Thermosetting resin composition and cured film formed using the same

Abstract

The present invention provides a thermosetting resin composition that allows for the application of an appropriate polishing rate during the CMP process and exhibits excellent flatness. [Solution] The present invention provides a thermosetting resin composition comprising a binder resin, a thermal initiator, a thermosetting agent, and a solvent, wherein the binder resin comprises an acrylic copolymer in which hydroxyalkylthio groups are bonded to both ends of a polymer chain containing repeating units derived from hydroxyethyl (meth)acrylate and repeating units derived from methyl (meth)acrylate, and a cured film formed using the same.

Description

[Technical Field]

[0001] The present invention relates to a thermosetting resin composition and a cured film formed using the same, and more particularly to a thermosetting resin composition that allows for the application of an appropriate polishing rate during the CMP process and exhibits excellent flatness, and a cured film formed using the same. [Background technology]

[0002] In semiconductor manufacturing processes, oxides and nitrides have primarily been used as sacrificial films. However, oxides and nitrides are difficult to remove by subsequent ashing processes, and they have the problem of poor gap-fill characteristics at narrow line widths.

[0003] Therefore, in recent years, techniques using polymer films as sacrificial films have been investigated. Polymer films are easily removed by the subsequent ashing process and have excellent gap-filling properties. In addition, they have the advantage of exhibiting high selectivity for various film materials such as polysilicon, oxides, and nitrides in wet processes using inorganic solvents.

[0004] However, for polymer films to be used as sacrificial films in the CMP (Chemical Mechanical Planarization) process, it is necessary to be able to apply an appropriate polishing rate (RR: removal rate) and for the surface to have excellent flatness after polishing.

[0005] Korean Patent Registration No. 10-1342665 discloses a CMP sacrificial film formation composition comprising a copolymer of styrene and maleic acid as a binder resin.

[0006] However, there is still a need for technological development regarding thermosetting resin compositions that can be polished at an appropriate rate during the CMP process and exhibit superior flatness. [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] One objective of the present invention is to provide a thermosetting resin composition that allows for the application of an appropriate polishing rate during the CMP process and exhibits excellent flatness.

[0008] Another object of the present invention is to provide a cured film formed from the thermosetting resin composition. [Means for solving the problem]

[0009] On the other hand, the present invention relates to a thermosetting resin composition comprising a binder resin, a thermal initiator, a thermosetting agent, and a solvent, The aforementioned binder resin provides a thermosetting resin composition comprising a resin represented by the following chemical formula 1.

[0010] [ka]

[0011] In the above formula, R a and R b These are, independently, a hydrogen atom or a methyl group. L 1 and L 2 These are each an independent C1-C6 alkylene group, m and n are independent integers between 30 and 300.

[0012] A thermosetting resin composition according to an embodiment of the present invention may be used for CMP sacrificial film formation.

[0013] In embodiments of the present invention, the ratio of m to n may be 1:9 to 9:1.

[0014] In one embodiment of the present invention, the weight-average molecular weight (Mw) of the binder resin may be 3,000 to 30,000.

[0015] In one embodiment of the present invention, the binder resin may be contained in an amount of 20 to 90% by weight based on 100% by weight of the entire thermosetting resin composition.

[0016] In one embodiment of the present invention, the thermal initiator may include one or more of the compounds represented by the following Chemical Formulas 2 to 4.

[0017]

Chemical Formula

[0018]

Chemical Formula

[0019]

Chemical Formula

[0020] In the above formula, R 1 is a C1-C 30 alkyl group, a C2-C 30 alkenyl group, a C3-C 20 cycloalkyl group, a C2-C 20 heterocycloalkyl group, a C6-C 20 aryl group, or a C5-C 20 heteroaryl group; R 2 is a C1-C 30 alkyl group, a C2-C 30 alkenyl group, a C3-C 20 cycloalkyl group, a C2-C 20 heterocycloalkyl group, a C6-C 20 aryl group, or a C5-C 20 heteroaryl group; R 1 and R 2 are each independently a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, -SO3M, -CO2M, a hydroxy group, a formyl group, an amino group, or a C1-C 20It is often substituted with an alkyl group; M indicates a metal ion; R 3 and R 4 These are C1-C, each independently. 30 alkyl group, C2-C 30 The alkenyl group, C3-C 20 Cycloalkyl groups, C2-C 20 heterocycloalkyl groups, C6-C 20 The aryl group of, or C5-C 20 It is a heteroaryl group; R 5 This includes hydrogen atoms, halogen atoms, hydroxyl groups, thioether groups, and C1-C 30 alkyl group, C2-C 30 The alkenyl group, C3-C 20 A cycloalkyl group, or C2-C 20 It is a heterocycloalkyl group; R 6 ~R 9 These are C1-C, each independently. 30 alkyl group, C2-C 30 The alkenyl group, C3-C 20 Cycloalkyl groups, C2-C 20 heterocycloalkyl groups, C6-C 20 The aryl group, C5-C 20 The heteroaryl group, or C6-C 20 It is an aralkyl group; X - PF6 - AsF6 - SbF6 - (CF3)2PF4 - (CF3)3PF3 - (CF3)4PF2 - (CF3)5PF - (CF3)6P - (C2F5SO2)2N - , (CF3SO3)2N - (CF3SO2)(CF3CO)N - CF3CF2(CF3)2CO - (CF3SO2) 2CH - (SF5)3C- (CF3SO2)3C - CF3COO - CF3SO3 - (C6F5)4B - , or C3F7COO - That is the case.

