Photosensitive resin composition, photosensitive resin film utilizing the same, and semiconductor device

Abstract

One embodiment provides a photosensitive resin composition having a low dielectric constant (Dk) and dielectric loss tangent (Df), as well as excellent elongation and reliability. Another embodiment provides a photosensitive resin film manufactured using the photosensitive resin composition. Yet another embodiment provides a semiconductor device comprising a photosensitive resin film. [Solution] A photosensitive resin composition comprising a polyimide resin represented by the following chemical formula 1, a photopolymerizable compound, a photopolymerization initiator, and a solvent is provided, as well as a photosensitive resin film manufactured using the same and a semiconductor device comprising the photosensitive resin film. [Chemical formula 1] [Formula 1] JPEG2026048030000037.jpg3768 (In chemical formula 1, each substituent is as defined in the specification.)

Description

[Technical Field]

[0001] This description relates to a photosensitive resin composition, a photosensitive resin film utilizing the same, and a semiconductor device. [Background technology]

[0002] As we enter an era of hyper-connected intelligence, encompassing artificial intelligence, big data, IoT, autonomous vehicles, and telemedicine, the development and widespread adoption of diverse electronic devices such as smartphones are accelerating.

[0003] As a result, the importance of 5G communication technology, which enables the wireless transmission of ultra-high-speed, large-capacity data, has become extremely significant. The market size for communication components, materials, and elements used in communication devices, including smartphones, is projected to expand geometrically from 2020 to 2026, reaching approximately US$2.3 billion (14,000 tons / year).

[0004] For dielectric substrates used in 5G communication frequency bands (Sub-6 and 28GHz), the dielectric constant (Dk) and dielectric loss tangent (Df) must be as low as possible to minimize radio wave loss. Therefore, the use of polyimide (PI), which was mainly used in existing 4G LTE communications, is difficult.

[0005] In 2018, TF International analyst Ming-Chi Kuo stated that he expected "modified polyimide (MPI) to replace LCP (Liquid Crystal Polymer) and become the main antenna technology for new iPhone® models in the second half of the year." This can be interpreted as meaning that the FCCL (Flexible Cupper Clad Laminate) manufacturing process is structured around polyimide film production lines (existing process), and module companies prefer to use existing processes rather than modifying equipment for LCP-using processes, thus hoping that MPI (Modified PI) will be developed and rapidly applied. It also suggests that MPI, which complements the shortcomings of LCP, has already been developed.

[0006] In other words, there has been a rapid increase in the need to develop polyimide precursor resins with low dielectric constant (Dk) and dielectric loss tangent (Df). [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Patent No. 5657882 [Overview of the project] [Problems that the invention aims to solve]

[0008] One object of this embodiment is to provide a photosensitive resin composition that has a low dielectric constant (Dk) and dielectric loss tangent (Df), as well as excellent elongation and reliability.

[0009] Another object of this embodiment is to provide a photosensitive resin film manufactured using a photosensitive resin composition.

[0010] Another object of this embodiment is to provide a semiconductor device that includes a photosensitive resin film. [Means for solving the problem]

[0011] According to one embodiment, there is provided a photosensitive resin composition containing a polyimide resin represented by the following Chemical Formula 1, a photopolymerizable compound, a photoinitiator, and a solvent. [Chemical Formula 1]

Chem.

[0012] , and R 2 are each independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group or a substituted or unsubstituted C2-C20 heterocyclic group, X 1 is represented by the following Chemical Formula 2, [Chemical Formula 2]

Chem.

[0013] The polyimide resin may contain a functional group represented by the following chemical formula S at at least one of both ends represented by ★ in Chemical Formula 1. [Chemical Formula S] [Chem.] In Chemical Formula S, R 4 is a hydrogen atom or a substituted or unsubstituted C1-C20 alkyl group, ★ indicates the part to be connected.

[0014] In Chemical Formula 1, n may be an integer from 0 to 2.

[0015] In Chemical Formula 1, Y 1 may be a C1-C20 alkylene group substituted or unsubstituted with an alkyl group.

[0016] In Chemical Formula 1, Y 1 may be an unsubstituted C6-C20 alkylene group.

[0017] The photosensitive resin composition may contain 5 to 20 parts by weight of a photopolymerizable compound, 3 to 10 parts by weight of a photoinitiator, and 100 to 500 parts by weight of a solvent with respect to 100 parts by weight of the polyimide resin.

[0018] The photosensitive resin composition may further contain a photosensitizer, a radical scavenger, a silane coupling agent, an organic acid, or a combination thereof.

[0019] The photosensitive resin composition may be a negative-type photosensitive resin composition.

[0020] Another embodiment provides a photosensitive resin film manufactured using a photosensitive resin composition.

[0021] The photosensitive resin film may also be a semiconductor redistribution layer insulating film.

[0022] Another embodiment provides a semiconductor device including a photosensitive resin film.

