. This planar liquid layer is typically cured under UV light; removing the superstrate yields a planar surface suitable for subsequent processing steps.

[0004] Existing photocurable compositions typically contain high levels of acrylate monomers.

[0005] US 2020 / 0339828 A1 describes the use of a specific photocurable composition comprising a polymerizable material and a photoinitiator, wherein at least 90% by weight of the polymerizable material comprises an acrylate monomer containing an aromatic group.

[0006] US 2021 / 0198400 A1 relates to specific light-curable compositions comprising 1,3-benzaxazine and acrylate monomers.

[0007] US 2020 / 201178 A1 describes a specific light-curable composition containing a shrinkage compensator.

[0008] US 2021 / 0070906 A1 describes a specific curable composition comprising a polymerizable material and an initiator, wherein the polymerizable material comprises a first monomer and a second monomer, and the second monomer comprises a ring structure selected from maleimide rings, pyranone rings, or 2-furanone rings.

[0009] US 2022 / 0185914 A1 describes a light-curable composition comprising a polymerizable material, wherein the polymerizable material comprises at least one polyfunctional vinylbenzene.

[0010] Another prior art document (US2023 / 0203210 A1) reports polymerizable compositions based on a dual aromatic system containing vinylbenzene or alkynyl groups. According to the dependent claims of that document, these compositions may contain acrylates.

[0011] Patent documents

[0012] 1. US 2020 / 0339828 A1

[0013] 2. US 2021 / 0198400 A1

[0014] 3. US 2020 / 201178 A1

[0015] 4. US 2021 / 0070906 A1

[0016] 5. US 2022 / 0185914 A1

[0017] 6. US 2023 / 0203210 A1

[0018] Non-patent literature

[0019] No literature Summary of the Invention

[0020] However, the inventors have recently discovered that one or more important issues still need to be addressed, as described below: improved thermal stability after curing (preferably at about 350°C or higher); reduced shrinkage after curing; improved etch resistance of the cured layer; improved planarization properties of the cured layer (i.e., on different pattern morphologies of the substrate); the composition having low viscosity and / or low vapor pressure (preferably suitable for inkjet printing); suitability for forming the cured layer by inkjet printing; and imparting mechanical durability to the cured layer.

[0021] The inventors aimed to solve one or more of the problems mentioned above.

[0022] Furthermore, the inventors have unexpectedly discovered that one or more of the aforementioned technical problems can be solved by the features defined in the claims.

[0023] Specifically, a novel curable composition, preferably a photocurable composition, has been discovered, comprising at least a first monomer compound and a polymerization initiator, wherein the first monomer compound is represented by chemical formula (I).

[0024] - (I)

[0025] in

[0026] m2 to m4 are each independently 0 or 1;

[0027] n1 to n4 are each independently 0, 1 or 2; n1 + n2 + n3 + n4 ≥ 1;

[0028] The first monomer currently has at least one vinyl group;

[0029] o2 to o4 are each independently 0 or 2;

[0030] When o2 is 2, the two R2s are adjacent methyl groups, which bond to each other to form a cyclobutene structure on the benzene ring; and the relationship between o3 and R3 and the relationship between o4 and R4 are the same.

[0031] L2 to L4 are each independently derived from direct bonds, C 1-15 Alkylene and C 2-15 Selected from the group composed of subalkenyl groups

[0032] One or more non-adjacent methylene groups in the alkylene or alkenylene group may be replaced by O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH; and

[0033] One or more H atoms can be replaced by D, F, Cl, Br, I, CN, or NO2.

[0034] The present invention also provides a composition further comprising a second monomeric compound represented by chemical formula (II),

[0035] -(II)

[0036] in

[0037] m6 and m7 are each independently 0 or 1;

[0038] o5 can be 0, 1, 2, 3, 4, 5, or 6;

[0039] o6 and o7 are each independently 0, 1 or 2;

[0040] R5 through R7 are each independently C 1-4 Alkyl, vinyl, or ethynyl;

[0041] The second monomer currently has at least one vinyl or acetylene group;

[0042] L6 and L7 are independently derived from direct bonds, C 1-15 Alkylene and C 2-15 Selected from the group composed of subalkenyl groups

[0043] One or more non-adjacent methylene groups in the alkylene or alkenylene group may be replaced by O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH; and

[0044] One or more H atoms can be replaced by D, F, Cl, Br, I, CN, or NO2.

[0045] In another form, the present invention also provides a method for preparing a composition, which includes at least the following step (A):

[0046] (A) Mixing a first monomer compound and a polymerization initiator in at least one embodiment.

[0047] As another embodiment, the present invention also provides a method for preparing a cured layer, which includes at least the following steps (i a ) and (i b ):

[0048] (i a The composition of any embodiment is provided onto a substrate, preferably by printing, more preferably by spin coating, slot coating or inkjet printing;

[0049] (i d Optionally, the composition can be brought into contact with a template;

[0050] (i b The composition is cured by heating and / or irradiating it with light to form a cured layer;

[0051] (i e Optionally, the template can be removed from the cured layer.

[0052] The present invention also provides a cured layer obtained by or achievable by the methods described above and below. As yet another embodiment, the present invention provides a stacked layer comprising a substrate and a cured layer according to any embodiment.

[0053] The present invention also provides a novel compound represented by formula (I).

[0054] Equation (I) is the same as described above. n1+n2+n3+n4≥2.

