Positive-type photosensitive resin composition, insulating film and manufacturing method of same, and semiconductor device

Abstract

The present specification relates to a positive-type photosensitive resin composition, an insulating film and a method for manufacturing the same, and a semiconductor device, wherein the positive-type photosensitive resin composition comprises an alkali-soluble polyimide resin; a curing agent; a photoactive compound; and a solvent, and the curing agent comprises an epoxy compound having a urethane group.

Description

Technology Field

[0001] This specification relates to a positive type photosensitive resin composition, an insulating film, a method for manufacturing the same, and a semiconductor device. Background Technology

[0002] Recently, as miniaturization and compactness are increasingly emphasized due to the trend toward thinner and lighter semiconductor chip packaging, Wafer Level Packaging (WLP) technology is gaining prominence. WLP technology involves finishing chip packages on a wafer, and Fan-Out Wafer Level Packaging (FOWLP) technology is a technology that takes this a step further.

[0003] Polyimide is preferred as a packaging material for FOWLP because it exhibits strong resistance to external heat, chemicals, and impact. In particular, the tensile properties of the cured film are closely related to the reliability against external physical stimuli. This is a characteristic that is generally difficult to secure in photosensitive polyimide compositions. This is because there is a trade-off relationship where the more processability (especially developability during the lithography process) is imparted, the more easily the cured film becomes brittle due to the corresponding functional groups.

[0004] Therefore, it is well known that alkylene oxide groups are introduced into epoxy to improve tensile properties. However, for epoxy containing alkylene oxide groups, as the proportion in the composition increases, the total content of flexible functional groups in the composition increases, and consequently, the glass transition temperature (T) of the final cured film g There is a problem with the Glass Transition Temperature decreasing.

[0005] Accordingly, there is a need to develop a composition that can increase tensile properties without lowering the glass transition temperature. Prior art literature

[0006] Korean Patent Publication No. 10-2013-0123164 The problem to be solved

[0007] The present specification aims to provide a positive type photosensitive resin composition, an insulating film, and a semiconductor device. means of solving the problem

[0008] One embodiment of the present specification provides a positive-type photosensitive resin composition comprising an alkali-soluble polyimide resin; a curing agent; a photoactive compound; and a solvent, wherein the curing agent comprises an epoxy compound having urethane groups.

[0009] Another embodiment of the present specification provides an insulating film comprising the positive type photosensitive resin composition or a cured product thereof.

[0010] Another embodiment of the present specification provides a semiconductor device including the insulating film.

[0011] Another embodiment of the present specification provides a method for manufacturing the insulating film. Effects of the invention

[0012] The positive type photosensitive resin composition according to the present specification can provide an insulating film having high tensile properties without lowering the glass transition temperature by using an epoxy compound having urethane groups as a curing agent. Brief explanation of the drawing

[0013] Figure 1 is a schematic cross-section of a device having two insulating layers (insulating films). Specific details for implementing the invention

[0014] The present specification will be described in more detail below.

[0015] In this specification, when a component is described as being located “on” another component, this includes not only cases where a component is in contact with another component, but also cases where another component exists between the two components.

[0016] In this specification, when a part is described as "comprising" a certain component, this means that, unless specifically stated otherwise, it does not exclude other components but may include additional components.

[0017] In this specification, the term "polymer" means a compound composed of the repetition of repeating units (basic units). The polymer may be represented as a polymer or a compound composed of polymers, and the polymer may have one or more repeating units.

[0018] In this specification, "alkali-soluble" refers to a property in which solubility in an alkaline substance (such as a developer) increases upon dissociation by an acid. For example, an alkali-soluble resin and an alkali-soluble group each refer to a resin and a substituent that increases solubility in an alkaline developer upon dissociation by an acid. The alkali-soluble group includes an alkali-soluble hydroxyl group. Such alkali-soluble hydroxyl groups include, but are not limited to, phenolic hydroxyl groups.

[0019] One embodiment of the present specification provides a positive-type photosensitive resin composition comprising an alkali-soluble polyimide resin; a curing agent; a photoactive compound; and a solvent, wherein the curing agent comprises an epoxy compound having urethane groups.

[0020] A positive-type photosensitive resin composition according to one embodiment of the present specification includes an epoxy compound having urethane groups as a curing agent, thereby providing an insulating film having high tensile properties without a decrease in glass transition temperature. Conventionally, epoxy compounds having alkylene oxide groups were used as curing agents to improve the tensile properties of insulating films; however, in this case, as the content of flexible functional groups in the composition increases, there is a problem that the glass transition temperature decreases when the composition is cured. Accordingly, the inventors have developed a positive-type photosensitive resin composition that uses an epoxy compound having urethane groups as a curing agent to improve tensile properties while maintaining the glass transition temperature after curing due to the formation of a network through hydrogen bonding.

[0021] In one embodiment of the present specification, the epoxy compound having the urethane group may be represented by the following chemical formula 1.

[0022] [Chemical Formula 1]

[0023]

[0024] In the above chemical formula 1,

[0025] R1, R2, and R4 are each divalent hydrocarbon groups having 1 to 20 carbon atoms, and

[0026] R3 is a divalent hydrocarbon group having 1 to 20 carbon atoms; or a divalent hydrocarbon group comprising a conjugated structure having 6 to 30 carbon atoms, and

[0027] n is an integer from 1 to 8.

