Photocurable composition comprising aromatic polyether-based polymer and cured film prepared therefrom

Abstract

An aspect of the present invention relates to: a photocurable composition comprising an aromatic polyether-based polymer, which includes a repeating unit represented by chemical formula 1, and a maleimide, which includes a siloxane unit; and a cured film prepared therefrom. [Chemical formula 1] (R1 to R8, R11 to R13, and X1 are as described in the specification.)

Description

Photocurable composition comprising aromatic polyether polymer and cured film produced therefrom

[0001] The present disclosure relates to a photocurable composition comprising an aromatic polyether polymer and a maleimide including a siloxane unit, and a cured film produced therefrom.

[0002] Semiconductor devices are required to be lightweight and miniaturized, while also having fast processing speeds and large storage capacities. Accordingly, the performance requirements for photosensitive resins, the main material for semiconductor packaging, are also becoming more advanced.

[0003] In particular, for application to high bandwidth memory (HBM), which has recently been in the spotlight, not only more precise and high resolution micro-patterning capabilities are required, but also securing the lowest possible dielectric constant is necessary to maintain high-speed data transmission speeds. However, materials such as photosensitive polyimide, which are widely used in existing semiconductor packaging, have limitations in meeting the low dielectric constant required for high bandwidth memory applications. In addition, attempts to lower the dielectric constant have limitations such as reduced solubility, making it difficult to implement micro-patterning, or deteriorating physical properties such as thermal stability.

[0004] One aspect of the present invention is to provide a photocurable composition capable of producing a cured film having a precise pattern implementation and excellent thermal stability and low dielectric constant.

[0005] Another aspect of the present invention is to provide a cured film applicable to semiconductor devices such as high-bandwidth memory using the photocurable composition.

[0006] One aspect of the present invention provides a photocurable composition comprising: an aromatic polyether polymer including a repeating unit represented by the following chemical formula 1; and a maleimide including a siloxane unit.

[0007] [Chemical Formula 1]

[0008]

[0009] (In the above chemical formula 1,

[0010] R 1 Inland R 8 are each independently halogen or halo(C1-C4)alkyl, and the above R 1 Inland R 8 At least four of which are fluoro groups (-F);

[0011] R 11 Inland R 13 are each independently hydrogen, halogen, (C1-C4)alkyl, or halo(C1-C4)alkyl;

[0012] X 1 is a single bond, -CO-, -SO2-, or -CR 14 R 15 -and;

[0013] R 14 and R 15 are each independently hydrogen, halogen or halo(C1-C4)alkyl.)

[0014] The above aromatic polyether polymer may further include a repeating unit represented by the following chemical formula 2.

[0015] [Chemical Formula 2]

[0016]

[0017] (In the above chemical formula 2,

[0018] R 1 Inland R 8 are each independently halogen or halo(C1-C4)alkyl, and the above R 1 Inland R 8 At least four of which are fluoro groups (-F);

[0019] R 16 and R 17 are each independently halogen, (C1-C4)alkyl, halo(C1-C4)alkyl;

[0020] X 2 is a single bond, -CO-, -SO2-, or -CR 18 R 19 -and;

[0021] R 18 and R 19 are each independently hydrogen, halogen or halo(C1-C4)alkyl;

[0022] p and q are each independently integers from 0 to 2.)

[0023] The repeating unit represented by the above chemical formula 1 may be represented by the following chemical formula 11.

[0024] [Chemical Formula 11]

[0025]

[0026] (In the above chemical formula 11,

[0027] R 1 Inland R 8 , R 14 and R 15 is the same as the definition in the above chemical formula 1.)

[0028] It may contain a repeating unit represented by the above chemical formula 1 and a repeating unit represented by the chemical formula 2 in a molar ratio of 1:0.1 to 10.

[0029] The number average molecular weight of the above aromatic polyether polymer may be 10,000 to 50,000 g / mol.

[0030] The above maleimide may be represented by the following chemical formula 3.

[0031] [Chemical Formula 3]

[0032]

[0033] (In the above chemical formula 3,

[0034] R 21 Inland R 24 are each independently (C1-C7)alkyl;

[0035] x to z are each independently integers from 1 to 10.)

[0036] The photocurable composition according to one aspect may contain 1 to 20 parts by weight of the maleimide based on 100 parts by weight of the aromatic polyether polymer.

[0037] Another aspect of the present invention provides a cured film prepared from the photocurable composition.

[0038] According to one aspect, the above cured film may be used as a sealing film or insulating film for a semiconductor device.

[0039] Another aspect of the present invention provides an aromatic polyether polymer comprising a repeating unit represented by the following chemical formula 1.

[0040] [Chemical Formula 1]

[0041]

[0042] (In the above chemical formula 1,

[0043] R 1 Inland R 8 , R 11 Inland R 13 and X 1 is the same as the definition described above.)

[0044] Another aspect of the present invention provides a method for producing an aromatic polyether polymer, comprising the step of reacting a reaction mixture comprising a compound represented by the following chemical formula A and a compound represented by the following chemical formula B in the presence of a metal base to produce an aromatic polyether polymer comprising a repeating unit represented by the following chemical formula 1.