[0055] Unless otherwise stated, the definitions and detailed descriptions of each part of formula (I) in a chemical compound are independently identical to the corresponding definitions and detailed descriptions of formula (I) in a curable composition.

[0056] Technical effects of the present invention

[0057] The present invention provides one or more of the following technical effects: improved thermal stability after curing (preferably at about 350°C or higher); reduced shrinkage after curing; improved etch resistance of the cured layer; improved planarization performance of the cured layer (i.e., on different pattern morphologies of the substrate); the composition has low viscosity and / or low vapor pressure (preferably suitable for inkjet printing); suitable for forming a cured layer by inkjet printing; and imparts mechanical durability to the cured layer. Attached Figure Description

[0058] [ Figure 1 ]

[0059] Gray (dashed line): Isothermal baking performance of existing technology (100% compound B + 4% by weight OXE02).

[0060] Black (solid line): Isothermal baking performance of WE1 (Working Example 1, 50 wt% Compound A + 50 wt% Compound + 4 wt% OXE02). Detailed Implementation

[0061] Terminology Definition

[0062] Unless otherwise specified, the definitions or examples set forth in this paragraph shall apply in this specification.

[0063] The singular form includes the plural form, and "a" or "the" means "at least one". An element in a concept can be expressed in multiple types, and when describing its quantity (e.g., mass% or mole%), the quantity refers to the sum of the multiple types.

[0064] "And / or" includes all combinations of elements, as well as cases where elements are used individually.

[0065] When using "~ / to" or "-" to represent a numerical range, it includes both endpoints and the units are the same. For example, 5 to 25 mol% means more than 5 mol% and less than 25 mol%.

[0066] Such as "C" x-y “C” x -C y "and "C x Descriptions like "" indicate the number of carbon atoms in a molecule or substituent. For example, C 1-6 Alkyl refers to an alkyl chain having one or more but no more than six carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).

[0067] When a polymer has multiple repeating units, these repeating units will copolymerize. The copolymerization of these repeating units can be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof. When a polymer or resin is represented by a structural formula, the symbols such as n and m outside the parentheses indicate the number of repeating units.

[0068] Temperature is measured in Celsius. For example, 20 degrees means 20 degrees Celsius.

[0069] Additives refer to compounds that have a specific function (e.g., a base-generating agent refers to a compound that can generate a base). An embodiment may also exist in which the compound is dissolved or dispersed in a solvent and added to the composition. As an embodiment of the invention, preferably, the solvent is included as solvent (B) or as another component in the composition according to the invention. Invention Details

[0071] According to the present invention, the curable composition (preferably a photocurable composition) comprises a first monomer compound and a polymerization initiator, wherein the first monomer compound is represented by chemical formula (I):

[0072] - (I)

[0073] in

[0074] m2 to m4 are each independently 0 or 1;

[0075] n1 to n4 are each independently 0, 1 or 2; n1 + n2 + n3 + n4 ≥ 1;

[0076] The first monomer currently has at least one vinyl group;

[0077] o2 to o4 are each independently 0 or 2;

[0078] When o2 is 2, the two R2s are adjacent methyl groups, which bond to each other to form a cyclobutene structure on the benzene ring; and the relationship between o3 and R3 and the relationship between o4 and R4 are the same.

[0079] L2 to L4 are each independently derived from direct bonds, C 1-15 Alkylene and C 2-15 Selected from the group composed of subalkenyl groups

[0080] One or more non-adjacent methylene groups (-CH2-) in the alkylene or alkenylene group may be replaced by O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH, and one or more H atoms may be replaced by D, F, Cl, Br, I, CN, or NO2.

[0081] In a preferred embodiment of the invention, the composition is a composition for inkjet adaptive planarization (IAP).

[0082] - First monomer compound

[0083] According to the present invention, the first monomeric compound is represented by chemical formula (I).

[0084] m2 to m4 are each independently 0 or 1. m2 is preferably 0 or 1; more preferably 0. m3 is preferably 0 or 1; more preferably 1. m3 being 0 is also a preferred embodiment of the present invention. m4 is preferably 0 or 1; more preferably 0.

[0085] As one embodiment of the present invention, the compound on the left below can be interpreted as the first monomer in the present invention, wherein "m2 to m4 are all 0 and n1=2". As another embodiment, the compound on the right below can be interpreted as the first monomer in the present invention, wherein "m2 and m4 are 0, m3 is 1, n3=2, o3=0, and L3 is methylene".

[0086] ;

[0087] n1 to n4 are each independently 0, 1 or 2.

[0088] n1+n2+n3+n4≥1. More preferably, n1+n2+n3+n4≥2. Further preferably, n1+n2+n3+n4=2 or 3. Even more preferably, n1+n2+n3+n4=2.

[0089] The first monomer currently has at least one vinyl group. Embodiments where n2=1, n1=n3=n4=0, and m2=0 are not included in the scope of this invention because the first monomer cannot contain a vinyl group enclosed in n2. If any of n1 to n4 is 2, it is preferable to have two meta- or para-vinyl groups substituted on the benzene ring; meta-is a more preferred choice.

[0090] o2 to o4 are each independently 0 or 2.

[0091] When o2 is 2, the two R2s are adjacent methyl groups, which bond to each other to form a cyclobutene structure on the benzene ring; and the relationship between o3 and R3 and the relationship between o4 and R4 are the same.

[0092] As one embodiment of the present invention, the following compound can be interpreted as the first monomer of the present invention, namely, "m2 and m4 are 0, m3=1, n1=1, n3=0, o3=2, the two R3 are adjacent methyl groups and bonded to each other, forming a cyclobutene structure on the benzene ring enclosed by m3, and L3 is a direct bond".