[0028] In one embodiment of the present specification, the divalent hydrocarbon group includes a divalent saturated hydrocarbon group and a divalent unsaturated hydrocarbon group.

[0029] In one embodiment of the present specification, the divalent hydrocarbon group includes a straight chain, a branched chain, and a cyclic chain.

[0030] In one embodiment of the present specification, the divalent hydrocarbon group is a divalent alkyl group, a divalent cycloalkyl group, or a divalent aryl group.

[0031] In one embodiment of the present specification, the divalent saturated hydrocarbon group may be a divalent alkyl group or a divalent cycloalkyl group.

[0032] In one embodiment of the present specification, the divalent unsaturated hydrocarbon group may be a divalent hydrocarbon group having a conjugated structure.

[0033] In one embodiment of the present specification, the divalent hydrocarbon group including the conjugated structure may be a divalent aromatic hydrocarbon group.

[0034] In one embodiment of the present specification, the divalent aromatic hydrocarbon group may be a divalent aryl group.

[0035] In one embodiment of the present specification, examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, etc., and include both straight chain and branched chain.

[0036] In one embodiment of the present specification, examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc.

[0037] In one embodiment of the present specification, examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, anthracenyl group, a triphenylenyl group, etc.

[0038] In one embodiment of the present specification, R3 may be a divalent hydrocarbon group having 1 to 20 carbon atoms.

[0039] In one embodiment of the present specification, R3 may be a divalent hydrocarbon group having a conjugated structure having 6 to 30 carbon atoms.

[0040] In one embodiment of the present specification, R3 may be a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms.

[0041] In one embodiment of the present specification, R3 may be a divalent aryl group having 6 to 30 carbon atoms.

[0042] A positive-type photosensitive resin composition containing the compound of Chemical Formula 1 as a curing agent has the effect of maintaining the glass transition temperature after curing while improving tensile properties.

[0043] In one embodiment of the present specification, the epoxy compound having urethane groups has a molecular weight of 100 g / mol to 5,000 g / mol, preferably 500 g / mol to 4,000 g / mol, and more preferably 800 g / mol to 3,000 g / mol. When using an epoxy compound having urethane groups having a molecular weight in the above range, it is effective in increasing elongation and can form a pattern without impairing the alkali-soluble properties of the composition.

[0044] In addition, urethane groups interact through hydrogen bonding. When urethane groups are directly introduced into a polymer exceeding the above molecular weight range, the polymers interact with each other, causing a rapid decrease in alkali solubility. On the other hand, when urethane groups are applied to a compound having a molecular weight within the above range, alkali solubility is not significantly reduced, and the effect of improving tensile properties is provided when used in a photosensitive resin composition.

[0045] In one embodiment of the present specification, the epoxy compound having a urethane group includes, but is not limited to, UME-208 (Kukdo Chemical), UME-305 (Kukdo Chemical), UME-330 (Kukdo Chemical), etc.

[0046] In one embodiment of the present specification, the curing agent may further comprise one or more compounds selected from a compound having an alkylol group and an epoxy compound having two or more epoxy groups.

[0047] In one embodiment of the present specification, the curing agent may further comprise a compound having an alkylol group and an epoxy compound having two or more epoxy groups.

[0048] In one embodiment of the present specification, the curing agent may further comprise an epoxy compound having two or more epoxy groups.

[0049] In one embodiment of the present specification, the compound having an alkylol group may be a compound having an alkylol group having 1 to 10 carbon atoms.

[0050] In one embodiment of the present specification, the compound having an alkylol group may be a compound having an alkylol group having 1 to 5 carbon atoms.

[0051] In one embodiment of the present specification, the compound having an alkylol group may be a compound having a methylol group.

[0052] In one embodiment of the present specification, the compound having a methylol group is not limited to those containing a methylol group, such as hexamethoxymethylmelamine (HMMM), and, for example, a compound having the following structure may be used.

[0053]

[0054] In one embodiment of the present specification, the epoxy compound having two or more epoxy groups may have two or three epoxy groups.

[0055] In one embodiment of the present specification, the epoxy compound having two or more epoxy groups may be an epoxy compound having two epoxy groups.

[0056] In one embodiment of the present specification, the epoxy compound having two or more epoxy groups may be an epoxy compound comprising the following structure.

[0057]

[0058] In the above structure, * indicates a position that is combined with another structure.

[0059] In one embodiment of the present specification, the epoxy compound having two or more epoxy groups may be represented by the following chemical formula 2.

[0060] [Chemical Formula 2]

[0061]

[0062] In the above chemical formula 2,

[0063] L1 to L5 are each a divalent hydrocarbon group having 1 to 20 carbon atoms, and may be further substituted with a hydroxyl group, and

[0064] m is an integer from 1 to 20.

[0065] In one embodiment of the present specification, the epoxy compound having two or more epoxy groups may have the following structure.

[0066]

[0067] In the above structure, the number of repetitions m1 is an integer from 4 to 8.

[0068] In one embodiment of the present specification, the epoxy compounds having two or more epoxy groups include, but are not limited to, YDF-170, YDF-172, YD-113, YD-114, YD-114E, YD-114F, YD-115, YD-115G, YD-115CA, KT-7804, KD-1818, YD-127, YD-128, YD-128S, YD-134, YD-136 (all from Kukdo Chemical), EXA-4850-150, EXA-4850-1000 (DIC).