[0023] Other specific aspects of the present invention are included in the detailed description below. [Effects of the Invention]

[0024] A photosensitive resin composition according to one embodiment includes a polyimide resin of a specific structure and can not only reduce the dielectric constant (Dk) and dielectric loss tangent (Df), but also improve elongation and reliability. [Modes for carrying out the invention]

[0025] Embodiments of the present invention will be described in detail below. However, these are presented as examples only and the present invention is not limited thereto, and the present invention is defined solely within the scope of the claims described below.

[0026] Unless otherwise specified herein, “alkyl group” means a C1-C20 alkyl group, “alkenyl group” means a C2-C20 alkenyl group, “cycloalkenyl group” means a C3-C20 cycloalkenyl group, “heterocycloalkenyl group” means a C2-C20 heterocycloalkenyl group, “aryl group” means a C6-C20 aryl group, “arylalkyl group” means a C7-C20 arylalkyl group, “alkylene group” means a C1-C20 alkylene group, “arylene group” means a C6-C20 arylene group, “alkylarylene group” means a C7-C20 alkylarylene group, “heteroarylene group” means a C3-C20 heteroarylene group, and “alkoxylene group” means a C1-C20 alkoxylene group such as ★-O-CH2-★. "Heterocyclic group" refers to a heteroaryl group and / or a heterocycloalkyl group and / or a heterocycloalkenyl group and / or a heterocycloalkynyl group.

[0027] Unless otherwise specified herein, “substitution” means a C1-C20 alkyl group, hydroxyl group, C1-C20 alkoxy group, nitro group, cyano group, amine group, imino group, azide group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamoyl group, thiol group, ester group, ether group, carboxyl group or its salts, sulfonic acid group or its salts, etc., in which at least one hydrogen atom is substituted with a halogen atom (F, Cl, Br, I), trifluoromethyl group or other halogen atom. This means that the molecule is substituted with substituents of acid or its salts, C1-C20 alkyl groups, C2-C20 alkenyl groups, C2-C20 alkynyl groups, C6-C20 aryl groups, C3-C20 cycloalkyl groups, C3-C20 cycloalkenyl groups, C3-C20 cycloalkynyl groups, C2-C20 heterocycloalkyl groups, C2-C20 heterocycloalkenyl groups, C2-C20 heterocycloalkynyl groups, C3-C20 heteroaryl groups, (meth)acrylate groups, or combinations thereof.

[0028] Furthermore, unless otherwise specified herein, "hetero" means that the chemical formula contains at least one heteroatom from at least one of N, O, S, and P.

[0029] Furthermore, unless otherwise specified herein, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible.

[0030] Unless otherwise defined herein, “combination” means mixing or copolymerization. “Copolymerization” means block copolymerization, alternating copolymerization or random copolymerization, and “copolymer” means block copolymer, alternating copolymer or random copolymer.

[0031] Unless otherwise specified herein, unsaturated bonds include not only carbon-carbon multiple bonds but also other molecular bonds such as carbonyl bonds and azo bonds.

[0032] Unless otherwise defined in the chemical formulas herein, the absence of a chemical bond in a position where one should be depicted means that a hydrogen atom is bonded to that position.

[0033] Unless otherwise defined herein, "★" means a portion linked to the same or different atoms or chemical formulas.

[0034] The increasing use of photosensitive materials for redistribution layers (RDLs) is driven by the growing demand for wafer-level packaging (WLP) and panel-level packaging (PLP) specifications. Currently, photosensitive materials include photosensitive polyimide resins, photosensitive benzocyclobutene (BCB) resins, and photosensitive phenol resins, with photosensitive polyimide resins being the most commonly used as they meet all the requirements for processability and reliability.

[0035] On the other hand, as redistribution layers are multilayered and high-speed processing is performed, high-frequency signals may be lost, necessitating designs that reduce the dielectric loss of the package material.

[0036] This invention relates to a photosensitive resin composition, a photosensitive resin film manufactured using the same, and a semiconductor device containing a photosensitive resin film. Recently, in line with the trend towards miniaturization, increased speed, and the integration of diverse functions in electronic devices, the signal transmission speed within electronic devices or to the outside of electronic devices is accelerating. As a result, there is a need for printed circuit boards that utilize insulators with lower dielectric constants and dielectric loss coefficients than existing insulators.

[0037] Some conventional technologies approach reducing dielectric loss by optimizing the adhesive layer and laminated structure of flexible printed circuit boards (PCBs). However, such methods have structural limitations and require control over the properties of each component. Recently, there has been a movement to apply liquid crystalline polymer (LCP), an insulator with a lower dielectric constant than conventional polyimide and less susceptible to moisture absorption, to flexible printed circuit boards. However, even with the application of LCP, the dielectric constant of LCP (Dk=2.9) is not significantly superior to that of polyimide (Dk=3.2), resulting in minimal application benefits. Furthermore, even with the application of LCP, its low heat resistance becomes a problem, particularly in the brazing process. Additionally, because LCP is a thermoplastic material, it has poor compatibility with existing polyimide-based PCB manufacturing processes when using laser-based via hole processing. Therefore, efforts continue to lower the dielectric constant of polyimide, which is used as an insulator in existing flexible printed circuit boards, as a solution to these problems.