[0021] In embodiments of the present invention, the thermal initiator may be included in an amount of 0.01 to 7% by weight relative to 100% by weight of the total thermosetting resin composition.

[0022] In one embodiment of the present invention, the thermosetting agent may include an amine-based curing agent.

[0023] In one embodiment of the present invention, the thermosetting agent may include a compound represented by the following chemical formula 5.

[0024] [ka]

[0025] In the above formula, R 10 ~R 13 Each of these is independently a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C2-C8 alkoxyalkyl group, or a thiol group. R 14 and R 15 These are, independently, hydrogen, a C1-C4 alkyl group, or an aryl group.

[0026] In embodiments of the present invention, the thermosetting agent may be included in an amount of 0.01 to 10% by weight relative to 100% by weight of the total thermosetting resin composition.

[0027] On the other hand, the present invention provides a cured film formed from the thermosetting resin composition.

[0028] The cured film according to the embodiment of the present invention may be a CMP sacrificial film. [Effects of the Invention]

[0029] The thermosetting resin composition according to the present invention allows for the application of an appropriate polishing rate during the CMP process and exhibits excellent flatness. [Modes for carrying out the invention]

[0030] The present invention will be described in more detail below.

[0031] One embodiment of the present invention relates to a thermosetting resin composition comprising a binder resin (A), a thermal initiator (B), a thermosetting agent (C), and a solvent (D), wherein the binder resin (A) comprises an acrylic copolymer in which hydroxyalkylthio groups are bonded to both ends of a polymer chain containing repeating units derived from hydroxyethyl (meth)acrylate and repeating units derived from methyl (meth)acrylate.

[0032] The thermosetting resin composition according to the embodiment of the present invention contains an acrylic copolymer as a binder resin, in which a hydroxyalkylthio group is bonded to both ends of a polymer chain containing repeating units derived from hydroxyethyl (meth)acrylate and repeating units derived from methyl (meth)acrylate, and by containing a thermal initiator and a thermosetting agent, an appropriate polishing rate can be applied during the CMP process and the composition exhibits excellent flatness.

[0033] Furthermore, the thermosetting resin composition according to one embodiment of the present invention exhibits excellent gap-fill properties and high selectivity for various film materials such as polysilicon, silicon oxide, and silicon nitride in a wet process using an inorganic solvent.

[0034] Therefore, the thermosetting resin composition according to one embodiment of the present invention can be advantageously used for CMP sacrificial film formation.

[0035] Furthermore, the thermosetting resin composition according to one embodiment of the present invention can be applied to various organic insulating films other than CMP sacrificial films, such as overcoat films and planarization films.

[0036] [Binder resin (A)] In one embodiment of the present invention, the binder resin (A) is reactive in response to heat, functions as a binder resin, and plays a role in controlling the polishing speed and flatness.

[0037] The binder resin (A) comprises an acrylic copolymer in which hydroxyalkylthio groups are bonded to both ends of a polymer chain containing repeating units derived from hydroxyethyl (meth)acrylate and repeating units derived from methyl (meth)acrylate.

[0038] Specifically, the binder resin (A) includes a resin represented by the following chemical formula 1.

[0039] [ka]

[0040] In the above formula, R a and R b These are, independently, a hydrogen atom or a methyl group. L 1 and L 2 These are each an independent C1-C6 alkylene group, m and n are independent integers between 30 and 300.

[0041] As used herein, the C1-C6 alkylene group refers to a linear or branched divalent hydrocarbon consisting of 1 to 6 carbon atoms, and includes, but is not limited to, methylene, ethylene, propylene, and butylene.