[0093]

[0094] o2 is preferably 0 or 2, more preferably 0. o3 is preferably 0 or 2, more preferably 0. o4 is preferably 0 or 2, more preferably 0.

[0095] The first monomer of the present invention preferably comprises one or two cyclobutene structures; more preferably, it comprises one cyclobutene structure.

[0096] L2 to L4 are each independently derived from direct bonds, C 1-15 Alkylene and C 2-15 The group is selected from the group consisting of alkenyl groups. This group is preferably a direct bond, C... 1-4 Alkylene and C 2-4 The group is alkenyl; more preferably a direct bond, methylene, and ethylene; further preferably a direct bond and methylene; even more preferably a direct bond. The fact that L2 to L4 are all methylene is also a preferred embodiment of the present invention.

[0097] As one embodiment of the present invention, the following compound can be interpreted as the first monomer of the present invention, namely, "m2=0, m3 and m4 are 1, n1=0, n3=n4=1, o3=o4=0, and L3 and L4 are methylene".

[0098]

[0099] One or more non-adjacent methylene groups (-CH2-) in any one or more of the alkylene or alkenylene groups described in L2 to L4 may optionally be replaced by O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH. In a preferred embodiment of the invention, none of the methylene groups in L2 to L4 are replaced by O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH.

[0100] One or more H atoms in the first monomer may optionally be replaced by D (deuterium), F, Cl, Br, I, CN, or NO2. In a preferred embodiment of the invention, none of the H atoms in the first monomer are replaced by D, F, Cl, Br, I, CN, or NO2.

[0101] For clarity, it goes without saying that the curable composition of the present invention may contain various types of "first monomers". As one embodiment, the curable composition of the present invention may contain two types of compounds as first monomers, both of which conform to chemical formula (I).

[0102] ;

[0103] While not bound by theory, it is believed that compounds with high carbon content (preferably 80% or more of the compound) contribute to the formation of a carbon-rich, flat underlayer; simultaneously, their low viscosity and relatively low vapor pressure make them well-suited for inkjet printing processes, namely the IAP process described in this invention. Furthermore, the first monomer compound is believed to contain benzocyclobutene, which, upon UV-initiated free radical polymerization, forms a highly crosslinked thermosetting material. This high crosslink density contributes to improved chemical and thermal stability, which is crucial for its function as a hard mask.

[0104] In a preferred embodiment of the present invention, formula (I) is represented by the following formula (I').

[0105]

[0106] The definitions, detailed descriptions, explanations, and implementation schemes of each part of Equation (I') are independently the same as those of Equation (I) above.

[0107] Table A below shows preferred examples of the first monomer compound.

[0108] Table A:

[0109]

[0110] In a preferred embodiment of the invention, the total amount of the first monomer compound is in the range of 5 to 99.99% by weight, based on the total amount of the composition; preferably 20 to 99.99% by weight; more preferably 40 to 99.9% by weight; further preferably 50 to 99.9% by weight; and even more preferably 80 to 99% by weight.

[0111] - Second monomer compound

[0112] According to the present invention, the composition may further comprise a second monomeric compound represented by chemical formula (II).

[0113] (II)

[0114] in

[0115] m6 and m7 are each independently 0 or 1;

[0116] o5 to o7 are each independently 0, 1 or 2;

[0117] The second monomer currently has at least one vinyl or acetylene group;

[0118] R5 through R7 are each independently C 1-4 Alkyl, vinyl, or ethynyl;

[0119] L6 and L7 are independently derived from direct bonds, C 1-15 Alkylene and C 2-15 Selected from the group composed of sub-alkenyl groups

[0120] One or more non-adjacent methylene groups in the alkylene or alkenylene group may be replaced by O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH; and

[0121] One or more H atoms can be replaced by D (deuterium), F, Cl, Br, I, CN, or NO2.

[0122] The first monomer compound and the second monomer compound are different from each other.

[0123] m6 and m7 are each independently 0 or 1. m6 is preferably 0 or 1; more preferably 0. m7 is preferably 0 or 1; more preferably 1. m7 being 0 is also another preferred embodiment of the present invention.

[0124] As one embodiment of the present invention, the compound on the left below can be interpreted as the second monomer of the present invention, wherein "m6 and m7 are 0, o5 is 3, and all three R5s are vinyl". As another embodiment, the compound on the right below can be interpreted as the second monomer of the present invention, wherein "m6 is 0, m7 is 1, o5 and o7 are 1, and R5 and R7 are vinyl".

[0125] ;

[0126] o5 is 0, 1, 2, 3, 4, 5 or 6 (preferably 1, 2, 3 or 4; more preferably 1, 2 or 3; even more preferably 1 or 2; even more preferably 2).

[0127] o6 and o7 are each independently 0, 1 or 2. o6 is preferably 0, 1 or 2; more preferably 1 or 2; even more preferably 1. o7 is preferably 0, 1 or 2; more preferably 1 or 2; even more preferably 1.

[0128] R5 through R7 are each independently C 1-4 Alkyl, vinyl, or ethynyl; preferably methyl, vinyl, or ethynyl; more preferably methyl or vinyl; even more preferably vinyl.

[0129] The second monomer currently has at least one of vinyl or ethynyl groups; at least one vinyl group is currently preferred.