[0069] In one embodiment of the present specification, the curing agent is included in an amount of 3 to 15 parts by weight, 4 to 12 parts by weight, or 5 to 10 parts by weight, based on 100 parts by weight of the total positive-type photosensitive resin composition. When the curing agent is included within the above ranges, it can provide excellent chemical resistance and facilitate pattern implementation by having sufficient curing degree and photo-specific properties. On the other hand, if it is included in an amount less than 3 parts by weight, the curing degree is insufficient, resulting in poor chemical resistance, and if it is included in an amount exceeding 15 parts by weight, the photo-specific properties are insufficient, making pattern implementation difficult.

[0070] In one embodiment of the present specification, the content of the epoxy compound having urethane groups in the curing agent may be 40 parts by weight or more and 80 parts by weight or less, 50 parts by weight or more and 77 parts by weight or less, and 65 parts by weight or more and 75 parts by weight or less. When the epoxy compound having urethane groups is included within the above range, it provides the effect of improving elongation while maintaining excellent chemical resistance.

[0071] If the above epoxy compound having urethane groups is included in an amount of less than 40 parts by weight out of 100 parts by weight of the total curing agent, there is no significant effect on the improvement of the elongation of the composition, and if it is included in an amount exceeding 80 parts by weight, the chemical resistance after curing may be poor.

[0072] In one embodiment of the present specification, the alkali-soluble polyimide resin may comprise a polymer of a diamine compound and an anhydride compound. The anhydride compound also comprises a dianhydride compound.

[0073] In one embodiment of the present specification, the alkali-soluble polyimide resin may include an anhydride compound as a terminal sealant.

[0074] In one embodiment of the present specification, the alkali-soluble polyimide resin may comprise repeating units derived from a diamine compound and repeating units derived from a dianhydride compound.

[0075] In one embodiment of the present specification, the alkali-soluble polyimide resin may comprise repeating units derived from a diamine compound, repeating units derived from a dianhydride compound, and terminal structures derived from an anhydride compound.

[0076] In one embodiment of the present specification, the alkali-soluble polyimide resin may include repeating units represented by the following chemical formulas 3 and 4.

[0077] [Chemical Formula 3]

[0078]

[0079] [Chemical Formula 4]

[0080]

[0081] In the above chemical formulas 3 and 4,

[0082] X1 and X2 are identical or different from each other, and each is independently a tetravalent organic group, and

[0083] Y1 and Y2 are identical or different from each other, and each is independently a divalent organic group, and

[0084] o and p are each independently integers from 1 to 500.

[0085] In one embodiment of the present specification, X1 and X2 are each independently tetravalent organic groups derived from acid anhydrides or derivatives thereof.

[0086] In one embodiment of the present specification, X1 and X2 are each independently tetravalent organic groups derived from acid dianhydrides or derivatives thereof.

[0087] In the present specification, the tetravalent organic group is an organic group having four bonding sites, for example, a tetravalent aromatic organic group, a tetravalent aliphatic organic group, or a tetravalent organic group in which an aromatic group and an aliphatic group are connected to each other, and at least one carbon may be replaced with C(=O), SO2, NRx, S, or O, and Rx is an alkyl group or an aryl group.

[0088] In the present specification, the alkyl group may be a straight chain or a branched chain, and the number of carbon atoms may be 1 to 20, although not particularly limited. According to another embodiment, the number of carbon atoms of the alkyl group is 1 to 10. Specific examples of the alkyl group include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, and n-heptyl groups.

[0089] In the present specification, the aryl group is not particularly limited but may have 6 to 60 carbon atoms and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the number of carbon atoms of the aryl group is 6 to 30. According to another embodiment, the number of carbon atoms of the aryl group is 6 to 20. As a monocyclic aryl group, the aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto. As a polycyclic aryl group, the aryl group may be a naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, triphenylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto.

[0090] In one embodiment of the present specification, X1 and X2 are each independently selected from any one of the following structures.

[0091]

[0092]

[0093] .

[0094] In one embodiment of the present specification, X1 and X2 are each independently selected from any one of the following structures.

[0095] .

[0096] In one embodiment of the present specification, Y1 and Y2 are each independently divalent organic groups derived from a diamine or a derivative thereof.

[0097] The above divalent organic group may be a divalent aliphatic organic group, a divalent aromatic organic group, or a divalent organic group in which an aliphatic group and an aromatic group are connected to each other, and at least one carbon may be replaced with C(=O), SO2, NRx, S, or O, and Rx may be an alkyl group or an aryl group and may be substituted with a halogen group, a hydroxyl group, a carboxyl group, a thiol group, a sulfonic acid group, or an alkyl group.

[0098] In one embodiment of the present specification, Y1 and Y2 are each independently selected from any one of the following structural formulas.

[0099]

[0100] .

[0101] In this specification, may mean a portion that is bonded to another substituent or bonding portion, and may mean a portion that is bonded to the main chain of the polymer of the present specification.

[0102] In one embodiment of the present specification, the imidation rate of the alkali-soluble polyimide resin may be 80% or more and 97% or less, 87% or more and 97% or less, preferably 90% or more and 95% or less. When an alkali-soluble polyimide having an imidation rate within the above range is included, a photosensitive composition having excellent thermal stability and improved mechanical properties can be provided.

