Photosensitive resin composition, photosensitive resin film, and semiconductor device

Abstract

The present invention provides a photosensitive resin composition comprising an alkali-soluble resin having a low dielectric constant (Dk) and dielectric loss tangent (Df). [Solution] A photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent, wherein the alkali-soluble resin comprises a polymer containing structural units represented by the following formula and a polyimide polymer containing specific structural units, and the polymer containing structural units represented by the following formula and the polyimide polymer containing specific structural units are present in a weight ratio of 1:1 to 1:2; a photosensitive resin film manufactured using this; and a semiconductor device comprising the photosensitive resin film. JPEG2026084638000034.jpg4544

Description

[Technical Field]

[0001] This disclosure 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 enormous. The market size for communication components, materials, and elements used in communication devices, including smartphones, is projected to expand explosively 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] Ming-Chi Kuo, an analyst at TF International, once stated in 2018 that "modified polyimide (MPI) is expected to replace liquid crystal polymer (LCP) and become the main antenna technology for new iPhone (registered trademark) models in the second half of the year." This means that the manufacturing process of flexible copper-clad laminate (FCCL) uses a structure with a polyimide film in the production line (existing process), and module companies prefer to use the existing process rather than modifying equipment in the process using LCP. Therefore, it can be seen that there is a hope that MPI (Modified PI) will be developed and quickly applied. It also suggests that MPI, which complements the shortcomings of LCP, has already been developed.

[0006] That is, the need to develop a polyimide precursor resin or other types of resins with low dielectric constant (Dk) and dielectric tangent (Df) has recently increased rapidly.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0008] One of the objectives of one embodiment is to provide a photosensitive resin composition containing an alkali-soluble resin with low dielectric constant (Dk) and dielectric tangent (Df).

[0009] Another objective of another embodiment is to provide a photosensitive resin film manufactured using the photosensitive resin composition.

[0010] Another objective of another embodiment is to provide a semiconductor device including the photosensitive resin film.

Means for Solving the Problem

[0011] According to one embodiment, a photosensitive resin composition is provided that contains an alkali-soluble resin, a photopolymerizable compound, a photoinitiator, and a solvent. The alkali-soluble resin contains a polymer containing a structural unit represented by the following chemical formula 1 and a polymer containing a structural unit represented by the following chemical formula 2, and the polymer containing a structural unit represented by the following chemical formula 1 and the polymer containing a structural unit represented by the following chemical formula 2 are contained in a weight ratio of 1:1 to 1:2.

[0012] [Chemical formula 1] [Chem.] [[ID=*17]]

[0013] [Chemical formula 2] [Chem.]

[0014] In the above chemical formula 1 and chemical formula 2, L , , , , 1 , , , 0 , , 0 , , 2 , ,

[0013] , , 0 , , , 3 ,

[0014] , 0 , , 1 , , , is a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C6-C20 arylene group, or a combination thereof, L 2 is a single bond, *-O-*, *-S-*, *-C≡C-*, *-C(=O)-*, *-NR 0 -*(R 0 is a substituted or unsubstituted C1-C10 alkyl group), a substituted or unsubstituted C1-C20 alkylene group, a substituted or unsubstituted C6-C20 arylene group, a substituted or unsubstituted C2-C20 heterocyclic linking group, or a combination thereof, L 3 is *-O-*, *-S-*, *-C≡C-*, *-C(=O)-*, *-NR 0 -*(R 0 is a substituted or unsubstituted C1-C10 alkyl group) or a combination thereof, R 1 and R2 is independently represented by the following chemical formula R, [Chemical formula R] [Chem.] in chemical formula R, R 3 is a (meth)acrylate group, L 4 is a substituted or unsubstituted C1-C20 alkylene group.

[0015] The polymer containing the structural unit represented by the above chemical formula 1 may contain a functional group represented by the following chemical formula S at at least one of both ends.

[0016] [Chemical formula S] [Chem.]

[0017] The polymer containing the structural unit represented by the above chemical formula 1 may contain a functional group represented by chemical formula S at one of both ends, and the other may be a hydrogen atom.

[0018] ​​​​​​​​​​​​​​​​​Another embodiment provides a photosensitive resin film manufactured using a photosensitive resin composition.