[0130] The implementation scheme of “o6=1, o5=o7=0 and m6=0” is not included in the scope of the second monomer of the present invention because the second monomer cannot contain R6 (vinyl or ethynyl group enclosed in o6).

[0131] When any one of O5 to O7 is 2, it is preferred that any one or more of R5 to R7 are substituted with benzene at the meta or para position; and the meta position is more preferred.

[0132] L6 and L7 are independently derived from direct bonds, C 1-15 Alkylene and C 2-15 Selected from the group consisting of alkenyl groups (preferably from those composed of direct bonds, C1-6 alkylene groups, and C1-6 alkylene groups). 2-4 The group consisting of alkenyl groups is selected; more preferably from the group consisting of direct bonds, methylene, ethylene (-CH2-CH2-) and propylene; even more preferably from the group consisting of direct bonds and ethylene; and even more preferably ethylene.

[0133] One or more non-adjacent methylene groups in the alkylene or alkenylene group may be replaced by O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH. In a preferred embodiment of the invention, no methylene groups in L6 and L7 are replaced by O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH.

[0134] One or more H atoms in the second monomer may optionally be replaced by D, F, Cl, Br, I, CN, or NO2. In a preferred embodiment of the invention, no H atoms in the second monomer are replaced by D, F, Cl, Br, I, CN, or NO2.

[0135] While not bound by theory, it is believed that compounds with high carbon content (preferably 80% or higher) contribute to the formation of a carbon-rich, flat underlayer; simultaneously, their low viscosity and relatively low vapor pressure make them well-suited for inkjet printing processes, specifically the IAP process described in this invention. Furthermore, it is believed that the second monomer compound, upon UV-initiated free radical polymerization, can form a highly cross-linked thermosetting material. This high cross-linking density contributes to improved chemical and thermal stability, which is crucial for its function as a hard mask.

[0136] By adding a second monomer compound to the first monomer compound and controlling their mixing ratio, the viscosity, crosslinking properties, vapor pressure and / or thermal stability, and post-curing shrinkage of the composition can be controlled; the etch resistance of the cured layer is improved; and the planarization properties of the cured layer are improved.

[0137] As a preferred embodiment of the present invention, the total amount of the first monomer compound and the second monomer compound is in the range of 10 to 99.9% by weight (preferably 50 to 99.9% by weight; more preferably 80 to 99% by weight) based on the total amount of the composition.

[0138] As another embodiment of the present invention, the amount of the second monomer compound is in the range of 10 to 90% by weight (preferably 20 to 80% by weight; more preferably 30 to 70% by weight; and even more preferably 40 to 60% by weight) based on the amount of the first monomer compound.

[0139] Table B below shows preferred examples of the second monomer compound.

[0140] Table B:

[0141]

[0142]

[0143]

[0144]

[0145] - Third / fourth monomeric compounds

[0146] In some embodiments of the invention, the composition may optionally comprise a third and / or a fourth monomeric compound. The third and / or fourth monomeric compounds are different from each other and also different from the first and second monomeric compounds.

[0147] - Polymerization initiator

[0148] The polymerization initiators of the present invention include polymerization initiators that generate acids, bases or free radicals by radiation, and polymerization initiators that generate acids, bases or free radicals by heat.

[0149] Preferably, the polymerization initiator is selected from photoradical initiators, photoacid generators, or combinations of photoradical initiators and photoacid generators. Examples include Irgacure OXE02 (Boc Sciences, CAS: 478556-66-0), Omnirad1316 (IGM Resins), Irgacure 651 (Merck, CAS: 24650-42-8), and Irgacure 819 (Merck, CAS: 162881-26-7).

[0150] According to the present invention, publicly available substances as described in EP3717966A1 or WO2021 / 099236A1 may preferably be used.

[0151] - Composition

[0152] In a preferred embodiment of the invention, the composition comprises 10% by weight or less of acrylate monomers based on the total amount of the composition, preferably in the range of 0 to 10% by weight, more preferably in the range of 0 to 5% by weight, and even more preferably an acrylate-free composition comprising 0% by weight of acrylate monomers.

[0153] While not bound by theory, it is believed that containing 10% by weight or less of acrylate monomers results in a significantly increased carbon content in the cured film obtained from the composition. This higher carbon content improves etch resistance, which is crucial for the function of carbon-rich hard masks and pattern etching transfer. Furthermore, acrylates are believed to reduce the temperature stability of the cured film and lead to greater UV-induced shrinkage in the photocuring system. These disadvantages of using acrylates can be reduced or eliminated by reducing the total amount of acrylate monomers in the composition to 10% by weight or less, more preferably in the range of 0 to 5% by weight.

[0154] As another embodiment of the invention, it is believed that adding a small amount of acrylate can provide flexibility in adjusting the viscosity, inkjetability, and / or vapor pressure of the composition. It can also improve the photocuring speed of the composition.

[0155] Preferably, the composition of the present invention contains 10% by weight or less of solvent based on the total amount of the composition, preferably in the range of 0 to 10% by weight, more preferably in the range of 0 to 5% by weight, and even more preferably a solvent-free composition containing 0% by weight of solvent.

[0156] While not bound by theory, it is believed that setting the total solvent content in the composition to 10% by weight or less based on the total composition amount is beneficial for reducing process steps, minimizing process time, facilitating handling (i.e. for inkjet printing), and / or minimizing / avoiding contamination by impurities.

[0157] - Additives

[0158] According to the present invention, in some embodiments, the composition may, as appropriate, include one or more additives selected from the group consisting of surfactants, wetting agents, release agents, oxygen quenchers and stabilizers.