[0045] [Chemical Formula A]

[0046]

[0047] [Chemical Formula B]

[0048]

[0049] [Chemical Formula 1]

[0050]

[0051] (In the above chemical formula 1, A and B,

[0052] X 1 , R 1 Inland R 8 , R 11 Inland R 13 is the same as the definition described above.)

[0053] The above reaction mixture may further include a compound represented by the following chemical formula C, and the aromatic polyether polymer may further include a repeating unit represented by the following chemical formula 2.

[0054] [Chemical Formula C]

[0055]

[0056] [Chemical Formula 2]

[0057]

[0058] (In the above chemical formula C and chemical formula 2,

[0059] X 2 , R 1 Inland R 8 , R 16 , R 17 , p and q are the same as defined above.)

[0060] The above metal base may be selected from CsF, KF, K2CO3, NaOH and KOH.

[0061] The above reaction may be carried out for 3 to 24 hours under temperature conditions of 30 to 100°C.

[0062] An aromatic polyether polymer according to one embodiment of the present invention has excellent solubility in organic solvents and can be effectively used as a negative photoresist material. In addition, a photocurable composition comprising an aromatic polyether polymer according to one embodiment and a maleimide including a siloxane unit can implement a precise pattern upon curing, and at the same time, can provide a cured film having high thermal stability and a sufficiently low dielectric constant, for example, a dielectric constant of 2.8 or less, after curing. In other words, the photocurable composition according to one embodiment is expected to be applicable to various semiconductor devices that require fast processing speeds and large-capacity storage capabilities, such as high-bandwidth memories.

[0063] Figure 1 is a photograph of a cured film manufactured in Example 1.

[0064] Figure 2 is a photograph of a cured film manufactured in Example 2 and Comparative Example 2.

[0065] Figure 3 is a photograph of a cured film manufactured in Example 3.

[0066] Figures 4 and 5 are photographs of a patterned cured film of Example 1 using a mask aligner.

[0067] Unless otherwise defined herein, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0068] As used herein, the singular forms may be intended to include the plural forms as well, unless the context clearly indicates otherwise.

[0069] Throughout this specification, the terms "comprises," "includes," "contains," or "has" a component, unless specifically stated to the contrary, do not exclude other components, but rather may include other components, and do not exclude additional unrecited elements, materials, or processes.

[0070] The numerical ranges used herein include the lower and upper limits and all values ​​within that range, increments logically derived from the shape and width of the defined range, all doubly defined values, and all possible combinations of the upper and lower limits of numerical ranges defined in different shapes. Unless otherwise specified herein, values ​​outside the defined range that may arise due to experimental error or rounding of values ​​are also included in the defined numerical range.

[0071] Unless otherwise specified herein, “about” may be considered a value within 30%, 25%, 20%, 15%, 10% or 5% of the stated value.

[0072] As used herein, “haloalkyl” means alkyl in which one or more hydrogen atoms are replaced with halogen atoms (F, Cl, Br, I).

[0073] As used herein, “fluoroalkyl” means alkyl in which one or more hydrogen atoms are replaced with fluoro (-F), and examples thereof include, but are not limited to, fluoromethyl, difluoromethyl, trifluoromethyl, fluoroethyl, difluoroethyl, perfluoroethyl, and the like.

[0074] Below, the present disclosure will be described in detail. However, this is merely exemplary and the present disclosure is not limited to the specific embodiments described as examples.

[0075] A photocurable composition according to one aspect of the present invention may include an aromatic polyether polymer including a specific structural unit and a maleimide including a siloxane unit.

[0076] Specifically, an aromatic polyether polymer according to one aspect may include a repeating unit represented by the following chemical formula 1, and can secure excellent solubility in an organic solvent, and when cured, can implement a fine pattern by combining it with a maleimide including the siloxane unit, and can provide a cured film having excellent thermal stability and low dielectric constant and excellent curing degree.

[0077] [Chemical Formula 1]

[0078]

[0079] (In the above chemical formula 1,

[0080] R 1 Inland R 8 are each independently halogen or halo(C1-C4)alkyl, and the above R 1 Inland R 8 At least four of which are fluoro groups (-F);

[0081] R 11 Inland R 13 are each independently hydrogen, halogen, (C1-C4)alkyl, or halo(C1-C4)alkyl;

[0082] X 1 is a single bond, -CO-, -SO2-, or -CR 14 R 15 -and;

[0083] R 14 and R 15 are each independently hydrogen, halogen or halo(C1-C4)alkyl.)

[0084] For example, the repeating unit represented by the above chemical formula 1 may be represented by the following chemical formula 11.

[0085] [Chemical Formula 11]

[0086]

[0087] (In the above chemical formula 11,

[0088] R 1 Inland R 8 are each independently halogen or halo(C1-C4)alkyl, and the above R 1 Inland R 8 At least four of which are fluoro groups (-F);

[0089] R 14 and R 15 are each independently hydrogen, halogen or halo(C1-C4)alkyl.)

[0090] For example, the above R 1 Inland R 8 Each of R may independently be a fluoro group (-F) or a fluoro (C1-C4) alkyl, and specifically may be a fluoro group or a perfluoro (C1-C4) alkyl, and the above R 1 Inland R 8 At least four of them can be fluoro groups (-F).

[0091] For example, the above R 1 Inland R 4 At least two of the above R 5 Inland R 8 At least two of them may be fluoro groups (-F).