[0103] In one embodiment of the present specification, the weight-average molecular weight of the alkali-soluble polyimide resin is 10,000 g / mol to 35,000 g / mol, 10,000 g / mol to 30,000 g / mol, 10,000 g / mol to 25,000 g / mol, and 10,000 g / mol to 20,000 g / mol.

[0104] When the weight-average molecular weight of the alkali-soluble polyimide resin satisfies the aforementioned range, the photosensitive resin composition containing it has excellent physical and chemical properties, appropriate viscosity, and excellent adhesion to the substrate.

[0105] The above weight-average molecular weight refers to one of the average molecular weights used as a standard when the molecular weight of a polymeric material is not uniform; it is a value obtained by averaging the molecular weights of the constituent molecular species of a polymeric compound with a molecular weight distribution by weight fraction.

[0106] The above weight-average molecular weight can be measured by the gel permeation chromatography (GPC) method.

[0107] In one embodiment of the present specification, the alkali-soluble polyimide resin is included in an amount of 15 to 35 parts by weight, 17 to 28 parts by weight, and 20 to 25 parts by weight, based on 100 parts by weight of the total positive-type photosensitive composition.

[0108] When the above alkali-soluble polyimide resin is included within the above range, it imparts developability to the alkali developer and obtains heat resistance characteristics; when it is 15 parts by weight or more, heat resistance is advantageous, and when it is 35 parts by weight or less, poor chemical resistance can be prevented.

[0109] In one embodiment of this specification, the photoactive compound is not particularly limited and may be used without limitation as long as it is applicable in the art.

[0110] In one embodiment of the present specification, the photoactive compound may include, but is not limited to, PAC430, 4PAC430, TPD420, TPD425, TPD520, TPD523, THPE515, TPA320, TPA523, TPD423, TPD425, TPD510, TPD511, TPD520 (Miwon Commercial Co., Ltd.).

[0111] In one embodiment of the present specification, the photoactive compound is included in an amount of 1 to 10 parts by weight, 1 to 8 parts by weight, or 2 to 5 parts by weight, based on 100 parts by weight of the total positive-type photosensitive composition. When the photoactive compound is included within the above range, photosensitive properties having sufficient resolution can be imparted.

[0112] A positive type photosensitive composition according to one embodiment of the present specification may further include one or more additives selected from an adhesion aid, an antioxidant, an antifoaming agent, and a surfactant.

[0113] In one embodiment of the present specification, the adhesive aid may be a silane coupling agent, an imidazole-based, a triazole-based, or a thiol-based agent.

[0114] In one embodiment of the present specification, the silane coupling agent refers to a compound comprising a hydrolyzable silyl group or a silanol group, which can increase the mutual adhesion between a cured film and a specific surface of a substrate, thereby increasing heat resistance and chemical resistance. Examples of the silane coupling agent may include one or more selected from octyltrimethoxysilane, dodecyltrimethoxysilane, octadecyltrimethoxysilane, etc., but are not limited thereto.

[0115] In one embodiment of the present specification, imidazole-based adhesive aids include 1-methylbenzimidazole, but are not limited thereto.

[0116] In one embodiment of the present specification, triazole-based adhesive promoters include, but are not limited to, TT-LX, BT-LX (Johoku Chemical), Irgamet 42 (Ciba), 1-methyl-1-H-benzotriazole, 3-mercapto-1,2,4-triazole, benzotriazole-5-carboxylic acid, N,N-dimethyl benzotriazole methanamine.

[0117] In one embodiment of this specification, thiol-based adhesive aids include, but are not limited to, Bismuthiol.

[0118] When a positive-type photosensitive resin composition according to one embodiment of the present specification includes the adhesive aid, the adhesive aid may be included in an amount of 0.01 to 1 weight part per 100 weight parts of the total positive-type photosensitive resin composition.

[0119] In one embodiment of the present specification, the antioxidant may serve to prevent a chain reaction in which radicals are generated during the formation of a polymer film. In this case, the antioxidant may include phenolic antioxidants, and may use antioxidants commonly used in the industry such as 2,2-thiobis(4-methyl-6-t-butylphenol) or 2,6-g,t-butylphenol, and the ultraviolet absorber may use 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chloro-benzotriazole or alkoxybenzophenone, but is not limited thereto.

[0120] When the above antioxidant is included, the antioxidant may be included in an amount of 0.01 to 1 weight part per 100 weight parts of the total positive-type photosensitive composition.

[0121] In one embodiment of the present specification, the defoaming agent is an additive that inhibits foam formation. When included in the photosensitive resin composition of the present invention, it has the effect of removing bubbles in the liquid phase to improve coating properties and removing bubbles that may exist in the film after coating.

[0122] Examples of the above-mentioned antifoaming agents include BYK-141 and BYK-392 from BYK-Chemie, but are not limited thereto.

[0123] In one embodiment of the present specification, the surfactant is a silicone-based surfactant or a fluorine-based surfactant, and specifically, the silicone-based surfactant is BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341, BYK-344, BYK-345, BYK-346, BYK-348, BYK-354, BYK-355, BYK-356, BYK-358 of BYK-Chemie. BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, BYK-390, etc. can be used, and as fluorinated surfactants, DIC (DaiNippon Ink & Chemicals)'s F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F-445, F-446, F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F-484, F-486, F-487, F-172D, R-40, R-41, MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130, TF-1116SF, TF-1131, TF1132, TF1027SF, TF-1441, TF-1442, etc. may be used, but are not limited to these.