[0042] The ratio of m to n may be 1:9 to 9:1, preferably 2:8 to 8:2, or 3:7 to 7:3. When the ratio of m to n satisfies the above range, an appropriate polishing speed can be applied during the CMP process and flatness is excellent. If the ratio of m to n is less than the above range, it may be difficult to secure a sufficient film thickness because there are fewer functional groups that can be bonded, and if it is more than the above range, wear resistance may decrease and flatness may decrease.

[0043] The method for producing the copolymer is not particularly limited, and conventionally known polymerization methods may be used. Among known polymerization methods, solution polymerization is preferred. Polymerization may be carried out, for example, at 60 to 130°C for 1 to 10 hours.

[0044] When a solvent is used during the polymerization, a solvent commonly used in radical polymerization reactions may be used. Specifically, the solvent may be tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, methanol, ethanol, propanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, toluene, xylene, ethylbenzene, chloroform, dimethyl sulfoxide, etc. These solvents may be used individually or in combination of two or more.

[0045] The polymerization initiator used in the polymerization described above may be any commonly used polymerization initiator, and is not particularly limited. Specifically, examples of the polymerization initiator include organic peroxides such as diisopropylbenzene hydroperoxide, di-t-butyl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, t-amyl peroxy-2-ethylhexanoate, and t-butyl peroxy-2-ethylhexanoate; and nitrogen compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and dimethyl-2,2'-azobis(2-methylpropionate). These may be used individually or in combination of two or more.

[0046] During polymerization, a chain transfer agent may be used to control the molecular weight and molecular weight distribution of the copolymer. The chain transfer agent may be a mercapto compound such as n-dodecanethiol, mercaptoacetic acid, or methyl mercaptoacetate; or an α-methylstyrene dimer.

[0047] The binder resin (A) may have a polystyrene-equivalent weight-average molecular weight (hereinafter simply referred to as "weight-average molecular weight (Mw)") of 3,000 to 30,000, preferably 5,000 to 25,000, and more preferably 7,000 to 25,000, as measured by gel permeation chromatography (GPC; using tetrahydrofuran as the elution solvent). When the weight-average molecular weight (Mw) of the binder resin satisfies the above range, an appropriate polishing rate can be applied during the CMP process and excellent flatness can be achieved. If the weight-average molecular weight (Mw) of the binder resin is less than the above range, it may be difficult to secure a sufficient film thickness, and if it is more than the above range, flatness may decrease.

[0048] In one embodiment of the present invention, the binder resin (A) may be present in an amount of 20 to 90% by weight, preferably 40 to 80% by weight, based on 100% by weight of the total thermosetting resin composition. If the content of the binder resin falls outside this range, the coating of the paint film may be too little or too much, making it impossible to have an appropriate selectivity ratio for the desired polishing speed or other film properties.

[0049] [Thermal initiator (B)] In one embodiment of the present invention, the thermal initiator (B) is a compound that generates an acid, such as sulfonic acid, upon the action of heat. The acid generated by heat triggers a curing reaction between the functional groups of the binder resin and the thermosetting agent.

[0050] The thermal initiator may contain one or more compounds represented by the following chemical formulas 2 to 4.

[0051] [ka]

[0052] [ka]

[0053] [ka]

[0054] In the above formula, R 1 C1-C 30 alkyl group, C2-C 30 The alkenyl group, C3-C 20 Cycloalkyl groups, C2-C 20 heterocycloalkyl groups, C6-C 20 The aryl group of, or C5-C 20 It is a heteroaryl group; R 2 C1-C 30 alkyl group, C2-C 30alkenyl group, C3-C 20 cycloalkyl group, C2-C 20 heterocycloalkyl group, C6-C 20 aryl group, or C5-C 20 heteroaryl group; R 1 and R 2 are each independently a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, -SO3M, -CO2M, a hydroxy group, a formyl group, an amino group, or C1-C 20 may be substituted by an alkyl group; M represents a metal ion; R 3 and R 4 are each independently C1-C 30 alkyl group, C2-C 30 alkenyl group, C3-C 20 cycloalkyl group, C2-C 20 heterocycloalkyl group, C6-C 20 aryl group, or C5-C 20 heteroaryl group; R 5 is a hydrogen atom, a halogen atom, a hydroxy group, a thioether group, C1-C 30 alkyl group, C2-C 30 alkenyl group, C3-C 20 cycloalkyl group, or C2-C 20 heterocycloalkyl group; R 6 ~R 9 are each independently C1-C 30 alkyl group, C2-C 30 alkenyl group, C3-C 20 cycloalkyl group, C2-C 20 heterocycloalkyl group, C6-C 20 aryl group, C5-C 20 heteroaryl group, or C6-C 20 aralkyl group; X - is PF6 - , AsF6 - , SbF6 -(CF3)2PF4 - (CF3)3PF3 - (CF3)4PF2 - (CF3)5PF - (CF3)6P - (C2F5SO2)2N - , (CF3SO3)2N - (CF3SO2)(CF3CO)N - CF3CF2(CF3)2CO - (CF3SO2) 2CH - (SF5)3C - (CF3SO2)3C - CF3COO - CF3SO3 - (C6F5)4B - , or C3F7COO - That is the case.