[0092] For example, the above R 14 and R 15 Each independently may be a fluoro group (-F) or a fluoro (C1-C4) alkyl, specifically a fluoro group or a perfluoro (C1-C4) alkyl, and the perfluoro (C1-C4) alkyl may be -CF3, -C2F5, -C3F7, -C4F9.

[0093] For example, the repeating unit represented by the above chemical formula 1 may be selected from the following structure.

[0094]

[0095]

[0096]

[0097] The above aromatic polyether polymer may further include a repeating unit represented by the following chemical formula 2, and may realize a lower dielectric constant and better thermal stability after curing.

[0098] [Chemical Formula 2]

[0099]

[0100] (In the above chemical formula 2,

[0101] R 1 Inland R 8 are each independently halogen or halo(C1-C4)alkyl, and the above R 1 Inland R 8 At least four of which are fluoro groups (-F);

[0102] R 16 and R 17 are each independently halogen, (C1-C4)alkyl, halo(C1-C4)alkyl;

[0103] X 2 is a single bond, -CO-, -SO2-, or -CR 18 R 19 -and;

[0104] R 18 and R 19 are each independently hydrogen, halogen or fluoro(C1-C4)alkyl;

[0105] p and q are each independently integers from 0 to 2.)

[0106] For example, the above R 1 Inland R 8 Each of R may independently be a fluoro group (-F) or a fluoro (C1-C4) alkyl, and specifically may be a fluoro group or a perfluoro (C1-C4) alkyl, and the above R 1 Inland R 8 At least four of them can be fluoro groups (-F).

[0107] For example, the repeating unit represented by the above chemical formula 2 may be represented by the following chemical formula 21 or 22.

[0108] [Chemical Formula 21]

[0109]

[0110] [Chemical Formula 22]

[0111]

[0112] (In the above chemical formulas 21 and 22,

[0113] R 1 Inland R 8 are each independently halogen or halo(C1-C4)alkyl, and the above R 1 Inland R 8 At least four of which are fluoro groups (-F);

[0114] R 16 and R 17 are each independently halogen, (C1-C4)alkyl, halo(C1-C4)alkyl;

[0115] R 18 and R 19 are each independently hydrogen, halogen or halo(C1-C4)alkyl;

[0116] p and q are each independently integers from 0 to 2.)

[0117] For example, the above R 1 Inland R 8 Each of R may independently be a fluoro group (-F) or a fluoro (C1-C4) alkyl, and specifically may be a fluoro group or a perfluoro (C1-C4) alkyl, and the above R 1 Inland R 8 At least four of them can be fluoro groups (-F).

[0118] For example, the above R 1 Inland R 4 At least two of the above R 5 Inland R 8At least two of them may be fluoro groups (-F).

[0119] For example, the above R 16 and R 17 Each of them can independently be a fluoro group (-F), (C1-C4)alkyl, or fluoro(C1-C4)alkyl, and the fluoro(C1-C4)alkyl can be perfluoro(C1-C4)alkyl.

[0120] For example, the above R 18 and R 19 Each independently may be a fluoro group (-F) or a fluoro (C1-C4) alkyl, specifically a fluoro group or a perfluoro (C1-C4) alkyl, and the perfluoro (C1-C4) alkyl may be -CF3, -C2F5, -C3F7, -C4H9.

[0121] For example, the repeating unit represented by the above chemical formula 2 may be selected from the following structure.

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128] When the aromatic polyether polymer according to one embodiment further includes a repeating unit represented by the chemical formula 2, the repeating unit represented by the chemical formula 2 may be included in an amount of 0.01 mol or more, 0.05 mol or more, 0.1 mol or more, 0.5 mol or more, 1 mol or more, 5 mol or more, or 10 mol or more, with respect to 1 mol of the repeating unit represented by the chemical formula 1, and may be included in an amount of 50 mol or less, 40 mol or less, 30 mol or more, 20 mol or less, or 10 mol or less, and may be an intermediate value among the respective values. Specifically, the repeating unit represented by the above chemical formula 1 and the repeating unit represented by the chemical formula 2 may be included in a molar ratio of 1:0.05 to 20, or a molar ratio of 1:0.1 to 20, a molar ratio of 1:0.1 to 10, or a molar ratio of 1:0.5 to 5, and may include all possible combinations of the upper and lower limits of the above numerical ranges, and may further improve the effects of forming a fine pattern, improving thermal stability, and lowering dielectric constant.

[0129] The aromatic polyether polymer according to one embodiment has a number average molecular weight that is not particularly limited, but may be, for example, 10,000 g / mol or more, 15,000 g / mol or more, 20,000 g / mol or more, 100,000 g / mol or less, 50,000 g / mol or less, and specifically, 10,000 to 50,000 g / mol, 20,000 to 50,000 g / mol, or 20,000 to 40,000 g / mol, but is not limited thereto.

[0130] For example, the maleimide containing the siloxane unit may be represented by the following chemical formula 3.

[0131] [Chemical Formula 3]

[0132]

[0133] (In the above chemical formula 3,

[0134] R 21 Inland R24 are each independently (C1-C7)alkyl;

[0135] x to z are each independently integers from 1 to 10.)