[0023] The photosensitive resin film may also be a semiconductor redistribution layer insulating film.

[0024] Another embodiment provides a semiconductor device including a photosensitive resin film.

[0025] Other specific aspects of the present invention are included in the detailed description below. [Effects of the Invention]

[0026] In one embodiment, the alkali-soluble resin in the photosensitive resin composition contains polymers with different structures in specific weight ratios, which can lower the dielectric constant (Dk) and dielectric loss tangent (Df). [Modes for carrying out the invention]

[0027] 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.

[0028] 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 C3-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.

[0029] 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 This means that the substituents are substituted with a salt thereof, phosphoric acid or a salt thereof, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C6-C20 aryl group, a C3-C20 cycloalkyl group, a C3-C20 cycloalkenyl group, a C3-C20 cycloalkynyl group, a C2-C20 heterocycloalkyl group, a C2-C20 heterocycloalkenyl group, a C2-C20 heterocycloalkynyl group, a C3-C20 heteroaryl group, or a combination thereof.

[0030] 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.

[0031] Furthermore, unless otherwise specified herein, "(meth)acrylate" means that both "acrylate" and "methacrylate" are possible.

[0032] 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.

[0033] 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.

[0034] Unless otherwise defined in the chemical formulas herein, the absence of a chemical bond at a position where one should be depicted means that a hydrogen atom is bonded to that position.

[0035] Unless otherwise defined herein, "*" means a portion linked to the same or different atoms or chemical formulas.

[0036] The growing wafer-level packaging (WLP) and panel-level packaging (PLP) markets are leading to increased use of photosensitive materials for redistribution layers (RDLs). Currently, photosensitive materials include photosensitive polyimide resins, photosensitive benzocyclobutene (BCB) resins, and photosensitive phenol (Phenol) resins, with photosensitive polyimide resins being the most commonly used as they meet all the requirements for processability and reliability.

[0037] 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.

[0038] 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. Polyimide (PI) or polybenzoxazole (PBO) resins are primarily used to ensure film properties such as elongation and Tg (glass transition temperature), which are crucial for reliability, as core elements of photosensitive resin compositions used in semiconductor circuit protective films. These resins, when used together with other photocrosslinkable monomers, photopolymerization initiators, etc., ensure excellent protective film properties. However, to achieve superior patterns, excellent sensitivity characteristics without leaving residue are required, and storage stability of at least two weeks at room temperature is necessary. Furthermore, high frequencies should be used to improve the processing speed of electronic devices, and materials with low dielectric constant (Dk) and dielectric loss (Df) are required to prevent transmission speed loss.

[0039] The object of the present invention is to provide a photosensitive resin composition that ensures low dielectric loss while facilitating the formation of negative patterns. 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 mixing a polymer containing structural units represented by the following chemical formula 1 with a polymer containing structural units represented by the following chemical formula 2.

[0040] [Chemical formula 1] [ka]

[0041] [Chemical formula 2] [ka]

[0042] In the above chemical formulas 1 and 2, L 1 These are substituted or unsubstituted C1-C20 alkylene groups, substituted or unsubstituted C6-C20 arylene groups, or combinations thereof. L 2 These are single bonds, *-O-*, *-S-*, *-C≡C-*, *-C(=O)-*, and *-NR 0 -*(R 0 These are substituted or unsubstituted C1-C10 alkyl groups, substituted or unsubstituted C1-C20 alkylene groups, substituted or unsubstituted C6-C20 arylene groups, substituted or unsubstituted C2-C20 heterocyclic linking groups, or combinations thereof. L 3 *-O-*, *-S-*, *-C≡C-*, *-C(=O)-*, *-NR 0 -*(R 0 This is a substituted or unsubstituted C1-C10 alkyl group) or a combination thereof. R 1 and R 2These are each 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.

[0043] The following provides a detailed explanation of each component.

[0044] (A) Resin The structural unit-containing polymer represented by chemical formula 1 and the structural unit-containing polymer represented by chemical formula 2 may be included in a weight ratio of 1:1 to 1:2. When the alkali-soluble resin is controlled with such a composition, the dielectric constant and dielectric loss can be reduced.