[0124] When the above surfactant is included, the surfactant may be included in an amount of 0.01 to 1 part by weight, 0.01 to 0.5 parts by weight, or 0.01 to 0.1 parts by weight, based on 100 parts by weight of the total positive-type photosensitive composition.

[0125] In one embodiment of the present specification, the total content of the additive may be 0.01 to 1 part by weight or 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the entire positive-type photosensitive composition.

[0126] If the above additive is included in an amount of less than 0.01 parts by weight, the effect of the additive is negligible, and if it is included in an amount exceeding 1 part by weight, the hydrophilicity of the surface is lowered, which may impede the penetration of the developer and thus impede the developability.

[0127] In one embodiment of the present specification, the positive type photosensitive composition may include a surfactant.

[0128] In one embodiment of the present specification, the positive type photosensitive composition may include a fluorine-based surfactant.

[0129] In one embodiment of the present specification, the positive type photosensitive composition comprises a solvent.

[0130] In one embodiment of the present specification, the solvent may be any compound known in the art to which the present invention belongs to be capable of enabling the formation of a photosensitive resin composition without particular limitation. As a non-limiting example, the solvent may be one or more compounds selected from the group consisting of esters, ethers, ketones, aromatic hydrocarbons, and sulfoxides.

[0131] The above ester solvents are ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, gamma-butyrolactone, epsilon-caprolactone, delta-valerolactone, alkyl oxyacetates (e.g., methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-oxypropionate esters (e.g., methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (e.g., 3-methyl methoxypropionate, 3-ethyl methoxypropionate, 3-methyl ethoxypropionate, 3-ethyl ethoxypropionate, etc.), 2-alkyl esters of oxypropionate (e.g., methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (e.g., methyl methoxypropionate, ethyl 2-methoxypropionate, propyl methoxypropionate, 2-methyl ethoxypropionate, ethyl 2-ethoxypropionate)), 2-methyl-2-methylpropionate and 2-ethyl-2-methylpropionate (e.g., methyl-2-methylpropionate, ethyl-2-ethoxypropionate, etc.), methyl pyruvate, It may be ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-methyl oxobutanate, 2-ethyl oxobutanate, etc.

[0132] The above ether solvents may be diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc.

[0133] The above ketone solvents may be methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc.

[0134] The above aromatic hydrocarbon solvents may be toluene, xylene, anisole, limonene, etc.

[0135] The above sulfoxide solvent may be dimethyl sulfoxide, etc.

[0136] In one embodiment of the present specification, the solvent may include one or more selected from propylene glycol monomethyl ether acetate and gamma-butyrolactone.

[0137] In one embodiment of the present specification, the solvent may consist solely of propylene glycol monomethyl ether acetate.

[0138] In one embodiment of the present specification, the solvent may be a mixture of propylene glycol monomethyl ether acetate and gamma-butyrolactone.

[0139] In one embodiment of the present specification, the solvent may be a mixture of propylene glycol monomethyl ether acetate and gamma-butyrolactone in a weight ratio of 2:1 to 4:1 or 3:1 to 4:1.

[0140] One embodiment of the present specification provides an insulating film comprising a positive type photosensitive resin composition or a cured product thereof.

[0141] The above insulating film may include the above positive-type photosensitive resin composition as is.

[0142] The insulating film may include a cured product of the positive-type photosensitive resin composition.

[0143] An insulating film according to one embodiment of the present specification may include repeating units derived from an epoxy compound having urethane groups in the main chain or side chain of a polymer constituting the insulating film.

[0144] The epoxy compound having the above urethane group can be represented by the following chemical formula 1.

[0145] [Chemical Formula 1]

[0146]

[0147] In the above chemical formula 1,

[0148] R1, R2, and R4 are each divalent hydrocarbon groups having 1 to 20 carbon atoms, and

[0149] R3 is a divalent hydrocarbon group having 1 to 20 carbon atoms; or a divalent hydrocarbon group comprising a conjugated structure having 6 to 30 carbon atoms, and

[0150] n is an integer from 1 to 8.

[0151] Specifically, the insulating film of the present invention is characterized by being formed by curing a composition using an epoxy compound having urethane groups as a curing agent, and the location where the epoxy is cured is determined according to the structure of the alkali-soluble polyimide resin.

[0152] In other words, repeating units derived from epoxy compounds containing urethane groups may be included in the main chain or the side chain depending on the structure of the alkali-soluble polyimide resin, and this results in an effect of improving the tensile properties of the insulating film.

[0153] In particular, when using an epoxy compound having a urethane group of the above chemical formula 1 having a molecular weight of 100 g / mol to 5,000 g / mol, it induces bonding between the resin and the epoxy during the curing of the composition, and ultimately has the effect of improving tensile properties.

[0154] The insulating film according to the present invention has a structure different from that of an insulating film obtained by curing a composition comprising a compound in which urethane groups are introduced into the alkali-soluble resin itself. This is applied by replacing alkali-soluble hydroxyl groups to reduce alkali solubility and is used to form a negative-type photosensitive composition by introducing acrylic groups.