[0055] C1-C used herein 30 The alkyl group refers to a linear or branched hydrocarbon consisting of 1 to 30 carbon atoms, and includes, but is not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl, 2-ethylhexyl, heptyl, 2-ethylheptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, stearyl, nonadecyl, eicosanyl, and behenyl.

[0056] C2-C used herein 30 The alkenyl group refers to a linear or branched unsaturated hydrocarbon consisting of 2 to 30 carbon atoms with one or more carbon-carbon double bonds, and includes, but is not limited to, ethilenyl, propenyl, butenyl, and pentenyl.

[0057] C3-C used in this specification 20The term "cycloalkyl group" refers to monocyclic or fused cyclic hydrocarbons consisting of 3 to 20 carbon atoms, and includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0058] C2-C used herein 20 A heterocycloalkyl group refers to a functional group in which one or more ring carbons of a monocyclic or fused cyclic hydrocarbon consisting of 2 to 20 carbon atoms are substituted with oxygen, sulfur, or nitrogen. Examples include, but are not limited to, thiazolidinyl and oxyranyl.

[0059] C6-C used in this specification 20 The aryl group includes all monovalent aromatic groups and their partially reduced derivatives. The aromatic group is a monocyclic or fused ring with 6 to 20 carbon atoms. Typical examples of aryl groups include, but are not limited to, phenyl, naphthyl, tetrahydronaphthyl, pyrenyl, fluorenyl, diphenylfluorenyl, dinaphthalenylfluorenyl, carbazolyl, and biphenyl.

[0060] C5-C used herein 20 The heteroaryl groups include all monovalent heteroaromatic groups and their partially reduced derivatives. The heteroaromatic groups are monocyclic or fused rings with 5 to 20 carbon atoms and contain one or more oxygen, sulfur, or nitrogen atoms. Representative examples of heteroaryl groups include, but are not limited to, pyridinyl, furanyl, thiophenyl, indolyl, quinolinyl, imidazolinyl, oxazolyl, and thiazolyl.

[0061] C1-C used herein 20The alkyl group refers to a linear or branched monovalent hydrocarbon consisting of 1 to 20 carbon atoms, and includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, and n-decyl.

[0062] In this specification, the metal ion refers to an alkali metal or alkaline earth metal ion.

[0063] The thioether group used herein is the group of the chemical formula -SR (where R is C1-C1). 30 This represents an alkyl or aryl group, and includes, but is not limited to, methylthio groups and ethylthio groups.

[0064] C6-C used in this specification 20 The aralkyl group refers to a complex group with 6 to 20 carbon atoms formed by the substitution of an aryl group (aromatic hydrocarbon group) with an alkyl group carbon. Examples include benzyl and phenethyl, but it is not limited to these.

[0065] Said C1-C 30 alkyl group, C2-C 30 The alkenyl group, C3-C 20 Cycloalkyl groups, C2-C 20 heterocycloalkyl groups, C6-C 20 The aryl group, C5-C 20 heteroaryl group, C1-C 20 alkyl groups, thioether groups and C6-C 20The aralkyl group may have one or more hydrogen atoms substituted with hydroxyl, thio, halogen, amino, carboxyl, cyano, nitro, etc.

[0066] Preferably, X - CF3SO3 - That is the case.

[0067] The compounds represented by chemical formulas 2 to 4 may have a decomposition initiation temperature of less than 200°C, for example, 100°C or higher but less than 200°C, preferably 150°C or higher but less than 180°C. Therefore, by using the compounds represented by chemical formulas 2 to 4 as thermal initiators, sufficient curing can be achieved within a few minutes even with relatively low-temperature firing at 220°C or lower.

[0068] For example, one or more compounds represented by the following chemical formulas 2-1 to 2-3 can be considered as compounds represented by the chemical formulas 2-1 to 2-3.

[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] Preferably, the compound represented by chemical formula 3 may be the compound represented by the following chemical formula 3a.