[0136] For example, the above R 21 Inland R 24 can each independently be (C1-C4)alkyl, or (C1-C3)alkyl, or methyl or ethyl.

[0137] For example, the above R 21 Inland R 24 are identical to each other and can be (C1-C4)alkyl, or (C1-C3)alkyl, or methyl or ethyl.

[0138] For example, x to y can each independently be an integer from 1 to 7, an integer from 1 to 5, or an integer from 1 to 3.

[0139] For example, the z may be an integer from 1 to 7, or an integer from 1 to 5, or an integer from 1 to 3, 1, or 2.

[0140] The above maleimide may be represented by the following chemical formula 31.

[0141] [Chemical Formula 31]

[0142]

[0143] According to one embodiment, the photocurable composition may contain the maleimide in an amount of 1 to 50 parts by weight, 1 to 20 parts by weight, or 5 to 20 parts by weight, or 5 to 10 parts by weight, or 5 to 15 parts by weight, based on 100 parts by weight of the aromatic polyether polymer, but is not limited thereto.

[0144] The photocurable composition according to one embodiment may further include a photoinitiator, and the photoinitiator is not particularly limited as long as it is commonly used in the relevant technical field, but may be, for example, one or more selected from acetophenone compounds, benzophenone compounds, triazine compounds, benzoin compounds, imidazole compounds, xanthone compounds, phosphine compounds, and oxime compounds.More specifically, the photoinitiator is 2,4-bistrichloromethyl-6-p-methoxystyryl-s-triazine, 2-p-methoxystyryl-4,6-bistrichloromethyl-s-triazine, 2,4-trichloromethyl-6-triazine, 2,4-trichloromethyl-4-methylnaphthyl-6-triazine, 2-(o-chlorophenyl)-4,5-diphenyl imidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl) imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenyl imidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenyl imidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenyl imidazole dimer, 2,4-di(p-methoxyphenyl) phenyl)-5-phenyl imidazole dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenyl imidazole dimer, 2-(p-methylmercaptophenyl)-4,5-diphenyl imidazole dimer, [1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazoyl-3-yl]-1-(O-acetyloxime), benzophenone, p-(diethylamino)benzophenone, 2,2-dichloro-4-phenoxyacetophenone, 2,2-diethoxyacetophenone, 2-dodecylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,2-bis2-chlorophenyl-4,5,4,5-tetraphenyl-2-1,2-biimidazole, One or more selected from the group consisting of (E)-2-(acetoxyimino)-1-(9,9-diethyl-9H-fluoren-2-yl)butanone, (E)-1-(9,9-dibutyl-7-nitro-9H-fluoren-2-yl)ethanone O-acetyl oxime, (Z)-2-(acetoxyimino)-1-(9,9-diethyl-9H-fluoren-2-yl)propanone, Irgacure 369, Irgacure 651, Irgacure 907, Darocur TPO, Irgacure 819, OXE-01, OXE-02, OXE-03, OXE-04 from Basf, N-1919, NCI-831, and NCI-930 from Adeka may be used, but is not limited thereto.

[0145] Additionally, the photocurable composition according to one aspect may further include a thermal initiator.

[0146] The photocurable composition according to one embodiment may further include a solvent. The solvent is an organic solvent, and specific examples thereof include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether; alkylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate; aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, and 4-hydroxy 4-methyl-2-pentanone;And 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 propoxy acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, 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, methyl 3-ethoxypropionate, Esters such as ethyl 3-ethoxypropionate, 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, butyl 3-butoxypropionate, etc.; may be one or two or more selected from the group consisting of, but not limited to;

[0147] The amount of the solvent used to achieve the desired viscosity is not limited, but may be included in an amount of 20 to 90 wt%, or 20 to 70 wt%, or 20 to 50 wt% relative to the entire photocurable composition.

[0148] The photocurable composition according to one embodiment may further include any additive commonly used in the art. In this case, the optional additive may be a silane coupling agent, a surfactant, a filler, a curing agent, a leveling agent, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-coagulant, a chain transfer agent, a solvent, etc., and preferably, at least one selected from a silane coupling agent, a surfactant, and a solvent.

[0149] Another aspect of the present invention provides a cured film obtained by curing the photocurable composition.

[0150] It goes without saying that any known method within the scope recognizable by those skilled in the art can be used for the manufacturing method of the cured film according to the aspect.

[0151] Hereinafter, a method for forming a cured film using the photocurable composition will be described in detail.

[0152] A cured film using a photocurable composition according to one embodiment can be manufactured by a manufacturing method including a step of forming a coating film by applying a photocurable composition according to the present invention on a substrate and removing a solvent by prebaking; and a step of photocuring the coating film by irradiating it with light.

[0153] For example, the above application may be performed using a conventional application method, and specific examples thereof include, but are not limited to, a spray method, a roll coater method, a rotary application method, and a spin coater method.

[0154] For example, the prebaking may be performed under normal temperature conditions, and in one specific example, may be performed at a temperature of 50 to 200°C for 1 to 5 minutes, but is not limited thereto.

[0155] For example, the light may be selected from visible light, ultraviolet rays, ultraviolet rays, electron rays, X-rays, etc., and it is of course possible to form a predetermined pattern using a pattern prepared in advance on the coating film. As a specific example, the ultraviolet rays may use g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), etc., and it is of course possible to appropriately select the irradiation amount of these ultraviolet rays as needed.