[0155] In one embodiment of the present specification, when an insulating film is loaded into a universal testing machine (UTM, Zwick) and the measurement length and pulling speed are set to 5 cm and 10.0 mm / min, respectively, and the elongation and tensile strength are measured at a temperature of 25°C, the elongation is 50% or more and the tensile strength is 90 MPa or more and 120 MPa or less.

[0156] In one embodiment of the present specification, the elongation of the insulating film may be 60% or more, and the upper limit is not specifically limited, but may be, for example, 120% or less.

[0157] In one embodiment of the present specification, the tensile strength of the insulating film may be 90 MPa or more and 110 MPa or less, or 90 MPa or more and 105 MPa or less.

[0158] An insulating film satisfying the above tensile properties is effective in improving the impact resistance of the device and exhibits excellent characteristics in drop and bending tests.

[0159] In one embodiment of the present specification, when the glass transition temperature is measured by heating the insulating film at a rate of 10°C / min from a temperature of 25°C under a nitrogen atmosphere using a TMA (Thermomechanical Analyzer, TA Q400) device, the glass transition temperature is 200°C or higher.

[0160] In one embodiment of the present specification, the glass transition temperature of the insulating film may be 210°C or higher. The upper limit of the glass transition temperature of the insulating film is not specifically limited, but may be, for example, 300°C or lower.

[0161] In one embodiment of the present specification, the coefficient of thermal expansion of the insulating film is 60 ppm / ℃ or less, and the lower limit is not limited but is 40 ppm / ℃ or more.

[0162] An insulating film satisfying the above glass transition temperature range and thermal expansion coefficient range prevents warping caused by the difference in thermal expansion coefficients with the substrate, thereby exhibiting good characteristics against thermal shock.

[0163] In one embodiment of the present specification, the glass transition temperature and the coefficient of thermal expansion were measured using a TMA (Thermomechanical Analyzer, TA Q400). First, the manufactured insulating film was dried in a convection oven at 40°C for 1 hour, then cut into a size of 10 cm × 1 cm to prepare a sample, and then the glass transition temperature and the coefficient of thermal expansion were measured using the Q400 instrument by increasing the temperature from 25°C at a rate of 10°C / min under a nitrogen atmosphere.

[0164] The above insulating film exhibits excellent chemical resistance and mechanical properties, and can be preferably applied as an insulating film for semiconductor devices, an interlayer insulating film for redistribution layers, etc. In addition, the above insulating film can be applied as a photoresist, an etching resist, a solder top resist, etc.

[0165] The above insulating film may include a support or a substrate.

[0166] The above support or substrate is not particularly limited and may use known materials in the art. Examples include a substrate for electronic components or one having a predetermined wiring pattern formed thereon. Examples of the substrate may include metal substrates such as silicon, silicon nitride, titanium, tantalum, palladium, tungsten titanium, copper, chromium, iron, aluminum, gold, nickel, etc., or glass substrates. As for the material of the wiring pattern, examples may include copper, solder, chromium, aluminum, nickel, gold, etc., but are not limited thereto. Preferably, the support or substrate may be a silicon wafer.

[0167] The above coating method is not particularly limited, but spraying, roll coating, spin coating, etc., may be used, and spin coating is generally widely used. In addition, after forming the coating film, residual solvent may be partially removed under reduced pressure depending on the case.

[0168] In the present specification, the thickness of the insulating film may be 1 μm to 50 μm, 1 μm to 30 μm, or 1 μm to 20 μm. When the thickness range of the insulating film is satisfied, an insulating film with excellent chemical resistance and mechanical properties intended in the present specification can be obtained. The thickness of the insulating film can be measured using a scanning electron microscope (SEM).

[0169] One embodiment of the present specification provides a semiconductor device including the insulating film.

[0170] The above semiconductor device may be manufactured to include various components commonly used in the field of technology in addition to the insulating film.

[0171] Figure 1 shows a cross-sectional view of a device including two insulating layers (insulating films). Specifically, it shows two insulating layers including a Cu redistribution layer between an IC chip and a solder ball.

[0172] Another embodiment of the present specification provides a method for manufacturing an insulating film comprising the steps of: preparing a positive-type photosensitive resin composition comprising an alkali-soluble polyimide resin; a curing agent; a photoactive compound; and a solvent; and curing the positive-type photosensitive resin composition, wherein the curing agent comprises an epoxy compound having urethane groups.

[0173] In one embodiment of the present specification, the alkali-soluble polyimide resin may be synthesized directly or a commercially available product may be used.

[0174] In one embodiment of the present specification, the curing agent, photoactive compound, and solvent may be commercially available products.

[0175] In one embodiment of the present specification, the step of curing the positive-type photosensitive resin composition may include the step of applying the positive-type photosensitive resin composition to a wafer to form a film; the step of initially curing the film; and the step of finally curing the initially cured film.

[0176] In one embodiment of the present specification, the step of initially curing the film may be performed at a temperature of 100°C to 140°C for 1 minute to 5 minutes. At the same time as initially curing the film, residual solvent may be evaporated.

[0177] In one embodiment of the present specification, the final curing step may use an oven in a nitrogen atmosphere.

[0178] In one embodiment of the present specification, the final curing step may be performed at a temperature of 160°C to 250°C for 1 hour to 3 hours.