[0073] [ka]

[0074] In the above formula, R 3 and R 4 These are C1-C, each independently.30 alkyl group, C2-C 30 The alkenyl group, C3-C 20 Cycloalkyl groups, C2-C 20 heterocycloalkyl groups, C6-C 20 The aryl group of, or C5-C 20 It is a heteroaryl group; R 5 This includes hydrogen atoms, halogen atoms, hydroxyl groups, thioether groups, and C1-C 30 alkyl group, C2-C 30 The alkenyl group, C3-C 20 A cycloalkyl group, or C2-C 20 It is a heterocycloalkyl group.

[0075] For example, examples of compounds represented by the chemical formula 3 include (4-methylthiophenyl)methylphenylsulfonium trifluoromethanesulfonate, (4-hydroxyphenyl)dimethylsulfonium trifluoromethanesulfonate, diphenyl(4-hydroxyphenyl)sulfonium trifluoromethanesulfonate, and methylphenyl(4-hydroxyphenyl)sulfonium trifluoromethanesulfonate.

[0076] Preferably, the compound represented by chemical formula 4 may be the compound represented by the following chemical formula 4a.

[0077] [ka]

[0078] In the above formula, R 6 ~R 9 These are C1-C, each independently. 30 alkyl group, C2-C 30 The alkenyl group, C3-C 20 Cycloalkyl groups, C2-C 20 heterocycloalkyl groups, C6-C 20 The aryl group, C5-C 20 The heteroaryl group, or C6-C20 It is an aralkyl group.

[0079] Preferably, R 6 and R 7 These are C1-C, each independently. 30 It is an alkyl group, R 8 C6-C 20 It is an aryl group, R 9 C6-C 20 It may be an aralkyl group.

[0080] For example, an example of a compound represented by chemical formula 4 is the compound represented by chemical formula 4-1 below.

[0081] [ka]

[0082] The thermal initiator (B) may be present in an amount of 0.01 to 7% by weight, preferably 0.1 to 4% by weight, based on 100% by weight of the total thermosetting resin composition. If the content of the thermal initiator falls outside this range, it may become difficult to ensure polishing speed and flatness.

[0083] [Thermosetting agent (C)] In one embodiment of the present invention, the thermosetting agent (C) is a component that undergoes a curing reaction with the functional groups of the binder resin.

[0084] As the aforementioned thermosetting agent, acid anhydride-based curing agents, amine-based curing agents, phenol-based curing agents, etc., may be used, but amine-based curing agents are preferred from the viewpoint of improving productivity and adhesion.

[0085] The amine-based curing agent may include a compound derived from a glycoluryl structure. The compound derived from a glycoluryl structure may include a compound represented by the following chemical formula 5.

[0086] [ka]

[0087] In the above formula, R 10 ~R 13 Each of these is independently a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C2-C8 alkoxyalkyl group, or a thiol group. R 14 and R 15 These are, independently, hydrogen, a C1-C4 alkyl group, or an aryl group.

[0088] As used herein, C1-C4 alkyl groups refer to linear or branched monovalent hydrocarbons consisting of 1 to 4 carbon atoms, and include, but are not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, and t-butyl.

[0089] As used herein, the C1-C4 alkoxy group refers to a linear or branched alkoxy group consisting of 1 to 4 carbon atoms, and includes, but is not limited to, methoxy, ethoxy, n-propanoxy, etc.

[0090] As used herein, C2-C8 alkoxyalkyl groups refer to complex groups consisting of 2 to 8 carbon atoms formed by the substitution of a linear or branched alkoxy group on the carbon atoms of an alkyl group, and include, but are not limited to, methoxymethyl, ethoxymethyl, and methoxyethyl.

[0091] The aryl groups used herein include all aromatic groups, heteroaromatic groups, and their partially reduced derivatives. Aromatic groups are monocyclic or fused rings with 5 to 15 members, while heteroaromatic groups are aromatic groups containing one or more oxygen, sulfur, or nitrogen atoms. Representative examples of aryl groups include, but are not limited to, phenyl, naphthyl, pyridinyl, furanyl, thiophenyl, indolyl, quinolinyl, imidazolinyl, oxazolyl, thiazolyl, and tetrahydronaphthyl.

[0092] Preferably, the compound represented by chemical formula 5 is one or more of the compounds represented by the following chemical formulas 5-1 to 5-4.

[0093] [ka]

[0094] [ka]

[0095] [ka]

[0096] [ka]

[0097] In the above formula, Pr is a propyl group, The "Ph" represents the phenyl group.