[0045] For example, the polymer containing the structural unit represented by chemical formula 1 and the polymer containing the structural unit represented by chemical formula 2 may be included in a weight ratio of 1:1 to 1:1.5, for example, 1:1. In this case, the dielectric constant and dielectric loss can be further reduced.

[0046] For example, a polymer containing a structural unit represented by chemical formula 1 may contain a functional group represented by the following chemical formula S at at least one of its ends.

[0047] [Chemical formula S] [ka]

[0048] For example, a polymer containing a structural unit represented by chemical formula 1 may have a functional group represented by chemical formula S at one of its ends, and the other end may be a hydrogen atom.

[0049] The structural unit represented by chemical formula 1 may be mixed with polyamic acid or polyamic ester resins, and the polyamic acid or polyamic ester resins are resins obtained by polymerizing dianehydride compounds and diamine compounds, and may include, for example, the structural unit represented by chemical formula 3 below.

[0050] [Chemical formula 3] [ka]

[0051] Chemical formula 3, X 1 This is a residue derived from a dianehydride compound, Y 1 This is a residue derived from a diamine compound, R 4 and R 5 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.

[0052] For example, R 4 and R 5 Each of these may independently be a C1-C20 alkyl group substituted or unsubstituted with a (meth)acrylate group.

[0053] Polyamic acids and polyamic ester resins containing structural units represented by chemical formula 3, when mixed with polymers containing structural units represented by chemical formula 1, can easily improve adhesion to metal layers (especially copper, silicon, and titanium layers) while minimizing dielectric loss. In addition, they can be applied to negative-type compositions to easily and significantly improve developability. Generally, copper layers in semiconductor redistribution layers contain small amounts of titanium in addition to copper and silicon. Since resins with structures are advantageous for improving adhesion to titanium, the photosensitive resin composition according to one embodiment has excellent adhesion to copper and silicon layers in semiconductor redistribution layers, and at the same time can have a low dielectric loss tangent, compared to photosensitive resin compositions using resins without structures.

[0054] Generally, resins with a closed-ring structure have the problem of slightly reduced film properties during low-temperature curing. However, polyamic acids and polyamic ester resins containing structural units represented by chemical formula 3 contain ester linking groups and, as described later, also contain divalent fusion rings of resonance structures as linking groups, which can greatly contribute to lowering the dielectric loss tangent. A photosensitive resin composition according to one embodiment, which is used as an alkali-soluble resin by mixing this with a structural unit-containing polymer represented by chemical formula 1, is optimized for low-temperature curing and can provide an insulating film (cured film) with low dielectric loss tangent and excellent sensitivity characteristics.

[0055] For example, L 1 It may also be represented by the following chemical formula 4.

[0056] [Chemical formula 4] [ka] Chemical formula 4, L 5 and L 8 These are, independently, substituted or unsubstituted C1-C20 alkylene groups. L 6 and L 7These are, independently, substituted or unsubstituted C6-C20 arylene groups.

[0057] For example, the dianehydride compound may further contain a compound represented by the following chemical formula D.

[0058] [Chemical formula D] [ka] Chemical formula D, L 2 These are single bonds, *-O-*, *-S-*, *-C≡C-*, *-C(=O)-*, and *-NR 0 -*(R 0 These are substituted or unsubstituted C1-C10 alkyl groups, substituted or unsubstituted C1-C20 alkylene groups, substituted or unsubstituted C6-C20 arylene groups, substituted or unsubstituted C2-C20 heterocyclic linking groups, or combinations thereof.

[0059] For example, L 2 If *-C≡C-*, the heat resistance, adhesive strength, and reliability of the insulating film (cured film) can be further improved.

[0060] For example, a compound represented by chemical formula D may include a compound represented by chemical formula D-1 below, a compound represented by chemical formula D-2 below, or a combination thereof.

[0061] [Chemical formula D-1] [ka]

[0062] [Chemical formula D-2] [ka]

[0063] Chemical formula D-1, L 9*-O-*, *-S-*, *-C≡C-*, *-C(=O)-*, *-NR 0 -*(R 0 These are substituted or unsubstituted C1-C10 alkyl groups, substituted or unsubstituted C1-C20 alkylene groups, substituted or unsubstituted C6-C20 arylene groups, substituted or unsubstituted C2-C20 heterocyclic linking groups, or combinations thereof.