[0179] Hereinafter, to specifically explain this specification, examples will be described in detail. However, the embodiments according to this specification may be modified in various different forms, and the scope of this specification is not to be interpreted as being limited to the embodiments described below. The embodiments of this specification are provided to more completely explain this specification to those with average knowledge in the art.

[0180] <Preparation Example>

[0181] 1) Synthesis of alkali-soluble polyimide resins

[0182] 14.4 g (0.31 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (Bis-AP-AF) was added to 500 g of propylene glycol monomethyl ether acetate (PGMEA) in a round-bottom flask and dissolved at 60°C. 91.1 g (0.29 mol) of 4,4'-oxydiphthalic anhydride (ODPA) was added and stirred for 2 hours, after which 7.2 g (0.03 mol) of phthalic anhydride was added as a terminal sealant and stirred for an additional 2 hours. Subsequently, the temperature was raised to 170°C and stirred for 6 hours. Afterward, it was cooled to room temperature. The weight-average molecular weight (Mw) of polymerized resin A, measured by gel permeation chromatography (GPC), was 15,000 g / mol, and the degree of imidization (DOI) of resin A was 93% as a result of infrared spectroscopy (IR) measurement. The weight-average molecular weight of polymerized resin A was measured by gel permeation chromatography in the solvent of tetrahydrofuran (THF).

[0183] 2) Preparation of a photosensitive resin composition

[0184] A positive-type photosensitive resin composition was prepared by mixing the alkali-soluble polyimide resin prepared above, a curing agent, a photoactive compound, a surfactant, and a solvent in the composition and content (parts by weight) listed in Table 1 below, and stirring for 24 hours.

[0185] The values ​​in Table 1 below represent the weight percentage of each component based on 100 weight percent of the total manufactured positive-type photosensitive resin composition.

[0186] Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 alkali Availability polyimide profit - 23.80% 23.80% 23.80% 23.80% 23.80% 23.80% 23.80% hardener UME-208 5.00% 5.00% - - - - - DE-208 - - 5.00% 5.00% - - - EXA-4850-1000 - - - - 5.00% - - SIB-1115 - - - - - 5.00% - KR-628 - - - - - - 5.00% YDF-170 1.45% 2.15% 1.45% 2.15% 2.15% 2.15% 2.15% HMMM 0.70% - 0.70% - - - - Photoactive compounds TPD523 3.60% 3.60% 3.60% 3.60% 3.60% 3.60% 3.60% surfactants R-40 0.05% 0.05% 0.05% 0.05% 0.05% 0.05% 0.05% menstruum PGMEA 50.40% 50.40% 50.40% 50.40% 50.40% 50.40% 50.40% GBL 15.00% 15.00% 15.00% 15.00% 15.00% 15.00% 15.00%

[0187] -UME-208: Urethane-based epoxy (Kukdo Chemical)

[0188] -DE-208: Alkylene oxide epoxy resin (polypropylene glycol diglycidyl ether) (Kukdo Chemical)

[0189] -EXA-4850-1000: Bisphenol A type epoxy resin (DIC)

[0190] -SIB-1115: Silicone-modified epoxy resin (1,3-bis(glycidoxypropyl)tetramethyldisiloxane) (Gelest)

[0191] -KR-628: Rubber-modified epoxy resin (Kukdo Chemical)

[0192] -YDF-170: Bisphenol F type epoxy resin (Kukdo Chemical)

[0193] -HMMM: Methylol curing agent (hexamethoxymethylmelamine) (TIC)

[0194] -TPD523: Photosensitive material (Miwon Trading Co.)

[0195] -R-40: Surfactant (DIC)

[0196] -PGMEA: Propylene glycol monomethyl ether acetate

[0197] -GBL: Gamma-butyrolactone

[0198] <Experimental Example>

[0199] 1) Preparation of measurement samples

[0200] The photosensitive resin composition prepared above was spin-coated onto a 6-inch wafer to form a film, and the solvent was evaporated and initial cured at 120°C for 2 minutes. This was then finally cured at 180°C for 2 hours in a nitrogen atmosphere oven (Koyo INH oven), and the thickness of the film after final curing was 10 μm. To remove the cured film from the wafer, it was immersed in 2.5% HF diluted in DI-water for 30 minutes; once the film floated to the surface, it was removed and washed three times with DI-water. The obtained cured film was dried in a convection oven at 40°C for 1 hour, then cut into a size of 10 cm × 1 cm to prepare a sample for tensile measurement.

[0201] 2) Measurement of Young's Modulus, Tensile Strength, and Elongation

[0202] After loading the above-prepared sample into a Universal Testing Machine (UTM, Zwick) at a temperature of 25℃, the Young's modulus, tensile strength, and elongation were measured. At this time, the measurement length of the sample was set to 5cm, and the pulling speed was set to 10.0 mm / min.

[0203] 3) Glass transition temperature (T g ) and measurement of coefficient of thermal expansion (CTE)

[0204] The glass transition temperature and coefficient of thermal expansion were measured by heating the sample prepared above using a TA Q400 instrument at a rate of 10℃ / min from 25℃ under a nitrogen atmosphere.