[0159] Another embodiment of the invention is that the composition comprises one or more additives, and the total amount of these additives accounts for 0 to 10% by weight of the total composition (preferably 0 to 5% by weight; more preferably 0 to 2% by weight; even more preferably 0% by weight).

[0160] Another preferred embodiment of the invention is a composition that does not contain additives (0% by weight).

[0161] As the additive, a known material preferably used in the semiconductor industry can be used in this invention.

[0162] It is believed that surfactants and release agents can be used to reduce the adhesiveness of the composition (preferably to the cover material) to improve processability.

[0163] - Viscosity

[0164] In a preferred embodiment of the invention, the viscosity of the composition at 23°C is in the range of 2 to 100 cP; from the perspective of achieving smooth inkjet printing, it is preferably 5 to 50 cP, more preferably 5 to 20 cP, and even more preferably 7 to 20 cP.

[0165] The viscosity of the composition can be adjusted, for example, by changing the type of the first monomer and / or the second monomer, and by changing the amount of the first monomer and / or the second monomer.

[0166] The viscosity of the compositions of this invention can be measured using an Anton Paar MCR92 rheometer (Anton Paar, Granz, Austria) using a conical plate geometry. Viscosity values ​​were measured at 23°C using a rotating conical plate geometry (d=25mm) for 500 s. -1 The shear rate was measured.

[0167] - Method for preparing the composition

[0168] In another embodiment, the present invention relates to a method for preparing the composition of the present invention, the method comprising at least the step (A):

[0169] (A) Mix at least the first monomer compound of formula (I) with a polymerization initiator.

[0170] - (I)

[0171] in

[0172] m2 to m4 are each independently 0 or 1;

[0173] n1 to n4 are each independently 0, 1 or 2; n1 + n2 + n3 + n4 ≥ 1;

[0174] The first monomer currently has at least one vinyl group;

[0175] o2 to o4 are each independently 0 or 2;

[0176] When o2 is 2, the two R2s are adjacent methyl groups, which bond to each other to form a cyclobutene structure on the benzene ring; and the relationship between o3 and R3 and the relationship between o4 and R4 are the same.

[0177] L2 to L4 are each independently derived from direct bonds, C 1-15 Alkylene and C 2-15 Selected from the group composed of sub-alkenyl groups

[0178] One or more non-adjacent methylene groups in the alkylene or alkenylene group may be replaced by O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH; and

[0179] One or more H atoms can be replaced by D, F, Cl, Br, I, CN, or NO2.

[0180] In another embodiment, the present invention also relates to a method for preparing a cured layer, which includes at least the following steps (i a ) and (i b ):

[0181] (i a The composition of the present invention is provided onto a substrate, preferably by printing, more preferably by spin coating, slot coating or inkjet printing, and even more preferably by inkjet printing;

[0182] (i d Optionally, the composition can be brought into contact with a template;

[0183] (i b The composition is cured by heating and / or irradiating it with light to form a cured layer;

[0184] (i e Optionally, the template can be removed from the cured layer.

[0185] As one implementation method, step (i) d ) and (i e The template used is preferably patterned or unpatterned; more preferably unpatterned. One embodiment of such an unpatterned template is a superstrate.

[0186] Regarding the cover plate, known materials can be used. For example, the cover plate and method described by Niyaz Khusnatdinov et al. in “Development of an inkjet-enabled Adaptive Planarization Process”, Proceedings Volume 10451, Photomask Technology 2017; 104511A (2017) are preferred.

[0187] In some implementations, the curing can be photocuring, thermocuring, or a combination of photocuring and thermocuring.

[0188] In a preferred embodiment, the photocuring is performed by irradiating the composition with UV light, with a curing energy ranging from 0.1 to 30 J / cm². 2 More preferably, it is 0.3 to 25 J / cm 2 More preferably 0.5 to 2 J / cm 2 The preferred UV light wavelength is 250 nm to 400 nm, more preferably about 350 nm.

[0189] In a preferred embodiment, the method in step (i) b This is followed by the following steps (i) c ):

[0190] (i c Bake the cured layer for a period of time ranging from 0.5 to 10 minutes at a temperature ranging from 180 to 450°C.

[0191] Although not bound by theory, it is believed that heat treatment (whether through proper post-exposure baking or through heat in subsequent thermal processes) can initiate ring-opening of the cyclobutene ring in compounds represented by formula (I) or (I'). This process generates a reactive o-quinodimethane intermediate that undergoes a cycloaddition reaction. These reactions contribute to improving the mechanical strength and enhancing the thermal stability of the cured material.

[0192] In a preferred embodiment, the method for preparing the cured layer is inkjet adaptive planarization (IAP).

[0193] In another embodiment, the present invention also relates to a cured layer, preferably a photocurable layer. More preferably, the cured layer is obtained by or can be obtained by the method of the present invention combining photocuring and thermal curing (dual curing). Another embodiment of the present invention relates to providing a method for manufacturing the aforementioned cured layer.

[0194] In another embodiment, the present invention also relates to a cured layer formed from the composition of the present invention, preferably a photocurable layer, more preferably a double-curable layer. In a preferred embodiment, the cured layer can be used as an interlayer insulating film in a semiconductor device, or as a bottom spin-coated carbon (SOC) in the manufacture of semiconductors, for example for LSI, system LSI, DRAM, SDRAM, RDRAM, or D-RDRAM.