[0038] The object of the present invention is to provide a photosensitive resin composition that can reduce dielectric constant and dielectric loss, thereby improving elongation and reliability, through structural modification of the polyimide resin. As redistribution layers are multilayered and high-speed processing is performed, high-frequency signals may be lost, requiring a design that reduces the dielectric loss of the package material. The inventors of the present invention were able to reduce dielectric loss by modifying the polyimide resin to a structure represented by the following chemical formula 1. [Chemical formula 1] [ka] Chemical formula 1, R 1 and R 2 Each of these is independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C2-C20 heterocyclic group. X 1 It is represented by the following chemical formula 2, [Chemical formula 2] [ka] Y 1 It is represented by the following chemical formula 3, [Chemical formula 3] [ka] Chemical formula 3, L 1 ~L 3 These are, independently, substituted or unsubstituted C1-C20 alkylene groups or substituted or unsubstituted C6-C20 arylene groups. n is an integer between 0 and 10. In chemical formulas 1-3, ★ indicates the part that is linked together.

[0039] The following provides a detailed explanation of each component.

[0040] (A) Resin By controlling the structure of the polyimide resin as shown in Chemical Formula 1, the dielectric constant and dielectric loss of the photosensitive resin composition containing it can all be reduced.

[0041] For example, by further controlling the types of linking groups and substituents in the polyimide resin represented by chemical formula 1, the dielectric constant and dielectric loss can be further reduced.

[0042] For example, in chemical formula 1, R 1 and R 2 These can each be independently represented by the following chemical formula R. [Chemical formula R] [ka] With the chemical formula R, R 3 is a (meth)acrylate group, L 4 These are substituted or unsubstituted C1-C20 alkylene groups, ★ indicates the parts that are connected.

[0043] For example, a polyimide resin represented by chemical formula 1 may further contain a functional group represented by the following chemical formula S at at least one of its ends. [Chemical formula S] [ka] With the chemical formula S, R 4 is a hydrogen atom or a substituted or unsubstituted C1-C20 alkyl group, ★ indicates the parts that are connected.

[0044] For example, a polyimide resin represented by chemical formula 1 may further contain functional groups represented by chemical formula S at both ends indicated by ★ in chemical formula 1.

[0045] A photosensitive resin composition containing a polyimide resin represented by chemical formula 1, which has a functional group represented by chemical formula S at the terminal end of chemical formula 1, can have improved elongation and reliability.

[0046] For example, in the chemical formula S, R 4 R may be a substituted or unsubstituted C1-C20 alkyl group. In this case, R 4 The elongation rate and reliability improvement effect are significantly greater than when hydrogen atoms are used.

[0047] For example, in chemical formula 1, n can be an integer between 0 and 2.

[0048] For example, in chemical formula 1, n may be an integer of 0. In this case, it can have a better growth rate than when n is an integer from 1 to 10.

[0049] For example, in chemical formula 1, n may be an integer from 1 to 10. In this case, the dielectric loss can be lower than when n is an integer of 0.

[0050] For example, in chemical formula 1, Y 1 This may be an alkyl group substituted with or unsubstituted with an alkyl group, or a C1-C20 alkylene group. In this case, Y 1 This can result in lower dielectric loss and higher elongation compared to the case where the group is an unsubstituted alkylene group.

[0051] In chemical formula 1, Y 1 Y may be an unsubstituted C6-C20 alkylene group. In this case, Y 1 It can have lower dielectric loss and higher elongation than when it is an unsubstituted C1-C5 alkylene group.

[0052] For example, the polyimide resin represented by chemical formula 1 may also be represented by any one of the following chemical formulas 1-1 to 1-4. [Chemical formula 1-1] [ka] [Chemical formula 1-2] [ka] [Chemical formula 1-3] [ka] [Chemical formula 1-4] [ka]

[0053] Using chemical formulas 1-1 to 1-4, R is represented by the following chemical formula 4: [Chemical formula 4] [ka] m is an integer between 1 and 100. ★ indicates the parts that are connected.

[0054] The weight-average molecular weight (M) of the polyimide resin represented by chemical formula 1. w The weight-average molecular weight of the polyimide resin may be between 3,000 g / mol and 300,000 g / mol. When the weight-average molecular weight of the polyimide resin is within this range, sufficient physical properties can be obtained, and it exhibits excellent solubility in organic solvents, making it easy to handle.

[0055] (B) Photopolymerizable compound The photosensitive resin composition according to one embodiment may further contain a photopolymerizable compound. The photopolymerizable compound may be a single compound or a mixture of two different compounds.

[0056] The photopolymerizable compound may also be a compound containing at least two functional groups represented by the following chemical formula 5. [Chemical formula 5] [ka] Chemical formula 5, R 8 is a hydrogen atom or a substituted or unsubstituted C1-C10 alkyl group, L 11 These are single-bonded, substituted, or unsubstituted C1-C10 alkylene groups. ★ indicates the parts that are connected.

[0057] For example, a compound containing at least two functional groups represented by chemical formula 5 may contain two to six functional groups represented by chemical formula 5. In this case, sufficient polymerization can occur during exposure in the pattern formation process, forming a pattern with excellent heat resistance, light resistance, and chemical resistance.