[0156] In addition, the substrate may be, but is not limited to, silicon, quartz, glass, a silicon wafer, a polymer, a metal, and a metal oxide. Specifically, the polymer substrate may be, but is not limited to, a film substrate such as triacetyl cellulose, acetyl cellulose butyrate, ethylene vinyl acetate copolymer, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, polyester, polystyrene, polyamide, polyetherimide, polyacrylic, polyimide, polyethersulfone, polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polyether ether ketone, polyether sulfone, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polycarbonate.

[0157] The method for manufacturing a cured film according to one embodiment may further include a developing step with a developer after the photocuring step when forming a pattern. This developing step is a process for removing unexposed areas after photocuring through a mask to form the desired pattern, and can be performed using conventional methods such as a liquid addition method, a dipping method, or a spraying method.

[0158] In one specific example, the developing step can be performed by tilting the substrate at an arbitrary angle and dipping it in the developing solution.

[0159] At this time, the developer may be, for example, alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether, and propylene glycol monoethyl ether, and their acetic acid esters, ketones such as methyl ethyl ketone, diacetone alcohol, acetone, methyl isobutyl ketone, and cyclohexanone, gamma-butyrolactone, ethyl lactate, butyl lactate, and ethyl pyruvate, but is not limited thereto.

[0160] The photocurable composition according to one aspect can secure a sufficient degree of curing after curing, has excellent chemical resistance and thermal stability, and can provide a cured film having a sufficiently low dielectric constant, for example, a dielectric constant of 5.0 F / m or less, 4.5 F / m or less, 4.0 F / m or less, 3.5 F / m or less, 3.0 F / m or less, 2.8 F / m or less, or 1.0 F / m to 5.0 F / m, or 1.0 F / m to 4.0 F / m, or 1.0 F / m to 3.0 F / m, or 1.0 F / m to 2.8 F / m.

[0161] The above cured film according to one aspect has a thermal decomposition temperature (T d,10% ) may be 400 ℃ or higher, or 450 ℃ or higher, or 500 ℃ or higher, or 700 ℃ or lower, or 650 ℃ or lower, or 600 ℃ or lower.

[0162] The cured film according to one aspect can be effectively used in electronic devices such as display devices, semiconductor devices, or optical waveguide materials, and specifically, can be used as a planarization film for a thin film transistor (TFT) substrate such as a liquid crystal display device or an organic EL display device, a protective film or insulating film for a touch panel sensor device, an interlayer insulating film for a semiconductor device, a planarization film for a solid-state imaging device, a micro lens array pattern, or a core or clad material for an optical waveguide such as an optical semiconductor device.

[0163] At this time, the thickness of the cured film can be appropriately changed depending on the purpose, but is preferably formed to be 1 to 30 ㎛, or 1 to 20 ㎛, or 1 to 20 ㎛, or 1 to 10 ㎛, or 1 to 5 ㎛, or 1 to 3 ㎛, or 1 to 2 ㎛.

[0164] According to one aspect, the aromatic polyether polymer can be produced through a method including a step of reacting a reaction mixture including a compound represented by the following chemical formula A and a compound represented by the following chemical formula B in the presence of a metal base to produce an aromatic polyether polymer including a repeating unit represented by the following chemical formula 1.

[0165] [Chemical Formula A]

[0166]

[0167] [Chemical Formula B]

[0168]

[0169] [Chemical Formula 1]

[0170]

[0171] (In the above chemical formula 1, A and B,

[0172] X 1 , R 1 Inland R 8 , R 11 Inland R 13 is the same as the definition described above.)

[0173] For example, the chemical formula A may be represented by the following structure.

[0174]

[0175] The above R 14 and R 15 is the same as the definition in the above chemical formula A.

[0176] The above metal base may be selected from, but is not limited to, CsF, KF, K2CO3, NaOH and KOH.

[0177] The above reaction may be carried out under temperature conditions of 30 to 100°C, or 40 to 100°C, or 40 to 80°C for 1 to 24 hours, or 1 to 10 hours, or 1 to 5 hours.

[0178] In addition, the reaction mixture may further include a compound represented by the following chemical formula C, and in this case, the aromatic polyether polymer may further include a repeating unit represented by the following chemical formula 2.

[0179] [Chemical Formula C]

[0180]

[0181] [Chemical Formula 2]

[0182]

[0183] (In the above chemical formula C and chemical formula 2,

[0184] X 2 , R 1 Inland R 8 , R 16 , R 17 , p and q are the same as defined above.)

[0185] For example, the compound represented by the above chemical formula C may be selected from the following structures.

[0186] [Chemical Formula C-1]

[0187]

[0188] [Chemical Formula C-2]

[0189]

[0190] The above R 16 Inland R 19 , p and q are the same as defined in the above chemical formula C.

[0191] Hereinafter, the above-described implementation examples will be described in more detail through examples. However, the following examples are for illustrative purposes only and do not limit the scope of the rights.

[0192] The physical properties of the examples were measured as follows.