[0064] For example, a compound represented by chemical formula D-1 may also be represented by the following chemical formulas D-1-1 or D-1-2.

[0065] [Chemical formula D-1-1] [ka]

[0066] [Chemical formula D-1-2] [ka]

[0067] For example, the diamine compound may include a compound represented by the following chemical formula E.

[0068] [Chemical formula E] [ka]

[0069] Chemical formula E, L 3 *-O-*, *-S-*, *-C≡C-*, *-C(=O)-*, *-NR 0 -*(R 0 This is a substituted or unsubstituted C1-C10 alkyl group, or a combination thereof.

[0070] For example, the diamine compound may further contain a compound represented by the following chemical formula F.

[0071] [Chemical formula F] [ka]

[0072] Chemical formula F, R 6 is a hydrogen atom or a substituted or unsubstituted C1-C20 alkyl group, L 10 This is a substituted or unsubstituted C6-C20 arylene group or a substituted or unsubstituted divalent fusion ring. A divalent fusion ring is represented by the following chemical formula G: [Chemical formula G] [ka] Chemical formula G, R 7 This is a hydrogen atom or a substituted or unsubstituted C1-C20 alkyl group.

[0073] When the diamine compound contains the compound represented by chemical formula E and / or the compound represented by chemical formula F, it is advantageous for lowering the dielectric loss tangent. Furthermore, the compounds represented by chemical formula E and chemical formula F may be present in a molar ratio of 3:7 to 7:3, for example, 50:50, in which case the dielectric loss tangent can be significantly reduced.

[0074] For example, a compound represented by chemical formula F may include a compound represented by the following chemical formula F-1, a compound represented by the following chemical formula F-2, or a combination thereof.

[0075] [Chemical formula F-1] [ka]

[0076] [Chemical formula F-2] [ka]

[0077] For example, the polymer containing the structural unit represented by chemical formula 2 may be a polymer in which a dianehydride compound and a diamine compound are polymerized in a molar ratio of 30:70 to 70:30, for example, 50:50.

[0078] The weight-average molecular weight (M) of an alkali-soluble resin containing a structural unit polymer represented by chemical formula 1 and a structural unit polymer represented by chemical formula 2. w The weight-average molecular weight of the alkali-soluble resin may be between 3,000 g / mol and 300,000 g / mol. When the weight-average molecular weight of the alkali-soluble resin is within the above range, sufficient physical properties are obtained, and it has excellent solubility in organic solvents, making it easy to handle.

[0079] (B) Photopolymerizable compound A 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.

[0080] The photopolymerizable compound may also be a compound containing at least two functional groups represented by the following chemical formula 5.

[0081] [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.

[0082] 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.

[0083] For example, a compound containing at least two functional groups represented by chemical formula 5 may be, but is not necessarily limited to, a compound represented by any one of the following chemical formulas 6 to 8.

[0084] [Chemical formula 6] [ka] [Chemical formula 7] [ka] [Chemical formula 8] [ka] Chemical formulas 6 to 8, p, q, r, s, and t are each independent integers between 1 and 10.

[0085] If the photopolymerizable compound is a mixture of two different compounds, one of the other compounds may be a monofunctional or polyfunctional ester compound of (meth)acrylic acid having at least one ethylenically unsaturated double bond.

[0086] 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.