[0058] For example, a compound containing at least two functional groups represented by chemical formula 5 may also be a compound represented by any one of the following chemical formulas 6 to 8, and is not necessarily limited to these. [Chemical formula 6] [ka] [Chemical formula 7] [ka] [Chemical formula 8] [ka]

[0059] Chemical formulas 6 to 8, p, q, r, s, and t are each independent integers between 1 and 10.

[0060] If the photopolymerizable compound is a mixture of two different compounds, one of the two different compounds may be a monofunctional or polyfunctional ester compound of (meth)acrylic acid having at least one ethylenically unsaturated double bond.

[0061] Examples of monofunctional or polyfunctional ester compounds of (meth)acrylic acid having at least one ethylenically unsaturated double bond include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, bisphenol A di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tri(meth)acrylate. This may include lithitol tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy(meth)acrylate, ethylene glycol monomethyl ether(meth)acrylate, trimethylolpropane tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, novolac epoxy(meth)acrylate, or a combination thereof.

[0062] Examples of commercially available monofunctional or polyfunctional ester compounds of (meth)acrylic acid having at least one ethylenically unsaturated double bond are as follows: Examples of monofunctional esters of (meth)acrylic acid include Arronix® M-101, Arronix® M-111, Arronix® M-114, etc., manufactured by Toagosei Chemical Industry Co., Ltd.; KAYARAD® TC-110S, KAYARAD® TC-120S, etc., manufactured by Nippon Kayaku Co., Ltd.; and Viscoat 158, Viscoat-2311, etc., manufactured by Osaka Organic Chemical Industry Co., Ltd. Examples of (meth)acrylic acid difunctional esters include Arronix® M-210, Arronix® M-240, and Arronix® M-6200 from Toagosei Chemical Industry Co., Ltd.; KAYARAD® HDDA, KAYARAD® HX-220, and KAYARAD® R-604 from Nippon Kayaku Co., Ltd.; and Viscoat 260, Viscoat 312, and Viscoat 335HP from Osaka Organic Chemical Industry Co., Ltd. Examples of trifunctional esters of (meth)acrylic acid include Arronix® M-309, Arronix® M-400, Arronix® M-405, Arronix® M-450, Arronix® M-7100, Arronix® M-8030, Arronix® M-8060, etc., manufactured by Toagosei Chemical Industry Co., Ltd.; KAYARAD® TMPTA, KAYARAD® DPCA-20, KAYARAD® DPCA-30, KAYARAD® DPCA-60, KAYARAD® DPCA-120, etc., manufactured by Nippon Kayaku Co., Ltd.; and Viscoat-295, Viscoat-300, V-360®, Viscoat GPT, Viscoat 3PA, Viscoat 400, etc., manufactured by Osaka Organic Chemical Industry Co., Ltd. The products can be used individually or in combination of two or more.

[0063] Photopolymerizable compounds can also be treated with acid anhydrides before use to impart better developability.

[0064] The photopolymerizable compound may be included in an amount of 5 to 20 parts by weight, for example, 7 to 15 parts by weight, per 100 parts by weight of the resin. When the photopolymerizable compound is included within this range, sufficient curing occurs, resulting in excellent reliability, excellent heat resistance, light resistance, and chemical resistance of the pattern, as well as excellent resolution and adhesion.

[0065] (C) Photopolymerization initiator A photosensitive resin composition according to one embodiment may further contain a photopolymerization initiator.

[0066] Photopolymerization initiators that can be used include acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, and oxime compounds.

[0067] Examples of acetophenone compounds include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one.

[0068] Examples of benzophenone compounds include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.

[0069] Examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone.

[0070] Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

[0071] Examples of triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl4,6-bis(trichloromethyl)-s-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-tri Examples include azines, 2-biphenyl 4,6-bis(trichloromethyl)-s-triazine, bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-4-bis(trichloromethyl)-6-piperonyl-s-triazine, and 2-4-bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine.

[0072] Examples of oxime compounds include O-acyl oxime compounds, 2-(O-benzoyl oxime)-1-[4-(phenylthio)phenyl]-1,2-octanedione, 1-(O-acetyl oxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone, and O-ethoxycarbonyl-α-oxyamino-1-phenylpropane-1-one. Specific examples of O-acyloxime compounds include 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholine-4-ylphenyl)-butan-1-one, 1-(4-phenylsulfanylphenyl)-butan-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylsulfanylphenyl)-octane-1-one oxime-O-acetate, and 1-(4-phenylsulfanylphenyl)-butan-1-one oxime-O-acetate.

[0073] In addition to the compound, other photopolymerization initiators that can be used include carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, non-imidazole compounds, and fluorene compounds.

[0074] The photoinitiator may be included in an amount of 3 to 10 parts by weight, for example, 4 to 9 parts by weight, per 100 parts by weight of resin. When the photoinitiator is included within this range, as described above, sufficient photopolymerization occurs, preventing a decrease in sensitivity characteristics and improving transmittance.