[0193] 1) Molecular weight

[0194] Gel permeation chromatography (GPC) was used for measurement. Shodex (KF-80), Shodex (KF-802), Shodex (KF-802.5), and Shodex (KF-803) were used as columns, polystyrene as standard samples, and tetrahydrofuran as solvent. The sample was prepared at a concentration of 0.1 g / 1 mL under the conditions of temperature 35 ℃ and flow rate 1.2 mL / min, and then supplied in an amount of 100 μL for measurement.

[0195] 2) Thermal decomposition temperature

[0196] The thermal decomposition temperature of the cured films manufactured in the examples and comparative examples was measured using thermogravimetric analysis (TGA, Perkin Elmer, Pyris 1 TGA). The measurement conditions were a temperature range of 140°C to 180°C, a heating rate of 10°C / min under N2, and the temperature at which a 10% mass loss occurred was defined as the thermal decomposition temperature (T d,10% ) was recorded.

[0197] 3) Permittivity

[0198] The dielectric constant of the cured films manufactured in the examples and comparative examples was measured using an LCR meter (Keysight (Agilent) B1500A). The electrode radius for measuring the dielectric constant was 5 mm, and the measurement frequency was 100 kHz.

[0199] [Manufacturing Example 1]

[0200]

[0201] Step 1: Synthesis of Compound 1-A

[0202] 2,2-Bis(4-hydroxyphenyl)hexafluoropropane (1eq) and K2CO3 (2.3eq) were dissolved in acetonitrile to a concentration of 5 M and placed in a three-necked flask. After adjusting the inside of the flask to 65℃, the mixture was refluxed and stirred for 1 hour, then allyl bromide (2.4eq) was added dropwise and refluxed at 65℃ for 12 hours. After completion of the reaction, acetonitrile was removed by concentration under reduced pressure, diluted with hexane, and extracted and separated with H2O:MeOH = 9:1 to obtain compound 1-A (98%).

[0203] Step 2: Synthesis of Compound 1

[0204]

[0205] Compound 1-A obtained above was placed in a three-necked flask without a solvent, the inside of the flask was adjusted to 200°C, and the mixture was stirred under reflux for 5 hours. Thereafter, compound 1 was obtained (90%) by column chromatography purification with dichloromethane.

[0206] 1 H-NMR (CDCl3), 400 MHz), δ (ppm): 7.25 (2H, d), 7.13 (2H, s), 6.80 (2H, d), 6.00 (2H, m), 5.15 (2H, s), 5.13 (4H, m), 3.36 (4H, d).

[0207] [Manufacturing Example 2]

[0208]

[0209] 0.035 mol of maleic anhydride was dissolved in 460 ml of toluene and placed in a 3 L flask, stirred at 25 °C for 2 hours, then 0.081 mol of 1,3-bis (3-aminopropyl) tetramethyldisiloxane, diluted in toluene, was added dropwise and stirred at 25 °C for 6 hours. Afterwards, ZnBr2 and hexamethyldisilazane were added, and the mixture was refluxed and stirred at 100 °C for 12 hours. Afterwards, the reaction was terminated with 0.5 N HCl, extracted with ethyl acetate / H2O, and the solvent was removed to obtain an ivory solid. The obtained solid was recrystallized using methanol and filtered to obtain a primary purified substance, which was dissolved in a small amount of dichloromethane, precipitated by adding hexane, filtered, and dried to obtain a powder, thereby obtaining compound 2, the target maleimide (70%).

[0210] 1 H-NMR (CDCl3), 400 MHz), δ (ppm): 6.6 (4H, s), 3.45 (4H, t), 1.58 (4H, m), 0.45 (4H, m), 0.02 (12H, s).

[0211] [Example 1]

[0212]

[0213] Preparation of aromatic polyether polymers

[0214] Compound 1 (0.5 eq), 2,2-bis(4-hydroxyphenyl)hexafluoropropane (0.5 eq), and perfluorobiphenyl (1.03 eq) obtained in the above Preparation Example 1 were dissolved in 1-methyl-2-pyrrolidone to a concentration of 0.45 M and placed in a flask. After adjusting the inside of the flask to 25°C, CsF (5 eq) and CaH2 (0.15 eq) were added as solids, and polymerization was performed at 50°C for 5 hours. After completion of the reaction, dilution was performed with tetrahydrofuran, and precipitation was separated using methanol to obtain the desired aromatic polyether polymer 1 (60%, Mn=21,249 g / mol, PDI=1.86).

[0215] Preparation of photopolymerizable composition

[0216] The aromatic polyether polymer 1 obtained above was dissolved at 25 wt% in a solvent of propylene glycol methyl ether acetate (PGMEA):cyclohexanone = 7:3 by weight ratio. The dissolved substance was precisely filtered through a 0.2 micron Teflon filter, and 9.2 parts by weight of the maleimide of Preparation Example 2 and 1.5 parts by weight of a photoinitiator (OXE-02) were mixed with 100 parts by weight of the aromatic polyether polymer to prepare a photocurable composition of Example 1.