[0205] 4) E op evaluation

[0206] The photosensitive resin composition prepared above was spin-coated onto a 6-inch wafer, and then a soft bake (prebake, SOB) was performed at 120°C for 2 minutes. Subsequently, an exposure machine was used at 200 mJ / cm² 2 From 500 mJ / cm² 2Exposure was performed at 10 mJ intervals up to, and a resist pattern was prepared by developing in a 2.38% TMAH (Tetramethylammonium hydroxide) aqueous solution at 23°C for 120 seconds, after which E was observed using a SEM (Scanning Electron Microscope). op confirmed.

[0207] Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 E op (mJ / cm 2 ) 320 380 220 240 280 340 400 Young's modulus (MPa) 2650 2600 2700 2600 2800 2700 2800 Tensile strength (MPa) 100 95 88 85 100 105 100 Growth Rate (%) 60 70 50 50 47 15 20 T- g (℃) 220 210 180 170 168 210 210 CTE(ppm / ℃) 58 60 75 80 82 59 63

[0208] According to Table 2 above, Comparative Examples 1 to 3 are films cured from a composition containing an epoxy compound having an alkylene oxide group as a curing agent, and it can be seen that compared to the embodiments according to the present invention, they are inferior in tensile strength, elongation, and glass transition temperature. In addition, there is a problem of poor thermal stability because they have a high coefficient of thermal expansion of 75 ppm or more.

[0209] Comparative Examples 4 and 5, using silicone-modified epoxy resin and rubber-modified epoxy resin respectively, can also be seen to be similar to the present invention in terms of tensile strength and glass transition temperature, but with significantly lower elongation.

[0210] On the other hand, it can be seen that Examples 1 and 2, which use the positive type photosensitive composition of the present invention, have excellent thermal properties as well as tensile properties.

Claims

Claim 1 A positive-type photosensitive resin composition comprising: an alkali-soluble polyimide resin comprising repeating units represented by the following chemical formulas 3 and 4; a curing agent comprising an epoxy compound having urethane groups; a photoactive compound; and a solvent: [Chemical Formula 3] [Chemical Formula 4] In the above chemical formulas 3 and 4, X1 and X2 are each independently a tetravalent organic group, Y1 and Y2 are each independently a divalent organic group, and o and p are each independently integers from 1 to 500. Claim 2 A positive-type photosensitive resin composition according to claim 1, wherein the molecular weight of the epoxy compound having a urethane group is 100 g / mol to 5,000 g / mol. Claim 3 A positive-type photosensitive resin composition according to claim 1, wherein the epoxy compound having a urethane group is represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, R1, R2, and R4 are each a divalent hydrocarbon group having 1 to 20 carbon atoms, R3 is a divalent hydrocarbon group having 1 to 20 carbon atoms; or a divalent hydrocarbon group including a conjugated structure having 6 to 30 carbon atoms, and n is an integer from 1 to 8. Claim 4 A positive-type photosensitive resin composition according to claim 1, wherein the curing agent further comprises one or more compounds selected from a compound having an alkylol group and an epoxy compound having two or more epoxy groups. Claim 5 A positive-type photosensitive resin composition according to claim 1, wherein the curing agent is included in an amount of 3 to 15 parts by weight per 100 parts by weight of the total positive-type photosensitive resin composition. Claim 6 A positive-type photosensitive resin composition according to claim 1, wherein the imidization rate of the alkali-soluble polyimide resin is 80% or more and 97% or less. Claim 7 A positive-type photosensitive resin composition according to claim 1, wherein the weight-average molecular weight of the alkali-soluble polyimide resin is 10,000 g / mol to 35,000 g / mol. Claim 8 A positive-type photosensitive resin composition according to claim 1, wherein the positive-type photosensitive resin composition further comprises one or more additives selected from an adhesion promoter, an antioxidant, an antifoaming agent, and a surfactant. Claim 9 A positive-type photosensitive resin composition according to claim 8, wherein the total content of the additive is 0.01 to 1 part by weight per 100 parts by weight of the positive-type photosensitive resin composition. Claim 10 An insulating film comprising a positive-type photosensitive resin composition according to any one of claims 1 to 9, or a cured product thereof. Claim 11 In claim 10, the insulating film is loaded into a Universal Testing Machine (UTM, Zwick) and the measurement length and pulling speed are set to 5 cm and 10.0 mm / min, respectively, and the elongation and tensile strength are measured at a temperature of 25°C, wherein the elongation is 50% or more and the tensile strength is 90 MPa or more and 120 MPa or less. Claim 12 In claim 10, the insulating film has a glass transition temperature of 200°C or higher when the insulating film is heated at a rate of 10°C / min from 25°C under a nitrogen atmosphere using a TMA (Thermomechanical Analyzer, TA Q400) device to measure the glass transition temperature. Claim 13 A semiconductor device comprising an insulating film according to claim 10. Claim 14 A method for manufacturing an insulating film, comprising the steps of: preparing a positive-type photosensitive resin composition comprising an alkali-soluble polyimide resin having repeating units represented by the following chemical formulas 3 and 4; a curing agent; a photoactive compound; and a solvent; and curing the positive-type photosensitive resin composition, wherein the curing agent comprises an epoxy compound having urethane groups: [Chemical Formula 3] [Chemical Formula 4] In the above chemical formulas 3 and 4, X1 and X2 are each independently a tetravalent organic group, Y1 and Y2 are each independently a divalent organic group, and o and p are each independently integers from 1 to 500.

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