[0075] (D) Solvent The solvent can be a substance that is compatible with but does not react with polyimide resin, photopolymerizable compounds, and photopolymerization initiators.

[0076] Examples of solvents include alcohols such as methanol and ethanol; ethers such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methylphenyl ether, and tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol dimethyl ether; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, and diethyl cellosolve acetate; carbitols such as methyl ethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, and diethylene glycol diethyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, cyclohexanone, 4- Ketones such as hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, and 2-heptanone; saturated aliphatic monocarboxylate alkyl esters such as ethyl acetate, n-butyl acetate, and isobutyl acetate; lactate esters such as methyl lactate and ethyl lactate; alkyl oxyacetates such as methyl oxyacetate, ethyl oxyacetate, and butyl oxyacetate; methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethoxyacetic acid Alkyl alkoxyacetates such as ethyl; alkyl 3-oxypropionates such as methyl 3-oxypropionate and ethyl 3-oxypropionate; alkyl 3-alkoxypropionates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methyl 3-ethoxypropionate; alkyl 2-oxypropionates such as methyl 2-oxypropionate, ethyl 2-oxypropionate, and propyl 2-oxypropionate;Alkyl esters of 2-alkoxypropionates such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, and methyl 2-ethoxypropionate; 2-oxy-2-methylpropionate esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate; monooxymonocarboxylate alkyl esters of alkyl 2-alkoxy-2-methylpropionates such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyethyl acetate, 2-hydroxy-3- Examples include esters such as methyl methylbutanoate; ketonic acid esters such as ethyl pyruvate; and high-boiling point solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, 3-methylbenzoic acid, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.

[0077] The solvent may be included in an amount of 100 to 500 parts by weight per 100 parts by weight of resin. When the solvent is included within this range, the photosensitive resin composition has an appropriate viscosity, resulting in excellent processability during the production of the photosensitive resin film.

[0078] (E) Other additives A photosensitive resin composition according to one embodiment may further contain other additives.

[0079] The photosensitive resin composition may contain additives such as diacides (e.g., malonic acid), alkanolamines (e.g., 3-amino-1,2-propanediol), light enhancers / subtractors, leveling agents, radical scavengers, silane coupling agents, surfactants, organic acids, epoxy compounds, thermal latent acid generators, developer modifiers, curing agents, or combinations thereof, to prevent stains and spots during coating, improve leveling properties, or prevent the formation of residues due to undeveloped material. The amount of these additives used can be easily adjusted according to the desired physical properties.

[0080] For example, organic acids can improve the electrical properties of a photosensitive resin composition according to one embodiment, ultimately contributing to a reduction in dielectric constant and dielectric loss.

[0081] For example, organic acids can include citric acid. Citric acid can play a role in improving ionic conductivity in electrolyte systems, which can affect electrical properties. For instance, when citric acid is doped into an alginate-based solid biopolymer electrolyte, the electrolyte exhibits non-Debye behavior, which can be analyzed through composite dielectric constant (ε*) and composite electrical modulus (M*). Such results suggest that abnormal dielectric behavior can be induced in systems containing citric acid. When such citric acid is added to a photosensitive resin composition, it can affect the dielectric properties through chemical interactions and structural changes in the resin, ultimately contributing to a reduction in dielectric constant and dielectric loss.

[0082] For example, silane coupling agents can have reactive substituents such as vinyl groups, carboxyl groups, methacryloxy groups, isocyanate groups, and epoxy groups to improve adhesion to the substrate, and their structure differs from that of silane compounds.

[0083] Examples of silane coupling agents include trimethoxysilyl benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatetopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, which can be used individually or in combination of two or more.

[0084] The silane coupling agent may be included in an amount of 0.01 to 10 parts by weight per 100 parts by weight of the photosensitive resin composition. When the silane coupling agent is included within this range, the adhesion, storage properties, etc., are excellent.

[0085] For example, surfactants are added to prevent film-thickness stains or improve developability, and may include fluorinated surfactants and / or silicone-based surfactants.

[0086] Examples of fluorinated surfactants include BM-1000 and BM-1100 from BM Chemie; Megafac F142D (registered trademark), Megafac F172, Megafac F173, Megafac F183, Megafac F554 from DIC Corporation; Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431 from 3M Japan Limited; Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145 from AGC Seimi Chemical Co., Ltd.; and DOWSIL SH 28PA, DOWSIL SH 190, DOWSIL SH Products commercially available under names such as 193, DOWSIL® SZ 6032, and DOWSIL® SF 8428 can be used.

[0087] As for silicone-based surfactants, you can use those commercially available from BYK Chem under names such as BYK-307, BYK-333, BYK-361N, BYK-051, BYK-052, BYK-053, BYK-067A, BYK-077, BYK-301, BYK-322, BYK-325, and BYK-378.

[0088] The surfactant can be used in an amount of 0.001 to 5 parts by weight per 100 parts by weight of the photosensitive resin composition. When the surfactant is included within this range, coating uniformity is ensured, stains do not occur, and excellent wetting properties are observed for ITO substrates or glass substrates, Si wafers, SiNx wafers, and Cu substrates.