[0217] Manufacturing of cured films

[0218] The photocurable composition obtained above was coated on a wafer using a spin coater at 500 rpm, heated on a hot plate at 110°C for 60 seconds to dry the solvent, and then cooled to room temperature to form a coating film having a thickness of 1.6 μm. The substrate coated with the coating film was exposed to UV light (Hg lamp, 320-390 nm) at 13 mW / cm using a mask with patterns of various sizes. 2The film was exposed to light for 60 seconds. Afterwards, it was heated at 130°C for an additional 60 seconds, and the unexposed area was dissolved and removed by dipping using a developer PGMEA for 30 seconds to obtain a patterned cured film (Fig. 1).

[0219] [Example 2]

[0220]

[0221] Preparation of aromatic polyether polymers

[0222] Compound 1 (1 eq) and perfluorobiphenyl (1 eq) obtained in the above Preparation Example 1 were dissolved in 1-methyl-2-pyrrolidone to a concentration of 1.9 M and placed in a flask. After adjusting the inside of the flask to 25°C, CsF (5 eq) and CaH2 (0.15 eq) were added as solids, and polymerization was performed at 50°C for 2 hours. After completion of the reaction, dilution was performed with tetrahydrofuran, and precipitation was separated using methanol to obtain the desired aromatic polyether polymer 2 (60%, Mn=22,985 g / mol, PDI=1.76).

[0223] Preparation of photocurable composition and cured film

[0224] The same procedure was followed as in Example 1 above, except that aromatic polyether polymer 2 was used instead of aromatic polyether polymer 1 (Fig. 2).

[0225] [Example 3]

[0226]

[0227] Preparation of aromatic polyether polymers

[0228] In the above Example 1, except that 3,3',4,4',5,5',-hexafluoro-1,1',-biphenyl was used instead of perfluorobiphenyl when producing an aromatic polyether polymer, the same procedure was performed to obtain aromatic polyether polymer 3 (60%, Mn=21,495 g / mol, PDI=1.65).

[0229] Preparation of photocurable composition and cured film

[0230] The same procedure was followed as in Example 1 above, except that aromatic polyether polymer 3 was used instead of aromatic polyether polymer 1 (Fig. 3).

[0231] [Example 4]

[0232]

[0233] Preparation of aromatic polyether polymers

[0234] In the above Example 1, the same procedure was followed except that 2,2',4,4',6,6'-hexafluoro-3,3',5,5'-tetrakis(trifluoromethyl)-1,1'-biphenyl was used instead of perfluorobiphenyl when producing an aromatic polyether polymer, thereby obtaining an aromatic polyether polymer 4 (58%, Mn=25,285 g / mol, PDI=1.75).

[0235] Preparation of photocurable composition and cured film

[0236] The same procedure was followed as in Example 1 above, except that aromatic polyether polymer 4 was used instead of aromatic polyether polymer 1.

[0237] [Example 5]

[0238]

[0239] Preparation of aromatic polyether polymers

[0240] Aromatic polyether polymer 5 was obtained in the same manner as in Example 1 except that bis(4-hydroxyphenyl)methanone was used instead of 2,2-bis(4-hydroxyphenyl)hexafluoropropane when producing an aromatic polyether polymer (63%, Mn=23,791 g / mol, PDI=1.70).

[0241] Preparation of photocurable composition and cured film

[0242] The same procedure was followed as in Example 1 above, except that aromatic polyether polymer 5 was used instead of aromatic polyether polymer 1.

[0243] [Comparative Example 1]

[0244] The same procedure as in Example 1 was followed except that bis(pentafluorophenyl)-1,3,4-oxadiazole was used instead of perfluorobiphenyl when producing an aromatic polyether polymer.

[0245] [Comparative Example 2]

[0246] The photocurable composition was manufactured in the same manner as in Example 1, except that the maleimide monomer of Manufacturing Example 2 was not used.

[0247] [Comparative Example 3]

[0248] In the above Example 1, instead of the maleimide obtained in Preparation Example 2, a photocurable composition was prepared using the same amount of butylene glycol diacrylate, and the same procedure as Example 1 was followed. As a result, it was confirmed that the curability was poor and the pattern was blurred.

[0249] Referring to FIGS. 1 and 2, it was confirmed that in the case of Comparative Example 2, a pattern was not properly formed, whereas the photocurable composition according to an embodiment of the present invention was able to implement a fine pattern.

[0250] In the case of Comparative Example 1, it was also confirmed that the solubility of the polymer in the organic solvent was low, so the unexposed area was not developed and the pattern was not properly formed.

[0251] In addition, a photomask (Fig. 4 - Pattern Ref) was used to form a film using the photocurable composition of Example 1, and a mask aligner (UV lamp, 250-350 nm, 350-450 nm) was used at 250 mJ / cm 2 and 300 mJ / cm 2 A patterned cured film was obtained using the same method using the light of the century, and the results are shown in FIGS. 4 and 5.

[0252] Referring to FIGS. 4 and 5, it can be seen that the photocurable composition according to an embodiment of the present invention has an excellent effect in implementing a precise fine pattern. Specifically, compared to the reference pattern on the pattern mask (Ref), the structure of the pattern was precisely reproduced without deformation even under the exposure conditions of 250 mJ / cm² and 300 mJ / cm², respectively, and the average dimension of each feature was maintained substantially the same as that of the reference pattern. For example, the line width was maintained at a level of about 7.4 to 7.6 ㎛ under all exposure conditions, which proves that high-resolution patterning is possible without diffusion or distortion of the pattern boundary. In addition, the pattern implemented under the condition of 300 mJ / cm² had a more distinct edge definition and was formed independently without interference or bridging between patterns.