[0195] In another embodiment, the invention relates to a stacked layer comprising a substrate and a cured layer of the invention at least partially covering the substrate. As another embodiment, the invention provides a method for manufacturing the aforementioned stacked layer.

[0196] - New compounds

[0197] The present invention also provides a novel compound represented by chemical formula (I).

[0198] - (I)

[0199] in

[0200] m2 to m4 are each independently 0 or 1;

[0201] n1 to n4 are each independently 0, 1, or 2; n1 + n2 + n3 + n4 ≥ 2

[0202] The first monomer currently has at least one vinyl group;

[0203] o2 to o4 are each independently 0 or 2;

[0204] When o2 is 2, the two R2s are adjacent methyl groups, which bond to each other to form a cyclobutene structure on the benzene ring; and the relationship between o3 and R3 and the relationship between o4 and R4 are the same.

[0205] L2 to L4 are each independently derived from direct bonds, C 1-15 Alkylene and C 2-15 Selected from the group composed of sub-alkenyl groups

[0206] One or more non-adjacent methylene groups in the alkylene or alkenylene group may be replaced by O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH; and

[0207] One or more H atoms can be replaced by D, F, Cl, Br, I, CN, or NO2.

[0208] In a preferred embodiment of the present invention, the new compound is represented by the following formula (I').

[0209]

[0210] The definitions, detailed descriptions, explanations, and implementation schemes of each part of the new compound represented by formulas (I) and (I') are the same as those of formulas (I) and (I') described in the "First Monomer" section above.

[0211] The embodiments provided below further illustrate the invention, but these embodiments should not in any way be construed as limiting the invention. Those skilled in the art will recognize that various modifications, additions, and alterations can be made to the invention without departing from the spirit and scope of the invention as defined by the appended claims.

[0212] Example

[0213] Part A: Synthesis Examples

[0214] Example 1: 3-(3,5-divinylphenyl)bicyclo[4.2.0]octyl-1,3,5-triene

[0215]

[0216] Step 1: Synthesis of 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)-m-phthalaldehyde

[0217]

[0218] 5-Bromo-isophthalaldehyde (Amadis Chemical, CAS: 120173-41-3, 28.2 mmol, 6 g), KOAc (Merck, CAS: 127-08-2, 84.5 mmol, 8.3 g), and bis(pinacol)diboron (Merck, CAS: 73183-34-3, 31 mmol, 7.9 g) were dissolved in 1,4-dioxane (100 mL), and the air was purged with nitrogen. Palladium catalyst (Merck, CAS: 72287-26-4, 0.85 mmol, 618 mg) was then added, and the reaction mixture was heated to 80 °C overnight. The reaction mixture was then diluted with water and extracted with ethyl acetate. The organic phase was subsequently washed successively with water (2 volumes) and brine, dried over Na₂SO₄, filtered, and the solvent evaporated. To purify the crude product mixture, it was dissolved in ethyl acetate and purified by silica gel column chromatography using a mixture of heptane / ethyl acetate (1:1 v / v). The fractions were combined and evaporated to give a yellow solid (6.2 g, 84.6%).

[0219] 1¹H NMR (500 MHz, chloroform-d): δ = 10.14 (s, 2H), 8.56 (d, J = 1.6 Hz, 2H), 8.46 (t, J = 1.7 Hz, 1H), 1.39 (s, 12H) ppm.

[0220] Step 2: Synthesis of 5-(bicyclo[4.2.0]oct-1,3,5-trien-3-yl)-m-phthalaldehyde

[0221]

[0222] A suspension of borate ester (step 1, 19 mmol, 5 g), palladium catalyst (Merck, CAS: 72287-26-4, 0.78 mmol, 574 mg), and potassium phosphate (57 mmol, 12.2 g) in THF / water (75 mL / 1.8 mL) was prepared. Under a nitrogen atmosphere, 4-bromobenzocyclobutene (Merck, CAS: 1073-39-8, 19 mmol, 3.5 g) was added to the solution, and the resulting mixture was stirred overnight at 70 °C. The reaction mixture was then extracted with ethyl acetate and water, dried over Na₂SO₄, filtered, and concentrated. To purify the crude product mixture, silica gel column chromatography was performed using a mixture of heptane / ethyl acetate (15:1) as eluent. This process yielded a colorless solid (3.7 g, 82%).

[0223] 1H NMR (500 MHz, chloroform-d): δ = 10.16 (s, 2H), 8.31 (s, 3H), 7.48 (dd,J = 7.6, 1.6 Hz, 1H), 7.35 (d, J = 1.6, 1H), 7.19 (d, J = 7.6, 1H) 3.26 (s,4H) ppm.

[0224] Step 3: Synthesis of 3-(3,5-divinylphenyl)bicyclo[4.2.0]octyl-1,3,5-triene

[0225]

[0226] Methyltriphenylphosphine bromide (Merck, CAS: 1779-49-3, 14 mmol, 5 g) was dissolved in 35 mL of THF and cooled to -18 °C. Potassium tert-butoxide (Merck, CAS: 865-47-4, 14 mmol, 1.6 g) was added to this solution. Dialdehyde (step 2, 6.3 mmol, 1.5 g) was dissolved in 15 mL of THF and slowly added dropwise to the above solution at 0 °C under controlled temperature conditions. The mixture was stirred overnight, then diluted with water and extracted with DCM (dichloromethane). The organic phase was washed twice with water and once with sodium chloride solution, then dried over Na2SO4, filtered, and concentrated. The crude product was purified by silica gel column chromatography (eluent: heptane) to give 1.1 g of a colorless oil (75%).