[0089] Furthermore, the photosensitive resin composition may further contain epoxy compounds as additives to improve adhesion and other properties. Examples of epoxy compounds that can be used include epoxy novolac acrylic carboxylate resin, orthocresol novolac epoxy resin, phenol novolac epoxy resin, tetramethylbiphenyl epoxy resin, bisphenol A type epoxy resin, alicyclic epoxy resin, or combinations thereof.

[0090] The epoxy compound can be used in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the photosensitive resin composition. When the epoxy compound is included within this range, it can improve shelf life, adhesion, and other properties.

[0091] The photosensitive resin composition may further contain a thermal latent acid generator. Examples of thermal latent acid generators include, but are not limited to, aryl sulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid; perfluoroalkyl sulfonic acids such as trifluoromethanesulfonic acid and trifluorobutanesulfonic acid; alkyl sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid; or combinations thereof.

[0092] Furthermore, the photosensitive resin composition may contain a certain amount of other additives, such as antioxidants and stabilizers, as long as they do not impair its physical properties.

[0093] Another embodiment provides a photosensitive resin film, such as a semiconductor redistribution layer insulating film, manufactured by exposing, developing, and curing the aforementioned photosensitive resin composition.

[0094] The manufacturing method for the photosensitive resin film (semiconductor redistribution layer insulating film) is as follows:

[0095] (1) Coating and film formation stage A photosensitive resin composition is applied to a substrate such as a glass substrate or ITO substrate, Si wafer, SiNx wafer, or Cu substrate that has undergone a predetermined pretreatment, to a desired thickness using methods such as spin or slit coating, roll coating, screen printing, or applicator coating. The coating is then formed by heating at 70°C to 150°C for 1 to 10 minutes to remove the solvent.

[0096] (2) Exposure step After a mask is placed over the resulting photosensitive resin film to form the necessary pattern, it is irradiated with active rays in the 200nm to 500nm range. Light sources that can be used for irradiation include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and argon gas lasers. In some cases, X-rays and electron beams can also be used.

[0097] The exposure dose varies depending on the type and amount of each component in the composition and the thickness of the dried film, but when using a high-pressure mercury lamp, it is 500 mJ / cm². 2 (Based on a 365nm sensor) The results are as follows:

[0098] (3) Development stage In the development method, following the exposure stage, an alkaline aqueous solution or organic solvent is used as a developer to dissolve and remove unnecessary parts, leaving only the exposed areas to form a pattern.

[0099] (4) Post-processing stage The development process includes a post-heating step to obtain an image pattern with superior properties in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength, and storage stability. For example, after development, the pattern can be heated in an oven at 200°C to 400°C under a nitrogen atmosphere for more than one hour.

[0100] Another embodiment provides a semiconductor device that includes a photosensitive resin film (a semiconductor redistribution layer insulating film). [Examples]

[0101] Preferred embodiments of the present invention are described below. However, the following embodiments are merely preferred embodiments of the present invention, and the present invention is not limited to the following embodiments.

[0102] (Synthesis of resins) Synthesis Example 1 65 mmol of 9,9-Bis(3,4-dicarboxyphenyl)fluorene dianhydride, 17.72 g (136 mmol) of 2-hydroxyethyl methacrylate (HEMA), and a catalytic amount of DBU (1,8-diazabicyclo[5.4.0]undeca-7-ene) were dissolved in four times the amount of pyromellitic dianhydride in N-methyl-2-pyrrolidone, and the mixture was stirred at room temperature for 48 hours to obtain ester solution 1.

[0103] 149 mmol of 9,9-Bis(3,4-dicarboxyphenyl)fluorene dianhydride, 42 g (323 mmol) of 2-hydroxyethyl methacrylate (HEMA), and a catalytic amount of DBU were dissolved in four times the amount of anhydride in N-methyl-2-pyrrolidone, and the mixture was stirred at room temperature for 48 hours to obtain ester solution 2. After mixing ester solution 1 and ester solution 2, 2.2 equivalents of thionyl chloride were added dropwise to the total volume of ester solution 1 and ester solution 2 while cooling at 0°C, and the mixture was stirred for 1 hour to prepare an acid chloride solution.

[0104] A solution was prepared by dissolving 90 mmol of heptane-1,7-diamine, 10 mmol of 4-amino-1-methyl-1H-pyrazole, and two equivalents of thionyl chloride of pyridine in 120 g of N-methyl-2-pyrrolidone. This solution was then added dropwise to the previously prepared 0°C acid chloride solution. After the addition was complete, the reaction mixture was added dropwise to distilled water, and the resulting precipitate was filtered and collected. After washing it three times with distilled water, it was vacuum-dried to obtain a polyimide resin. The weight-average molecular weight of the obtained polymer (polyimide resin) was 25,500 g / mol.

[0105] Synthesis Example 2 The synthesis was carried out in the same manner as in Synthesis Example 1, except that 1,5-diamino-1-methylpentane was used instead of heptane-1,7-diamine.

[0106] Synthesis Example 3 The synthesis was carried out in the same manner as in Synthesis Example 1, except that pentane-1,5-diamine was used instead of heptane-1,7-diamine.