[0253] Dielectric constant (F / m) Thermal decomposition temperature (℃) Example 12.8544 Example 22.9521

[0254] In addition, referring to Table 1 above, it can be seen that the cured film according to the embodiment of the present invention can secure low dielectric constant and excellent thermal stability.

[0255] That is, the photocurable composition comprising an aromatic polyether polymer and a maleimide including a siloxane unit according to the present invention can implement a precise pattern and provide a cured film having a low dielectric constant and high thermal stability after curing, and is expected to be applicable to various semiconductor devices requiring fast processing speed and large-capacity storage capacity, such as high-bandwidth memory.

[0256] As described above, the present invention has been described through specific matters and limited examples, but these are provided only to help a more general understanding of the present invention, and the present invention is not limited to the above examples, and those skilled in the art to which the present invention pertains can make various modifications and variations based on this description.

[0257] Therefore, the idea of ​​the present invention should not be limited to the described embodiments, and all things that are equivalent or equivalent to the following claims as well as the claims are considered to fall within the scope of the idea of ​​the present invention.

Claims

1. A photocurable composition comprising an aromatic polyether polymer including a repeating unit represented by the following chemical formula 1; and a maleimide including a siloxane unit: [Chemical Formula 1] In the above chemical formula 1, R 1 Inland R 8 are each independently halogen or halo(C1-C4)alkyl, and the above R 1 Inland R 8 At least four of which are fluoro groups (-F); R 11 Inland R 13 are each independently hydrogen, halogen, (C1-C4)alkyl, or halo(C1-C4)alkyl; X 1 is a single bond, -CO-, -SO2-, or -CR 14 R 15 -and; R 14 and R 15 are each independently hydrogen, halogen or halo(C1-C4)alkyl.

2. In paragraph 1, A photocurable composition wherein the aromatic polyether polymer further comprises a repeating unit represented by the following chemical formula 2: [Chemical Formula 2] In the above chemical formula 2, R 1 Inland R 8 are each independently halogen or halo(C1-C4)alkyl, and the above R 1 Inland R 8 At least four of which are fluoro groups (-F); R 16 and R 17 are each independently halogen, (C1-C4)alkyl, halo(C1-C4)alkyl; X 2 is a single bond, -CO-, -SO2-, or -CR 18 R 19 -and; R 18 and R 19 are each independently hydrogen, halogen or halo(C1-C4)alkyl; p and q are each independently integers from 0 to 2.

3. In paragraph 1, A photocurable composition in which the repeating unit represented by the above chemical formula 1 is represented by the following chemical formula 11: [Chemical Formula 11] In the above chemical formula 11, R 1 Inland R 8 , R 14 and R 15 is the same as the definition in paragraph 1 above.

4. In paragraph 2, A photocurable composition comprising a repeating unit represented by the above chemical formula 1 and a repeating unit represented by the chemical formula 2 in a molar ratio of 1:0.1 to 10.

5. In paragraph 1, A photocurable composition, wherein the number average molecular weight of the aromatic polyether polymer is 10,000 to 50,000 g / mol.

6. In paragraph 1, A photocurable composition wherein the maleimide is represented by the following chemical formula 3. [Chemical Formula 3] In the above chemical formula 3, R 21 Inland R 24 are each independently (C1-C7)alkyl; x to z are each independently integers from 1 to 10.

7. In paragraph 1, A photocurable composition, wherein the maleimide is contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the aromatic polyether polymer.

8. A cured film prepared from a photocurable composition according to any one of claims 1 to 7.

9. In paragraph 8, The above cured film is a cured film used as a sealing film or insulating film for semiconductor devices.

10. An aromatic polyether polymer comprising a repeating unit represented by the following chemical formula 1: [Chemical Formula 1] In the above chemical formula 1, R 1 Inland R 8 , R 11 Inland R 13 and X 1 is the same as the definition in paragraph 1 above.

11. A method for producing an aromatic polyether polymer, comprising the step of producing an aromatic polyether polymer including a repeating unit represented by chemical formula 1 by reacting a reaction mixture containing a compound represented by chemical formula A and a compound represented by chemical formula B in the presence of a metal base. [Chemical Formula A] [Chemical Formula B] [Chemical Formula 1] In the above chemical formula 1, A and B, X 1 , R 1 Inland R 8 , R 11 Inland R 13 is the same as the definition in paragraph 1 above.

12. In paragraph 11, A method for producing an aromatic polyether polymer, wherein the reaction mixture further comprises a compound represented by the following chemical formula C, and the aromatic polyether polymer further comprises a repeating unit represented by the following chemical formula 2. [Chemical Formula C] [Chemical Formula 2] In the above chemical formula C and chemical formula 2, X 2 , R 1 Inland R 8 , R 16 , R 17 , p and q are the same as defined in the second paragraph above.

13. In paragraph 11, A method for producing an aromatic polyether polymer, wherein the metal base is selected from CsF, KF, K2CO3, NaOH and KOH.

14. In paragraph 11, A method for producing an aromatic polyether polymer, wherein the above reaction is performed under temperature conditions of 30 to 100°C for 3 to 24 hours.

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