[0098] The compound represented by chemical formula 5 undergoes a curing reaction with the binder resin during post-baking, thereby improving stability. Furthermore, because the compound represented by chemical formula 5 hardens after being positioned in the space between the binder resins, it can maintain a constant space between the binder resins, and because N reacts with the acid, it can suppress the occurrence of unevenness due to the acid and improve transmittance.

[0099] The thermosetting agent (C) may be present in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on 100% by weight of the total thermosetting resin composition. If the content of the thermosetting agent falls outside this range, it may become difficult to ensure polishing speed and flatness.

[0100] [Solvent (D)] The solvent (D) is not particularly limited, and various organic solvents used in the art may be used.

[0101] Specific examples of the solvent (D) include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate; and alkylene glycol alkyl ethers such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate. Telacetates; Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether, propylene glycol propyl methyl ether, and propylene glycol ethyl propyl ether; Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, and propylene glycol butyl ether propionate; Butanediol monoalkyl ethers such as methoxybutyl alcohol, ethoxybutyl alcohol, propoxybutyl alcohol, and butoxybutyl alcohol;Butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate, and butoxybutyl acetate; butanediol monoalkyl ether propionates such as methoxybutyl propionate, ethoxybutyl propionate, propoxybutyl propionate, and butoxybutyl propionate; dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol methyl ethyl ether; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin;Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2-methoxypropionate Butyl pionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethoxypropionic acid Examples include esters such as ethyl ester, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate; cyclic ethers such as tetrahydrofuran and pyran; and cyclic esters such as γ-butyrolactone. The solvents (D) exemplified here may be used individually or in combination of two or more.

[0102] When considering the applicability and drying properties, the solvent (D) may preferably be esters such as diethylene glycol dialkyl ethers, alkylene glycol alkyl ether acetates, ketones, butanediol alkyl ether acetates, butanediol monoalkyl ethers, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate. More preferably, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutanol, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate may be used.

[0103] The content of the solvent (D) may be, for example, 5 to 90% by weight, preferably 20 to 90% by weight, and more preferably 20 to 70% by weight, based on 100% by weight of the total thermosetting resin composition. When the content of the solvent satisfies the above range, the film thickness can be easily adjusted.

[0104] [Additive (E)] The thermosetting resin composition according to one embodiment of the present invention may contain, in addition to the above-mentioned components, additives known in the art, to the extent that they do not impede the effects of the present invention.

[0105] For example, surfactants may be used to improve wettability, coatability, and leveling properties.

[0106] Examples of the aforementioned surfactants include silicone-based and fluorine-based surfactants. Commercially available examples include SH-8400 from Dow Corning, Fluorinert FC430 and Fluorinert FC431 from Sumitomo 3M Co., Ltd., Megafac F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac R30, Megafac R08, Megafac R09, Megafac BL20, Megafac 475, Megafac 489, Megafac 544 and Megafac F443 from Dainippon Ink and Chemicals, Inc., and F-430, F-510, F-554, F-563, R-40, R-41, and R-43 from DIC Corporation.

[0107] The surfactant may be present in an amount of 0.001 to 0.1% by weight, preferably 0.001 to 0.07% by weight, based on 100% by weight of the total thermosetting resin composition. If the amount of the surfactant falls outside this range, it may become difficult to ensure flatness.

[0108] The thermosetting resin composition of the present invention may be produced, for example, by adding and mixing a binder resin (A), a thermal initiator (B), a thermosetting agent (C), and other additives (E) as needed to a solvent (D). However, the present invention is not limited to such methods.

[0109] The thermosetting resin composition produced as described above may be used after being filtered using a filter with a pore size of approximately 0.1 to 5 μm.

[0110] One embodiment of the present invention relates to a cured film formed from the thermosetting resin composition described above. According to the present invention, the cured film may be produced by applying the above-described thermosetting resin composition onto a substrate and then applying heat.

[0111] A preferred example of the manufacturing process involves applying a thermosetting resin composition onto a substrate (usually a silicon wafer) or a layer consisting of the solid components of a pre-formed resin composition, and then heating and drying it to remove volatile components such as solvents, thereby obtaining a smooth coating film.

[0112] The coating method may include, for example, spin coating, casting, roll coating, slit and spin coating, or slit coating.

[0113] After application, the desired cured film can be obtained by heating and curing it at a temperature of 100-300°C for several minutes (approximately 3 minutes or less).

[0114] The cured film obtained in this way can be used as a CMP sacrificial film in the CMP process because it allows for the application of an appropriate polishing rate and exhibits excellent flatness.

[0115] At this time, the polishing speed will vary depending on the type of film to be polished, the conditions for sacrificial film formation, etc., but it may be approximately 1,000 to 15,000 Å / min.