[0107] Synthesis Example 4 The synthesis was carried out in the same manner as in Synthesis Example 1, except that a diamine represented by the following chemical formula N was used instead of heptane-1,7-diamine. [Chemical formula N] [ka]

[0108] Comparative Synthesis Example 1 In a four-necked flask equipped with a stirrer, temperature control device, nitrogen gas injection device, and condenser, 600 g of γ-butyrolactone (GBL) was mixed with 0.58 mol of a dianehydride monomer represented by chemical formula A, while passing nitrogen through the flask. 1.22 mol of 2-hydroxyethyl methacrylate (HEMA) was added, and 1.16 mol of pyridine was added while stirring at room temperature to obtain the reaction mixture. After reacting at room temperature for 16 hours, the mixture was cooled to -10°C, and a solution of 1.17 mol of dichlorohexylcarbodiimide (DCC) dissolved in 250 g of GBL was added dropwise over 30 minutes. After stirring for an additional 5 minutes, a solution of 0.54 mol of a diamine monomer represented by chemical formula B and 300 g of GBL was added over 40 minutes, followed by stirring for an additional 2 hours. After reacting at room temperature for 1 hour, 30 g of ethanol was added and stirred for 1 hour. Next, GBL was added to 3 liters of ethanol to obtain a precipitate, with the solid content of the reaction solution being increased to 18%. The polymer was filtered and separated, dissolved in 1.5 liters of tetrahydrofuran (THF), and added dropwise to 30 liters of water to form a precipitate. This precipitate was then filtered and vacuum-dried. By drying at 50°C under reduced pressure for more than 24 hours, a polyimide resin containing the structural unit represented by the following chemical formula C was produced. (Chemical formulas A and B are polymerized in a 1:1 molar ratio.) [Chemical formula A] [ka] [Chemical formula B] [ka] [Chemical formula C] [ka]

[0109] Comparative Synthesis Example 2 78.0 g of 3,3',4,4'-Biphenyltetracarboxylic dianhydride (BPDA) and 123.4 g of 4,4'-Oxydianiline (ODA) were placed in a 2-liter separable flask, and 181.2 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of γ-butyrolactone were added. The reaction mixture was obtained by adding 52.4 g of pyridine while stirring at room temperature. After the exothermic reaction was complete, the mixture was allowed to cool to room temperature and stand for an additional 16 hours. Next, under ice cooling, a solution of 280.0 g of dicyclohexylcarbodiimide (DCC) dissolved in 150 ml of γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Next, a suspension of 123.4 g of 4,4'-oxybisbenzenamine in 440 ml of γ-butyrolactone was added over 30 minutes with stirring. After further stirring at room temperature for 2 hours, 30 ml of N,N-carbonyldiimidazole was added and stirred for 1 hour. Subsequently, 400 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain the reaction solution.

[0110] The resulting reaction solution was added to 3 liters of ethyl alcohol to produce a polymer precipitate. The resulting polymer was filtered and dissolved in 1.5 liters of γ-butyrolactone to obtain a polymer solution. The obtained polymer solution was added dropwise to 14 liters of water to precipitate the polymer, and the resulting precipitate was filtered and then vacuum-dried to obtain a polyimide resin represented by the following chemical formula C-1. [Chemical formula C-1] [ka]

[0111] Comparative Synthesis Example 3 The procedure was the same as in Comparative Synthesis Example 1, except that 9,9-Bis(3,4-dicarboxyphenyl)fluorene dianhydride was used instead of the dianehydride monomer represented by chemical formula A.

[0112] Comparative Synthesis Example 4 The procedure was the same as in Comparative Synthesis Example 2, except that a diamine represented by chemical formula N was used instead of 4,4'-oxydianiline.

[0113] (Manufacturing of photosensitive resin composition) Examples 1 to 4 and Comparative Examples 1 to 4 A photosensitive resin composition was prepared according to the composition shown in Table 1 below. Specifically, a polyimide resin and a photopolymerizable compound were mixed, and a photopolymerization initiator, photosensitizer, radical scavenger, silane coupling agent, organic acid, and solvent were added and thoroughly stirred. The mixture was then filtered through a 0.45 μm polypropylene resin filter to obtain a negative-type photosensitive resin composition.

[0114] [Table 1] Photopolymerizable compound: Tetraethylene glycol dimethacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) Photopolymerization initiator: PBG-305 (manufactured by Tronly) Photosensitizer: N-phenyldiethanolamine (manufactured by Shin-Etsu Chemical Co., Ltd.) Radical Scavenger: CX-1790 (manufactured by Syensqo) Silane coupling agent: A-187 (manufactured by Momentive Performance Materials) Organic acid: Citric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) Solvent 1: γ-Butyrolactone (manufactured by DaeJung Chemicals & Metals) Solvent 2: Dimethyl sulfoxide (manufactured by DaeJung Chemicals & Metals)

[0115] (evaluation) The photosensitive resin compositions from Examples 1 to 4 and Comparative Examples 1 to 4 were coated onto 8-inch silicon wafers and baked at 100°C for 4 minutes to obtain films with a thickness of approximately 10.0 μm. After cooling at room temperature for 60 seconds, the film was irradiated with light for 700 msec using an i-line stepper (Nikon, NSR-2005i10C) to induce the photocuring reaction of the photosensitive portion. The exposed substrate was developed twice at room temperature with 100% cyclopentanone solvent using a 60-second paddle method, and then washed with 100% propylene glycol monomethyl ether acetate (PGMEA) solvent for 60 seconds. The developed wafer was then cured in a 220°C oven under a nitrogen atmosphere for 2 hours.