[0087] 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 Aronics M-101 (registered trademark), Aronics M-111 (registered trademark), Aronics M-114 (registered trademark) from Toagosei Chemical Industry Co., Ltd., KAYARAD TC-110S (registered trademark), KAYARAD TC-120S (registered trademark) from Nippon Kayaku Co., Ltd., and V-158 (registered trademark), V-2311 (registered trademark) from Osaka Organic Chemical Industry Co., Ltd. Examples of (meth)acrylic acid difunctional esters include Aronics M-210 (registered trademark), Aronics M-240 (registered trademark), and Aronics M-6200 (registered trademark) from Toagosei Chemical Industry Co., Ltd., KAYARAD HDDA (registered trademark), KAYARAD HX-220 (registered trademark), and KAYARAD R-604 (registered trademark) from Nippon Kayaku Co., Ltd., and V-260 (registered trademark), V-312 (registered trademark), and V-335HP (registered trademark) from Osaka Organic Chemical Industry Co., Ltd. Examples of trifunctional esters of (meth)acrylic acid include Aronics M-309 (registered trademark), Aronics M-400 (registered trademark), Aronics M-405 (registered trademark), Aronics M-450 (registered trademark), Aronics M-7100 (registered trademark), Aronics M-8030 (registered trademark), Aronics M-8060 (registered trademark) from Toagosei Chemical Industry Co., Ltd., and KAYARAD TMPTA (registered trademark), KAYARAD DPCA-20 (registered trademark), KAYARAD DPCA-30 (registered trademark), KAYARAD DPCA-60 (registered trademark) from Nippon Kayaku Co., Ltd. Examples include DPCA-120 (registered trademark), as well as V-295 (registered trademark), V-300 (registered trademark), V-360 (registered trademark), V-GPT (registered trademark), V-3PA (registered trademark), and V-400 (registered trademark) manufactured by Osaka Organic Chemical Industry Co., Ltd. Such products can be used individually or in combination of two or more.

[0088] Photopolymerizable compounds can also be treated with acid anhydrides before use to impart better developability.

[0089] 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 the above 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.

[0090] (C) Photoinitiator The photosensitive resin composition according to one embodiment may further contain a photoinitiator.

[0091] For example, the photoinitiator may be included in an amount of 2% to 5% by weight, for example, 2% to 4% by weight, relative to the total amount of the photosensitive resin composition. When the photoinitiator is included within the above range, it is possible to maintain low dielectric loss while simultaneously suppressing a decrease in sensitivity characteristics. Even if the alkali-soluble resin contains a structural unit-containing polymer represented by chemical formula 1 and a structural unit-containing polymer represented by chemical formula 2 in a weight ratio of 1:1 to 1:2, if the photoinitiator is not included within the above range, it may be difficult to maintain excellent sensitivity characteristics despite low dielectric loss.

[0092] The photoinitiators that can be used include acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, triazine compounds, and oxime compounds.

[0093] 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.

[0094] 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.

[0095] Examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone.

[0096] Examples of benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.

[0097] 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.

[0098] 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.

[0099] In addition to compounds, other photoinitiators that can be used include carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, imidazole compounds, non-imidazole compounds, and fluorene compounds.

[0100] The photoinitiator may be included in an amount of 3 to 20 parts by weight, for example, 3 to 10 parts by weight, or for example, 4 to 9 parts by weight, per 100 parts by weight of resin. When the photoinitiator is included within the above range, as described above, sufficient photopolymerization occurs, preventing a decrease in sensitivity characteristics and improving transmittance.

[0101] (D) Solvent The solvent can be an alkali-soluble resin, a photopolymerizable compound, or a substance that is compatible with but does not react with the photoinitiator.

[0102] 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-hydroxy-4-methyl-2-pentanone, methyl- Ketones such as n-propyl ketone, methyl-n-butyl ketone, methyl-n-amyl ketone, 2-heptanone, saturated aliphatic monocarboxylate alkyl esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, lactate esters such as methyl lactate, ethyl lactate, alkyl oxyacetates such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, alkyl alkoxyacetates such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionic acid 3-hydroxypropionate alkyl esters such as ethyl 3-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, alkyl 3-alkoxypropionate esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, propyl 2-hydroxypropionate, alkyl 2-hydroxypropionate esters, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate,Alkyl 2-alkoxypropionates such as methyl 2-ethoxypropionate, 2-oxy-2-methylpropionates such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate, alkyl monooxymonocarboxylates of alkyl 2-alkoxy-2-methylpropionates such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate, esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyethyl acetate, methyl 2-hydroxy-3-methylbutanoate, pyruvate Examples include ketonic acid esters such as ethyl ester, as well as 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.

[0103] 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 within the above range, the photosensitive resin composition has an appropriate viscosity, resulting in excellent processability during the production of the photosensitive resin film.

[0104] (E) Other additives The photosensitive resin composition according to one embodiment may further contain other additives.

[0105] 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.

[0106] 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.