[0227] Example 2: 2,5-Divinylbicyclo[4.2.0]octyl-1,3,5-triene

[0228]

[0229] 2,5-Dibromobicyclo[4.2.0]octyl-1,3,5-triene (Merck, CAS: 145708-71-0, 9.5 mmol, 2.5 g) was dissolved in anhydrous THF (130 mL). NaOH was dissolved in water (40 mL), cooled, and treated with potassium vinyltrifluoroborate (Merck, CAS: 13682-77-4, 2.8 g, 21 mmol). Pd(amphos)Cl2 (Merck, CAS: 887919-35-9, 0.27 g, 0.38 mmol) was then added, and the reaction mixture was stirred for 15 minutes under argon protection. The THF reactant solution prepared above was then added dropwise, and the mixture was stirred overnight at 50 °C. The mixture was then cooled to room temperature, and the aqueous phase was separated. The organic phase was washed once with saturated sodium chloride solution, twice with water, dried over Na2SO4, and concentrated to dryness. The crude product was dissolved in heptane and purified by filtration through a silica gel stopper to obtain 1.3 g (87%) of the target product as a colorless liquid.

[0230] 1H NMR (500 MHz, chloroform-d): δ = 7.11 (s, 2H), 6.64 (dd, J = 17.7, 10.9Hz, 2H), 5.67 (dd, J = 17.6, 1.3, 2H), 5.31 (dd, J = 10.8, 1.3, 2H) 3.34 (s,4H) ppm.

[0231] Example 3 (Indicative): 3-(3,5-divinylbenzyl)bicyclo[4.2.0]octyl-1,3,5-triene

[0232]

[0233] Step 1: Synthesis of bicyclo[4.2.0]octyl-1,3,5-trien-3-yl(3,5-dibromophenyl)methanol

[0234]

[0235] 4-Bromobenzocyclobutene (Merck, CAS: 173-39-8, 2.6 g, 14.3 mmol) was dissolved in anhydrous diethyl ether (Merck, 60 mL). The solution was cooled to -78 °C, and a solution of n-butyllithium (1.6 M hexane, 10 mL, 1.6 mmol) was added dropwise. Then, 3,5-dibromobenzaldehyde (Merck, CAS: 56990-02-4, 3.4 g, 13 mmol) was added, and the reaction mixture was stirred while warming to room temperature. The mixture was carefully quenched with 50 mL of brine, separated, and the aqueous phase was extracted three times with DCM. The organic phases were combined, dried over Na₂SO₄, filtered, and the solvent was removed under vacuum to give 4.7 g (99%) of a brown oily product, which could be used without further purification.

[0236] Step 2: Synthesis of 3-(3,5-dibromobenzyl)bicyclo[4.2.0]octyl-1,3,5-triene

[0237]

[0238] Bicyclo[4.2.0]octyl-1,3,5-trien-3-yl(3,5-dibromophenyl)methanol (4.7 g, 12.8 mmol) was dissolved in 40 mL of DCM, and triethylsilane (Merck, CAS: 617-86-7, 4.1 mL, 25.6 mmol) was added. The mixture was cooled to 0 °C. Trifluoromethanesulfonic acid (Merck, CAS: 1493-13-6, 2.2 mL, 25.6 mmol) was added dropwise, and the mixture was stirred at room temperature for 3 hours. Ice was carefully added, and the aqueous phase was extracted three times with DCM. The organic phases were combined, dried over Na2SO4, filtered, and the solvent was removed under vacuum. The crude product was purified by recrystallization from ethanol to give 3.6 g (80%) of the target product.

[0239] Step 3: Synthesis of 3-(3,5-divinylbenzyl)bicyclo[4.2.0]octyl-1,3,5-triene

[0240]

[0241] 3-(3,5-dibromobenzyl)bicyclo[4.2.0]octyl-1,3,5-triene (3.6 g, 10 mmol) was dissolved in anhydrous THF (0.2 L), and potassium vinyltrifluoroborate (Merck, CAS: 13682-77-4, 21.8 mmol, 2.9 g) was added. The mixture was stirred at room temperature for 1 hour under nitrogen protection. Then, NaOH solution (30 mL, 10 wt%) and Pd(amphos)Cl2 (Merck, CAS: 887919-35-9, 0.28 g, 0.4 mmol) were added, and the reaction mixture was stirred at 50 °C for 12 hours. The mixture was cooled to room temperature, treated with water, and extracted three times with ethyl acetate. The organic phases were combined, dried over Na2SO4, filtered, and the solvent was removed under vacuum. The crude product was purified by silica gel column chromatography (using heptane as solvent) to give 1.85 g (75%) of a colorless liquid.

[0242] Part B: Thermal stability of the photocurable layer

[0243] The cured film was prepared by coating a 60µm thick coating (made from the working composition and the comparative composition described below, respectively) in a sandwich device consisting of two glass plates, and then cured at room temperature using a wavelength of 365nm and a dose of 5 J / cm. 2 The UV-cured film was prepared by curing with UV light. Subsequently, the UV-cured film was placed on a hot plate and baked at 300°C for 2 minutes, followed by TGA (TA Discovery or TA TGA Q50) measurement. The thermal stability of the composition was assessed by the percentage weight loss per minute at different temperatures; this was determined by an isothermal baking test, where the sample was heated to a predetermined temperature (e.g., 400°C) within 20 minutes and held at that temperature for 60 minutes.