[0116] Elongation Evaluation: A cured wafer was immersed in a 5% HCl solution for 1 hour to perform PID coating. A test specimen was cut into 1cm x 10cm pieces and prepared. The elongation at room temperature was measured using a tensile tester (HZ-1003) from Shimadzu Corporation, and the results are shown in Table 2 below.

[0117] Evaluation of dielectric loss tangent (Df): The manufactured film (cured film) was dried at 100°C for 30 minutes, and then pre-treated by aging for 24 hours in a constant temperature and humidity chamber maintained at 23°C and 50% relative humidity. Subsequently, dielectric properties were measured at a frequency of 10 GHz using the SPDR (Split Post Dielectric Resonator) measurement method with Keysight's ENA, and the results are shown in Table 2 below.

[0118] Reliability Evaluation: The manufactured film (cured film) was subjected to 2000 cycles of a thermal cycle (-55°C to 125°C), which is the reliability condition. Subsequently, the presence or absence of crack formation between PI and Cu was checked using FE-SEM, and the results are shown in Table 2 below.

[0119] [Table 2]

[0120] Table 2 confirms that the photosensitive resin composition according to one embodiment has a low dielectric loss tangent while also exhibiting excellent elongation and reliability, making it suitable for use as a semiconductor redistribution layer composition.

[0121] The present invention is not limited to the embodiments described above and can be manufactured in a variety of different forms. Those with ordinary skill in the art to which the invention pertains should understand that the invention can be implemented in other specific forms without altering the technical idea or essential features of the invention. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not limiting.

Claims

1. Polyimide resin represented by the following chemical formula 1, photopolymerizable compound, Photopolymerization initiator, and solvent Photosensitive resin composition containing: [Chemical formula 1] 【Chemistry 1】 In the aforementioned chemical formula 1, R １ and R ２ Each of these is independently a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C2-C20 heterocyclic group. X １ It is represented by the following chemical formula 2, [Chemical formula 2] 【Chemistry 2】 Y １ It is represented by the following chemical formula 3, [Chemical formula 3] 【Transformation 3】 In the aforementioned chemical formula 3, L １ ~L ３ These are, independently, substituted or unsubstituted C1-C20 alkylene groups or substituted or unsubstituted C6-C20 arylene groups. n is an integer between 0 and 10. In chemical formulas 1-3, ★ indicates the part that is linked together.

2. The aforementioned R １ and R ２ The photosensitive resin composition according to claim 1, each independently represented by the following chemical formula R: [Chemical formula R] 【Chemistry 4】 In the aforementioned chemical formula R, R ３ is a (meth)acrylate group, L ４ These are substituted or unsubstituted C1-C20 alkylene groups, ★ indicates the parts that are connected.

3. The photosensitive resin composition according to claim 1, wherein the polyimide resin contains a functional group represented by the following chemical formula S at at least one of the two ends indicated by ★ in chemical formula 1: [Chemical formula S] 【Transformation 5】 In the aforementioned chemical formula S, R ４ is a hydrogen atom or a substituted or unsubstituted C1-C20 alkyl group, ★ indicates the parts that are connected.

4. The photosensitive resin composition according to claim 1, wherein n is an integer from 0 to 2.

5. The polyimide resin represented by chemical formula 1 is the photosensitive resin composition according to claim 1, which is represented by any one of the following chemical formulas 1-1 to 1-4: [Chemical formula 1-1] 【Transformation 6】 [Chemical formula 1-2] 【Transformation 7】 [Chemical formula 1-3] 【Transformation 8】 [Chemical formula 1-4] 【Chemistry 9】 In the aforementioned chemical formulas 1-1 to 1-4, R is represented by the following chemical formula 4, [Chemical formula 4] 【Chemistry 10】 m is an integer between 1 and 100. ★ indicates the parts that are connected.

6. The aforementioned photosensitive resin composition is With respect to 100 parts by weight of the polyimide resin The above photopolymerizable compound is contained in an amount of 5 to 20 parts by weight, The above photopolymerization initiator is contained in an amount of 3 to 10 parts by weight, The photosensitive resin composition according to claim 1, comprising 100 to 500 parts by weight of the solvent.

7. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is a negative-type photosensitive resin composition.

8. A photosensitive resin film manufactured using the photosensitive resin composition described in any one of claims 1 to 7.

9. The photosensitive resin film according to claim 8, wherein the photosensitive resin film is a semiconductor redistribution layer insulating film.

10. A semiconductor element comprising the photosensitive resin film described in claim 8.

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