[0116] Furthermore, the cured film can be usefully used as various organic insulating films, such as overcoat films and planarization films.

[0117] The present invention will be described in more detail below with reference to examples, comparative examples, and experimental examples. It should be noted that these examples, comparative examples, and experimental examples are merely for illustrative purposes, and it will be obvious to those skilled in the art that the scope of the present invention is not limited thereto.

[0118] [Synthesis Examples 1-11: Synthesis of Binder Resins] A condenser and thermometer were placed in a 500 mL three-necked flask, and a magnetic bar was inserted. 100 g each of methyl methacrylate (MMA) and hydroxyethyl methacrylate (HEMA) were added to the flask in the molar ratio shown in Table 1 below, and 100 g of PGMEA was added and dissolved. 1 g of AIBN and 0.5 g of mercaptoethanol were added, and the temperature was raised to 90°C while stirring, and the mixture was heated for 6 hours. 1 g of AIBN was added, and the reaction was continued at the same temperature for 3 hours. The reaction mixture was cooled to room temperature to obtain a binder resin solution with a solid content of 50% by weight. The obtained binder resin was diluted with 20% by weight of tetrahydrofuran (THF), and GPC analysis was performed to determine the weight-average molecular weight (Mw). The results are shown in Table 1 below.

[0119] [Table 1]

[0120] [Examples and Comparative Examples: Production of Thermosetting Resin Compositions] Thermosetting resin compositions were prepared by mixing the components according to the compositions shown in Tables 2 and 3 below (unit: weight %).

[0121] [Table 2]

[0122] [Table 3]

[0123] A-1 to A-11: Binder resins synthesized in synthesis examples 1 to 11, respectively. B-1 Thermal Initiator: Compound represented by the following chemical formula 4-1

[0124] [ka]

[0125] B-2 Thermal Initiator: Compound represented by the following chemical formula 3a-1

[0126] [ka]

[0127] C-1 Thermosetting agent: Compound represented by the following chemical formula 5-3

[0128] [ka]

[0129] D-1 Solvent: Propylene glycol methyl ether acetate E-1 additive: SH-8400 (manufactured by Dow Corning).

[0130] Experimental example: Using the thermosetting resin compositions produced in the above examples and comparative examples, cured films were prepared as described below, and CMP tests were performed on the cured films using the method described below. The results are shown in Table 4 below.

[0131] <Manufacturing of hardened films> A thermosetting resin composition was spin-coated onto a 200 mm silicon wafer at 1300 RPM, and then cured on a hot plate at 150°C. The thickness of the cured film was 7.9 μm.

[0132] (1) CMP test Polishing was performed for 60 seconds using a CTS AP-200 CMP device. The polishing speed at this time was 6,200 Å / min. Film thickness was measured at 31 points using filmetrics f54 and calculated according to Equation 1 below. Flatness was evaluated based on the evaluation criteria below.

[0133] [Formula 1] [(max-min) / (max+min)] × 100 In the above formula, max represents the maximum film thickness and min represents the minimum film thickness.

[0134] <Evaluation Criteria> ◎: Less than 5% ○: 5% or more but less than 10% △: 10% or more but less than 15% ×: 15% or more.

[0135] [Table 4]

[0136] As shown in Table 4 above, the thermosetting resin compositions of Examples 1 to 14 according to the present invention, which include an acrylic copolymer in which repeating units derived from hydroxyethyl (meth)acrylate and repeating units derived from methyl (meth)acrylate are bonded to both ends of a polymer chain, can be used as a binder resin, and it has been confirmed that they can be polished at an appropriate rate during the CMP process and exhibit excellent flatness.

[0137] On the other hand, the thermosetting resin compositions of Comparative Examples 1 and 2, which did not contain the acrylic copolymer of the specified structure as the binder resin, showed inferior flatness during the CMP process.

[0138] Although specific parts of the present invention have been described in detail above, it is clear to any person with ordinary skill in the art to which the present invention belongs that such specific descriptions are merely preferred examples and do not limit the scope of the present invention. A person with ordinary skill in the art to which the present invention belongs will be able to make various applications and modifications within the scope of the present invention based on the above content.

[0139] Therefore, the substantial scope of the present invention can be defined by the claims and their equivalents.

Claims

1. A thermosetting resin composition comprising a binder resin, a thermal initiator, a thermosetting agent, and a solvent, The binder resin is a thermosetting resin composition comprising a resin represented by the following chemical formula 1; 【Chemistry 1】 In the above formula, R ａ and R ｂ These are, independently, a hydrogen atom or a methyl group. L １ and L ２ Each of them is independently C １ -C ６ It is an alkylene group, m and n are independent integers between 30 and 300.