[0244] Formulations containing the first monomer of this invention exhibit better thermal stability than formulations in comparative examples (see Table 1 and...). Figure 1 ).

[0245]

[0246] The composition of Working Example 1 was prepared by mixing compound A (first monomer, 50 wt%) and compound B (second monomer, 50 wt%) as described below. Subsequently, 4 wt% of Irgacure OXE02 was added relative to the resulting formulation.

[0247] The composition of Comparative Example 1 was prepared by adding Irgacure OXE02 to component B, with the addition amount being 4% by weight of the total weight of the resulting formulation.

[0248] .

Claims

1. A curable composition, preferably a photocurable composition, comprising a first monomer compound and a polymerization initiator, wherein the first monomer compound is represented by chemical formula (I); - (I) in m2 to m4 are each independently 0 or 1; n1 to n4 are each independently 0, 1 or 2; n1 + n2 + n3 + n4 ≥ 1; The first monomer currently has at least one vinyl group; o2 to o4 are each independently 0 or 2; When o2 is 2, the two R2s are adjacent methyl groups, which bond to each other to form a cyclobutene structure on the benzene ring; and the relationship between o3 and R3 and the relationship between o4 and R4 are the same. L2 to L4 are each independently derived from direct bonds, C 1-15 Alkylene and C 2-15 Selected from the group composed of sub-alkenyl groups One or more non-adjacent methylene groups in the alkylene or alkenylene group may be replaced by O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH; and One or more H atoms can be replaced by D, F, Cl, Br, I, CN, or NO2.

2. The composition according to claim 1, wherein the total amount of the first monomer compound is in the range of 5 to 99.99% by weight, based on the total amount of the composition; preferably 20 to 99.99% by weight; more preferably 40 to 99.9% by weight.

3. The composition according to claim 1 or 2 further comprises a second monomeric compound represented by chemical formula (II); (II) in m6 and m7 are each independently 0 or 1; o5 can be 0, 1, 2, 3, 4, 5, or 6; o6 and o7 are each independently 0, 1 or 2; R5 through R7 are each independently C 1-4 Alkyl, vinyl, or ethynyl; The second monomer currently has at least one vinyl or acetylene group; L6 and L7 are independently derived from direct bonds, C 1-15 Alkylene and C 2-15 Selected from the group composed of sub-alkenyl groups One or more non-adjacent methylene groups in the alkylene or alkenylene group may be replaced by O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH; and One or more H atoms can be replaced by D, F, Cl, Br, I, CN, or NO2.

4. The composition according to any one or more of claims 1 to 3, wherein the total amount of the first monomer compound and the second monomer compound is in the range of 10% to 99.99% by weight, based on the total amount of the composition.

5. The composition according to any one or more of claims 1 to 4, comprising 10% or less of acrylate monomer based on the total amount of the composition; preferably 0 to 10% by weight; more preferably 0 to 5% by weight; and even more preferably 0% by weight.

6. The composition according to any one or more of claims 1 to 5, comprising 10% by weight or less of solvent based on the total amount of the composition; preferably 0 to 10% by weight; more preferably 0 to 5% by weight; and even more preferably 0% by weight.

7. The composition according to any one or more of claims 1 to 6, comprising one or more additives selected from the group consisting of surfactants, wetting agents, release agents, oxygen quenchers and stabilizers.

8. The composition according to any one or more of claims 1 to 7, wherein the viscosity at 23°C is in the range of 2 to 100 cP.

9. A method for preparing the composition according to any one or more of claims 1 to 8, comprising at least the following: Step (A); (B) Mix at least the first monomer compound and the polymerization initiator.

10. A method for preparing a cured layer, comprising at least the following steps (i a ) and (i b ): (i a The composition of any one of claims 1 to 10 is provided onto a substrate, preferably by printing, more preferably by spin coating, slot coating or inkjet printing; (i d Optionally, the composition can be brought into contact with a template; (i b The composition is cured by heating and / or irradiating it with light to form a cured layer; (i e Optionally, the template can be removed from the cured layer.

11. The method according to claim 10, wherein in step (i) b This is followed by the following steps (i) c ); (i c Bake the cured layer for a period of time ranging from 0.5 to 10 minutes at a temperature ranging from 180 to 450°C.

12. A cured layer, preferably a light-cured layer obtained by or obtainable by the method of any one or more of claims 9 to 11.

13. A cured layer, preferably a light-cured layer formed from the composition of any one of claims 1 to 8.

14. A stack layer comprising a substrate and a cured layer as claimed in claim 12 or 13, which at least partially covers the substrate.

15. A compound represented by chemical formula (I); - (I) in m2 to m4 are each independently 0 or 1; n1 to n4 are each independently 0, 1 or 2; n1 + n2 + n3 + n4 ≥ 2; The first monomer currently has at least one vinyl group; o2 to o4 are each independently 0 or 2; When o2 is 2, the two R2s are adjacent methyl groups, which bond to each other to form a cyclobutene structure on the benzene ring; and the relationship between o3 and R3 and the relationship between o4 and R4 are the same. L2 to L4 are each independently derived from direct bonds, C 1-15 Alkylene and C 2-15 Selected from the group composed of sub-alkenyl groups One or more non-adjacent methylene groups in the alkylene or alkenylene group may be replaced by O, C=S, C=Se, C=NH, SiH2, SO, SO2, OS, or CONH; and One or more H atoms can be replaced by D, F, Cl, Br, I, CN, or NO2.

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