[0107] For example, organic acids may include citric acid. Citric acid can play a role in improving ionic conductivity in electrolyte systems, which can affect electrical properties. For example, when citric acid is doped into an alginate-based solid biopolymer electrolyte, the electrolyte exhibits non-Debye behavior, which is analyzed through the composite dielectric constant (ε*) and composite electrical modulus (M*). Such results suggest that anomalous 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.

[0108] 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.

[0109] Examples of silane coupling agents include trimethoxysilylbenzoic 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.

[0110] 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 the above range, excellent adhesion, storage properties, etc., are obtained.

[0111] For example, surfactants are added to prevent film thickness stains or to improve developability, and may include fluorine-based surfactants and / or silicone-based surfactants.

[0112] Examples of fluorinated surfactants include BM-1000 (registered trademark), BM-1100 (registered trademark) from BM Chemie, Megafac F142D (registered trademark), Megafac F172 (registered trademark), Megafac F173 (registered trademark), Megafac F183 (registered trademark), Megafac F554 (registered trademark) from DIC Corporation, and Florad FC-135 (registered trademark), Florad FC-170C (registered trademark), Florad FC-430 (registered trademark), Florad FC-4 Products sold under names such as 31 (registered trademark), Surflon S-112 (registered trademark), Surflon S-113 (registered trademark), Surflon S-131 (registered trademark), Surflon S-141 (registered trademark), Surflon S-145 (registered trademark) manufactured by Asahi Glass Co., Ltd., and SH-28PA (registered trademark), SH-190 (registered trademark), SH-193 (registered trademark), SZ-6032 (registered trademark), SF-8428 (registered trademark) manufactured by Toray Silicon Corporation can be used.

[0113] 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.

[0114] 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 within the above 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.

[0115] 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.

[0116] 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, the shelf life, adhesion, and other properties can be improved.

[0117] 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.

[0118] Furthermore, the photosensitive resin composition may also contain a certain amount of other additives, such as antioxidants and stabilizers, as long as they do not impair its physical properties.

[0119] 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.

[0120] The manufacturing method for the photosensitive resin film (semiconductor redistribution layer insulating film) is as follows:

[0121] (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.

[0122] (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.

[0123] 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:

[0124] (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.

[0125] (4) Post-processing stage The image pattern obtained by development in the above process is subject to a post-heating step to obtain a 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, it can be heated in an oven at 200°C to 400°C under a nitrogen atmosphere for more than one hour.

[0126] Another embodiment provides a semiconductor device that includes a photosensitive resin film (a semiconductor redistribution layer insulating film).

[0127] Preferred embodiments of the present invention are disclosed below. However, the following embodiments are merely preferred embodiments of the present invention, and the present invention is not limited to the following embodiments. [Examples]

[0128] (Synthesis of resins) <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 added to 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 dicyclohexylcarbodiimide (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 for 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. Then, GBL was added until the solid content of the reaction solution reached 18%, and the mixture was added to 3 liters of ethanol to obtain a precipitate. The polymer was filtered and separated, dissolved in 1.5 liters of tetrahydrofuran (THF), and then 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 precursor resin (polyamic ester 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]

[0129] <Synthesis Example 2> MIR-3000 (manufactured by Nippon Kayaku Co., Ltd.) (Manufacturing of photosensitive resin composition) <Examples 1-7 and Comparative Examples 1-6> A photosensitive resin composition was prepared according to the composition shown in Table 1 below. Specifically, an alkali-soluble resin and a photopolymerizable compound were mixed, and a photoinitiator, 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.

[0130] [Table 1] (Unit: weight %) Alkali-soluble resin 1: Resin of synthesis example 1 Alkali-soluble resin 2: Resin of synthesis example 2 Photopolymerizable compound: Tetraethylene glycol dimethacrylate (manufactured by TCI) Photoinitiator: PBG-450 (manufactured by Changzhou Tronly Co., Ltd.) Photosensitizer: N-phenyldiethanolamine (manufactured by MORIN) Radical Scavenger: CX-1790 (manufactured by Solvay) Silane-based coupling agent: KBM-403 (manufactured by Shinetsu) Organic acid: Citric acid (manufactured by SAMCHUN) Solvent 1: γ-butyrolactone (manufactured by DAEJUNG) Solvent 2: Dimethyl sulfoxide (manufactured by DAEJUNG)

[0131] (evaluation) The photosensitive resin compositions from Examples 1 to 7 and Comparative Examples 1 to 6 were coated onto 8-inch Cu wafers and baked at 100°C for 4 minutes to obtain a 7 μm film. The wafers were then exposed using a Nikon i10C and developed with cyclopentanone for 20 seconds and 20 seconds using a paddle-type filter to form a 20 μm hole pattern. The developed wafers were then cured in a 220°C oven under a nitrogen atmosphere for 2 hours.