2. A thermosetting resin composition according to claim 1, used for forming a CMP sacrificial film.

3. The thermosetting resin composition according to claim 1, wherein the ratio of m to n is 1:9 to 9:

1.

4. The thermosetting resin composition according to claim 1, wherein the weight-average molecular weight (Mw) of the binder resin is 3,000 to 30,000.

5. The thermosetting resin composition according to claim 1, wherein the binder resin is contained in an amount of 20% to 90% by weight based on 100% by weight of the total thermosetting resin composition.

6. The thermosetting resin composition according to claim 1 comprises one or more compounds represented by the following chemical formulas 2 to 4; 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 In the above formula, R １ is C １ -C ３０ alkyl group, C ２ -C ３０ alkenyl group, C ３ -C ２０ cycloalkyl group, C ２ -C ２０ heterocycloalkyl group, C ６ -C ２０ aryl group, or C ５ -C ２０ heteroaryl group; R ２ C １ -C ３０ alkyl group, C ２ -C ３０ The alkenyl group, C ３ -C ２０ Cycloalkyl groups, C ２ -C ２０ heterocycloalkyl groups, C ６ -C ２０ The aryl group of, or C ５ -C ２０ It is a heteroaryl group; R １ and R ２ These are, independently, a halogen atom, a cyano group, a nitro group, a carbonyl group, a sulfonic acid group, and -SO ３ M, -CO ２ M, hydroxyl group, formyl group, amino group, or C １ -C ２０ It is often substituted with an alkyl group; M indicates a metal ion; R ３ and R ４ Each of them is independently C １ -C ３０ alkyl group, C ２ -C ３０ The alkenyl group, C ３ -C ２０ Cycloalkyl groups, C ２ -C ２０ heterocycloalkyl groups, C ６ -C ２０ The aryl group of, or C ５ -C ２０ It is a heteroaryl group; R ５ C is a hydrogen atom, halogen atom, hydroxyl group, thioether group, C １ -C ３０ alkyl group, C ２ -C ３０ The alkenyl group, C ３ -C ２０ A cycloalkyl group, or C ２ -C ２０ It is a heterocycloalkyl group; R ６ ~R ９ Each of them is independently C １ -C ３０ alkyl group, C ２ -C ３０ The alkenyl group, C ３ -C ２０ Cycloalkyl groups, C ２ -C ２０ heterocycloalkyl groups, C ６ -C ２０ The aryl group, C ５ -C ２０ The heteroaryl group of, or C ６ -C ２０ It is an aralkyl group; X － は、PF ６ － 、AsF ６ － 、SbF ６ － 、(CF ３ ) ２ PF ４ － 、(CF ３ ) ３ PF ３ － 、(CF ３ ) ４ PF ２ － 、(CF ３ ) ５ PF － 、(CF ３ ) ６ P － 、(C ２ F ５ SO ２ ) ２ N － 、(CF ３ SO ３ ) ２ N － 、(CF ３ SO ２ )(CF ３ CO)N － 、CF ３ CF ２ (CF ３ ) ２ CO － 、(CF ３ SO ２ ) ２ CH － 、(SF ５ ) ３ C － 、(CF ３ SO ２ ) ３ C － 、CF ３ COO － 、CF ３ SO ３ － 、(C ６ F ５ ) ４ B － 、またはC ３ F ７ COO － That is the case.

7. The thermosetting resin composition according to claim 1, wherein the thermal initiator is contained in an amount of 0.01 to 7% by weight based on 100% by weight of the total thermosetting resin composition.

8. The thermosetting resin composition according to claim 1, wherein the thermosetting agent comprises an amine-based curing agent.

9. The thermosetting agent comprises a compound represented by the following chemical formula 5, wherein the thermosetting resin composition is according to claim 8; 【Transformation 5】 In the above formula, R １０ ~R １３ These are hydrogen and C, respectively, independently. １ -C ４ alkyl group, C １ -C ４ The alkoxy group of C ２ -C ８ It is an alkoxyalkyl group or a thiol group, R １４ and R １５ These are hydrogen and C, respectively, independently. １ -C ４ It is an alkyl or aryl group.

10. The thermosetting resin composition according to claim 1, wherein the thermosetting agent is contained in an amount of 0.01 to 10% by weight based on 100% by weight of the total thermosetting resin composition.

11. A cured film formed from the thermosetting resin composition according to any one of claims 1 to 10.

12. The cured film according to claim 11, which is a CMP sacrificial film.

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