[0132] Eop evaluation: Using a CD-SEM, the exposure dose required to form a 20 μm hole was determined, and the results are shown in Table 2 below.

[0133] Evaluation of dielectric loss tangent (Df): The manufactured film (cured film) was dried at 130°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.

[0134] Reliability Evaluation: The manufactured film (cured film) was subjected to a thermal cycle (-55°C to 125°C) under reliability conditions for 2000 cycles. 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.

[0135] [Table 2]

[0136] From Table 2, it was confirmed that the photosensitive resin composition according to one embodiment has a low dielectric loss tangent, as well as excellent sensitivity characteristics and reliability, making it suitable for use as a composition for semiconductor redistribution layers.

[0137] The present invention is not limited to the embodiments described herein and can be manufactured in a variety of different forms. Those with ordinary skill in the art to which the present invention pertains should understand that it can be implemented in other specific forms without altering the technical idea or essential features of the present invention. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not limiting.

Claims

1. Alkali-soluble resin, photopolymerizable compound, Photoinitiator, and solvent Includes, The alkali-soluble resin comprises a structural unit-containing polymer represented by the following chemical formula 1 and a structural unit-containing polymer represented by the following chemical formula 2, wherein the structural unit-containing polymer represented by the following chemical formula 1 and the structural unit-containing polymer represented by the following chemical formula 2 are present in a weight ratio of 1:1 to 1:2 in the photosensitive resin composition: [Chemical formula 1] 【Chemistry 1】 [Chemical formula 2] 【Chemistry 2】 In the aforementioned chemical formulas 1 and 2, L １ These are substituted or unsubstituted C1-C20 alkylene groups, substituted or unsubstituted C6-C20 arylene groups, or combinations thereof. L ２ These are single bonds, *-O-*, *-S-*, *-C≡C-*, *-C(=O)-*, and *-NR ０ - * (R ０ These are substituted or unsubstituted C1-C10 alkyl groups, substituted or unsubstituted C1-C20 alkylene groups, substituted or unsubstituted C6-C20 arylene groups, substituted or unsubstituted C2-C20 heterocyclic linking groups, or combinations thereof. L ３ *-O-*, *-S-*, *-C≡C-*, *-C(=O)-*, *-NR ０ - * (R ０ This is a substituted or unsubstituted C1-C10 alkyl group) or a combination thereof. R １ and R ２ are each independently represented by the following chemical formula R, [Chemical formula R] 【Transformation 3】 In the aforementioned chemical formula R, R ３ is a (meth)acrylate group, L ４ These are substituted or unsubstituted C1-C20 alkylene groups.

2. The photosensitive resin composition according to claim 1, wherein the polymer containing the structural unit represented by chemical formula 1 contains a functional group represented by the following chemical formula S at at least one of its ends. [Chemical formula S] 【Chemistry 4】

3. The photosensitive resin composition according to claim 2, wherein the polymer containing the structural unit represented by chemical formula 1 contains a functional group represented by chemical formula S at one of its ends, and the other end is a hydrogen atom.

4. The photosensitive resin composition according to claim 1, wherein the photoinitiator is contained in an amount of 2% to 5% by weight relative to the total amount of the photosensitive resin composition.

5. The aforementioned photosensitive resin composition, Amount of 100 parts by weight of the alkali-soluble resin The photopolymerizable compound is contained in an amount of 5 to 20 parts by weight, The photoinitiator is contained in an amount of 3 to 20 parts by weight, The photosensitive resin composition according to claim 1, wherein the solvent is contained in an amount of 100 to 500 parts by weight.

6. The photosensitive resin composition according to claim 1, further comprising a photosensitizer, a radical scavenger, a silane coupling agent, an organic acid, or a combination thereof.

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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